Process for producing liquid transport fuel component

Abstract

The present invention provides a process for producing at least one liquid transport fuel component wherein in a first mode of operation of the process, a paraffin hydrocarbon feed is converted to a hydroisomerization effluent, fractionated, and its fraction is recycled back to fractionation via a hydrocracking reactor, from which the liquid transport fuel component is recovered, and in a second mode of operation of the process, the liquid transport fuel component is recovered. Preferably an aviation fuel component. In the process, parameters indicative of the deactivation of the hydroisomerization catalyst are monitored, and when these parameters reach predetermined values, the process is switched to a second operating mode in which the hydroisomerization effluent is hydrocracked and the obtained hydrocracked effluent is fractionated to obtain a liquid transport fuel component, preferably an aviation fuel component.

Description

Technical Field

[0001] The present invention generally relates to a method for producing a renewable fuel component. The present invention specifically, but not exclusively, relates to a method for producing at least one or more liquid transportation fuel components, preferably at least an aviation fuel component. Systems and computer programs that can be used to run the method are also disclosed. 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 aviation, 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 the described methods, the yield of aviation fuel components (compared to other fuel components) is relatively low. In addition, there is a need to improve the quality of renewable aviation fuel components. In particular, there is still interest in the production of aviation fuel components that can be used in higher amounts in aviation fuels, or, when appropriately added, even used as aviation fuels themselves. Summary of the invention

[0005] The 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 appended claims define the scope of protection. Any examples and technical descriptions of devices, products, systems 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 for 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, of which at most 30 wt% are 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;

[0010] i) fractionating the hydroisomerization effluent to separate from the fractionation a recycle stream having at least a T5 temperature of 270° C. or more (recovery 5 vol%, EN ISO 3405-2019);

[0011] ii) hydrocracking a second reactor feed comprising the recycle stream in the presence of a hydrocracking catalyst in a second reactor to obtain a recycle effluent;

[0012] iii) feeding the recycle effluent to a fractionation as a co-feed with the hydroisomerization effluent and recovering at least one or more liquid transportation fuel components from the fractionation; and

[0013] monitoring a parameter indicative of hydroisomerization catalyst deactivation to receive a value;

[0014] comparing the received value to a predetermined value; and

[0015] When the received value reaches a predetermined value, switch from i), ii), and iii) to:

[0016] I) hydrocracking a second reactor feed comprising the hydroisomerization effluent in the presence of a hydrocracking catalyst in a second reactor to obtain a hydrocracked effluent;

[0017] II) subjecting the hydrocracking effluent to fractionation and recovering at least one or more liquid transportation fuel components from the fractionation.

[0018] In certain embodiments, in steps iii) and II), at least one or more of the aviation fuel component, the diesel fuel component, the gasoline fuel component and / or the marine fuel component are recovered from the fractionation, preferably at least the aviation fuel component, more preferably at least the aviation fuel component and the diesel fuel component or at least the aviation fuel component and the gasoline fuel component.

[0019] In certain preferred embodiments, in steps iii) and II), at least an aviation fuel component having a density at 15°C of 730 to 772 kg / m 3 (EN ISO 12185-1996), with a T10 temperature of up to 205°C (EN ISO 3405-2019), a final boiling point of up to 300°C (EN ISO 3405-2019), a flash point of at least 38°C (IP170-2013, Abel closed-cup method) and a freezing point of up to -40°C (IP 529-2016).

[0020] The present method is particularly suitable for producing aviation fuel components. Compared with conventional methods of producing fuel components by hydrodeoxygenation (HDO) and hydroisomerization (HI) of renewable fats and oils, the present method enables a higher yield of aviation fuel components to be obtained. In addition, compared with aviation fuel components produced by the above conventional methods, the method of the present invention enables the production of aviation fuel components with improved quality that can be used in aviation fuel in increased amounts or even when appropriately added. In addition, compared with the above conventional methods, the present method extends the life of the hydroisomerization (HI) catalyst and enables the use of a wider range of feeds, including heavier and more impure feeds.

[0021] According to a second exemplary aspect, there is provided a system for producing at least one liquid transportation fuel component, wherein the system is configured to operate a method using i), ii), iii) or I), II), III) of the system, the system comprising:

[0022] a device configured to provide 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;

[0023] a first reactor configured to hydroisomerize a paraffinic hydrocarbon feed in the first reactor in the presence of a hydroisomerization catalyst to obtain a hydroisomerization effluent;

[0024] a fractionation system configured to i) fractionate a hydroisomerization effluent to separate from the fractionation at least a recycle stream having a T5 temperature (recovery 5 vol%, EN ISO 3405-2019) of 270°C or more, and to fractionate the recycle effluent (after ii) and iii)); and to II) fractionate a hydrocracking effluent;

[0025] a second reactor configured to ii) hydrocrack a second reactor feed comprising a recycle stream in the second reactor in the presence of a hydrocracking catalyst to obtain a recycle effluent; and i) hydrocrack a second reactor feed comprising a hydroisomerization effluent in the second reactor in the presence of a hydrocracking catalyst to obtain a hydrocracking effluent;

[0026] a pipeline configured to feed iii) the recycle effluent and the hydroisomerization effluent to the fractionation system, and to feed III) the hydrocracking effluent to the fractionation system;

[0027] an apparatus configured to recover at least one or more liquid transportation fuel components from the fractionation system; and

[0028] A control device configured to monitor a parameter indicative of hydroisomerization catalyst deactivation to receive a value; compare the received value to a predetermined value; and when the received value reaches the predetermined value, switch from (system) i), ii), iii) to I), II), III).

[0029] According to a third exemplary aspect, a computer program product is provided comprising instructions, which, when executed by a processor of a control device in a system for producing at least one liquid transportation fuel component, causes the control device to compare a received value with a predetermined value in the method according to the first exemplary aspect, and to switch from i), ii), iii) to I), II) when the received value reaches the predetermined value. The computer program product may cause a control device or a control device in a system for producing at least one liquid transportation fuel component to implement at least the following steps of the method as defined in the first exemplary aspect: comparing the received value with a predetermined value; and switching from i), ii), iii) to I), II).

[0030] To name just a few of the advantages, the computer program product according to the third example aspect enables the method as defined in the first example aspect to be run more accurately, monitor a greater number of different parameters, compare the values ​​obtained with massive data sets, use the values ​​obtained in complex models, adjust and / or switch the method more quickly based on the comparison, improve or adjust the yield and / or quality of the recovered liquid transportation fuel components as required, and enhance the safety of the present method.

[0031] 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

[0032] Some example embodiments will be described with reference to the accompanying drawings, in which:

[0033] Figure 1 Schematically illustrates a method according to an example embodiment before switching from i), ii), iii) to I), II), i.e., operating according to the example embodiment of i), ii), iii) (first mode); and

[0034] Figure 2 The method according to the exemplary embodiment is schematically shown after switching from i), ii), iii) to I), II), ie, operating according to the exemplary embodiment of I), II) (second mode). DETAILED DESCRIPTION

[0035] In the following description, like reference symbols denote like elements or steps.

[0036] Unless otherwise stated, all standards referred to herein are to the latest revision available on the date of submission.

[0037] Unless otherwise stated, for distillation characteristics such as initial boiling point (IBP), final boiling point (FBP), T5 temperature (5 vol% recovery), T95 temperature (95 vol% recovery) and boiling range, reference is made to EN ISO 3405-2019. IBP is the temperature at which the first drop of condensate falls from the lower end of the condenser tube, and FBP is the maximum thermometer reading obtained during the test, which usually occurs after all the liquid at the bottom of the flask has evaporated. For boiling point distribution, reference may also be made to the GC-based method (simdis) ASTM D2887-19e1, or, for gasoline range hydrocarbons, to ASTM D7096-19.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] As used herein, hydrocarbon refers to a compound consisting of carbon and hydrogen. Hydrocarbons of particular interest in the context of this article include paraffins, n-paraffins, isoparaffins, mono-branched isoparaffins, multi-branched isoparaffins, olefins, cycloalkanes, and aromatic compounds. Oxygenated hydrocarbons refer to hydrocarbons comprising covalently bonded oxygen in this article.

[0043] As used herein, paraffin refers to non-cyclic alkanes, i.e., non-cyclic, open-chain saturated hydrocarbons that are straight (n-paraffin) or branched (isoparaffin). In other words, paraffin refers herein to n-paraffin and / or isoparaffin.

[0044] In the context of the present disclosure, isoparaffin refers to branched open-chain alkanes, i.e., non-cyclic, open-chain saturated hydrocarbons with one or more alkyl side chains. In this article, isoparaffins with one alkyl side chain or branch are referred to as monobranched isoparaffins, and isoparaffins with two or more alkyl side chains or branches are referred to as multi-branched isoparaffins in this article. In other words, isoparaffins refer to monobranched isoparaffins and / or multi-branched isoparaffins in this article. For example, the alkyl side chain of isoparaffins can be a C1-C9 alkyl side chain, preferably a methyl side chain. The amount of monobranched and multi-branched isoparaffins can be given respectively. The term "isoparaffin" refers to the total amount of any monobranched isoparaffins and any multi-branched isoparaffins (if present), which represents the total amount of any isoparaffins present without considering the number of branches. Accordingly, "paraffin" refers to the total amount of any normal paraffins, any monobranched and any multi-branched isoparaffins (if present).

[0045] In the context of the present disclosure, olefin refers to an unsaturated, linear, branched or cyclic hydrocarbon, excluding aromatic compounds. In other words, olefin refers to a hydrocarbon having at least one unsaturated bond, excluding unsaturated bonds in aromatic rings.

[0046] As used herein, cyclic hydrocarbons refer to all hydrocarbons containing a ring structure, including cycloolefins, cycloalkanes, and aromatic compounds. Cycloalkanes (naphthenes) herein refer to cycloalkanes, 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 compounds herein refer to hydrocarbons containing at least one aromatic ring structure, i.e., a ring structure with delocalized alternating π bonds around the ring structure.

[0047] In the context of the present disclosure, for compositions boiling at or above 36°C (at standard atmospheric pressure), the content of n-paraffins, isoparaffins, mono-branched isoparaffins, multiple multi-branched isoparaffins, cycloparaffins and aromatic compounds 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 a GC×GC-FID / GC×GC-MS method, preferably performed as follows: as generally disclosed in UOP 990-2011 and in the experimental part of Nousiainen M. in his master's thesis Comprehensive two-dimensional gas chromatography with mass spectrometric and flame ionization detectors in petroleum chemistry, University of Helsinki, August 2017, with the following modifications to run the GC×GC (2D GC) method. The GC×GC was operated in reverse mode, using first a semipolar column (Rxi17Sil) and then a nonpolar column (Rxi5Sil), followed by an FID detector, using the following operating parameters: carrier gas: helium 31.7 cm / sec (column flow 1.60 ml / min at 40 °C); split ratio: 1:350; injector: 280 °C; column T program: 40 °C (0 min)–5 °C / min–250 °C (0 min)–10 °C / min–300 °C (5 min), run time: 52 min; modulation period: 10 s; detector: 300 °C, using H2 40 ml / min and air 400 ml / min; makeup gas flow: helium 30 ml / min; sampling rate: 250 Hz, and injection volume: 0.2 μL. Individual compounds were identified using GC×GC-MS with the following MS parameters: ion source: 230°C; interface: 300°C; scan range: 25–500 amu; event time (seconds): 0.05; scan speed: 20,000. Data processing was performed using commercial tools (Shimadzu's LabSolutions, Zoex's GC Image), including identification of the detected compounds or hydrocarbon radicals and determination of their mass concentrations by applying a response factor relative to n-heptane to the volume of the detected peaks and then normalizing to 100 wt%. Unless reported separately, olefins were classified as cycloalkanes and heteroatom-containing substances were classified as aromatics. The quantification limit for individual compounds of this method was 0.1 wt%.

[0048] 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.

[0049] 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 component.

[0050] In the context of the present disclosure, the feed to a reactor, in particular the first reactor and / or the second reactor, is defined such that H2 that may be fed to the respective reactor, e.g. H2 fed to hydroisomerization and H2 fed to hydrocracking, is excluded from the definition of feed.

[0051] 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.

[0052] 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.

[0053] In the context of the present disclosure, CY-paraffin, CY-n-paraffin, CY-isoparaffin, CY-monobranched isoparaffin, CY-multibranched isoparaffin, CY-hydrocarbon or CY-fatty acid refers to paraffin, n-paraffin, isoparaffin, monobranched isoparaffin, multibranched isoparaffin, hydrocarbon or fatty acid having a carbon number up to Y, respectively, wherein Y is any feasible integer. It should be understood that every compound falling within the scope of this definition does not necessarily have to be present.

[0054] In the context of this disclosure, CX Y -CX Z (or CX Y To CX Z ) Paraffin, CX Y -CXZ 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 Is a feasible end value integer, wherein the carbon number within the range is indicated by any integer between the end value integer and the end value (if any). However, unless explicitly stated, all the carbon numbers are within the range, and paraffins, normal paraffins, isoparaffins, monobranched isoparaffins, multi-branched isoparaffins, hydrocarbons or fatty acids at or near the endpoints are not necessarily present, as the case may be. On the other hand, according to the definition, isomers can include several compounds with the same carbon number, such as C15 isomers can include methyl tetradecane (different positions of methyl branches), dimethyl tridecane (different positions of two methyl branches), etc., wherein "C15 isomers" include the sum of all these variants.

[0055] Usually, the sum of the weight or volume of paraffin, normal paraffin, isoparaffin, monobranched isoparaffin, multibranched isoparaffin, hydrocarbon or fatty acid, as defined each time, means to include all carbon numbers.For example, C15 to C22 normal paraffin refers to any normal paraffin in the described scope, such 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 adding 0 (referring to non-existent C15 normal paraffin) to the gross weight of all other C15 to C22 normal paraffins present, the total amount is obtainable.

[0056] Isomerization converts at least a certain amount of normal paraffins into isoparaffins, in particular 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 multibranched isoparaffins, such as dibranched and / or triplanched isoparaffins, or even isoparaffins containing more than three branches.

[0057] 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 in particular as expressed herein as the ratio of the C8 to C14 hydrocarbon content in the hydrocracking effluent (step i)) or the recycle effluent (step ii)) to the C8 to C14 hydrocarbon content in the second reactor feed.

[0058] As used herein, as long as the reaction step is defined as occurring in a "reactor", such as a first reactor and a second reactor, the expression is primarily for illustrative purposes. Those skilled in the art recognize that any "reactor" is implemented in practice as a reactor system that can be composed of one or more reactors. Whether the reactor is actually arranged in a single reactor or in several reactors is an engineering problem and may be affected by practical issues such as the maximum height of the field facility, the reactor diameter, the management and maintenance issues on site, the wind conditions on site and / or the available equipment. Similarly, "fractionation" can be carried out in a fractionation system, which typically includes (for example) separation and distillation units, which can be arranged according to conventional engineering practices in the art.

[0059] 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.

[0060] As used herein, the term catalyst deactivation refers to the change in the activity and / or selectivity of the catalyst at a given time point (t0) compared to the activity and / or selectivity of the catalyst at the start of the process (t0). n The term catalyst deactivation is defined as a decrease in catalyst activity (reflected by the amount of unconverted feed in the reactor effluent) and / or a decrease in catalyst selectivity (reflected by a decrease in the amount of desired reaction product in the reactor effluent). As used herein, the term catalyst deactivation is not limited to any particular deactivation type or mechanism, although catalyst deactivation observed in the present process is generally believed to be due to poisoning and fouling phenomena, and encompasses both reversible and irreversible deactivation.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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) and EN 16640 (2017). The methods are based on the fact that carbon atoms of renewable or biological origin contain a higher number of unstable radiocarbons ( 14 C) atoms. Therefore, it is possible to analyze 12 C and 14 C isotope ratios are used to distinguish carbon compounds derived from renewable or biological sources or raw materials from carbon compounds derived from non-renewable or fossil sources or raw materials. Therefore, a specific ratio of the isotopes can be used as a "tag" to identify a renewable carbon compound and distinguish it from a non-renewable carbon compound. The isotope ratio does not change during a chemical reaction. Therefore, the isotope ratio can be used to identify renewable compounds, components and compositions and distinguish them from non-renewable, fossil materials in reactor feeds, reactor effluents, separated product fractions and various blends thereof. Numerically, the biochar content can be expressed as the amount of biochar in the material as a weight percentage of the total carbon (TC) in the material (according to ASTM D6866 (2020) or EN 16640 (2017)). In the context of the present invention, the term renewable preferably refers to a material having a biocarbon content of 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)).

[0065] According to a first exemplary aspect, provided herein is a method of producing at least one liquid transportation fuel component, the method comprising:

[0066] providing a paraffinic feed comprising at least 60 wt% paraffinic hydrocarbons based on the total weight of the paraffinic feed, of which at most 30 wt% are isoparaffinic hydrocarbons;

[0067] subjecting the paraffin feed in the first reactor to hydroisomerization in the presence of a hydroisomerization catalyst to obtain a hydroisomerization effluent;

[0068] i) subjecting the hydroisomerization effluent to fractionation to separate from the fractionation effluent at least a recycle stream having a T5 temperature (recovery 5 vol%, EN ISO 3405-2019) of 270°C or more;

[0069] ii) subjecting a second reactor feed comprising the recycle stream to hydrocracking in a second reactor in the presence of a hydrocracking catalyst to obtain a recycle effluent;

[0070] iii) feeding the recycle effluent to a fractionation as a co-feed with the hydroisomerization effluent and recovering at least one or more liquid transportation fuel components from the fractionation; and

[0071] monitoring a parameter indicative of hydroisomerization catalyst deactivation to receive a value; comparing the received value to a predetermined value; and when the received value reaches the predetermined value, switching from i), ii), iii) to:

[0072] I) subjecting a second reactor feed comprising a hydroisomerization effluent to hydrocracking in a second reactor in the presence of a hydrocracking catalyst to obtain a hydrocracking effluent;

[0073] II) subjecting the hydrocracking effluent to fractionation and recovering at least one or more liquid transportation fuel components from the fractionation.

[0074] Preferably, the process of the present invention is a continuous process.

[0075] The method operating according to steps i), ii), iii) may be referred to as an initial / first mode of the method / operation, whereas the method operating according to steps I), II) may be referred to as a switching / second mode of the method / operation.

[0076] A first exemplary aspect provides a method for producing at least one liquid transportation fuel component, wherein in a first mode of operating the method, a paraffinic hydrocarbon feed can be converted into a hydroisomerization effluent, fractionated, and its fractions recycled back to fractionation via a second hydrocracking reactor, from which a liquid transportation fuel component, preferably an aviation fuel component, can be recovered. In the method, parameters indicative of deactivation of the hydroisomerization catalyst are monitored, and when these parameters reach predetermined values, the method can be switched to a second mode of operation, wherein the hydroisomerization effluent can be hydrocracked, and the obtained hydrocracking effluent can be fractionated to obtain a liquid transportation fuel component, preferably an aviation fuel component.

[0077] At least one or more liquid transportation fuel components recovered from the fractionation may be one or more of an aviation fuel component, a diesel fuel component, a gasoline fuel component and / or a marine fuel component. Preferably, at least an aviation fuel component is recovered, more preferably at least an aviation fuel component and a diesel fuel component are recovered, or at least an aviation fuel component and a gasoline fuel component are recovered.

[0078] Compared to conventional methods of producing fuel components, for example, by hydrodeoxygenation (HDO) and HI of renewable fats and oils, using the method of the present invention, it is possible to obtain higher yields of aviation fuel components over the entire hydroisomerization (HI) catalyst life without reducing the capacity of HI in the first reactor, and / or to improve the quality of aviation fuel components.

[0079] Using the process of the present invention, even near the end of the HI catalyst life, it is possible to produce an aviation fuel component that has excellent low temperature properties and is therefore usable in aviation fuel at high blending ratios or even by itself (i.e., unblended) when properly added. In addition, compared to conventional processes for producing fuel components from HDO and HI of renewable fats and oils, the process of the present invention enables the HI catalyst life to be extended and enables the use of a wider range of feeds, including heavier and more impure feeds.

[0080] Furthermore, even at the end of the HI catalyst life, the process of the present invention enables flexible adjustment of product selectivity to various 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.

[0081] The process of the present invention proposes to subject the HI effluent or a portion thereof to hydrocracking (HC), which cracks the longer paraffinic hydrocarbon chains into paraffinic hydrocarbons boiling, for example, in the range of aviation fuel, and can even isomerize the n-paraffinic hydrocarbons in the HC feed and the n-paraffinic hydrocarbons formed during the cracking reaction, and further isomerize the isoparaffinic hydrocarbons by increasing the number of branches in the isoparaffinic hydrocarbon molecules, for example, producing multi-branched isoparaffinic hydrocarbons. Hydrocracking can increase the yield of aviation fuel components and improve their quality, such as their low temperature properties, especially reducing their freezing point and / or viscosity at sub-zero temperatures (such as -20°C).

[0082] During the continuous operation of catalytic hydroisomerization, the HI catalyst (for example) gradually deactivates due to impurities and coking in the process stream. The method of the present invention is highly flexible and involves multiple possibilities for adjusting the yield and / or quality of the recovered liquid transportation fuel components and extending the life of the HI catalyst in particular. Adjusting the amount of the recycle stream subjected to hydrocracking and / or the amount of heavy substances (heavy molecules) removed from the method as diesel fuel, marine fuel or other heavy product components is a convenient means for adjusting the yield and / or quality of the recovered liquid transportation fuel components and responding to catalyst deactivation and / or changing market demands. In addition, when (for example) only the recycle stream (i.e., only the heavy fraction of the HI effluent) is hydrocracking, the gaseous impurities that are usually present in the gas phase of the HI effluent are not in contact with the hydrocracking (HC) catalyst. Compared with the conventional method of producing liquid fuel components by HDO and HI of renewable fats and oils, the present method compensates for the multiple possibilities of HI catalyst deactivation in particular, enabling the use of paraffin feeds with higher impurity contents. Additionally, the hydrocracking step enables the use of feedstocks containing heavier and longer chain molecules than described conventional processes for producing liquid fuel components (typically diesel components), while enabling the production of lower boiling liquid transportation fuel components, such as aviation fuel components and / or gasoline fuel components, in good yield and quality.

[0083] The method of the present invention includes monitoring a parameter indicative of HI catalyst deactivation to receive a value; comparing the received value with a predetermined value; and when the received value reaches or equals the predetermined value, switching from i), ii), iii) to I), II), i.e., switching from the first mode to the second mode. Preferably, the received value is compared with the corresponding predetermined value. Switching from i), ii), iii) to I), II) can compensate for HI catalyst deactivation, thereby allowing the recovered at least one liquid transportation fuel component to maintain good yield and quality for a longer period of time before the HI catalyst in the first reactor needs to be changed or regenerated.

[0084] Initially, at the beginning of the process operation, the activity of the HI catalyst is usually good or sufficient and the value received from the monitoring is not equal to the (corresponding) predetermined value. However, at some point during the process operation, the deactivation of the HI catalyst usually reaches a point when the value received from the monitoring reaches a (corresponding) predetermined value, which has been identified as indicating that the performance of the HI catalyst is insufficient or close to insufficient, for example, in terms of the volume (yield) and / or composition and / or physicochemical characteristics of the recovered liquid transportation fuel component. At this point, when the value received from the monitoring reaches the (corresponding) predetermined value, a switch from i), ii), iii) to I), II) is usually performed in order to restore and preferably even exceed the target minimum value of the process performance. By switching from i), ii), iii) to I), II), the process can be operated for a longer time, thereby producing the desired liquid transportation fuel component in the desired amount and the desired quality.

[0085] In certain embodiments, in addition to switching from the first mode to the second mode, the method of the present invention may include adjusting one or more operating conditions of the first reactor and / or the second reactor to reach, maintain or even exceed the target minimum value of the method performance. In these embodiments, the switch from the first mode to the second mode can be performed at some point after the operating conditions of the first reactor and / or the second reactor have been adjusted in one or more cases. The operating conditions can be adjusted to their feasible limits and then the switch is performed, or alternatively, the operating conditions can be adjusted to a certain extent and the switch has been performed before the limit is reached. The adjustment of one or more operating conditions can be based on the same or different parameters as the switch from i), ii), iii) to I), II). Preferably, the first reactor and / or the second reactor, in particular one or more operating conditions of the first reactor are first adjusted to compensate for catalyst deactivation, especially HI catalyst deactivation, and when it is no longer feasible (or no longer necessary) to compensate for catalyst deactivation only by adjusting the operating conditions in the first reactor and / or the second reactor, the switch from i), ii), iii) to I), II) is performed. In certain embodiments, after switching from i), ii), iii) to i), II), when the HI effluent is substantially completely fed to the second reactor for hydrocracking, the operating conditions of the first reactor may be mitigated, and thus the target yield and / or quality of the recovered fuel component may be achieved in the first reactor at a lower temperature and / or a higher WHSV than before the switch (for example). In these embodiments, after the switch, it may be beneficial to increase the temperature in the second reactor to compensate for the generally increased WHSV therein. During the second operating mode, one or more operating conditions of the first reactor and / or the second reactor may be (again) adjusted to compensate for further catalyst deactivation, in particular deactivation of the HI catalyst in the first reactor.

[0086] When the process has been run for a sufficiently long time in the switched modes i), ii), and the operating conditions in the first reactor and / or the second reactor have been optionally adjusted to their feasible limits, the target performance of the process, for example in terms of the yield, and / or composition, and / or physicochemical characteristics of the recovered liquid transport fuel components, can no longer be achieved due to the degree of catalyst deactivation. Then, usually before optionally starting to run the process in the first mode, i.e., running the series i), ii), iii), the catalyst is replaced with a fresh catalyst or regenerated.

[0087] In certain embodiments, the method does not include adjusting operating conditions to compensate for catalyst deactivation, i.e., is performed without adjustment, and the deactivation of the HI catalyst in the first reactor is compensated by switching from i), ii), iii) to I), II). In these embodiments, the total feasible operating time of the method can be shorter than the time in the embodiment in which the operating conditions of at least the first reactor are adjusted in addition to switching from i), ii), iii) to I), II).

[0088] Other variations of the process of the present invention may include switching from I), II) back to i), ii), iii), and thereafter operating the first and / or second reactor, adjusting the operating conditions to compensate for at least the deactivation of the HI catalyst. In addition, the operating conditions may be adjusted to their feasible limits and then switched from i), ii), iii) to I), II), or alternatively, the operating conditions may be adjusted to a certain extent and the switch from i), ii), iii) to I), II) may be performed before reaching the extreme values.

[0089] An example sequence for applying these variants includes operating the method in a first mode and adjusting the operating conditions up to the feasible limit; thereafter, switching to a second mode and adjusting the operating conditions up to the feasible limit; then switching back, i.e. switching from I), II) to i), ii), iii), and operating until the target is no longer met despite adjusting the operating conditions, and then switching from i), ii), iii) to I), II) and operating until the target is no longer met despite adjusting the operating conditions, which results in regeneration or modification of the catalyst.

[0090] The first and second operating modes, combined with appropriate temperatures and other operating conditions in the first and second reactors, provide the possibility to flexibly adjust the process to meet and even optimize target yields and / or qualities of various recovered components.

[0091] In certain preferred embodiments of the process of the present invention, in step ii), a portion of the hydroisomerization effluent is fed to the second reactor for hydrocracking as a co-feed with the recycle stream (as part of the feed to the second reactor); and / or in step II), 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 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 in the operation of the process of the present invention and provide the possibility of even more precisely adjusting the process to meet the target yield and quality of more than one recovered component at the same time. In this way, it may be possible to avoid a situation in which the target yield and quality of one recovered fuel component is met, but at the expense of producing an excessively high quality of another recovered fuel component (e.g., producing a diesel fuel component with an unnecessarily low cloud point). When switching the process from i), ii), iii) to I), II), it may also be beneficial to split the HI effluent, thereby providing a smooth transition between the modes. For example, switching from i), ii), iii) to I), II) may include feeding a decreasing portion of the HI effluent to fractionation starting from i), ii), iii), and simultaneously feeding an increasing portion of the HI effluent to hydrocracking as a co-feed with a recycle stream (as part of the second reactor feed) until substantially all of the (degassed) HI effluent is fed thereto, i.e., the process is operated according to I), II).

[0092] In an embodiment, when a portion of the hydroisomerization effluent is fed to the fractionation in step II) as a co-feed with the hydrocracking effluent, the amount of this portion of the HI effluent in step II) may vary, but is typically only a small portion (outside of the switch). For example, the portion of the HI effluent optionally fed to the fractionation in step II) as a co-feed with the hydrocracking effluent may be less than 50 wt %, preferably less than 30 wt %, more preferably less than 10 wt % of the HI effluent.

[0093] In the process of the present invention, parameters indicative of HI catalyst deactivation are monitored to receive values, and comparison of the received values ​​with predetermined values ​​can be used to select appropriate adjustments to operating conditions in the first reactor and optionally other process units, in addition to the initiation of any switchover.

[0094] The parameters indicating HI catalyst deactivation can be freely selected, but preferably at least two monitored parameters belong to one or more of the following items a, b, c, d, e, f, g, h and / or i. For example, two parameters can be selected from one item and more parameters can be selected from other items, or one parameter can be selected from one item and at least one more parameter can be selected from other items. Therefore, in certain preferred embodiments, the parameters indicating HI catalyst deactivation include at least two or more of the following parameters:

[0095] a. 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, in particular a deactivator of a non-sulfurized bifunctional HI catalyst containing a precious metal. In addition, the substance or impurity is usually present in different amounts in feeds derived from vegetable oils, animal fats, microbial oils, organic wastes and residues from thermal liquefaction and / or enzymatic liquefaction, as well as in feeds derived from the Fischer-Tropsch process, and therefore can be brought into and present in the paraffin feed in different amounts in certain embodiments. Typically, elemental impurities themselves are not present in the paraffin feed, but their content indicates the presence of compounds containing the impurities. Elemental impurities and coke-forming compounds are determined by standard laboratory analysis. An increase in the content of any of these impurities may result in an increase in catalyst deactivation.

[0096] b. NH3 and / or H2S content in the gas phase of the hydroisomerization effluent; In some cases, an increase in the NH3 and / or H2S content in the gas phase of the hydroisomerization effluent may indicate an increase in the exposure of the catalyst to the impurities. An increase in the content of any of these impurities may result in an increase in catalyst deactivation.

[0097] c. Physicochemical characteristics of the hydroisomerization 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 an increase in catalyst deactivation. Distillation characteristics, where increases may indicate catalyst deactivation, include T5, T50, FBP, etc. As for other distillation characteristics, a shift in the boiling point distribution toward higher boiling compounds may indicate catalyst deactivation.

[0098] d. Compositional characteristics of the hydroisomerization 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; a decrease in the isoparaffin, multi-branched isoparaffin, and / or C8-C14 hydrocarbon content may indicate an increase in catalyst deactivation. The content of C1-C4 hydrocarbons may decrease with increasing catalyst deactivation. However, increasing the operating temperature to compensate for catalyst deactivation may result in an increase in the content of C1-C4 hydrocarbons.

[0099] e. Yield of at least one or more of recovered liquid transportation fuel components and / or separated recycle streams, preferably yield of aviation fuel components; increased yields of high boiling hydrocarbons and increased volumes of recovered recycle streams may indicate increased catalyst deactivation.

[0100] f. At least one or more physicochemical characteristics of the recovered liquid transportation fuel component and / or the separated recycle stream, preferably at least one or more of cloud point, freezing point, pour point, cold filter plugging point, kinematic viscosity, density, research octane number (RON), cetane number, and / or distillation characteristics; a decrease in cetane number can indicate an increase in catalyst deactivation. Among the distillation characteristics, for example, an increase in T5, T50, T95, FBP, etc. can indicate catalyst deactivation. As for other distillation characteristics, a change in the boiling point distribution toward higher boiling point compounds can indicate catalyst deactivation. To some extent, the physicochemical characteristics can indicate or be related to the content of isoparaffins or multi-branched isoparaffins in the recovered liquid transportation fuel component and / or the separated recycle stream.

[0101] g. Compositional characteristics of at least one or more of the recovered liquid transportation fuel components and / or separated recycle streams, preferably the isoparaffin content and / or the multi-branched isoparaffin content in one or more of the recovered liquid transportation fuel components and / or separated recycle streams; 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 components and / or separated recycle streams.

[0102] h. Temperature differentials across the first reactor or one or more catalyst beds therein; such temperature differentials are relatively easy to monitor, and a decrease in the temperature differential may indicate an increase in catalyst deactivation.

[0103] and / or

[0104] i. The operating conditions in the first reactor are selected from the group consisting of temperature, pressure, weight hourly space velocity (WHSV), feed ratio of H2 to paraffinic hydrocarbons and / or H2 partial pressure at the inlet of the first reactor. For example, the temperature and / or WHSV and / or pressure may have required adjustment during the continuous operation of the process to compensate for HI catalyst deactivation, so that increased temperature, decreased WHSV and / or increased pressure may indicate an increase in catalyst deactivation. Conveniently, the temperature in the reactor is measured at the inlet of the reactor.

[0105] The active sites of the HI catalyst may be occupied and the catalyst pores 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, aromatic compounds 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 which the HI catalyst has encountered at a given time point from the start of operation, and compare the received value with a value that has been predetermined, for example, based on historical data or a model based on historical data to reflect excessive HI catalyst deactivation, so that it is no longer possible to foresee that the target yield and / or quality of the desired fuel component can be met.

[0106] In certain preferred embodiments, the method includes monitoring at least two or at least three of the above parameters indicating HI catalyst deactivation. For example, the increase in the amount of shorter carbon chains caused by the increased cracking occurring in the first reactor, rather than a sufficient degree of isomerization, can achieve good low temperature properties (e.g., cloud point, pour point, sub-zero viscosity) of the HI effluent. Therefore, in order to better understand the state of HI catalyst deactivation, it may be beneficial to monitor at least two or three or even more parameters. For example, it is convenient to monitor one or more operating conditions in the first reactor and one or more physicochemical characteristics and / or yields of the recovered liquid transportation fuel components, and it enhances the understanding of the deactivation state of the HI catalyst. In certain exemplary embodiments, the monitoring parameters indicating HI catalyst deactivation include temperature, and optionally WHSV in the first reactor, and for the recovered diesel fuel component yield, at least one or more distillation characteristics and / or cloud point, and / or for the recovered aviation fuel component yield, at least one or more distillation characteristics and / or freezing point.

[0107] Monitoring parameters indicative of HI catalyst deactivation may be performed continuously, repeatedly, persistently, periodically, intermittently, discontinuously, or the monitored parameters may be monitored once. Monitoring of parameters indicative of HI catalyst deactivation may be performed online, for example, using one or more sensors located in any of the process stream, feed tank and / or product tank, including slip-stream arrangements, or may be performed offline based on samples collected from any of the process stream, feed tank and / or product tank. The frequency and manner of monitoring one or more parameters may be performed independently of other monitored parameters, i.e., certain parameters may be monitored, for example, continuously online, while other parameters may be monitored, for example, periodically offline.

[0108] How to select HI and hydrocracking conditions, preferably within the range of HI and hydrocracking conditions specified below, is well known to those skilled in the art, taking into account the selected HI catalyst, the composition and target degree of isomerization of the paraffin feed, and the target content of multi-branched isoparaffins in the HI effluent; and taking into account the selected hydrocracking (HC) catalyst, the composition and target effective cracking degree of the second reactor feed, and the target isoparaffin content in the effluent of the second reactor, the target degree of isomerization, and the target multi-branched isoparaffin content 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. As the catalyst deactivates, the catalyst activity decreases and the selectivity is affected, and at some point, the desired properties of the HI effluent, the recycle effluent, the hydrocracking effluent, the recovered liquid transportation fuel component and / or the separated recycle stream can no longer be achieved. When this occurs, at least one or more operating conditions of the first reactor and / or the second reactor, including, for example, the temperature, pressure, WHSV and / or H2 partial pressure at the inlet of the first reactor and / or the second reactor, can be adjusted, preferably within the range of operating conditions specified below, to compensate for catalyst deactivation so that the desired properties of the HI effluent, the recycle effluent, the hydrocracking effluent, the recovered liquid transportation fuel component and / or the separated recycle stream can be achieved again. Typically, this means increasing the temperature and / or reducing the WHSV and / or adjusting the feed ratio of H2 to paraffin hydrocarbons and / or increasing the pressure. 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 recovered liquid transportation fuel component. For example, when the operating temperature is increased to a sufficiently high value, thermal cracking side reactions increase, which increases the formation of gaseous hydrocarbons and thus reduces the yield of liquid products. Therefore, it is generally advantageous to begin operating the HI reactor (first reactor) at low temperature (using, for example, the lowest feasible temperature within the ranges specified) at the start 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 continued operation, although generally at a slower rate than the HI catalyst, so similar considerations apply to adjusting the operating conditions of the second reactor.

[0109] In certain preferred embodiments, the process of the present invention comprises separating a recycle stream from the fractionation and feeding the recycle stream to the first reactor as a co-feed with the paraffinic feed, and / or separating a side cut from the fractionation and feeding the side cut to the first reactor as a co-feed with the paraffinic feed, and / or feeding a portion of the paraffinic feed to the second reactor, the portion being obtained by splitting the paraffinic feed between the first reactor and the second reactor. In addition to the possibility of adjusting the operating conditions in the first reactor and / or the second reactor, these embodiments provide further increased flexibility in operating the process, including the possibility of adjusting the process, for example, in accordance with fluctuations in the characteristics of the paraffinic feed, in accordance with the demand and / or quality of one or more liquid transportation fuel components recovered, and / or in accordance with the changing activity and / or selectivity of the HI and / or HC catalyst throughout its lifetime.

[0110] The desired properties of the HI effluent, recycle effluent, hydrocracking effluent, recovered liquid transportation fuel components and / or separated recycle stream include composition and / or physicochemical characteristics, for example, at least one or more of the wt% of isoparaffins, the wt% of multi-branched isoparaffins, the wt% of hydrocarbons in a specific carbon number range, cloud point, freezing point, pour point, cold filter plugging point, kinematic viscosity, density and / or distillation characteristics. The properties of the HI effluent, recycle effluent, hydrocracking effluent, recovered liquid transportation fuel components and / or separated recycle stream may change during the operation of the method due to deactivation of the HI and / or HC catalyst, but also due to other reasons, such as changes in the composition of the paraffin feed. Therefore, one or more parameters indicating HI and / or HC catalyst deactivation and / or indicating paraffin feed properties can be monitored to receive one or more values, and the received values ​​are compared with predetermined adjustment values. The predetermined adjustment value is generally closer to the initial process setting than the predetermined value used to trigger the switch from the first mode to the second mode.

[0111] Thus, according to one embodiment, the method further comprises monitoring at least one or more parameters indicative of HI catalyst deactivation to receive at least one or more values; and / or monitoring at least one or more parameters indicative of HC catalyst deactivation to receive at least one or more values; and / or monitoring at least one or more parameters indicative of paraffinic hydrocarbon feed properties to receive at least one or more values; comparing the received values ​​with predetermined adjustment values, and based on the comparison, adjusting at least one or more operating conditions in the first reactor and / or the second reactor, and / or adjusting the composition of the paraffinic hydrocarbon feed and / or the second reactor feed, preferably adjusting at least one or more of the following: the temperature, pressure and / or weight hourly space velocity (WHSV) in the first reactor and / or the second reactor, the ratio of H2 to paraffinic hydrocarbon feed, and and / or the ratio of H2 to the feed to the second reactor, and / or the H2 partial pressure at the inlet of the first reactor and / or the second reactor, the weight ratio of the separated recycle stream in the feed to the second reactor or the optional other recycle stream optionally fed to the second reactor, the split ratio of the HI effluent between the second reactor and the fractionation, and / or the weight ratio of the separated side stream recycled back to the process (fed to the first reactor) in the feed to the first reactor, more preferably increasing the temperature and / or the pressure in the first reactor and / or the second reactor, and / or reducing the WHSV in the first reactor and / or the second reactor, and / or adjusting the weight ratio of the separated recycle feed and / or the optional other recycle feed fed to the second reactor, and / or adjusting the split ratio of the HI effluent between the second reactor and the fractionation.

[0112] For example, adjustments to operating conditions to obtain or maintain desired properties of the HI effluent, recycle effluent, hydrocracking effluent, recovered liquid transportation fuel component, and / or separated recycle stream may be made based on historical process data, models (e.g., theoretical models or models based on historical process data), and / or one or more parameters related to or indicative of properties of one or more of the HI effluent, recycle effluent, hydrocracking effluent, recovered liquid transportation fuel component, and / or separated recycle stream. For example, the adjustments may be based on historical process data from an earlier process run using a similar feed and similar qualitative and quantitative expectations of the recovered liquid transportation fuel component, such as using a model based on historical process data and / or a spectrum of operating conditions.

[0113] In the method of the present invention, the paraffin feed that carries out hydroisomerization in the first reactor comprises at least 60wt% of the paraffin feed total weight of paraffin, and the paraffin is at most 30wt% isoparaffin.This means that when the paraffin feed comprises 60wt% of the paraffin of the paraffin feed total weight, at most 30wt% of the paraffin total weight in the paraffin feed, i.e. at most 18wt% of the paraffin feed total weight is isoparaffin.Preferably, the paraffin feed comprises at least 70wt% of the paraffin feed total weight, more preferably at least 80wt%, even more preferably at least 90wt% paraffin.The paraffin feed of the present disclosure may comprise even at least 95wt% of the paraffin of the paraffin feed total weight, or may be substantially composed 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, based on the total weight of the paraffinic feedstock, and small amounts of aromatic compounds and / or cycloalkanes.

[0114] An advantage of using a highly paraffinic feed in the process of the present invention is that paraffins are relatively easy to isomerize and are isomerized under milder conditions when subjected to HI than, for example, cyclic hydrocarbons. In addition, paraffins are relatively easy to crack and are cracked under milder conditions when subjected to hydrocracking.

[0115] 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.

[0116] 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 having a higher content of multi-branched isoparaffins than an otherwise similar feed that does not contain isoparaffins.

[0117] 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 with carbon numbers 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 with carbon numbers in the range of C14 to C22. Paraffinic hydrocarbon feeds with high C12 to C30 hydrocarbon content are preferred because they allow good yields of two or more different types of liquid transportation fuel components. For the same reason, C14 to C22 hydrocarbons are particularly preferred, and also because they are easily (for example) obtained from conventional HDO of vegetable oils, animal fats and / or microbial oils containing fatty acids.

[0118] 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.

[0119] 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 hydroprocessing 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 oils, animal fats, microbial oils, thermally liquefied organic waste and residues and / or enzymatically liquefied organic waste and residues, more preferably, the oxidized hydrocarbon feed comprises at least one or more of vegetable oils, animal fats and / or microbial oils, 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.

[0120] 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%, further 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).

[0121] In certain embodiments, the paraffin feed comprises a degassed paraffin Fischer-Tropsch effluent or a fraction thereof or consists essentially of it. The Fischer-Tropsch process comprises a synthesis gas comprising carbon monoxide and hydrogen, which is usually catalytically converted into a substantially Gaussian distributed hydrocarbon chain, mainly normal paraffins, which have a wide carbon chain length distribution, such as from C2 to C100+, usually from about C5 to about C50. The FT effluent is usually highly paraffinic, and it mainly comprises normal paraffins. The catalytic FT conversion of synthesis gas can result in a lesser degree of isomerization, and the FT effluent usually comprises about 10wt% or less of the total weight of the FT effluent. The synthesis gas used in the FT process can be produced by renewable materials, natural gas, coal or a combination thereof.

[0122] 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.

[0123] The term "catalytic hydroprocessing", sometimes also referred to as hydrotreating, refers to a catalytic process for treating organic materials with molecular hydrogen. Preferably, the catalytic hydroprocessing removes oxygen from organic oxygen compounds in the form of water, i.e., hydrodeoxygenation (HDO), removes sulfur from organic sulfur compounds in the form of dihydrosulfide (H2S), i.e., hydrodesulfurization (HDS), removes nitrogen from organic nitrogen compounds in the form of ammonia (NH3), i.e., hydrodenitrogenation (HDN), removes halogens, for example, chlorine from organic chlorine compounds in the form of hydrochloric acid (HCl), i.e., hydrodechlorination (HDCl), and / or removes metals by hydrodemetallization, and / or hydrogenates olefinic bonds if present in the hydroprocessing feed. Depending on the composition of the hydroprocessing feed, different reactions may occur and / or predominate.

[0124] Preferably, the paraffinic feed of the present disclosure comprises or consists essentially of a degassed 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.

[0125] 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 paraffinic hydrocarbon feed fractionation 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, a H2 partial pressure at the reactor inlet in the range of 1 MPa to 20 MPa, a weight hourly space velocity in the range of 0.1 to 10 kg oxygenated hydrocarbon feed / kg catalyst / hour, and a feed ratio of H2 to oxygenated hydrocarbon in the range of 50 to 2000 standard liters of H2 / liter of oxygenated hydrocarbon feed. Preferably, the oxygenated hydrocarbon feed comprises at least one or more of vegetable oil, animal fat and / or microbial oil. The hydrodeoxygenation is preferably carried out as described in prior art publications, such as FI100248B, EP1741768A1, EP2155838B1 or FI129220 B1.

[0126] The optional paraffinic feed fractionation is usually carried out in a fractionation unit different from the fractionation unit used to recover liquid transportation fuel components and / or separate recycle streams. The optional paraffinic feed fractionation can be considered separate from the fractionation of the process of the present invention, which includes fractionation to recover liquid transportation fuel components and / or separate recycle streams.

[0127] 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, NiMoW. These catalysts are effective, readily available and well tolerate typical impurities of fatty feedstocks. If a catalyst having hydrodewaxing properties, such as a catalyst containing NiW, is used in the hydrodeoxygenation as a hydrodeoxygenation catalyst or as a co-catalyst, an HDO effluent having a slightly increased isoparaffin content can be obtained.

[0128] In certain embodiments, the paraffin feed may include a side cut separated in the fractionation of the inventive method. The side cut is preferably included in the paraffin feed as a minor component. The side cut is preferably a cut rich in C14-18 hydrocarbons, more preferably a cut rich in C15-C17 hydrocarbons. The side cut is preferably a relatively narrow cut to allow accurate change of the boiling point distribution of the total feed of the fractionation. Introducing this side cut in the paraffin feed can improve the quality of the liquid transportation fuel component recovered or at least some of the liquid transportation fuel components recovered, particularly the aviation fuel component. When the side cut is separated after HI and hydrocracking, it generally has a high isoparaffin content. Therefore, including a side cut in the paraffin feed can improve the isoparaffin content in the paraffin feed to a certain extent, preferably increased to at most 30wt% of the total weight of paraffins in the paraffin feed. HI in the first reactor, hydrocracking in the second reactor, and optionally HDO and / or hydrodearomatization (HDA) steps may have an impurity removal effect on the treated streams, especially when subsequently subjected to gas-liquid separation. Introducing even a small amount of a side draw containing at most very low amounts of impurities into the paraffinic feed can reduce or dilute the impurity content of the paraffinic feed, which can slow down HI catalyst deactivation.

[0129] In the process of the present invention, the paraffin feed is hydroisomerized (HI) in the presence of a HI catalyst in a 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.

[0130] Preferably, the hydroisomerization in the first reactor is carried out at a temperature of 200 to 500°C, preferably 230 to 500°C, more preferably 250 to 450°C, even more preferably 280 to 400°C, at a pressure of 1 MPa to 10 MPa, preferably 2 MPa to 8 MPa or 3 MPa to 10 MPa, a H2 partial pressure at the inlet of the first reactor of 1 MPa to 10 MPa, preferably 2 MPa to 8 MPa, at 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 at a feed ratio of H2 to paraffin of 10 to 2000, preferably 50 to 1000 standard liters of H2 / liter of paraffin feed.

[0131] According to certain embodiments, the hydroisomerization in the first reactor is carried out under the following conditions: temperature in the range of 200°C to 500°C, pressure in the range of 1MPa to 10MPa, H2 partial pressure at the inlet of the first reactor in the range of 1MPa to 10MPa, weight hourly space velocity in the range of 0.1 to 10kg paraffin feed / kg catalyst / hour, and feed ratio of H2 to paraffin in the range of 10 to 2000 standard liters of H2 / liter of paraffin feed.

[0132] 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 2 to 8 MPa, the H2 partial pressure at the inlet of the first reactor is in the range of 2 to 8 MPa, the weight hourly space velocity is in the range of 0.2 to 8 kg paraffin feed / kg catalyst / hour, and the feed ratio of H2 to paraffin is in the range of 50 to 1000 standard liters of H2 / liter of paraffin feed.

[0133] 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 hyperbranched isoparaffin content of up to 25 wt%, or a total isoparaffin content in the range of 85 wt% to 95 wt% and a hyperbranched isoparaffin content in the range of 25 wt% to 55 wt%, or at least 95 wt% total isoparaffin content and greater than 55 wt% hyperbranched isoparaffin content, 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.

[0134] Preferably, the hydroisomerization in the first reactor is operated such that the ratio of the amount of wt% of isoparaffins by weight of the total weight of paraffins in the HI effluent to the amount of wt% of isoparaffins by weight of the total weight of paraffins in the paraffin feed is at least 2, or at least 4, or at least 6, or at least 8, or at least 10, or at least 12, and / or such that the ratio of the amount of wt% of multibranched isoparaffins by weight of the total weight of paraffins in the HI effluent to the amount of wt% of multibranched isoparaffins by weight of the total weight of paraffins in the paraffin feed is at least 2, or at least 4, or at least 6, or at least 8, or at least 10, or at least 12, and / or such that the (total) HI effluent comprises less than 20 wt%, or less than 10 wt%, preferably less than 5 wt%, more preferably less than 3 wt% of C1 to C4 hydrocarbons, based on the total weight of the HI effluent. This 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.

[0135] Preferably, the HI effluent is subjected to a gas-liquid separation, i.e. to removal of compounds which are gaseous at least at NTP. This can be carried out before carrying out step i) or I), for example as an integrated step within the first reactor, or when operating the process in the first mode as part of the fractionation in step i).

[0136] When the process of the present invention is operated in the second mode, there is no need to perform gas-liquid separation on the HI effluent, and in certain embodiments, substantially all of the HI effluent can be fed to the second reactor. Omitting gas-liquid separation of the HI effluent can reduce investment and operating costs, and can also improve energy efficiency.

[0137] However, preferably, the HI effluent is subjected to a gas-liquid separation prior to performing step i) or I), or when the process is operated in the first mode as part of the fractionation in step i). More preferably, the HI effluent is subjected to a gas-liquid separation at least prior to performing step I). Degassing removes, for example, gaseous impurities from the HI effluent and increases the hydrogen partial pressure in the feed to the second reactor. Furthermore, the operating conditions in the second reactor are easier to optimize when the reactor feed is less homogeneous.

[0138] 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% paraffinic hydrocarbons based on the total weight of the HI effluent. In certain embodiments, the HI effluent may even consist essentially of paraffinic hydrocarbons.

[0139] Typically, the HI effluent may comprise at least 50 wt%, preferably at least 60 wt%, more preferably at least 70 wt%, even more preferably at least 80 wt% of isoparaffins, and optionally at least 5 wt%, more preferably at least 10 wt%, even more preferably at least 15 wt%, or at least 20 wt% of multi-branched isoparaffins, based on the total weight of paraffins in the HI effluent. Typically, the HI effluent may comprise up to 75 wt%, or up to 70 wt%, or up to 60 wt%, such as up to 50 wt%, or up to 40 wt%, sometimes up to 30 wt%, or even up to 20 wt% of multi-branched isoparaffins, based on the total weight of paraffins in the HI effluent. Typically, the cloud point of the HI effluent may be 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).

[0140] 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 to C8 to C14 hydrocarbons and to 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 component, especially the low temperature properties of the aviation fuel component and / or the diesel fuel component and / or the RON of the gasoline fuel component. Without being bound by any theory, it is believed that multi-branched isoparaffins are more likely to form two branched paraffin molecules rather than one branched paraffin and one normal paraffin when cracking in the second reactor, which therefore increases the isoparaffin content of the recycled effluent or the hydrocracking effluent.

[0141] When operating in the first mode, the process of the invention comprises subjecting the HI effluent to fractionation to separate from the HI effluent a recycle stream having at least a T5 temperature of 270° C. or higher (recovery 5 vol%, EN ISO 3405-2019). The total feed subjected to fractionation in the first mode is initially the HI effluent, optionally after gas-liquid separation integrated in the first reactor, and when the process remains in operation, the total feed subjected to fractionation comprises the HI effluent and the recycle effluent, and preferably said effluents are combined.

[0142] Preferably, the recycle stream has a T5 temperature of 275°C or higher. In certain preferred embodiments, the T5 temperature of the recycle stream is in the range of 270°C to less than 300°C, preferably in the range of 270°C to less than 295°C, more preferably in the range of 270°C to less than 290°C; and / or the initial boiling point (IBP, EN ISO 3405-2019) is less than 290°C, preferably less than 288°C, more preferably less than 285°C, or less than 280°C. The recycle stream may have the FBP of the total feed to be fractionated, i.e., the recycle stream may comprise the bottom heavy product of the total feed to be fractionated.

[0143] Preferably, the T5 temperature of the recycle stream is selected so that at least a portion of the C16 normal paraffins present in the total feed to be fractionated, such as the C16 normal paraffins present in the HI effluent (if any), are recovered in the recycle stream. Recovery of the C16 normal paraffins in the recycle stream can be achieved by appropriately selecting the T5 temperature and / or IBP of the recycle stream. The boiling point of C16 normal paraffins is 287° C. (at atmospheric pressure), but since fractionation (such as distillation separation) is not very precise, it is possible to recover C16 normal paraffins within a temperature range near this boiling point. Preferably, the recycle stream contains C16 normal paraffins.

[0144] It is beneficial to recycle at least some C16 normal paraffins to the second reactor for hydrocracking because C16 normal paraffins have a relatively high melting point. Therefore, any large presence of C16 normal paraffins (for example) in the recovered aviation fuel component may even make the aviation fuel component unusable in the aviation fuel composition due to poor low temperature properties, especially poor freezing points, and / or poor, i.e. high, kinematic viscosity at sub-zero temperatures, such as -20°C or -40°C. In any case, the C16 normal paraffins in the recovered aviation fuel component impair its low temperature properties, i.e., increase one or more of the cloud point, freezing point, pour point, cold filter plugging point and / or sub-zero kinematic viscosity compared to the aviation fuel component with less or no C16 normal paraffin content. Preferably, the recycle stream comprises at least 20wt% or at least 30wt%, more preferably at least 40wt% or at least 50wt% of the C16 normal paraffins in the total feed for fractionation. In the total feed to fractionation, the amount of n-paraffins, including C16 n-paraffins, may increase upon deactivation of the HI catalyst and may also be formed by cracking in the second reactor.

[0145] In some particularly preferred embodiments, the recycle stream comprises at least 85wt% of the total weight of paraffins in the recycle stream, preferably at least 90wt%, more preferably at least 95wt% C16+ paraffins. It is useful to hydrocracking C16+ paraffins in the second reactor because it can improve the yield of aviation fuel components and / or improve its quality. The low temperature properties of C16+ normal paraffins are poor, and C18+ normal paraffins boil outside the aviation fuel boiling range usually.

[0146] 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 certain particularly preferred embodiments, 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 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 hyperbranched isoparaffins, typically in the range of 5 wt% to 95 wt%, preferably 5 wt% to 80 wt%, or 5 wt% to 70 wt%, such as 10 wt% to 70 wt%, or 15 wt% to 65 wt% of hyperbranched 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).

[0147] Such a recycle stream has a 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 easier to crack than cyclic hydrocarbons, longer paraffins are easier to crack than shorter paraffins, and isoparaffins are expected to be easier to crack 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.

[0148] The process of the invention may also comprise, in step II), recovering from the fractionation a further recycle stream having a T5 temperature of 270° C. or higher (recovery of 5 vol%, EN ISO 3405-2019), and feeding the recovered further recycle stream to the second reactor as a co-feed with the HI effluent (i.e. as part of the second reactor feed). In this case, the second reactor feed comprises the combined HI effluent and the recovered further recycle stream. The further recycle stream is preferably a recycle stream as defined above. Preferably, the further recycle stream comprises C16 normal paraffins.

[0149] In certain preferred embodiments, the second reactor feed consists essentially of the recycle stream and / or at least a portion of the hydroisomerization effluent and / or optional other recycle streams. For example, the second reactor feed may consist essentially of the recycle stream in step i), or of the recycle stream and a portion of the HI effluent, and / or the second reactor feed may consist essentially of the HI effluent and optional other recycle streams, or of at least a portion of the HI effluent and optional other recycle streams in step II).

[0150] In an embodiment, when the second reactor feed comprises a portion of the HI effluent in step i), the amount of that portion may vary, but typically only by a small amount (outside of a switch). For example, the second reactor feed may optionally comprise less than 50 wt%, preferably less than 30 wt%, more preferably less than 10 wt% of the HI effluent in step i), preferably as a degassed form, based on the total weight of the second reactor feed.

[0151] The process of the present invention comprises hydrocracking a second reactor feed comprising a recycle stream in the presence of an HC catalyst in a second reactor in step ii) to obtain a recycle effluent, and hydrocracking a second reactor feed comprising an HI effluent in the presence of an HC catalyst in a second reactor in step II) to obtain a hydrocracking effluent.

[0152] Typically, the hydrocracking is performed in the second reactor so that the cracking reactions, predominantly those that increase the effective degree of cracking, are more abundant than the hydroisomerization reactions in the first reactor. Preferably, the cracking reactions, particularly those that increase the effective degree of cracking, predominate in the hydrocracking in the second reactor, but typically without overcracking and excess fuel gas formation.

[0153] In certain preferred embodiments, the hydrocracking in the second reactor is 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, a H2 partial pressure at the second reactor inlet 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 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 feed ratio of H2 to the second reactor of 10 to 2000, preferably 50 to 1000 standard liters of H2 / liter of second reactor feed. Typically, in the process of the present invention, the hydrocracking in the second reactor is carried out under the following conditions: the temperature is in the range of 200°C to 450°C, the pressure is in the range of 0.4 MPa to 8 MPa, the H2 partial pressure at the inlet of the second reactor is in the range of 0.4 MPa to 8 MPa, preferably in the range of 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 the feed ratio of H2 to the second reactor is in the range of 10 to 2000, preferably 50 to 1000 standard liters of H2 / liter of second reactor feed.

[0154] According to certain embodiments, the hydrocracking in the second reactor is carried out under the following conditions: temperature in the range of 220°C to 430°C, pressure in the range of 1MPa to 7MPa, weight hourly space velocity in the range of 0.2 to 8kg second reactor feed / kg catalyst / hour, and H2 to the feed ratio of the second reactor in the range of 50 to 1000 standard liters of H2 / liter of second reactor feed. In certain preferred embodiments, the hydrocracking in the second reactor is carried out under the following conditions: temperature in the range of 280 to 350°C, pressure in the range of 2.5 to 7MPa, H2 partial pressure at the inlet of the second reactor in the range of 2.5 to 7MPa, weight hourly space velocity in the range of 0.4 to 6kg second reactor feed / kg catalyst / hour, and H2 to the feed ratio of the second reactor in the range of 50 to 1000 standard liters of H2 / liter of second reactor feed. When operating HC at lower temperatures and sufficiently high pressures, aromatization side reactions can be better suppressed or even dearomatization can be enhanced.

[0155] 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 (step i)) and / or the recycle effluent (step ii)) to the wt% amount of isoparaffins based on the total weight of paraffins in the feed to the second reactor is at least 0.5, or at least 0.7, or at least 0.8, or at least 0.9, or at least 1.0; and / or so that the ratio of the C8-C14 hydrocarbon content in the hydrocracking effluent (step i)) or the recycle effluent (step ii)) to the C8-C14 hydrocarbon content in the feed to the second reactor is at least 1.1, preferably at least 1.3, more preferably at least 1.5, even more preferably at least 1.8 or at least 2.0.

[0156] In certain preferred embodiments, the hydrocracking in the second reactor is operated such that the ratio of the amount of wt% of C1-C4 hydrocarbons formed during hydrocracking in the (total) recycle effluent (step ii)) or the total hydrocracking effluent (step i)) to the amount of wt% of C1-C4 hydrocarbons in the (total) HI effluent is in the range of 1.1 to 5.0, preferably 1.1 to 4.0, more preferably 1.2 to 3.0; and / or such that the (total) recycle effluent (step ii)) or the (total) hydrocracking effluent (step i)) contains less than 20 wt%, or less than 10 wt%, or less than 5 wt% of C1-C4 hydrocarbons, based on the total weight of the recycle effluent or the hydrocracking effluent, respectively.

[0157] This may 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 as defined below, preferably in the presence of a non-sulphided bifunctional HC catalyst comprising at least one or more Group VIII noble metals, more preferably Pt and / or Pd.

[0158] Typically, the hydrocracking effluent (step i)) and / or the recycle effluent (step ii)) 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 hydrocracking effluent or the recycle effluent, respectively. The hydrocracking effluent (step i)) and / or the recycle effluent (step ii)) may even consist essentially of paraffinic hydrocarbons.

[0159] According to certain preferred embodiments, the hydrocracking effluent (step i)) and / or the recycle effluent (step ii)) 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 or the recycle effluent, respectively, and / or comprises 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 or the recycle effluent, respectively.

[0160] 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.

[0161] 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.

[0162] Both the hydroisomerization (HI) and hydrocracking (HC) catalysts may be arranged in one or more catalyst beds within the respective reactors. The HI catalyst and the HC catalyst may be arranged in at least one or more fixed beds, respectively. The HI catalyst may be any conventionally used HI catalyst, and the HC catalyst may be any conventionally used HC catalyst. Preferably, the HI catalyst in the first reactor 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.

[0163] 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.

[0164] 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 comprise less than 50 wt-ppm, preferably less than 30 wt-ppm, more preferably less than 10 wt-ppm sulfur (ppm by weight, calculated as elemental S) of the respective total feed as determined according to ISO 20846-2019.

[0165] Sulfur content can be determined from liquids according to ISO 20846-2019 or from gas fractions according to ASTM-D6667.

[0166] Non-sulfided bifunctional catalysts are preferred because they do not require sulfidation to maintain their activity during operation, and thus the sulfur content of the various process streams can be kept lower and less efficient HS separation and recovery from the various process streams is required. In particular, non-sulfided bifunctional catalysts containing noble metals can be active at lower temperatures and show higher selectivity for isomerization reactions than sulfided catalysts, but are sensitive to deactivation by HS.

[0167] 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) of sulfur as determined according to ISO 20846-2019. The very low sulfur content in the stream entering the first reactor is beneficial because only very low amounts of HS or substantially no HS are formed in the HI in the first reactor, and thus very low amounts of HS or substantially no HS are present in the HI effluent. In these embodiments, gas-liquid separation of the HI effluent is not necessary for protecting the HC catalyst in the second reactor before feeding the HI effluent to the second reactor for hydrocracking (step I), but gas-liquid separation of the HI effluent may still be optionally performed. Therefore, the overall process can be simpler, and liquid transportation fuel components with ultra-low sulfur content are obtainable. Furthermore, due to the presence of less H2S, less corrosion is also expected in the long term, and potentially for some equipment materials even less stringent corrosion resistance requirements may apply.

[0168] 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.

[0169] The bifunctional HC catalyst and the bifunctional HI catalyst are similar in that both contain metal sites capable of catalyzing the hydrogenation (dehydrogenation) of normal / isoparaffins to the 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 catalyzing the cracking of normal / isocarbocations to lighter normal / isoolefins and lighter normal / isocarbocations, and catalyzing the 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 is 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 content of metal in the catalyst.

[0170] 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.

[0171] Preferably, the bifunctional HI and HC catalysts independently of each other comprise at least one or more porous acidic materials having a microporous, mesoporous or hierarchical (microporous-mesoporous) structure. A variety of zeolite-type materials, such as SAPO and zeolites are available to provide the desired acidity and pore characteristics.

[0172] According to certain embodiments, the HI catalyst is a bifunctional HI catalyst, preferably a non-sulfided bifunctional HI catalyst, comprising

[0173] 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

[0174] 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

[0175] Optionally at least one or more of alumina, silica, amorphous silica-alumina, titania, titania and / or zirconia.

[0176] 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.

[0177] 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 aromatic compounds by side reactions. Providing a bifunctional HC catalyst to the second reactor makes it possible to achieve that the isoparaffin content (wt% of isoparaffins to the total weight of paraffins) in the recycle effluent and / or the hydrocracking effluent does not have to be significantly lower than that in the HI effluent, or may be the same or even higher.

[0178] Thus, according to certain embodiments, the hydrocracking catalyst is a bifunctional hydrocracking catalyst, preferably a non-sulfided bifunctional hydrocracking catalyst, comprising

[0179] 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

[0180] 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, SAOP-11, ZSM-23, β-zeolite, Y-type zeolite and / or amorphous silica-alumina; and

[0181] Optionally, at least one or more of alumina, silica, titanium alumina, titania and / or zirconium oxide.

[0182] In certain embodiments, the HI catalyst in the first reactor and the HC catalyst in the second reactor have different acidity-related characteristics. The acidity-related characteristics of an acidic porous material, such as a zeolite, can include the nature, number and distribution of acid sites in terms of relative strength and can be determined by well-known methods, such as by adsorption-desorption methods, in which the release of adsorbed basic substances, such as ammonia or pyridine at higher temperatures indicates the presence of strong acid sites. As an example of a useful adsorption-desorption method, 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 bytemperature programmed desorption of ammonia. Catalysis Surveys from Asia 1, 215–226 (1997)). Another well-known method for determining the acidity of a zeolite, including the strength of the acidity, is 1 H-NMR method, for example, as described in Heeribout et al. (Heeribout L., Semmer V., Batamack P., Dorémieux-Morin C., Fraissard J. Brønsted acid strength of zeolites studied by 1 H NMR: scaling, influence of defects. Microporous and Mesoporous Materials, Vol. 21, No. 4–6, May 1998, pp. 565-570). In certain embodiments, the bifunctional HC catalyst of the second reactor has a higher number of Bronsted acid sites as determined by NH3-TPD than the bifunctional HI catalyst of the first reactor. In certain embodiments, the bifunctional HC catalyst has a higher total number of acid sites as determined by NH3-TPD than the bifunctional HI catalyst.

[0183] 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 these embodiments, good or better yields of aviation fuel components are achieved at lower temperatures than in otherwise similar processes but using a bifunctional HC catalyst that does not have a higher content of said noble metal than the bifunctional HI catalyst.

[0184] If one of the HI catalyst of the first reactor and the HC catalyst of the second reactor deactivates faster than the other, the need to replace the catalyst with a new catalyst or to regenerate the catalyst may be determined based on the faster deactivated catalyst.

[0185] In the process of the present invention, a paraffinic feed is subjected to HI in the presence of a HI catalyst, and the recycle stream and the hydroisomerization effluent are 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 a recycle stream or a HI effluent is contacted with an HC catalyst under hydrocracking conditions, more cracking can be expected compared to contacting a paraffinic feed with a HI catalyst under HI conditions, even if the catalyst is the same. Preferably, when the paraffinic feed is contacted with a HI catalyst under HI conditions, the feed isomerizes rather than cracks, and when the recycle stream or HI effluent is contacted with a HC catalyst under hydrocracking conditions, the feed cracks rather than isomerizes.

[0186] The HI catalyst and the HC catalyst may be in a ready-to-use state as such, or they may be treated in any conventional manner to adjust their properties (such as selectivity and / or activity) before or during startup by subjecting them to reduction, sulfidation and / or passivation, for example, with nitrogen-containing compounds such as amines or ammonia, to obtain ready-to-use fresh or regenerated HI catalyst and / or HC catalyst. As used herein, HI catalyst, HC catalyst, fresh catalyst and regenerated catalyst generally refer to catalysts in a ready-to-use state.

[0187] In certain embodiments, hydrocracking is followed by further hydroisomerization in the presence of additional HI 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.

[0188] 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-sulfided bifunctional HI catalyst. The HI catalyst in the first reactor and the optional additional HI catalyst in the second 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, then preferably the HC catalyst is different from the HI catalyst and the optional additional HI catalyst.

[0189] The process of the present invention may include hydrodearomatization (HDA) of one or more process streams or products. In certain embodiments, the process includes subjecting at least one or more of the HI effluent, hydrocracking effluent, recycle effluent, recycle stream, recovered liquid transportation fuel components, and / or any fraction thereof to hydrodearomatization in an HDA reactor in the presence of an HDA catalyst to reduce the aromatics level to, for example, less than 5000 w-ppm, or less than 300 w-ppm, preferably less than 100 w-ppm, or less than 50 w-ppm, preferably as determined according to UOP 495-03.

[0190] The HDA step may be beneficial in particular if the paraffinic feed to the first reactor contains elevated amounts of aromatics, and / or if the HI in the first reactor and / or the hydrocracking in the second reactor are operated using catalysts and / or conditions that promote the formation of aromatics as a side reaction, or if ultra-low aromatics content is desired for all or some of the recovered liquid transportation fuel components or for other product fractions that may be recovered from the process. Examples of such other product fractions include product fractions intended for use in cosmetics, pharmaceuticals, and / or other applications involving close contact with humans.

[0191] Preferably, the temperature is in the range of 80°C to 350°C, the pressure is in the range of 3MPa to 16MPa, and the temperature is in the range of 0.2 to 8hr. -1 HDA was carried out at a liquid hourly space velocity in the range of , and a H2 to HDA ​​reactor feed ratio in the range of 50 to 2000 standard liters of H2 / liter of HDA reactor feed.

[0192] HDA can be carried out using any catalyst commonly used for hydrodearomatization. Preferably, non-sulfided catalysts containing precious metals are used because these catalysts are already active in HDA at lower temperatures, which is beneficial because at low temperatures the thermodynamic equilibrium tends to shift in the direction of dearomatization. In addition, in embodiments in which the first reactor and the second reactor are also operated using non-sulfided precious metal catalysts, no sulfur needs to be added to maintain catalyst activity, and less or no work is required to separate sulfur-containing compounds, especially H2S, from the gaseous fractions of the effluent of the first reactor, the second reactor and / or the HAD reactor, and the recovered liquid transportation fuel components and optional other product fractions are obtainable with ultra-low aromatic compound and sulfur content.

[0193] The present invention is a process comprising fractionation, wherein at least one or more liquid transportation fuel components are recovered, and the recycle stream (and optionally other recycle streams) can be separated. The amount of the separated recycle stream and the amount of the recycle stream fed to the second reactor can be varied within a wide range. Other liquid streams or fractions, such as side streams, can optionally be separated and / or recovered in the fractionation and optionally recycled back into the process.

[0194] Preferably, in step iii), the weight ratio of the recycle effluent to the HI effluent subjected to fractionation is from 1:10 to 10:1, such as from 1:5 to 5:1. Preferably, the ratio is the ratio of the recycle effluent to the HI effluent. When processing paraffinic feeds boiling at lower temperatures, a ratio of the recycle effluent to the HI effluent close to the lower limit may be preferred, while when processing paraffinic feeds boiling at higher temperatures, such as paraffinic feeds containing paraffins heavier than C18, a ratio close to the upper limit may be preferred.

[0195] The fractionation of the process of the invention may comprise any commonly used fractionation technique. Preferably, the fractionation comprises distillation, such as atmospheric distillation or vacuum distillation, optionally preceded by a gas-liquid separation, for example, as described below.

[0196] The fractionation can be performed in a fractionation system comprising one or more fractionation units. For example, the gas and light naphtha can be separated in a pre-fractionation unit, while the liquid transportation fuel components and the recycle stream are recovered and separated from the main distillation unit downstream of the pre-fractionation unit. In an alternative example, a single fractionation unit can be used.

[0197] As described above, in the first mode, the recycle effluent and / or the HI effluent can be combined or independently subjected to gas-liquid separation. Similarly, in the second mode, the hydrocracking effluent and / or the HI effluent can be subjected to gas-liquid separation. Gas-liquid separation can be performed as an integrated step, for example, in each reactor or in a fractionation system. Typically, 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 originates, gas-liquid separation is performed. 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.

[0198] 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.

[0199] 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, 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) are recovered from the separated recycle stream. Other products may be recovered from the fractionation, such as diverting or further separating other products from the recycle stream. Examples of these other products include components for solvents, electrical fluids, and base oils.

[0200] 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).

[0201] Therefore, in a preferred embodiment of the process of the present invention, in steps iii) and II), 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 205°C (EN ISO 3405-2019), a final boiling point of at most 300°C (EN ISO 3405-2019), a flash point of at least 38°C (IP 170-2013, Abel closed cup method) and a freezing point of at most -40°C (IP 529-2016). In these embodiments, the recovered aviation fuel component has a high quality and can be blended into the aviation fuel composition in an increased amount. Typically, the T10 and T90 temperatures of the recovered aviation fuel component are in the range of 120°C to 295°C, preferably in the range of 130°C to 295°C, as determined according to EN ISO 3405-2019.

[0202] The method of the present invention is capable of recovering at least the aviation fuel component at a surprisingly high yield, even near the end of the life of the HI catalyst. In certain preferred embodiments of the method of the present invention, the aviation fuel component is recovered at a yield of at least 30wt%, preferably at least 40wt%, more preferably at least 50wt%, such as 30wt% to 90wt% of the total weight of the paraffin feed. It is believed that this is due to the high content of C8-C14 hydrocarbons and isoparaffins in the feed subjected to fractionation, 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°C to 150°C, preferably in the range of 80°C 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 low temperature property requirements, which would also limit the T90 temperature and narrow the T90-T10 difference. However, in this context, the process of the present invention is able to provide 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.

[0203] Typically, in the process of the present invention, in steps iii) and II), 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, or at least an aviation fuel component and a gasoline fuel component, even more preferably at least an aviation fuel component, a diesel fuel component and a gasoline fuel component. Typically, preferably at least at least one heavy product, such as a diesel fuel component, a marine fuel component and / or a base oil component, is recovered from the fractionation at regular intervals. In this way, the heaviest components can be removed from the recycle loop.

[0204] 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 certain 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.

[0205] 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 to 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 method of the present invention contain at least 70wt% of the weight of the diesel fuel component, preferably at least 75wt%, more preferably at least 80wt%, even more preferably at least 90wt% of C15-C22 isoparaffins; and / or at least 60wt% of the weight of the diesel fuel component, preferably at least 63wt%, more preferably at least 65wt% of the C15-C22 multi-branched isoparaffins. Typical gasoline fuel components recovered from the method of the present invention contain at least 50wt% of the weight of the gasoline fuel component, preferably at least 55wt%, more preferably at least 60wt%, even more preferably at least 65wt% of the C4-C9 isoparaffins; and / or at least 5wt% of the weight of the gasoline fuel component, preferably at least 6wt%, more preferably at least 7wt%, even more preferably at least 10wt%, or at least 11wt% of the C6-C9 multi-branched isoparaffins.

[0206] 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.

[0207] The products recovered from the process of the invention have excellent characteristics. The recovered liquid transportation fuel component is suitable for use as a blending component in a fuel composition and, when appropriately added, can even be used as a fuel itself, ie as an unblended component. The recovered liquid transportation fuel components and optional other products are suitable for a wide variety of other uses, such as in feedstocks for industrial conversion processes, preferably in thermal cracking feedstocks, such as steam cracking feedstocks and / or catalytic cracking feedstocks, in transformer oils, heat transfer media, switchgear oils, shock absorber oils, insulating oils, hydraulic fluids, gear oils, transmission fluids, degreasing compositions, penetrating oils, anti-corrosion compositions, multi-purpose oils, metalworking fluids, rolling oils, especially for aluminum, cutting oils, drilling fluids, solvents, lubricants, extender oils, carriers, dispersant compositions, demulsifiers, extractants, paint compositions, coating fluids or pastes, adhesives, resins, varnishes, printing pastes or inks, detergents, cleaning agents, plasticizing oils, turbine oils, hydrophobic compositions, agriculture, crop protection fluids, construction, concrete release formulations, electronic equipment, medical devices, compositions for the automotive, electrical, textile, packaging, paper, cosmetic and / or pharmaceutical industries, and / or intermediates for their manufacture. It is foreseen that a relatively high degree of isomerization and an increase in the shorter carbon chain fraction improves the flowability, pumping and mixing characteristics and miscibility of the recovered components and / or fractions. These are generally desirable and beneficial properties for a wide range of uses, particularly those involving spraying, injection and / or mixing with other ingredients.

[0208] Process diagram

[0209] Figure 1 The method according to the example embodiment is schematically shown before switching from i), ii), iii) to I), II), that is, before the example embodiment according to i), ii), iii) is executed. 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 compounds that are gaseous at least at NTP 160 from the HDO effluent to obtain a degassed HDO effluent 170, which in this example embodiment is a paraffinic hydrocarbon feed as described 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 the gas-liquid separation 210 to separate the gaseous compounds at least at the NTP 220 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 the gasoline fuel component 250, the aviation fuel component 260 and / or the diesel fuel component 270 are recovered. In addition, a recycle stream 280 having a T5 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 the gaseous compounds at NTP 330 from the recycle effluent 310 to obtain a degassed recycle effluent 340, and then the degassed recycle effluent 340 is fed to the distillation unit 240 for fractionation as a co-feed with the degassed HI effluent 230. In certain embodiments, a portion of the HI effluent 200, 230 may be fed as a co-feed 500 with the recycle stream 280 to the hydrocracking in the second reactor 290.

[0210] Not limited to Figure 1In certain preferred embodiments of the process of the present invention in which at least an aviation fuel component is recovered from fractionation, when operating in the first mode, the monitored parameters indicative of HI catalyst deactivation include two 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, a temperature difference across the first reactor 180 or the HI catalyst bed 190, a cloud point and / or pour point of the degassed HI effluent 230, a cloud point and / or pour point of the recycle stream 280 or the diesel fuel component 270, a freezing point of the aviation fuel component 260, and / or one or more distillation characteristics, the respective received values ​​of which are compared to predetermined values. When the monitored parameter is temperature, for example, as monitored at the inlet of the first reactor 180, the predetermined value may be, for example, a maximum of 450°C; for the WHSV in the first reactor 180, the predetermined value may be, for example, 6 kg paraffin feed / kg catalyst / hour; for the cloud point of the degassed HI effluent 230, the predetermined value may be, for example, a maximum of -5°C; for the cloud point of the recycle stream 280 or the diesel fuel component 270, the predetermined value may be, for example, a maximum of -15°C (ASTM D 5771-2017); for the freezing point of the aviation fuel component 260, the predetermined value may be, for example, a maximum of -40°C (IP 529-201); for the distillation characteristics of the aviation fuel component 260, the predetermined value may be, for example, for T10, a maximum of 205°C, or for the T90-T10 difference, for example, a minimum of 22°C (EN ISO 9001-2017). 3405-2019); for the distillation characteristics of the diesel fuel component 270, the predetermined value may be, for example, T95 maximum value of 360°C (EN ISO 3405-2019). When the received value for the monitored parameter reaches the corresponding predetermined value, the process is switched to and operated in the second mode. After switching, the monitored parameter and the predetermined value may be the same as in the first mode, or different parameters may be monitored and / or different predetermined values ​​may be selected, depending on, for example, whether the same product and its quality are still targeted.

[0211] Figure 2 The method according to the example embodiment is schematically shown after switching from i), ii), iii) to I), II), i.e. after running according to the example embodiment of I), II). Figure 2In 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 compounds that are gaseous at least at NTP 160 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 the gas-liquid separation 210 to separate the gaseous compounds at least at the NTP 220 from the HI effluent 200 to obtain the degassed HI effluent 230. Figure 2 In the embodiment, 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 compounds that are gaseous at least at NTP 370 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, from which several streams or fractions may be obtained. Figure 2 In the distillation of , a gasoline fuel component 390, an aviation fuel component 400 and a diesel fuel component 410 are recovered. In addition, another 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 part. Figure 2 In the embodiment, the other recycle stream 420 can be fed to the second reactor 290 as a co-feed with the degassed HI effluent 230 for hydrocracking. In certain embodiments, a portion of the HI effluent 200, 230 can be fed to the fractionation 240 as a co-feed 500 with the hydrocracking effluent 350, 380.

[0212] The method as described herein can be controlled by prior art means, in particular by a computer-implemented device. In certain exemplary embodiments, the method of the present invention further comprises causing the control device to perform at least the following steps: comparing the received value with a predetermined value; and switching from i), ii), iii) to I), II). In certain exemplary embodiments, the method of the present invention is controlled by a computer program product, as defined as a third exemplary aspect, which comprises instructions, when executed by a processor of a control device in a system for producing at least one liquid transportation fuel component, in the method defined in the first exemplary aspect, the instructions cause the control device to at least compare the received value with a predetermined value, and when the received value reaches the predetermined value, switch from i), ii), iii) to I), II). The control device that executes the instructions of the computer program product can be (for example) a general-purpose computer or some other electronic data processing device including a processor and a (non-transitory) memory. The instructions of the computer program product can be stored in the memory for execution by the processor to cause the operation of the control device.

[0213] A number of embodiments have been provided.It should be understood that in this document, the words "comprise", "include" and "contain" are each used as open expressions and are not intended to be exclusive.

[0214] 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.

[0215] 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; i) subjecting the hydroisomerization effluent to fractionation to separate from the fractionation a recycle stream having at least a T5 temperature of 270° C. or more (recovery 5 vol%, EN ISO 3405-2019); ii) hydrocracking a second reactor feed comprising the recycle stream in a second reactor in the presence of a hydrocracking catalyst to obtain a recycle effluent; iii) feeding the recycle effluent to the fractionation as a co-feed with the hydroisomerization effluent and recovering at least one or more liquid transportation fuel components from the fractionation; as well as monitoring a parameter indicative of deactivation of the hydroisomerization catalyst to receive a value; comparing the received value to a predetermined value; and When the received value reaches the predetermined value, switch from i), ii), and iii) to: I) 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; II) subjecting said hydrocracking effluent to fractionation and recovering at least one or more liquid transportation fuel components from said fractionation.

2. The method according to claim 1, wherein the parameters indicating deactivation of the hydroisomerization catalyst include at least two or more of the following parameters: a. 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; b. the content of NH3 and / or H2S in the gas phase of the hydroisomerization effluent; c. the physicochemical characteristics of the hydroisomerization 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; d. Composition characteristics of the hydroisomerization 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; e. the yield of at least one or more of the recovered liquid transportation fuel components and / or the separated recycle stream, preferably the yield of aviation fuel components; f. at least one or more physicochemical characteristics of the recovered liquid transportation fuel component and / or the separated recycle stream, preferably at least one or more of cloud point, freezing point, pour point, cold filter plugging point, kinematic viscosity, density, research octane number (RON), cetane number and / or distillation characteristics; g. The compositional characteristics of at least one or more of the recovered liquid transportation fuel components and / or the recycle stream, preferably the isoparaffin content and / or the multi-branched isoparaffin content of one or more of the recovered liquid transportation fuel components and / or the separated recycle stream; h. a temperature difference in the first reactor or one or more catalyst beds; and / or i. The operating conditions in the first reactor are selected from the group consisting of temperature, pressure, weight hourly space velocity (WHSV), feed ratio of H2 to paraffin hydrocarbons and / or H2 partial pressure at the inlet of the first reactor.

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

4. A process according to any one of the preceding claims, wherein the recycle stream and optional further recycle streams comprise C16 n-paraffins.

5. A process according to any one of the preceding claims, comprising feeding a portion of the hydroisomerisation effluent to a second reactor for hydrocracking as part of the second reactor feed in step ii); and / or feeding a portion of the hydroisomerisation effluent to fractionation as a co-feed with the hydrocracking effluent in step II).

6. The process according to any one of the preceding claims, said switching comprising feeding a decreasing portion of said hydroisomerization effluent to said fractionation in step i) while feeding an increasing portion of said hydroisomerization effluent to hydrocracking as part of said second reactor feed in step ii) until said process is operated according to I) and II).

7. The process according to any one of the preceding claims, wherein the hydroisomerization in the first reactor is carried out at a temperature 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 of 1 MPa to 10 MPa, preferably 2 MPa to 8 MPa or 3 MPa to 10 MPa, a H2 partial pressure at the inlet of the first reactor of 1 MPa to 10 MPa, preferably 2 MPa to 8 MPa, a weight hourly space velocity of 0.1 to 10, preferably 0.2 to 8, more preferably 0.4 to 6 kg paraffin feed / kg catalyst / hour, and a feed ratio of H2 to paraffin of 10 to 2000, preferably 50 to 1000 standard liters of H2 / liter of paraffin feed.

8. The process according to any one of the preceding claims, wherein the hydrocracking in the second reactor is carried out at a temperature of 200 to 450°C, preferably 220 to 430°C, more preferably 280 to 350°C, a pressure of 0.4 to 8 MPa, preferably 1 to 7 MPa, more preferably 2.5 to 7 MPa, a H2 partial pressure at the second reactor inlet of 0.4 to 8 MPa, preferably 1 to 7 MPa, more preferably 2.5 to 7 MPa, a weight hourly space velocity 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 feed ratio of H2 to the second reactor of 10 to 2000, preferably 50 to 1000 standard liters H2 / liter second reactor feed.

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

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

11. The process according to any one of the preceding claims, wherein the hydroisomerization catalyst is a non-sulfided bifunctional hydroisomerization catalyst and the hydrocracking catalyst is a non-sulfided bifunctional hydrocracking catalyst and the non-sulfided bifunctional catalyst comprises at least one or more 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 comprise less than 50 wt-ppm, preferably less than 30 wt-ppm, more preferably less than 10 wt-ppm of sulfur (ppm by weight, calculated as elemental S) of the respective total feed as determined according to ISO 20846-2019.

12. 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 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, SAOP-11, ZSM-23, β-zeolite, Y-type zeolite and / or amorphous silica-alumina; and Optionally, at least one or more of alumina, silica, titanium alumina, titania and / or zirconium oxide.

13. The process according to any one of the preceding claims, wherein the 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 metals of 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.

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

15. A process according to any one of the preceding claims, wherein the paraffinic feed comprises at least 70 wt%, preferably at least 80 wt%, more preferably at least 90 wt% of paraffinic hydrocarbons, 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 paraffinic hydrocarbons 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 C12-C30 hydrocarbons, based on the total weight of 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 C14-C22 hydrocarbons, based on the total weight of the paraffinic feed.

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

17. The 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.

18. The process according to any one of the preceding claims, wherein in steps iii) and II), 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, or at least an aviation fuel component and a gasoline fuel component.

19. A process according to any one of the preceding claims, wherein in steps iii) and II) at least an aviation fuel component having a density at 15°C of between 730 kg / m 3 Up to 772kg / m 3 range (EN ISO12185-1996), T10 temperature not more than 205 °C (EN ISO 3405-2019), final boiling point not more than 300 °C (EN ISO 3405-2019), flash point at least 38 °C (IP 170-2013, Abel closed cup method) and freezing point not more than -40 °C (IP 529-2016).

20. The process according to claim 18 or 19, wherein the aviation fuel component is recovered in a yield of at least 30 wt%, preferably in the range of 30 wt% to 90 wt%, of the total weight of the paraffinic feed.

21. A system for producing at least one liquid transportation fuel component, wherein the system is configured to use the method i), ii), iii) or I), II), III) of operating the system, the system comprising: a device configured to provide 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 isoparaffins; a first reactor configured such that the paraffinic hydrocarbon feed is hydroisomerized in the first reactor in the presence of a hydroisomerization catalyst to obtain a hydroisomerization effluent; a fractionation system configured to i) fractionate the hydroisomerization effluent to separate a recycle stream having at least a T5 temperature of 270°C or more (recovery 5 vol%, EN ISO 3405-2019) from the fractionation and fractionate the recycle effluent (after ii) and iii)); and II) fractionate the hydrocracking effluent; a second reactor configured to ii) hydrocracking a second reactor feed comprising the recycle stream in the second reactor in the presence of a hydrocracking catalyst to obtain a recycle effluent; and I) subjecting a second reactor feed comprising said hydroisomerization effluent to hydrocracking in a second reactor in the presence of a hydrocracking catalyst to obtain a hydrocracked effluent; a pipeline configured to feed iii) the recycle effluent and the hydroisomerization effluent to the fractionation system, and III) the hydrocracking effluent to the fractionation system; a device configured to recover at least one or more liquid transportation fuel components from said fractionation system; and A control device configured to monitor a parameter indicating deactivation of the hydroisomerization catalyst to receive a value; compare the received value with a predetermined value; and when the received value reaches the predetermined value, switch from i), ii), iii) of the system to I), II), III).

22. A computer program product comprising instructions which, when executed by a processor of a control device in a system for producing at least one liquid transportation fuel component, cause the control device to compare a received value with a predetermined value and, when the received value reaches the predetermined value, switch from i), ii), iii) to i), II).

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