A process for producing liquid transport fuel component

Abstract

A method of producing at least one liquid transport fuel component is provided. In the process, a paraffin feed is hydrocracked in a first reaction section as part of the first reaction section feed to obtain a hydrocracked effluent, which hydrocracked effluent is hydroisomerized in a second reaction section as part of the second reaction section feed to obtain a hydroisomerized effluent, the hydroisomerized effluent is fed to fractionation from which at least one liquid transport fuel component is recovered.

Description

Technical Field

[0001] The present invention generally relates to a method of producing a renewable fuel component. The present invention particularly, but not exclusively, relates to a method of producing at least one or more liquid transportation fuel components, preferably at least one aviation fuel component. Background Art

[0002] This section provides useful background information, but no admission is made that any of the techniques described herein represent prior art.

[0003] The transportation industry, and aviation in particular, needs to continually reduce greenhouse gas emissions and / or carbon footprint. As a result, interest in renewable aviation fuels and aviation fuel components is growing and continues to grow.

[0004] Methods for producing aviation fuel components from renewable raw materials have been proposed. However, in the methods described, 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 an interest in producing aviation fuel components that can be used in large quantities for aviation fuel or, in the case of appropriate additions, can even be used as aviation fuel. Summary of the invention

[0005] The object is to solve or alleviate at least some of the problems associated with the prior art. The object is to improve the quality of aviation fuel components obtainable from renewable sources. Another object is to increase the yield of aviation fuel components. Another object is to reduce the formation of C1-C4 hydrocarbons, in particular C1-C2 hydrocarbons, during the production of renewable liquid transportation fuel components. In addition, the object is to extend the life of the hydroisomerization catalyst during the production of renewable liquid transportation fuel components.

[0006] The attached claims define the scope of protection. Any examples and technical descriptions of devices, systems, products and / or methods in the description and / or drawings that are not covered by the claims are provided as examples to help understand the present invention.

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

[0008] providing a paraffin feed comprising at least 60 wt% paraffins based on the total weight of the paraffin feed, wherein at least 5 wt% of the paraffins are isoparaffins;

[0009] subjecting a first reaction stage feed comprising said paraffinic feed and optionally a recycle stream and / or a side draw to hydrocracking in a first reaction stage in the presence of a hydrocracking catalyst to obtain a hydrocracking effluent;

[0010] subjecting a second reaction stage feed comprising the hydrocracking effluent to hydroisomerization in a second reaction zone in the presence of a hydroisomerization catalyst to obtain a hydroisomerization effluent; and

[0011] The hydroisomerization effluent is fed to a fractionation and at least one or more liquid transportation fuel components and optionally the recycle stream and / or the side draw are recovered from the fractionation.

[0012] The present process enables the yield and / or quality of recovered fuel components, in particular preferably recovered aviation fuel components, to be increased, while the amount of low-profit products (fuel gas) can be kept at a low level. In the present process, the first reaction stage feed comprising a paraffinic feed containing isoparaffins is subjected to hydrocracking, followed by hydroisomerization (HI), and then fractionation, which has been shown to successfully convert the paraffinic feed into high-quality liquid fuel components with excellent cold properties, with very high total yields of aviation fuel components and diesel fuel components. In the present process, the proportions of these components can be easily adjusted, for example by recovering a recycle stream and / or a side draw from the fraction and adding the recycle stream and / or the side draw to the first reaction stage feed to increase the content of heavier hydrocarbons and / or highly isomerized paraffins therein.

[0013] Various non-binding example aspects and embodiments have been described above. The above embodiments are only used to explain selected aspects or steps that can be used in different implementations. Some embodiments may be presented with reference to only certain example aspects. It should be understood that the corresponding embodiments may also be applied to other example aspects. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Some example embodiments will be described with reference to the accompanying drawings, in which:

[0015] Figure 1 An exemplary embodiment of the present process involving hydrocracking is schematically illustrated for producing at least one or more liquid transportation fuel components.

[0016] Figure 2 Another exemplary embodiment of the present process involving hydrocracking for producing at least one or more liquid transportation fuel components is schematically illustrated.

[0017] Figure 3 Distillation curves of the degassing effluent (liquid product) of one test run according to an exemplary embodiment of the present process and three comparative test runs as shown in Example 1 are shown.

[0018] Figure 4 A process involving hydrocracking is illustratively shown for producing at least one or more liquid transportation fuel components.

[0019] Figure 5 Another process involving hydrocracking is illustratively shown for producing at least one or more liquid transportation fuel components. DETAILED DESCRIPTION

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

[0021] Unless otherwise stated, all standards cited herein are the latest versions available on the filing date.

[0022] Unless otherwise stated, for distillation characteristics such as initial boiling point (IBP), final boiling point (FBP), T5 temperature (5% volume recovery), T95 temperature (95% volume recovery) and boiling range, please refer to EN ISO 3405-2019. IBP is the temperature at the moment when the first drop of condensate drips from the lower end of the condenser tube, while 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, you can also refer to the GC-based method (simulated distillation (simdis)) ASTM D2887-19e1, or for gasoline fraction hydrocarbons, you can refer to ASTM D7096-19.

[0023] As used in the context of the present disclosure, an aviation fuel composition refers to a hydrocarbon component suitable for use in a fuel composition that conforms to a standard specification for aviation fuel, such as that specified in ASTM D7566-21. Typically, such aviation fuel components boil in the range of about 100°C to about 300°C, such as in the range of about 150°C to 300°C, i.e. have an IBP and a FBP, as determined in accordance with EN ISO 3405-2019.

[0024] In the context of the present disclosure, a diesel fuel component refers to a hydrocarbon composition suitable for use in a fuel composition that complies with a diesel fuel standard specification, such as the specifications set forth in EN590:2022 or EN 15940:2016+A1:2018+AC:2019. Typically, such diesel fuel components boil in the range of about 160°C to about 380°C, i.e. have an IBP and a FBP, as determined in accordance with EN ISO 3405-2019.

[0025] In the context of the present disclosure, a gasoline fuel component or naphtha refers to a hydrocarbon component suitable for use in a fuel composition that complies with a gasoline fuel standard specification, such as the specifications set forth in EN 228-2012+A1-2017. Typically, such gasoline fuel components boil in the range of about 25°C to about 210°C, i.e. have an IBP and a FBP, as determined in accordance with EN ISO 3405-2019.

[0026] As used in the context of the present disclosure, a marine fuel component refers to a hydrocarbon component suitable for use in a fuel composition that complies with a marine fuel standard specification, such as that specified in ISO 8217-2017. Typically, such marine fuel components boil in the range of about 180°C to about 600°C, such as about 180°C to about 400°C, as determined in accordance with EN ISO 3405-2019, i.e. have an IBP and a FBP.

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

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

[0029] In the context of the present invention, isoparaffin refers to branched open chain alkanes, i.e., non-cyclic open chain saturated hydrocarbons with one or more alkyl side chains. In this article, isoparaffins with one alkyl side chain or branch are referred to as monobranched isoparaffins, and isoparaffins with two or more alkyl side chains or branches are referred to as multi-branched isoparaffins in this article. In other words, isoparaffin refers to monobranched isoparaffins and / or multi-branched isoparaffins in this article. The alkyl side chain of isoparaffins can be, for example, a C1-C9 alkyl side chain, preferably a methyl side chain. The amount of monobranched and multi-branched isoparaffins can be given separately. The term "isoparaffin" refers to the total amount of any monobranched isoparaffin and any multi-branched isoparaffin (if present), indicating the total amount of any isoparaffin present regardless of the number of branches. Accordingly, "paraffin" refers to the total amount of any normal alkane, any monobranched and any multi-branched isoparaffin (if present).

[0030] In the context of the present invention, 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.

[0031] As used herein, cyclic hydrocarbons refer to all hydrocarbons containing a ring structure, including cycloolefins, cyclic hydrocarbons and aromatic hydrocarbons. Cyclic hydrocarbons herein refer to cycloalkanes, i.e., saturated hydrocarbons containing at least one ring structure, with or without side chains. Since cyclic hydrocarbons are saturated compounds, they are compounds in which aromatic ring structures are not present. Aromatic hydrocarbons herein refer to hydrocarbons containing at least one aromatic ring structure, i.e., ring structures having delocalized, alternating π bonds around the ring structure.

[0032] In the context of the present invention, for compositions boiling at temperatures above 36°C (at standard atmospheric pressure), the content of normal paraffins, isoparaffins, monobranched isoparaffins, various multibranched isoalkenes, cyclic hydrocarbons and aromatic hydrocarbons is expressed as weight % (wt-%) relative to the degassed weight of the feed, stream, effluent, product, component or sample in question or, where so defined, as weight % (wt-%) relative to the (total) weight of the paraffins or as the (total) weight of the isoparaffins of the feed, stream, effluent, product, component or sample. The content can be determined by a GCxGC-FID / GCxGC-MS method, preferably performed as follows: The GCxGC (2D GC) method is run according to the general disclosure in UOP 990-2011 and in the experimental part of Nousiainen M. Master's thesis "Comprehensive two-dimensional gas chromatography withmass spectrometric and flame ionization detectors in petroleum chemistry", University of Helsinki, August 2017, with the following modifications. The GCxGC was operated in reverse mode using first a semipolar column (Rxi17Sil) and then a nonpolar column (Rxi5Sil) followed by an FID detector with the following operating parameters: carrier gas helium 31.7 cm / sec (column flow 1.60 ml / min at 40 °C); distribution ratio 1:350; injector 280 °C; T column 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 sec; detector 300 °C, H2 40 ml / min, air 400 ml / min; helium make-up flow 30 ml / min; sampling rate 250 Hz, injection size 0.2 μl. Individual compounds were identified using GCxGC-MS with the following MS parameters: ion source 230°C; interface 300ºC; scan range 25-500 amu; event time (seconds) 0.05; scan speed 20000. Commercial tools (LabSolutions from Shimadzu, GC Image from Zoex) were used for data processing, including identification of detected compounds or hydrocarbon radicals and determination of their mass concentrations by applying a response factor related to n-heptane to the volume of the detected peaks and then normalizing to 100 wt%. Olefins were grouped with cyclic hydrocarbons and heteroatom species with aromatics unless reported separately. The method had a limit of quantification of 0.1 wt% for individual compounds.

[0033] In the context of the present invention, various characteristics of appropriately prepared feeds, streams, effluents, products, components or samples are determined according to standard methods described or disclosed herein. For example, cloud point is determined from degassed feeds, streams, effluents, products, components or samples according to ASTM D 5771-17.

[0034] In general, the various paraffinic feeds, streams, effluents, and fuel components described herein as recovered products or fractions thereof, in addition to hydrocarbons, may contain varying amounts of impurities, such as heteroatom-containing hydrocarbons and inorganic compounds, and varying amounts of oxygenated hydrocarbon feeds (e.g., 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 then decrease to negligible or even below the detection limit in the recovered liquid transportation fuel components.

[0035] In the context of the present disclosure, the feed to a reaction stage, in particular to the first reaction stage and / or the second reaction stage, is defined in such a way that H2 which may be fed to the respective reaction stage, for example H2 fed to hydrocracking and / or H2 fed to hydroisomerization, is not included in the definition of said feed.

[0036] As used herein, hydrocracking (HC) effluent refers to either total HC effluent or degassed HC effluent, as the case may be, and the term HC effluent may include both.

[0037] In the context of the present disclosure, CX+alkanes, CX+normal alkanes, CX+isoalkanes, CX+monobranched isoalkanes, CX+multi-branched isoalkanes, CX+hydrocarbons or CX+fatty acids refer to alkanes, normal alkanes, isoalkanes and mono-branched isoalkanes, multi-branched isoalkanes, hydrocarbons or fatty acids having at least X carbon atoms, respectively, wherein X is any feasible integer. It is understood that not every compound falling within the definition is necessarily present.

[0038] In the context of the present disclosure, CY-alkane, CY-normal alkane, CY-isoalkane, CY / monobranched isoalkane, SY-multibranched isoalkane, CY-hydrocarbon or CY-fatty acid refers to an alkane, normal alkane, isoalkane, monobranched isoalkane, multibranched isoalkane, hydrocarbon or fatty acid having a carbon number of up to Y, wherein Y is any feasible integer. It is understood that not every compound falling within the definition is necessarily present.

[0039] In the context of this disclosure, CX Y -CX Z (or from CX Y To CX Z ) Alkanes, CX Y -CX Z n-Alkanes, CX Y -CXZ Isoparaffin, CX Y -CX Z Monobranched isoparaffin, or CX Y -CX Z Multi-branched isoparaffins, CX Y -CX Z Hydrocarbon, or CX Y -CX Z Fatty acids refer to a series of paraffins, normal paraffins, isoparaffins, mono-branched isoparaffins, or multi-chain isoparaffins, hydrocarbons, or fatty acids, respectively, wherein X Y and X Z is a feasible terminal integer, wherein the carbon number within the range is represented by the terminal integer and any integer between the terminal integer (if any). However, unless explicitly stated, all the paraffins, normal paraffins, isoparaffins, monobranched isoparaffins, multi-branched isoparaffins, hydrocarbons or fatty acids (as the case may be) of the carbon numbers stated within the stated range, particularly at or near the endpoints, do not necessarily exist. On the other hand, by definition, isomers may contain several hydrocarbon compounds with the same carbon number, such as C15 isomers may contain methyltetradecane (different positions of the methyl branches), dimethyltridecane (different positions of the two methyl branches), etc., wherein "C15 isomers" includes the sum of all these variants.

[0040] Generally, the sum of the weight or volume of each paraffin, normal paraffin, isoparaffin, monobranched isoparaffin, multibranched isoparaffin, hydrocarbon or fatty acid defined refers to all carbon numbers of paraffin. For example, C15 to C22 normal paraffin refers to any normal paraffin in the range (if present), 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, the total weight can be obtained by adding 0 (referring to the absence of C15 normal paraffin) to the total weight of all other C15 to C22 normal paraffins present.

[0041] Isomerization converts at least a certain amount of normal paraffins into isoparaffins, in particular monobranched isoparaffins. By (further) increasing the degree of isomerization, for example by increasing the severity of the hydroisomerization described below, more normal paraffins can be converted into isoparaffins, and monobranched isoparaffins can be converted into multi-branched isoparaffins, such as di-branched, tri-branched isoparaffins, or even isoparaffins containing more than three branches.

[0042] As used herein, in the context of the first reaction stage, effective cracking degree refers to cracking that produces non-gaseous (NTP) cracked products, particularly expressed as the ratio of the C8-C14 hydrocarbon content in the hydrocracking effluent to the C8-C14 hydrocarbon content in the first reaction stage feed.

[0043] As used herein, whenever a reaction step is defined as occurring in a "reactor", the expression is primarily for illustrative purposes. It is contemplated by those skilled in the art that any "reactor" is implemented in practice as a reactor system that may be composed of one or more reactors. Whether the reactor is actually configured in a single reactor or in several reactors is an engineering question that may be affected by practical issues such as the maximum height of the on-site facility, the reactor diameter, on-site supervision and maintenance issues, on-site wind conditions, and / or available equipment. Similarly, "fractionation" can be carried out in a fractionation system, which typically includes, for example, separation and distillation devices that can be configured according to conventional engineering practices in the field.

[0044] Catalyst properties, such as the total number of acid sites, in the context of this disclosure refer to the properties of the catalyst in a ready-to-use state at the start of the process.

[0045] 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 ) a decrease in catalyst activity (reflected by the amount of unconverted feed in the reaction zone effluent) and / or a decrease in catalyst selectivity (reflected by a decrease in the amount of the desired reaction product in the reaction zone 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 caused by poisoning and contamination phenomena and includes both reversible and irreversible deactivation.

[0046] As used herein, the term renewable refers to compounds or compositions that are obtainable, derivable, or derived from plants and / or animals, including compounds or compositions that are obtainable, derivable, or derived from fungi and / or algae in whole or in part. As used herein, renewable compounds or compositions may include genetically manipulated compounds or compositions. Renewable feeds, components, compounds, or compositions may also be referred to as biofeeds, components, compounds, or compositions, or as biogenic feeds, components, compounds, or compositions.

[0047] As used herein, the term "fossil" refers to a compound or composition that is obtainable, derivable, or derived from naturally occurring non-renewable components, such as crude oil, petroleum / natural gas, shale oil / gas, natural gas, or coal deposits, and combinations thereof, including any hydrocarbon-rich deposits that are accessible from above-ground / underground sources.

[0048] The term "recycled" refers to recycled materials that are usually derived from non-renewable resources. For example, the term "recycled" may refer to recycled materials derived from waste plastics. The renewable and recycled and fossil compounds or compositions are considered different from each other based on their sources and impact on environmental issues. Therefore, they can be treated differently under legislative and regulatory frameworks. Generally, renewable, recycled and fossil compounds or compositions are distinguished based on their sources and information provided by the producers.

[0049] Chemically, the renewable or fossil origin of any organic compound, including hydrocarbons, can be determined by appropriate methods for analyzing the carbon content of renewable origin (e.g. DIN 51637 (2014), ASTM D6866 (2020), or EN 16640 (2017)). The methods are based on the fact that carbon atoms of renewable or biological origin contain a greater amount of unstable radiocarbon ( 14 C) atoms. Therefore, by analyzing 12 C and 14 The ratio of C isotopes can distinguish between carbon compounds from renewable or biogenic sources or raw materials and carbon compounds from non-renewable or fossil sources or raw materials. Therefore, the specific ratio of the isotopes can be used as a "tag" to identify renewable carbon compounds and distinguish them from non-renewable carbon compounds. The isotope ratio does not change during the chemical reaction. Therefore, the isotope ratio can be used to identify renewable compounds, components and compositions in reaction stage feeds, reaction stage effluents, separated product fractions and various mixtures thereof, and distinguish them from non-renewable fossil materials. Numerically, the biogenic carbon content can be expressed as the amount of biogenic carbon in the material as a weight percentage of the total carbon (TC) in the material (according to ASTM D6866 (2020) or EN 16640 (2017)). In this context, the term renewable preferably refers to a material having a biogenic carbon content of more than 50 wt.-%, in particular more than 60 wt.-% or more than 70 wt.-%, preferably more than 80 wt.-%, more preferably more than 90 wt.-% or more than 95 wt.-%, even more preferably about 100 wt.-%, based on the total weight of carbon in the material (EN 16640 (2017)).

[0050] The present invention provides a method for producing at least one liquid transportation fuel component, the method comprising: providing a paraffin feed comprising at least 60 wt% paraffins based on the total weight of the paraffin feed, wherein at least 5 wt% of the paraffins are isoparaffins; subjecting a first reaction stage feed comprising the paraffin feed and an optional recycle stream and / or a side draw to hydrocracking (HC) in a first reaction stage in the presence of a hydrocracking catalyst to obtain a hydrocracking effluent; subjecting a second reaction stage feed comprising the hydrocracking effluent to hydroisomerization (HI) in a second reaction stage in the presence of a hydroisomerization catalyst to obtain a hydroisomerization effluent; and feeding the hydroisomerization effluent to a fractionation and recovering at least one or more liquid transportation fuel components and the optional recycle stream and / or the side draw from the fractionation.

[0051] Preferably, the method is a continuous process.

[0052] Typically, in the present method, at least one or more of aviation fuel components, diesel fuel components, gasoline fuel components, and / or marine fuel components are recovered from the fractionation, preferably at least one aviation fuel component, more preferably at least one aviation fuel component and a diesel fuel component. Compared with the conventional method of producing fuel components by hydrodeoxygenation (HDO) and HI of renewable fats and oils, the present method can obtain a higher yield of aviation fuel components, in particular a higher total yield of aviation and diesel fuel components, and / or improve their quality. These benefits are shown in comparative experiments in which the paraffin feed is subjected to only HI, only HC, or HI followed by HC before fractionation and product recovery.

[0053] By means of the present method, it is possible to produce aviation fuel components having excellent cold properties, and therefore can be used for aviation fuel even at high mixing ratios. In addition, compared with conventional methods for producing fuel components by HDO and HI of renewable fats and oils, the present method is able to extend the life of the HC and / or HI catalysts and is able to utilize a wider range of feeds, including heavier and more impure feeds. In addition, the present method is able to flexibly adjust the product selectivity for various liquid transportation fuel components, in particular aviation fuel components and diesel fuel components, based on, for example, market dynamics, even at the end of the life of the HC catalyst and / or HI catalyst. The present method proposes to hydrocracking a paraffinic feed containing isoparaffins in a first reaction stage, which hydrocracking cracks longer paraffinic molecules into paraffins boiling in the range of, for example, aviation fuel. Having at least some isoparaffins in the paraffinic feed helps to achieve the desired effective cracking degree in the first reaction stage under milder operating conditions (compared to paraffinic feeds containing no or only a small amount of isoparaffins), thereby effectively reducing the formation of low-profit products (such as fuel gas). The hydrocracking of the paraffinic feed containing isoparaffins in the first reaction stage may even isomerize the normal paraffins in the feed and the normal paraffins formed during the cracking reaction, and further isomerize the isoparaffins by increasing the number of branches in the isoparaffin molecules, thereby producing multi-branched isoparaffins. Therefore, by running the process of the present invention, the degree of isomerization of the paraffinic feed in the first reaction stage can be maintained but preferably increased. This is conducive to achieving a high isoparaffin content in the HC effluent, even at the end of the life of the HC catalyst. Preferably, by running the process of the present invention, the content of multi-branched isoparaffins in the HC effluent is effectively increased compared to their content in the feed of the first reaction stage. The increase in the effective cracking degree without excessive formation of gaseous hydrocarbons in the first reaction stage, as well as the increase in the isoparaffin content in the HC effluent, are beneficial to the yield and quality of the transportation fuel components recovered from the fractionation, in particular to the yield and quality of the aviation fuel components. The hydrocracking in the first reaction stage can increase the yield of aviation fuel components and improve their quality, such as their cold performance. The hydroisomerization in the second reaction stage (further) reduces the content of normal paraffins in the HI effluent and the recovered fuel components and (further) increases the content of isoparaffins, preferably the content of multi-branched isoparaffins.

[0054] During the continuous operation of catalyzing HC and HI, the catalyst gradually deactivates, for example due to impurities and coking in the process stream. The present method is highly flexible, involving various possibilities to adjust the output and / or quality of the liquid transportation fuel components recovered, and to extend the life of the HI and HC catalysts. Convenient means for adjusting the yield and / or quality of the liquid transportation fuel components recovered and / or responding to catalyst deactivation or changing market demands may include, for example, adjusting the amount of the recycle stream and / or side fraction that is optionally recovered and hydrocracking, distributing the paraffin feed between the first reaction section and the second reaction section with an adjustable weight ratio, and / or in an embodiment, recovering the recycle stream, adjusting the amount of the heavies that are optionally removed from the method as a diesel fuel component, a marine fuel component, or some other heavy product components. The various possibilities of adjusting the method enable the use of paraffin feeds with higher impurity content than the traditional method of producing liquid fuel components by HDO and HI of renewable fats and oils. Furthermore, the hydrocracking step enables the use of feedstocks containing heavier and longer chain molecules, while enabling the production of lower boiling liquid transportation fuel components, particularly aviation fuel components, in good yield and quality, compared to conventional methods of producing liquid fuel components, typically diesel components.

[0055] In certain preferred embodiments of the present method, the second reaction stage feed also comprises a portion of a paraffin feed, and the paraffin feed is distributed between the first reaction stage feed and the second reaction stage feed. These embodiments provide further flexibility for running the present method, and the possibility of adjusting the method according to fluctuations in the characteristics of the paraffin feed. In addition, the method can be run more accurately to meet the target yield and quality of multiple recovered components at a time. In this way, it is possible to avoid the situation where the target yield and quality of a recovered fuel component are met, but at the expense of producing another recovered fuel component of too high quality (e.g., producing a diesel fuel component with an unnecessary low cloud point).

[0056] In certain preferred embodiments, the process comprises recovering the recycle stream from the fractionation and feeding the recycle stream to the first reaction stage as part of the feed to the first reaction stage, and / or recovering the side draw from the fractionation and feeding the side draw to the first reaction stage as part of the feed to the first reaction stage; and / or feeding a portion of the paraffin feed to the second reaction stage as part of the feed to the second reaction stage, the portion of the paraffin feed being obtained by dividing the paraffin feed between the first reaction stage and the second reaction stage. These embodiments provide (further) enhanced flexibility in operating the process, including the possibility to adjust the process, for example according to fluctuations in the characteristics of the paraffin feed, according to the requirements for the share and quality of the diesel and aviation fuel components produced, and / or according to the changing activity and / or selectivity of the HI and HC catalysts throughout their lifetime. Furthermore, the process can be operated more precisely to meet the target yields and qualities of multiple recovered components at a time, without producing excessively high qualities of some other recovered fuel components.

[0057] In the present method, the paraffin feed that is hydroisomerized in the first reactor comprises at least 60% by weight of paraffins accounting for the total weight of the paraffin feed, wherein at least 5% by weight of paraffins are isoparaffins. This means that when the paraffin feed comprises at least 60% by weight of paraffins accounting for the total weight of the paraffin feed, at least 5% by weight of the total weight of paraffins in the paraffin feed, i.e. at least 3% by weight of the total weight of the paraffin feed, are isoparaffins. Typically, the paraffin feed comprises at least 70% by weight, preferably at least 80% by weight, more preferably at least 90% by weight, even more preferably at least 95% by weight of paraffins accounting for the total weight of the paraffin feed. Based on the gross weight of the paraffin feed, the paraffin feed of the present invention may contain a small amount of olefins, preferably less than 5% by weight, more preferably less than 1% by weight, and a small amount of aromatics and / or cyclopentanes. The advantage of using a highly paraffinic feed in the present process is that paraffins are relatively easy to crack when subjected to HC and are cracked under milder conditions than, for example, cyclic hydrocarbons. In addition, paraffins are relatively easy to isomerize under milder conditions when subjected to HI.

[0058] Among the paraffins in the paraffin feed of the present disclosure, typically at least 8 wt%, or at least 10 wt%, preferably at least 20 wt%, further preferably at least 30 wt%, more preferably at least 40 wt%, still further preferably at least 50 wt%, even more preferably at least 60 wt%, most preferably at least 70 wt% or at least 80 wt% of the total weight of paraffins in the paraffin feed are isoparaffins.

[0059] A high weight ratio (wt %:wt %) of isoparaffins to normal paraffins in the paraffin feed may help to increase the effective degree of cracking in the first reaction stage HC process because isoparaffins are more easily cracked than normal paraffins of the same carbon number. In addition, the presence of isoparaffins in the paraffin feed may produce an HC effluent with a higher content of multi-branched isoparaffins. Similar considerations may apply to the content of multi-branched isoparaffins, as described in detail later in conjunction with the composition of the first reaction stage feed. Therefore, in certain preferred embodiments, the paraffin feed contains at least 3 wt %, preferably at least 5 wt %, more preferably at least 10 wt %, and even more preferably at least 15 wt % of multi-branched isoparaffins based on the total weight of paraffins in the paraffin feed. Preferably, the first reaction stage feed may contain the largest proportion of the paraffin feed compared to other feed streams of the process.

[0060] Preferably, the paraffinic feed of the present invention comprises hydrocarbons with carbon numbers in the range of C12 to C30 of at least 70 wt %, preferably at least 80 wt %, more preferably at least 90 wt %, even more preferably at least 95 wt %, of the total weight of the paraffinic feed. In some particularly preferred embodiments, the paraffinic feed comprises hydrocarbons with carbon numbers in the range of C14 to C22 of at least 70 wt %, preferably at least 80 wt %, more preferably at least 90 wt %, even more preferably at least 95 wt %, of the total weight of the paraffinic feed. Paraffinic feeds with high content of C12-C30 hydrocarbons are preferred because they allow good yields of two or more different types of liquid transportation fuel components. For the same reason, C14-C22 hydrocarbons are particularly preferred because they are easy to obtain from conventional hydrodeoxygenation processes of, for example, vegetable oils, animal fats and / or microbial oils (comprising fatty acids).

[0061] In order to improve the yield of aviation and / or diesel fuel components, it is particularly preferred that the paraffin feed comprises at least 50 weight %, preferably at least 60 weight %, more preferably at least 70 weight %, even more preferably at least 80 weight %, or at least 90 weight % of the C16+ paraffins accounting for the total weight of paraffins in the paraffin feed. In some embodiments, the paraffin feed comprises at least 50 weight %, preferably at least 60 weight %, more preferably at least 70 weight % of the C17+ paraffins accounting for the total weight of paraffins in the paraffin feed. In some embodiments, the paraffin feed comprises at least 40 weight %, preferably at least 50 weight %, more preferably at least 60 weight % of the C18+ paraffins accounting for the total weight of paraffins in the paraffin feed. By appropriately selecting heavier paraffin feeds, particularly by appropriately selecting the raw materials for producing them, such as oxygenated hydrocarbons, this composition can be obtained. Examples of suitable heavier oxygenated hydrocarbon feeds include oils from energy crops such as Brassica, algae oil, crude tall oil (CTO), tall oil fatty acids (TOFA), tall oil pitch (TOP), and / or feeds from lignocellulosic sources. C17+ paraffins can also be obtained by Fischer-Tropsch conversion of synthesis gas. Hydrocracking of C16+, C17+ or C18+ paraffins in the first reaction stage is beneficial because it can improve quality, but particularly improves the yield of the aviation and diesel fuel components. C16+ normal paraffins have poor cold properties, while C18+ normal paraffins and C19+ paraffins typically boil outside the aviation fuel boiling range. In addition, as described below, this paraffin feed composition facilitates increasing the content of heavier paraffins in the first reaction stage feed to provide further benefits.

[0062] The paraffinic feed may comprise any suitable paraffinic composition or combination thereof. Preferably, in the present method, the step of providing the paraffinic feed comprises (catalytic) hydrotreating a hydrotreated feed, preferably (catalytic) hydrodeoxygenating an oxygenated hydrocarbon feed, optionally followed by initial (catalytic) hydroisomerization, to obtain a paraffinic hydrotreated effluent, wherein the hydrotreated feed preferably comprises at least one or more of vegetable oil, animal fat, microbial oil, thermally liquefied organic waste and residues, and / or enzymatically liquefied organic waste and residues, more preferably the oxygenated hydrocarbon feed comprises at least one or more of vegetable oil, animal fat and / or microbial oil, and / or subjecting synthesis gas to Fischer-Tropsch (FT) conversion, optionally followed by initial dewaxing, to obtain a paraffinic FT effluent; subjecting the paraffinic hydrotreated effluent and / or the paraffinic FT effluent to gas-liquid separation, and optionally subjecting the paraffinic feed to fractionation, to provide the paraffinic feed. Gas-liquid separation refers to the removal of compounds that are gaseous at least at NTP.

[0063] Although paraffinic FT effluents of, for example, fossil origin are readily available (in addition to FT effluents of renewable origin), it is preferred that the paraffinic feedstock of the present invention is at least partially renewable, i.e. comprises biogenic components. In certain preferred embodiments, the paraffinic feedstock has a biogenic carbon content of at least 50 wt%, preferably at least 70 wt%, more preferably at least 90 wt%, even more preferably at least 95 wt%, or even about 100 wt%, based on the total weight of carbon (TC) in the paraffinic feedstock, preferably as determined in EN 16640 (2017).

[0064] 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 involves catalytic conversion of a synthesis gas comprising carbon monoxide and hydrogen into a substantially Gaussian distribution of hydrocarbon chains (primarily normal alkanes) having a broad carbon chain length distribution (such as C2 to C100+, typically about C5 to about C50). The synthesis gas used in the FT process can be produced from renewable materials, natural gas, coal, or a combination thereof. The FT effluent is typically a high-chain alkane consisting primarily of normal alkanes. Catalytic FT conversion of synthesis gas may result in slight isomerization, and the FT effluent typically contains about 10 wt % or less of iso-paraffins, based on the total weight of the FT effluent. The isoparaffin content in the paraffinic FT effluent can be effectively increased by initially dewaxing the paraffinic FT effluent using any dewaxing technique, such as isodewaxing based on a bifunctional catalyst, for example Ni-W and a zeolite or zeolite-type material, for example HZSM-5, ZSM-22, ZSM-23 and / or SAPO11, on an amorphous aluminosilicate, preferably in combination with hydrogen pretreatment and hydrofinishing.

[0065] Preferably, the paraffinic feed of the present invention comprises or consists essentially of a degassed paraffinic hydroprocessing effluent or a fraction thereof, the degassed paraffinic hydroprocessing effluent or a portion thereof being in particular 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, optionally followed by an initial (catalytic) hydroisomerization to obtain a paraffinic hydroprocessing effluent, which is then subjected to a gas-liquid separation of the paraffinic hydroprocessing effluent and optionally subjected to a paraffinic feed fractionation to provide a degassed hydroprocessing effluent or a portion thereof.

[0066] The term "hydrotreating", sometimes also referred to as hydroprocessing, refers to a catalytic process of treating an organic material in the presence of molecular hydrogen. Preferably, hydrotreating removes oxygen from organic oxygen-containing compounds as water, i.e., hydrodeoxygenation (HDO), sulfur from organic sulfur compounds as dihydrogen sulfide (H2S), i.e., hydrodesulfurization (HDS), nitrogen from nitrogen-containing compounds as ammonia (NH3), i.e., hydrodenitrogenation (HDN), halogens, such as chlorine from organic chloride compounds as hydrochloric acid (HCl), i.e., hydrodechlorination (HDCl), and metals by hydrodemetallization, and / or hydrogenation of olefinic bonds, if present in the hydroprocessing feed. In this context, hydrotreating may also include a preferably initial hydroisomerization carried out in the presence of molecular hydrogen and preferably an initial HI catalyst.

[0067] Preferably, the paraffinic feed of the present invention comprises or consists essentially of a degassed hydroprocessing effluent or a fraction thereof, in particular obtained by hydrodeoxygenation (HDO) of at least one or more of vegetable oils, animal fats, and / or microbial oils, followed by initial hydroisomerization. The initial hydroisomerization can be carried out, for example, by subjecting the HDO effluent to gas-liquid separation to remove water and compounds that are gaseous at least at NTP, and contacting the degassed HDO effluent with an initial HI catalyst under HI operating conditions, preferably as disclosed in connection with the HI catalyst used in the second reaction stage, preferably as disclosed in connection with the HI in the second reaction stage.

[0068] In certain preferred embodiments, providing the paraffin feed comprises hydrodeoxygenating an oxygenated hydrocarbon feed in the presence of a hydrodeoxygenation catalyst, preferably in a hydrodeoxygenation (HDO) reactor, to obtain a hydrodeoxygenation effluent, and subjecting the hydrodeoxygenation effluent to gas-liquid separation and optional paraffin feed fractionation to obtain a degassed hydrocarbon effluent or a fraction thereof as the paraffin feed, wherein the hydrodeoxygenation is preferably carried out at a temperature in the range of 200°C to 500°C, a pressure in the range of 1 MPa to 20 MPa, a H2 partial pressure in the range of 1 MPa to 20 MPa at the reactor inlet, a weight hourly space velocity in the range of 0.1 to 10 kg oxygenated hydrocarbon feed / kg catalyst / hour, and a H2 to oxygenated hydrocarbon feed ratio 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 FI129220B1.

[0069] Preferably, the HDO catalyst is a sulphurized catalyst comprising at least one or more metals of Group VIII and / or Group VIB of the Periodic Table, preferably at least one or more of Ni, Mo, W, and / or Co, even more preferably at least one or more of Ni and / or Co and Mo and / or W, such as NiMo, CoMo, NiCoMo, NiW, and / or NiMoW. These catalysts are highly efficient, readily available, and well tolerate typical impurities of fatty feedstocks. If a catalyst having hydrodewaxing properties is used in the hydrodeoxygenation, such as a catalyst containing NiW, as a hydrodeoxygenation catalyst or co-catalyst in the hydrodeoxygenation, an HDO effluent with a slightly higher content of isoparaffins can be obtained.

[0070] The optional paraffinic feed fractionation is typically performed in a fractionation unit different from the fractionation unit used to recover the liquid transportation fuel component, and is optionally performed in a recycle stream and / or a side draw. The optional paraffinic feed fractionation can be considered separate from the fractionation of the present process, which fractionation of the present process includes fractionation to recover the liquid transportation fuel component, and the optional recycle stream and / or side draw.

[0071] The method comprises hydrocracking a first reaction stage feed comprising the paraffin feed and an optional recycle stream and / or side draw in a first reaction stage in the presence of a hydrocracking catalyst to obtain a hydrocracking effluent. Hydrocracking heavy paraffins in the first reaction stage feed can increase the yield of aviation fuel components. In addition, hydrocracking provides flexibility for using different types of paraffin feeds, and in particular it allows the use of various oxygenated hydrocarbon feeds that are converted to paraffins. Typically, hydrocracking is operated in the first reaction stage so that cracking reactions, particularly those that increase the effective degree of cracking, are more abundant than hydroisomerization in the second reaction stage. Preferably, cracking reactions, particularly those that increase the effective degree of cracking, dominate the hydrocracking of the first reaction stage, but there is generally no overcracking and excess fuel gas formation.

[0072] Preferably, the first reaction stage feed contains elevated or even high levels of isoparaffins, preferably at least some multi-branched isoparaffins. The presence of isoparaffins in the first reaction stage feed may be considered beneficial because it is believed that it can mitigate the cracking reactions in the first reaction stage and beneficially increase the degree of effective cracking. When the desired degree of effective cracking is achieved in the first reaction stage under milder operating conditions, in particular for C8-C14 hydrocarbons, but also for lighter non-gaseous hydrocarbons, overcracking can be avoided and the formation of gaseous hydrocarbons can be reduced. Therefore, it is preferred that the first reaction stage feed contains at least 30% by weight, preferably at least 40% by weight, further preferably at least 50% by weight, more preferably at least 60% by weight, further more preferably at least 70% by weight, and even more preferably at least 80% by weight of isoparaffins based on the total weight of paraffins in the first reaction stage feed. In addition, the presence of multi-branched isoparaffins in the first reaction stage feed may beneficially contribute to the degree of effective cracking in the first reaction stage. Surprisingly, it was found that when the content of multi-branched isoparaffins in the first reaction stage feed was increased, the weight ratio of the aviation fuel component to the diesel fuel component recovered from the fractionation also increased, as shown in the Examples. In addition, without being bound by any theory, it is believed that when cracked in the first reaction stage, the multi-branched isoparaffins are more likely to form two branched alkane molecules rather than one branched alkane and one normal alkane, which may increase the isoparaffin content of the HC effluent. Therefore, the increase in the multi-branched isoparaffin content in the first reaction stage feed can improve the cold performance of the recovered liquid transportation fuel component, especially the cold performance of the aviation fuel component and / or the diesel fuel component, and / or the gasoline fuel component RON. The increase in the multi-branched isoparaffin content may be particularly beneficial at the end of the life of the HI catalyst when the HI catalyst has begun to lose activity and / or selectivity. Thus, the first reaction stage feed may contain at least 3 wt% or at least 5 wt%, preferably at least 10 wt%, more preferably at least 15 wt%, even more preferably at least 20 wt% of multi-branched isoparaffins based on the total weight of paraffins in the first reaction stage feed. Generally, it is beneficial to start operating the first reaction stage at low temperatures at the start of the run, for example using the lowest feasible temperature within the hydrocracking range specified later, as this provides the widest window for increasing the temperature as the catalyst gradually deactivates. Therefore, in order to extend the run time and catalyst replacement / regeneration intervals, it is preferred to increase the content of isoparaffins, preferably multi-branched isoparaffins, in the first reaction stage feed.

[0073] In the present method, in addition to the paraffin feed, the first reaction stage feed may also include a recycle stream and / or a side draw recovered from the fractionation. The HI in the second reaction stage effectively increases the degree of isomerization, including the isomerization of normal alkanes in the second reaction stage feed and / or the further isomerization of monobranched isoparaffins and multi-branched isoparaffins. Therefore, the HI effluent fed to the fractionation contains a large amount of isoparaffins, and at least some multi-branched isoparaffins. Therefore, the recycle stream and / or the side draw optionally recovered from the fractionation fed with the HI effluent also contain a large amount of isoparaffins, typically at least some multi-branched isoparaffins. As previously described, the increase in the content of isoparaffins and optionally at least some multi-branched isoparaffins in the first reaction stage feed provides certain benefits. Therefore, in certain preferred embodiments, the process comprises recovering the recycle stream and / or the side draw from the fractionation and feeding the recycle stream and / or the side draw to the first reaction stage as part of the feed to the first reaction stage. Preferably, the recycle stream and / or the side draw respectively comprises at least 50 wt.%, preferably at least 60 wt.%, more preferably at least 70 wt.%, even more preferably at least 80 wt.% of isoparaffins, based on the total weight of paraffins in the recycle stream or the side draw; and / or at least 10 wt.%, preferably at least 15 wt.%, more preferably at least 20 wt.%, even more preferably at least 30 wt.% of multi-branched isoparaffins, based on the total weight of paraffins in the recycle stream or the side draw, respectively. Such a high isoparaffin content and an increased multi-branched isoparaffin content can be obtained in the recycle stream and / or the side draw due to the specific sequence of the HC and the HI steps. By blending the recycle stream and / or the side draw into the first reaction stage feed, the yield of the aviation fuel component can be increased and the quality of the recovered transportation fuel components, in particular the diesel fuel component and / or the aviation fuel component, can be improved.

[0074] The recycle stream and / or the side draw can be incorporated into the first reaction stage feed in a wide ratio. By adjusting the ratio at which the recycle stream and / or the side draw are optionally incorporated into the first reaction stage feed, the weight ratio of the aviation fuel component to the diesel fuel component recovered from the fractionation, as well as their quality, especially cold performance, can be adjusted. This is a valuable and simple method for adjusting the share and quality of the diesel and aviation fuel components produced, for example, to cope with fluctuations and / or seasonal changes in market demand for these products or their different grades. Preferably, the first reaction stage feed comprises the paraffin feed and the recycle stream and / or the side draw, and the weight ratio of the paraffin feed to the total amount of the recycle stream and / or the side draw is in the range of 10:90 to 90:10, preferably in the range of 20:80 to 80:20.

[0075] In certain preferred embodiments, the first reaction stage feed consists essentially of the paraffin feed and optionally a recycle stream and / or a side draw.

[0076] In certain preferred embodiments, a side draw is recovered from the fractionation and fed to the first reaction stage as part of the first reaction stage feed. The HC of the first reaction stage and the HI of the second reaction stage may have an impurity removal effect on the treated stream, particularly in the presence of a gas-liquid separation. The incorporation of even a small amount of a high purity side draw in the first reaction stage feed may reduce or dilute the impurity content of the first reaction stage feed. This may slow down the deactivation of the catalyst. The side draw is typically a fraction rich in C14-18 hydrocarbons, more preferably rich in C15-C17 hydrocarbons. The side draw is preferably a relatively narrow fraction to allow precise modification of the boiling point distribution of the total feed for fractionation. Thus, in certain preferred embodiments, the side draw has T5 and T95 temperatures, determined according to EN ISO 3405-2019, in the range of 250°C to 320°C, preferably in the range of 260°C to 310°C, more preferably in the range of 270°C to 300°C; and / or the difference between T95 and T5 temperatures (95% by volume and 5% by volume recovered, EN ISO 3405-2019) is below 40°C, preferably below 30°C, more preferably below 20°C.

[0077] In certain preferred embodiments, a recycle stream is recovered from the fractionation and fed to the first reaction stage as part of the first reaction stage feed. It has been found that when the content of heavier paraffins in the first reaction stage feed is increased, the weight ratio of the diesel fuel component recovered from the fractionation to the aviation fuel component may also increase, as shown in the Examples. By adjusting the ratio at which the recycle stream is incorporated into the first reaction stage feed, the weight ratio of the diesel fuel component recovered from the fractionation to the aviation fuel component can be adjusted. This is a valuable and simple method for adjusting the share of the diesel and aviation fuel components produced, for example to cope with fluctuations and / or seasonal changes in market demand for these products or their different grades. In certain preferred embodiments, the T5 temperature (recovery rate of 5% by volume, EN ISO 3405-2019) of the recycle stream is above 270°C; and / or the T5 temperature 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. Preferably, the T5 temperature of the recycle stream is selected so as to recover in the recycle stream at least a portion of any C16 normal alkanes present in the total feed to be fractionated, such as C16 normal alkanes present in the HI effluent (if any). Recovery of C16 normal alkanes in the recycle stream can be achieved by appropriately selecting the IBP or T5 temperature of the recycle stream. The boiling point of C16 normal alkanes is 287°C (at standard atmospheric pressure), but since fractionation (such as distillation separation) is not completely severe, C16 normal alkanes can be recovered at a temperature in the range near this boiling point. It is beneficial to recycle at least some C16 normal alkanes to the first reaction stage for hydrocracking because C16 normal alkanes have a relatively high melting point. Therefore, due to poor cold performance, particularly poor freezing point, any large amount of C16 normal alkanes present in the recovered aviation fuel component may even make it unusable for aviation fuel composition. In any case, the C16 normal alkanes in the aviation fuel component preferably recovered will impair its cold performance, that is, compared with aviation fuel components with less or no C16 normal alkanes content, one or more of the cloud point, freezing point, pour point and cold filter plugging point, as well as the kinematic viscosity below zero will be increased. After the HI catalyst is deactivated, the amount of normal paraffins (including C16 normal paraffins) in the total feed to be fractionated increases and may also be formed by cracking in the first reaction stage (and / or the second reaction stage).

[0078] The above recycle stream characteristics are particularly beneficial in view of the effective degree of cracking in the hydrocracking to form hydrocarbons boiling in the aviation fuel range, because generally paraffins are more easily cracked than cyclic hydrocarbons, longer paraffins are more easily cracked than shorter paraffins, and isoparaffins, especially multi-branched isoparaffins, are more easily cracked than normal paraffins. In addition, these embodiments facilitate easy separation by separating only diesel fuel components, bunker fuel components, base oil components, and / or transformer oil components from the recycle stream, to name just a few examples of components that can be extracted from such a recycle stream.

[0079] In some particularly preferred embodiments, the first reaction stage feed comprises at least 85% by weight, preferably at least 90% by weight, more preferably at least 95% by weight of C16+ paraffins accounting for the total weight of paraffins in the first reaction stage feed, and / or at least 40% by weight, preferably at least 50% by weight, more preferably at least 60% by weight of C18+ paraffins accounting for the total weight of paraffins in the first reaction stage feed. This composition can be obtained by appropriately selecting a heavier paraffin feed and / or by incorporating a sufficient amount of the recycle stream into the first reaction stage feed. It is beneficial to hydrocracking C16+ paraffins in the first reaction stage because it can increase the yield of aviation fuel components and / or improve their quality. The cold performance of C16+ normal paraffins is poor, while C18+ normal paraffins and C19+ paraffins usually boil outside the aviation fuel boiling range. Furthermore, as mentioned above, by increasing the content of heavier paraffins in the feed to the first reaction stage, the weight ratio of the diesel fuel component to the aviation fuel component recovered from the fractionation can also be adjusted to be higher.

[0080] In the present process, the hydrocracking in the first reaction stage can be carried out at a temperature in the range of 200°C to 500°C, preferably 220°C to 430°C, more preferably 280°C to 400°C, a pressure in the range of 0.5MPa to 20MPa, preferably 1MPa to 20Mpa, more preferably 3MPa to 15MPa, a H2 partial pressure in the range of 0.5MPa to 20MPa, preferably 1MPa to 20MPa, more preferably 3MPa to 15MPa at the inlet of the first reaction stage, in a weight hourly space velocity in the range of 0.1 to 10, preferably 0.2 to 10, more preferably 0.4 to 8, even more preferably 0.5 to 5 kg first reaction stage feed / kg catalyst / hour, an H2 and first reaction stage feed ratio in the range of 10 to 2000, preferably 50 to 1000 standard liters of H2 / liter of first reaction stage feed. Typically in the present process, the hydrocracking in the first reaction stage is carried out at a temperature in the range of 200°C to 500°C, a pressure in the range of 0.5MPa to 20MPa, a H2 partial pressure in the range of 0.5MPa to 20MPa at the inlet of the first reaction stage, a weight hourly space velocity in the range of 0.1 to 10kg first reaction stage feed / kg catalyst / hour, and a H2 and first reaction stage feed ratio in the range of 10 to 2000 standard liters of H2 / liter of first reaction stage feed.

[0081] According to certain preferred embodiments, the hydrocracking in the first reaction stage is carried out at a temperature in the range of 220°C to 430°C, a pressure in the range of 1MPa to 20MPa, a H2 partial pressure range at the inlet of the first reaction stage of 1MPa to 20MPa, a weight hourly space velocity range of 0.2 to 10kg first reaction stage feed / kg catalyst / hour, and a H2 to first reaction stage feed ratio range of 50 to 1000 standard liters of H2 / liter of first reaction stage feed. When the HC is operated at a lower temperature and a sufficiently high pressure, the aromatization side reaction can be better suppressed, and dearomatization can even be enhanced. The first reaction stage and the second reaction stage can be configured in the same reactor or in separate reactors. Preferably, the first reaction stage and the second reaction stage are configured in separate reactors.

[0082] When the first reaction stage and the second reaction stage are operated in separate reactors, the HC effluent is preferably subjected to a gas-liquid separation, i.e. to removal of compounds which are gaseous at least at NTP. This may be done before feeding the HC effluent to the second reaction stage or reactor, e.g. as an integral step within the first reaction stage or reactor, or in a separate gas-liquid separator.

[0083] Preferably, the hydrocracking is operated in the first reaction stage such that the ratio of the mass % amount of isoparaffins based on the total weight of paraffins in the HC effluent to the mass % amount of isoparaffins based on the total weight of paraffins in the feed to the first reaction stage 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 such that the ratio of the C8-C14 hydrocarbon content in the HC effluent to the C8-C14 hydrocarbon content in the feed to the first reaction stage 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.

[0084] In certain preferred embodiments, the hydrocracking in the first reaction stage is operated such that the ratio of the content of C1-C4 hydrocarbons formed during the hydrocracking in the (total) HC effluent to the content of C1-C4 hydrocarbons in the (total) first reaction stage feed 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) HC effluent contains less than 20% by weight, or less than 10% by weight, or less than 5% by weight of C1-C4 hydrocarbons, based on the total weight of the HC effluent.

[0085] These objectives can be achieved when operating the first reaction stage using the above specified first reaction stage feed and / or under the above specified hydrocracking operating conditions and / or in the presence of a HC catalyst as defined below, in particular in the presence of a non-sulfided bifunctional HC catalyst, preferably a non-sulfided bifunctional HC catalyst comprising at least one or more Group VIII noble metals, more preferably Pt and / or Pd.

[0086] Typically, the HC effluent comprises at least 60 wt.-%, preferably at least 70 wt.-%, more preferably at least 80 wt.-%, even more preferably at least 90 wt.-% or at least 95 wt.-% paraffins based on the total weight of the HC effluent. The HC effluent may even consist predominantly of paraffins.

[0087] According to a preferred embodiment, the HC effluent comprises at least 30 wt.-%, preferably at least 40 wt.-%, more preferably at least 50 wt.-%, even more preferably at least 60 wt.-%, or at least 70 wt.-% of isoparaffins, based on the total weight of paraffins in the HC effluent; and / or at least 3 wt.-%, or at least 5 wt.-%, preferably at least 10 wt.-%, more preferably at least 15 wt.-%, even more preferably at least 20 wt.-% of multi-branched isoparaffins, based on the total weight of paraffins in the HC effluent. In other words, the degree of isomerization of the HC effluent is not necessarily significantly less than the degree of isomerization in the first reaction stage feed, but may also be the same or even higher. This can be achieved in particular by using a bifunctional HC catalyst and / or a first reaction stage feed having an elevated content of isoparaffins and / or multi-branched isoparaffins.

[0088] In the present process, a second reaction stage feed comprising said hydrocracking effluent and optionally a portion of said paraffinic feed is hydroisomerized in a second reaction stage in the presence of a hydroisomerization catalyst to obtain a hydroisomerized effluent. Typically, in the context of the present invention, the HI of the second reaction stage feed in said second reaction stage is operated such that the isomerization reaction predominates while the cracking reaction is controlled or suppressed.

[0089] In certain preferred embodiments, the second reaction stage feed consists essentially of the hydrocracking effluent and optionally a portion of the paraffinic feed.

[0090] Preferably, the hydroisomerization in the second reaction stage is carried out at a temperature in the range of 200°C to 500°C, preferably 230°C to 500°C, more preferably 250°C to 450°C, even more preferably 280°C to 400°C, a pressure in the range of 1 MPa to 20 MPa, preferably 2 MPa to 15 MPa, or 3 MPa to 10 MPa, a H2 partial pressure in the range of 1 MPa to 20 MPa, preferably 2 MPa to 15 MPa, or 3 MPa to 10 MPa at the inlet of the second reaction stage, in a weight hourly space velocity in the range of 0.1 to 10, preferably 0.2 to 8, more preferably 0.4 to 6 kg second reaction stage feed / kg catalyst / hour, a H2 to second reaction stage feed ratio in the range of 10 to 2000, preferably 50 to 1000 standard liters of H2 / liter of second reaction stage feed.

[0091] According to certain embodiments, the hydroisomerization in the second reaction stage is carried out at a temperature in the range of 200°C to 500°C, a pressure in the range of 1MPa to 20MPa, an H2 partial pressure in the range of 1MPa to 20MPa at the inlet of the second reaction stage, a weight hourly space velocity in the range of 0.1 to 10kg second reaction stage feed / kg catalyst / hour, and an H2 to second reaction stage feed ratio in the range of 10 to 2000 standard liters of H2 / liter of second reaction stage feed.

[0092] According to a particularly preferred embodiment, the hydroisomerization in the second reaction stage is carried out at a temperature in the range of 230°C to 500°C, a pressure in the range of 2MPa to 15MPa, an H2 partial pressure in the range of 2MPa to 15MPa at the inlet of the second reaction stage, a weight hourly space velocity in the range of 0.2 to 8kg second reaction stage feed / kg catalyst / hour, and an H2 to second reaction stage feed ratio in the range of 50 to 1000 standard liters of H2 / liter of second reaction stage feed.

[0093] The HI effluent may be subjected to gas-liquid separation, i.e. at least the gaseous compounds in the NTP are removed before the HI effluent is directed to fractionation, e.g. as an integral step in the second reaction stage or in the corresponding reactor. Gas separation may also be performed as part of the fractionation.

[0094] The degree of isomerization of the HI effluent can be increased (improved) by increasing the severity of the HI (e.g., by at least one or more of decreasing the WHSV, increasing the temperature, and / or increasing the pressure). When using a fresh HI catalyst, high severity HI conditions can be achieved at lower temperatures and / or pressures, and / or using higher WHSVs, while near the end of the HI catalyst life, higher temperatures and / or pressures, and / or lower WHSVs may be required to achieve even moderate severity HI. In this context, expressed as the weight percent of paraffins in the liquid effluent, an HI that produces a liquid effluent having a total isoparaffin content of 50-85 weight percent and a multi-branched isoparaffin content of up to 25 weight percent, or a total isoparaffin content of 85-95 weight percent and a multi-branched isoparaffin content of 25-55 weight percent, or a total isoparaffin content of at least 95 weight percent and a multi-branched isoparaffin content of more than 55 weight percent, is generally considered to be a low severity HI, a medium severity HI, or a high severity HI, respectively, although these content ranges are intended to illustrate the order of magnitude only and may overlap to some extent and vary from case to case.

[0095] In certain preferred embodiments of the present method, in addition to the hydrocracking effluent, the second reaction stage feed also comprises a portion of the paraffin feed, and the paraffin feed is distributed between the first reaction stage feed and the second reaction stage feed in a weight ratio range of 1:99 to 99:1, preferably 10:90 to 95:5, more preferably 20:80 to 90:10, and even more preferably 30:70 to 80:20. This can be done by simply distributing the paraffin feed between the first reaction stage and the second reaction stage using, for example, a fixed or preferably gradually adjusted ratio. These embodiments provide the benefits described above, such as further flexibility in running the method, and the possibility of adjusting the method according to fluctuations in the characteristics of the paraffin feed. In addition, these embodiments allow the method to be run more accurately to meet the target yield and quality of multiple recovered components at a time. Furthermore, adjusting the split weight ratio helps to optimize the process based on the activity / gradual deactivation of the HI catalyst, for example allowing more of the paraffin feed to be incorporated into the second reaction stage feed at the start of a run, and for example gradually reducing the amount of the paraffin feed in the second reaction stage feed after the HI catalyst has deactivated.

[0096] Typically, the second reaction stage feed comprises at least 30% by weight, preferably at least 40% by weight, further preferably at least 50% by weight, more preferably at least 60% by weight, further more preferably at least 70% by weight, even more preferably at least 80% by weight of isoparaffins based on the total weight of paraffins in the second reaction stage feed; and / or at least 3% by weight or at least 5% by weight, preferably at least 10% by weight, more preferably at least 15% by weight, even more preferably at least 20% by weight of multi-branched isoparaffins based on the total weight of paraffins in the second reaction stage feed.

[0097] The HC in the first reaction stage effectively changes the carbon number distribution of the first reaction stage feed, increasing the content of hydrocarbons in the aviation fuel range. Therefore, in certain preferred embodiments, the weight ratio of C14-C18 (total) alkanes to C6-C13 (total) paraffins in the second reaction stage feed is in the range of 0.6 to 10, preferably 0.8 to 8.0, more preferably 0.8 to 7.0, even more preferably 1.0 to 7.0, and further more preferably 1.1 to 6.0. These ratios provide a sufficiently long aviation fuel range paraffin content to allow effective isomerization, preferably to form multi-branched isoparaffins, and short enough so that they can be recovered from the fractionation as part of the aviation fuel components by effective isomerization in the second reaction stage, thereby improving the yield and quality of the aviation fuel components, especially in terms of cold performance.

[0098] Preferably, the hydroisomerization in the second reaction stage is operated such that the ratio of the amount of isoparaffins by weight of the total weight of paraffins in the HC effluent to the amount of isoparaffins by weight of the total weight of paraffins in the first reaction stage 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 multi-branched isoparaffins by weight of the total weight of paraffins in the HI effluent to the amount of multi-branched isoparaffins by weight of the total weight of paraffins in the second reaction stage 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 contains less than 20% by weight or less than 10% by weight, preferably less than 5% by weight, more preferably less than 3% by weight of C1-C4 hydrocarbons, based on the total weight of the HI effluent. This can be achieved in particular when operating the second reaction stage under HI operating conditions and / or using the HI catalyst and / or the second reaction stage feed as defined herein.

[0099] 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% of paraffins based on the total weight of the HI effluent. In certain embodiments, the HI effluent may even consist essentially of paraffins.

[0100] Typically, the HI effluent comprises at least 50 wt%, preferably at least 60 wt%, more preferably at least 70 wt%, even more preferably at least 80 wt% of isoparaffins, based on the total weight of paraffins in the HI effluent, and at least 5 wt%, more preferably at least 10 wt%, even more preferably at least 15 wt%, or at least 20 wt% of optional highly branched isoparaffins, based on the total weight of paraffins in the HI effluent.

[0101] In certain preferred embodiments, the HI effluent comprises 50% to 100% by weight, preferably 60% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight of isoparaffins, based on the total weight of paraffins in the hydroisomerization effluent; and / or 5% to 75% by weight, preferably 10% to 70% by weight, more preferably 15% to 70% by weight, even more preferably 15% to 65% by weight of multi-branched isoparaffins, based on the total weight of paraffins in the HI effluent. Such HI effluent is particularly preferably used to recover the liquid transportation fuel components in good yield and / or high quality, especially with excellent cold properties, and optionally with a recycle stream and / or side draw with a high content of isoparaffins, especially multi-branched isoparaffins, which may be preferred when incorporated into the first reaction stage feed.

[0102] Preferably, the first reaction section is operated at a lower temperature than the second reaction section. The temperature at the inlet of the reaction section or reactor is compared at a given time point (including short time intervals). In other words, in this case, the highest temperature during the entire operation from the startup process to the shutdown process is not compared. It has been found that the embodiment in which the first reaction section is operated at a lower temperature than the second reaction section is particularly advantageous for suppressing aromatization side reactions, even enhancing dearomatization in the first reaction section, and helping to reduce the introduction of aromatics into the second reaction section. As coking compounds, aromatics are expected to promote the deactivation of the HI catalyst. In addition, in these embodiments, it is beneficial to start operating the first reaction section at a low temperature at the beginning of the operation, for example, using the lowest feasible temperature within the specified hydrocracking range, because this provides the widest window for increasing the temperature when the catalyst gradually deactivates, and prolongs the operating time and catalyst replacement / regeneration interval.

[0103] By operating the first reaction section and the second reaction section within the above-specified operating conditions, especially when the first reaction section is operated at a lower temperature than the second reaction section, thermal cracking is controlled, reduced or minimized in the first reaction section, while a high degree of isomerization can be achieved in the second reaction section, and the content of multi-branched isoparaffins in the HI effluent is increased. At the same time, the desired effective cracking degree can be achieved in the first reaction section under milder operating conditions, especially at lower temperatures, which increases the yield of hydrocarbons in the aviation fuel boiling range without excessive thermal cracking resulting in gas formation.

[0104] The HC catalyst and the hydroisomerization (HI) catalyst may be respectively arranged in one or more catalyst beds in the first reaction section and the second reaction section. The HC catalyst and the HI catalyst may be respectively arranged in at least one or more fixed beds. Preferably, the hydrocracking catalyst is arranged in one or more catalyst beds in the first reaction section, the HI catalyst is arranged in one or more catalyst beds in the second reaction section, and the first reaction section and the second reaction section are arranged in the same reactor or in separate reactors, preferably in separate reactors.

[0105] 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 second reaction stage is a bifunctional HI catalyst, more preferably a non-sulfided bifunctional HI catalyst. More preferably, the HI catalyst in the second reaction stage and the HC catalyst in the first reaction stage are bifunctional HI and HC catalysts, respectively, more preferably non-sulfided bifunctional HI or HC catalysts, respectively.

[0106] 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, providing a synergistic effect between the metal sites and the acid sites. Bifunctional HI and HC catalysts are also beneficial because molecular access and diffusion to the catalytic sites can be controlled by appropriately selecting the porosity characteristics of the catalyst, in particular the pore size, pore diameter and / or pore interconnectivity in the catalyst.

[0107] In certain particularly preferred embodiments, the HI catalyst is a non-sulfided bifunctional hydroisomerization catalyst, the HC 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, more preferably metals selected from Pt and / or Pd, and at least one or more acidic porous materials, and wherein preferably each of the first reaction stage feed and the second reaction stage feed comprises 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) based on the total feed to each reaction stage as determined according to ISO 20846-2019.

[0108] The sulfur content can be determined from the liquid according to ISO 20846-2019, or from the gas fraction according to ASTM-D6667.

[0109] Unsulfided bifunctional catalysts are preferred because they do not require sulfidation to maintain their activity during operation, so the sulfur content of the various process streams can be kept low and less efficient separation and recovery of H2S from the various process streams is required. In particular, unsulfided bifunctional catalysts containing noble metals may be active at lower temperatures and show higher selectivity for isomerization reactions, but are sensitive to deactivation by H2S, compared to sulfided catalysts.

[0110] Preferably, the paraffinic feed contains less than 50 wt ppm, preferably less than 30 wt ppm, more preferably less than 10 wt ppm sulfur (ppm weight, calculated as elemental S) as determined according to ISO 20846-2019. The very low sulfur content of the stream entering the first reaction stage is beneficial because only very low amounts of H2S or substantially no H2S is formed in the hydrocracking in the first reaction stage and is therefore present in the HC effluent. In these embodiments, gas-liquid separation of the HC effluent before feeding it to the second reaction stage is not necessary for protecting the HI catalyst in the second reaction stage, but the HC effluent may still be optionally subjected to gas-liquid separation. As a result, the overall process may be simpler and a liquid transportation fuel component with an ultra-low sulfur content may be obtained. In addition, due to the lower H2S content, corrosion is also expected to be reduced in the long term, and less stringent corrosion resistance requirements may apply to some equipment materials.

[0111] Various different types of bifunctional HI and HC catalysts are commercially available, for example having different metals or metal combinations, different metal loadings, different acid strengths and / or total acidities, and / or different porosities.

[0112] Bifunctional HC catalysts and bifunctional HI catalysts are similar in that they both contain metal sites capable of catalyzing the (de)hydrogenation of n / isoparaffins to the corresponding n / isoolefins, and acid sites capable of catalyzing the protonation of n / isoolefins to n / isocarbocations, further isomerization of n / isocarbocations or isocarbocations, and / or cracking of n / isocarbocations to lighter n / isoolefins and lighter n / isocarbocations, and deprotonation of n / isocarbocations to n / isoolefins. The hydrogenation of various n / isoolefins is again catalyzed by the metal sites of these bifunctional catalysts to form n / isoparaffins. Under given operating conditions and given feed composition, whether isomerization or cracking reactions predominate may be particularly affected by the characteristics of the bifunctional catalyst in contact with the feed. These characteristics of the bifunctional catalyst include, for example, the total acidity of the catalyst, the number of Bronsted acid sites, the strength and / or density of the acid sites, and the content of the metal in the catalyst.

[0113] 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, preferably noble metals selected from group VIII, more preferably selected from Pt and / or Pd. Noble metals are preferred, especially in the bifunctional HI catalyst, because they have a higher selectivity for the isomerization reaction under the conditions of the second reaction stage 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, typically increased, during operation. 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 of the reaction stage.

[0114] 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 (micro-mesoporous) structure. Various zeolite-type materials, such as SAPO and zeolites, can provide the desired acidity and porosity characteristics.

[0115] According to certain embodiments, the hydroisomerization catalyst is a bifunctional hydroisomerization catalyst, preferably a non-sulfided bifunctional hydroisomerization catalyst, comprising

[0116] 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 selected from Pt and / or Pd; and

[0117] At least one or more acidic porous materials selected from zeolites and / or zeolite-type materials, wherein preferably at least one and / or more of the zeolites and / or zeolite-type materials have a framework type selected from AEL, ATO, AFO, MRE, MTT, MTW, TON, MRT, MOR, FER and / or MWW, preferably at least one or more acidic porous materials are 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 are selected from SAPO-11, SAPO-41, ZSM-23 and / or ZSM-48; and

[0118] Optionally, at least one or more of alumina, silica, amorphous silica-alumina, titanium-alumina, titania and / or zirconia.

[0119] It has been found that this catalyst selection provides high isomerization selectivity in the second reaction stage, achieving higher amounts of isoparaffins, particularly multi-branched isoparaffins, in the HI effluent. As a result, normal paraffins present in the second reaction stage feed or formed during the hydrocracking process are effectively isomerized to at least mono-branched isoparaffins, thereby obtaining high-quality liquid fuel components in excellent yields. The above-mentioned SAPOs and zeolites are commercially available, and their acidity and porosity characteristics allow isomerization of normal paraffins, even long-chain normal paraffins (such as C16+ paraffins), including multi-branching.

[0120] In particular for the hydrocracking reaction in the first reaction stage of the process, 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 compared to HC catalysts comprising non-noble metals, thereby providing better control of thermal cracking. At low temperatures, the thermodynamic equilibrium tends to shift towards dearomatization, thereby reducing the aromatics formed by side reactions. Providing the first reaction stage with a bifunctional HC catalyst makes it possible to achieve an isoparaffin content (weight % of isoparaffins to the total weight of paraffins) in the hydrocracking effluent which is not necessarily significantly less than that in the feed to the first reaction stage, but may also be the same or even higher.

[0121] Therefore, according to certain embodiments, the hydrocracking catalyst is a bifunctional hydrocracking catalyst, preferably a non-sulfided bifunctional hydrocracking catalyst, comprising

[0122] 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

[0123] 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 of the 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, beta zeolite, Y-type zeolite and / or amorphous silica-alumina, more preferably at least one or more acidic porous materials selected from SAPO-5, SAPO-11, ZSM-23, beta zeolite, Y-type zeolite and / or amorphous silica-alumina; and

[0124] Optionally, at least one or more of alumina, silica, titanium alumina, titania and / or zirconia.

[0125] In certain embodiments, the HC catalyst in the first reaction stage and the HI catalyst in the second reaction stage have different acidity-related properties. The acidity-related properties of an acidic porous material such as a zeolite may include the nature, quantity and distribution of the acidic sites, in terms of relative strength, and may be determined by well-known methods, such as by an adsorption-desorption method, 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 usable adsorption-desorption method, mention may be made of the temperature-programmed desorption of ammonia, for example according to the procedure described in Niwa et al. (Niwa, M., Katada, N. Measurements of acidic property of zeolites by temperatureprogrammed desorption of ammonia. Catalysis Surveys from Asia 1, 215–226 (1997)). Catalysis Surveys from Asia 1, 215–226 (1997)). Another well-known method for determining the acidic properties of zeolites, including acidity strength, is 1H-NMR method, for example according to the procedure described in Heeribout et al. (Heeribout L., Semmer V., Batamack P., Dorémieux-Morin C., Fraissard J. Brønsted acid strength of zeolites studied by 1H NMR: scaling,influence of defects. Microporous and Mesoporous Materials, Volume 21, Issues 4–6, May 1998, Pages 565-570). Microporous and Mesoporous Materials, Volume 21, Issues 4–6, May 1998, Pages 565-570). In certain preferred embodiments, the bifunctional HC catalyst in the first reaction stage has a greater number of Brønsted acid sites than the bifunctional HI catalyst in the second reaction stage, as determined by NH3-TPD. In certain preferred embodiments, the bifunctional HC catalyst in the first reaction stage has a greater total number of acid sites as measured by NH3-TPD than the bifunctional HI catalyst in the second reaction stage.

[0126] In certain preferred embodiments, the bifunctional HC catalyst of the first reaction stage has a higher Group VIII noble metal content (wt%) than the bifunctional HI catalyst of the second reaction stage. In these embodiments, good or better aviation fuel component yields can be achieved at lower temperatures than other similar processes but using a bifunctional HC catalyst that does not have a higher noble metal content than the bifunctional HI catalyst.

[0127] In the present process, a first reaction stage feed comprising a paraffinic feed is subjected to HC in the presence of an HC catalyst, and the HC effluent and optionally a portion of the paraffinic feed are subjected to HI in the presence of an HI 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 be different from each other, for example by selecting at least one or more of catalyst components, acidity, and / or metal loading, to name a few. However, when the hydrocracking and the HI are carried out in separate reactors, the same catalyst as the HC catalyst in the first reaction stage and the HI catalyst of the second reaction stage may also be used. Not only the catalyst, but also the operating conditions and the composition of the reaction stage feed contribute to the reaction dominating. For example, when the first reaction stage feed is contacted with the HC catalyst under hydrocracking conditions, more cracking can be expected compared to contacting the second reaction stage feed with the HI catalyst under the HI conditions, even if the catalysts are the same. Preferably, when the second reaction stage feed is contacted with the HI catalyst under the HI conditions, isomerization of the feed is preferentially performed over cracking.

[0128] The HI catalyst and the HC catalyst may be in a ready-to-use state or may be treated in any conventional manner before or during startup to adjust its properties, such as selectivity and / or activity, by, for example, reduction, sulfidation and / or passivation with nitrogen-containing compounds such as amines or ammonia, thereby obtaining a 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.

[0129] The HI catalyst in the optional initial hydroisomerization and the HI catalyst in the second reaction stage 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. In order to simplify the process, it is preferred that the HI catalyst in the optional initial hydroisomerization is the same as the HI catalyst in the second reaction stage, in which case the HC catalyst is preferably different from the HI catalysts in the initial HI and the second reaction stage.

[0130] In certain embodiments, the weight ratio of the hydrocracking catalyst in the first reaction stage to the hydroisomerization catalyst in the second reaction stage is in the range of 5:95 to 70:30, preferably 10:90 to 65:35, more preferably 20:80 to 60:40. Such ratios are beneficial because they enable the recovered liquid transportation fuel component to have a high degree of isomerization, generally improving the cold properties of the recovered liquid transportation fuel component, in particular the cold properties of the aviation fuel component and / or the diesel fuel component, and / or the gasoline fuel component RON. In addition, the ratio of the HC catalyst to the HI catalyst is beneficial because they allow a freer choice of the HC catalyst in the first reaction stage.

[0131] It is well known to those skilled in the art how to select the HC and HI conditions, preferably within the range of HC and HI conditions specified above, taking into account the selected HC catalyst, the composition of the first reaction stage feed, the target effective cracking degree, and the target isomerization degree; and taking into account the selected HI catalyst, the composition of the second reaction stage feed, the target isomerization degree, and the target content of multi-branched isoparaffins in the second reaction stage effluent. To a certain extent, catalyst aging or catalyst deactivation can also be considered when selecting or adjusting the operating conditions of the first reaction stage and / or the second reaction stage. During continued operation, the HC catalyst and the HI catalyst gradually deactivate, for example due to impurities and coking in the process stream. As the catalyst deactivates, catalyst activity decreases, selectivity is affected, and at some point, the desired properties of the HC effluent and / or the HI effluent are generally no longer achieved. In addition, changes in the composition of the paraffin feed during operation may cause the recovered liquid transportation fuel component to deviate from the desired properties and / or yield. In addition, the target product composition and quality may vary due to market demand and seasonal changes.

[0132] The method involves various possibilities to meet the above challenges posed by a plant, i.e. hydrocracking before hydroisomerization, followed by recovery of liquid transport fuel components from said fractionation, with the possibility of distributing said paraffinic feed between said first reaction stage and said second reaction stage, with the possibility of recovering a recycle stream and / or a side draw from said fractionation and sending it back to said hydrocracking. Preferably, the method comprises monitoring at least one or more parameters, generally indicative of deactivation of said HC and / or HI catalyst, to receive at least one or more values, to compare the received values ​​with predetermined values ​​and to utilize at least one of the various adjustment possibilities of said method based on said comparison.

[0133] Therefore, according to certain preferred embodiments, the method further comprises monitoring to receive at least one or more values ​​of at least one or more of the following parameters:

[0134] -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 coking compounds in the paraffin feed; the species or impurities are known catalyst deactivators, in particular deactivators of non-sulfided bifunctional catalysts containing precious metals. In addition, the species or impurities are usually present in different amounts in feeds derived from vegetable oils, animal fats, microbial oils, heat and / or enzyme liquefaction of organic waste and residues, and in feeds derived from Fischer-Tropsch processes. Therefore, in certain embodiments, they may be carried and present in the paraffin feed in different amounts. Typically, elemental impurities are not present in the paraffin feed, but their content indicates the presence of compounds containing the impurities. Elemental impurities and coking 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.

[0135] - the content of NH3 and / or H2S in the gas phase of the hydrocracking effluent and / or the content of NH3 and / or H2S in the gas phase of the HI effluent; in some cases, an increase in the content of NH3 and / or H2S in the gas phase of the HC effluent may indicate an increased exposure of the catalyst to the impurities. An increase in the content of any of these impurities may result in an increased catalyst deactivation.

[0136] -Physicochemical properties of the paraffin feed, the first reaction stage feed, the hydrocracking effluent, the second reaction stage feed, and / or 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 properties; 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 properties, including increases in T5, T50, FBP, etc. may indicate catalyst deactivation. As for further distillation properties, a shift in the boiling point distribution to higher boiling point compounds may indicate catalyst deactivation. To some extent, the physicochemical properties may indicate or be related to the content of isoparaffins or multi-branched isoparaffins in the paraffin feed, the first reaction stage feed, the hydrocracking effluent, the second reaction stage feed, and / or the hydroisomerization effluent.

[0137] - Compositional characteristics of the paraffin feed, the first reaction stage feed, the hydrocracking effluent, the second reaction stage feed, and / or the hydroisomerization effluent, preferably at least one or more of the isoparaffin content, C8-C14 hydrocarbon content, multi-branched isoparaffin content, normal alkane content, and / or C1-C4 hydrocarbon content in the hydrocracking effluent and / or the hydroisomerization effluent; 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 paraffin feed, the first reaction stage feed, the hydrocracking effluent, the second reaction stage feed, and / or the hydroisomerization effluent. The content of C1-C4 decreases with increasing catalyst deactivation. However, increasing the operating temperature to compensate for catalyst deactivation may result in an increase in the C1-C4 content of the corresponding effluent.

[0138] - the yield of at least one or more of the recovered liquid transportation fuel component, the optionally recovered recycle stream, and / or the optionally recovered side draw, preferably at least the yield of the recovered aviation fuel component; an increased yield of higher boiling hydrocarbons and an increased volume of the optionally recovered recycle stream may indicate increased catalyst deactivation.

[0139] - At least one or more physicochemical properties of the recovered liquid transportation fuel component, the optionally recovered recycle stream, and / or the optionally recovered side draw, 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 may indicate increased catalyst deactivation. In distillation characteristics, for example, an increase in T5, T50, T95 FBP or a shift in boiling point distribution to higher boiling compounds may indicate catalyst deactivation. To some extent, the physicochemical properties may indicate or be related to the content of isoparaffins or multi-branched isoparaffins in the recovered liquid transportation fuel component and / or the optionally recovered recycle stream and / or side draw.

[0140] - Compositional characteristics of at least one or more of the recovered liquid transportation fuel component, the optionally recovered recycle stream, and / or the optionally recovered side draw, preferably the content of isoparaffins and / or the content of multi-branched isoparaffins and / or normal paraffins; a decrease in the content of isoparaffins, multi-branched isoparaffins, and / or C8-C14 hydrocarbons may indicate increased catalyst deactivation. To some extent, the content of isoparaffins or multi-branched isoparaffins may be indicative of, or correlated with, the physicochemical characteristics of the recovered liquid transportation fuel component and / or the optionally recovered recycle stream and / or side draw.

[0141] - and / or a temperature difference in the first reaction stage or the catalyst bed therein and / or in the second reaction stage or the catalyst bed therein; said temperature difference is relatively easy to monitor and a decrease in said temperature difference may be a typical sign of catalyst deactivation.

[0142] The method includes comparing the received value to a predetermined value, and based on the comparison;

[0143] adjusting the weight ratio of the paraffin feed to the total amount of recycle stream and / or side draw in the first reaction stage feed;

[0144] adjusting the distribution weight ratio of the paraffin feed fed to the first reaction stage as part of the first reaction stage feed and the paraffin feed fed to the second reaction stage as part of the second reaction stage feed; and / or

[0145] Adjust at least one or more operating conditions in the first reaction stage and / or the second reaction stage, preferably adjust at least one or more of the temperature, pressure, weight hourly space velocity (WHSV), H2 to first reaction stage feed ratio, H2 to second reaction stage feed ratio, and / or H2 partial pressure at the inlet of the first reaction stage and / or the inlet of the second reaction stage, respectively, more preferably increase the temperature and / or pressure in the first reaction stage and / or the second reaction stage and / or reduce the WHSV in the first reaction stage and / or the second reaction stage, respectively.

[0146] For example, different parameters may be monitored and / or different predetermined values ​​may be selected during the process depending on changes in target product composition and quality.

[0147] In certain preferred embodiments, the method includes monitoring at least two or at least three of the above parameters, which are generally indicative of deactivation of the HC catalyst and / or the HI catalyst. For example, good cold properties (e.g., cloud point, pour point, sub-zero viscosity) of the HI effluent may be due to an increase in the number of shorter carbon chains resulting from increased cracking (e.g., due to increased temperature) rather than a sufficient degree of isomerization. Therefore, it may be beneficial to monitor at least two or three or even more parameters in order to better understand the state of catalyst deactivation. The monitoring may be performed continuously, repeatedly, continuously, periodically, intermittently, discontinuously, such as one-time monitoring, online, or offline.

[0148] Once the operating conditions in the first and / or second reaction stage, respectively, have been adjusted to their feasible limits, preferably within the hydrocracking or hydroisomerization conditions, respectively, as described above, the catalyst needs to be changed to fresh catalyst or regenerated catalyst in order to be able to reach the target product composition and the quality of the recovered liquid transport product again. The present method helps to extend the operating time and the catalyst replacement / regeneration interval.

[0149] The present method comprises fractionation, wherein reclaims at least one or more liquid transportation fuel components and optional recycle stream and / or side draw.The amount of the separated recycle stream and / or side draw and the amount of the recycle stream and / or side draw fed to the first reaction section can vary over a wide range, as discussed in conjunction with the recycle stream and the side draw, respectively.Further liquid streams or fractions, such as further side draw, can optionally be recovered from the fractionation and optionally recycled back into the method.

[0150] The fractionation of the present method can include any conventionally used fractionation technique. Preferably, the fractionation includes distillation, such as atmospheric distillation or vacuum distillation, optionally with gas-liquid separation prior to the distillation, as described below. The fractionation can be carried out in a fractionation system including one or more fractionation units. For example, gas and light naphtha can be separated in a pre-fractionation unit, while the liquid transportation fuel component and the optional recycle stream and / or the side draw are recovered from the main distillation unit downstream of the pre-fractionation unit. In another example, a single fractionation unit can be used.

[0151] The HI effluent can be subjected to gas-liquid separation in the corresponding reactor or in the fractionation system, for example as an integral step. Typically, the gas-liquid separation is carried out at a temperature in the range of 0°C to 500°C, such as 15°C to 300°C or 15°C to 150°C, preferably 15°C to 65°C, such as 20°C to 60°C, and preferably carried out under the same pressure as the reactor in the source of the effluent. Typically, the pressure during the gas-liquid separation can be in the range of 0.1MPa to 20MPa, preferably 1MPa to 10MPa or 3MPa to 7MPa. These conditions are applicable to any gas-liquid separation carried out in the present method.

[0152] According to embodiments of the present process, different products may be recovered from the fractionation as liquid transportation fuel components depending on, for example, the operating conditions selected, the composition of the paraffinic feed used, and / or market demand at a given time.

[0153] As shown in the examples, by the present process, at least one aviation fuel component and a diesel fuel component can be produced, both with good or improved cold properties, with unexpectedly high overall yields of each of the aviation and diesel fuel components, compared to processes using only HI, only HC, or HI followed by HC prior to fractionation and product recovery.

[0154] Therefore, in a preferred embodiment of the present method, at least one of the liquid transportation fuel components recovered from the fractionation is an aviation fuel component having a density at 15°C of 730 kg / m 3 Up to 772kg / m 3 In some embodiments, the recovered aviation fuel component has a T10 and T90 temperature in the range of 120°C to 295°C, preferably in the range of 130°C to 295°C, as determined in accordance with EN ISO 3405-2019.

[0155] The present method is capable of recovering at least one aviation fuel component at surprisingly high yields, even at the end of the life cycle of the HI catalyst. In certain preferred embodiments of the present method, the recovery rate of the aviation fuel component is at least 30 wt %, preferably at least 40 wt %, more preferably at least 50 wt %, such as 30 wt % to 90 wt %, 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 multi-branched isoparaffins account for a large proportion.

[0156] Typically, in the present method, at least one or more of an aviation fuel component, a diesel fuel component, a gasoline fuel component, and / or a marine fuel component is recovered from the fractionation, preferably at least one aviation fuel component, more preferably at least one aviation fuel component and a diesel fuel component, and even more preferably at least one aviation fuel component, a diesel fuel component, and a gasoline fuel component are recovered from the fractionation. In embodiments involving recovery and hydrocracking of the recycle stream, it is typically preferred to at least periodically recover at least one heavy product such as a diesel fuel component, a marine fuel component, a transformer oil component, and / or a base oil component from the fractionation to avoid accumulation of the heaviest components in the recycle loop.

[0157] In a preferred embodiment, the biogenic carbon content (EN 16640 (2017)) of the recycled liquid transport fuel component is at least 50 wt%, preferably at least 70 wt%, more preferably at least 90 wt%, even more preferably at least 95 wt%, or even about 100 wt%, based on the total weight of carbon (TC) in the corresponding recycled liquid transport fuel component. The biogenic carbon content of the recycled liquid transport fuel component is mainly influenced by the biogenic carbon content of the paraffinic feed and, in a preferred embodiment, the oxygenated hydrocarbon feed after HDO and optionally the initial HI. There is a strong demand in the field for hydrocarbon components with increased biogenic content for various end uses.

[0158] Process diagram

[0159] Figure 1 and Figure 2 The method according to the example embodiment is shown exemplarily. Figure 1 and Figure 2 In the process, an oxygenated hydrocarbon feed 510 is fed to an HDO reactor 520, and is hydrodeoxygenated in the presence of an HDO catalyst 530 to obtain a hydrodeoxygenated effluent (HDO effluent) 540, and the obtained HDO effluent 540 is subjected to a gas-liquid separation 550 to separate a compound that is gaseous at least at NTP 560 from the HDO effluent, thereby obtaining a degassed HDO effluent 570. Figure 1 and Figure 2 In the embodiment of the present invention, the degassed HDO effluent 570 is subsequently fed to an initial hydroisomerization reactor 580, wherein the degassed HDO effluent 570 is subjected to initial hydroisomerization in the presence of an initial HI catalyst 590 to obtain a paraffin hydroprocessing effluent 600, and the obtained paraffin hydroprocessing effluent 600 is subjected to a gas-liquid separation 610 to separate compounds that are gaseous at least at NTP 620 from the paraffin hydroprocessing effluent 600 to obtain a degassed paraffin oxygenation effluent 630. In these example embodiments, the degassed paraffin oxygenation effluent 630 is a paraffin feed as defined herein. Figure 1 and Figure 2 The possibility of allocating a portion 650 from the paraffin feed 630 and feeding the allocated portion 650 to the second reaction stage 740 is shown. Figure 1 and Figure 2 In the embodiment of the present invention, a first reaction stage feed 660 comprising the paraffin feed 630 (or 640 if the portion 650 is allocated therefrom) is fed to a first reaction stage 670, wherein the first reaction stage feed 660 is hydrocracked in the presence of a hydrocracking catalyst 680 to obtain a hydrocracking effluent ( Figure 2 690 in ). Figure 1 In the embodiment, the first reaction section 670 including the HC catalyst 680 and the second reaction section 740 including the HI catalyst 750 are arranged in the same reactor, and Figure 2 are configured in separate reactors. Figure 2 The possibility of subjecting the hydrocracking effluent 690 to a gas-liquid separation 700 is shown in order to separate from the hydrocracking effluent 690 at least the compounds that are gaseous at NTP 710 to obtain a degassed hydrocracking effluent 720. Figure 2 In the process, the hydrocracking effluent 690 or the degassed HC effluent 720 is optionally combined with a portion 650 allocated from the paraffin feed 630 as a feed for the second reaction stage ( Figure 2 730 in the reaction section), and then HI is carried out in the second reaction section 740 in the presence of the HI catalyst 750 to obtain a HI effluent 760, and the obtained HI effluent 760 is subjected to a gas-liquid separation 770 to separate a compound that is gaseous at least at NTP 780 from the HI effluent 760 to obtain a degassed HI effluent 790. Then, Figure 1 and Figure 2 In the embodiment, the degassed HI effluent 790 is fed to a distillation unit 800, which may include a column, or a pre-fractionation column and a main distillation column, from which multiple streams or fractions are obtained. Figure 1 and Figure 2 In the embodiment of the present invention, a gasoline fuel component 810, an aviation fuel component 820, and / or a diesel fuel component 830 are recovered from the distillation, as well as an optional recycle stream 840. The optional recovered recycle stream 840 can be fed to the first reaction stage 670 as part of the first reaction stage feed 660.

[0160] Figure 3 The distillation curves determined according to ASTM D2887-19e1, i.e., the function of temperature and distillate recovered (wt. %), are shown for the degassing effluent (liquid product) of a test run according to an exemplary embodiment of the present method, TR4b_INV (i.e., using the catalyst system HC-HI), and three comparative test runs, TR1b using only HI catalyst, TR2b using the catalyst system HI-HC, and TR3b using only HC catalyst. The test run conditions for obtaining the degassing test run effluent are disclosed in Example 1, and the results are discussed.

[0161] Figure 4 An illustrative process involving hydrocracking is shown schematically. This process is used as HC process 1 in Example 2. Figure 4In the process, an oxygenated hydrocarbon feed 110 is fed into an HDO reactor 120, and is hydrodeoxygenated in the presence of an HDO catalyst 130 to obtain a hydrodeoxygenated effluent (HDO effluent) 140, and the obtained HDO effluent 140 is subjected to a gas-liquid separation 150 to separate a compound that is gaseous at least at NTP 160 from the HDO effluent, thereby obtaining a degassed HDO effluent 170. Figure 4 In the first reactor 180, the degassed HDO effluent 170 is then fed to the first reactor 180, in which the degassed HDO effluent 170 is hydroisomerized in the presence of the HI catalyst 190 to obtain the HI effluent 200, and the obtained HI effluent 200 is subjected to gas-liquid separation 210 to separate the compounds that are gaseous at least at NTP 220 from the HI effluent 200, thereby obtaining the degassed HI effluent 230. Figure 4 In the embodiment of the present invention, the degassed HI effluent 230 is fed to a distillation unit 240, which may include a column, or a pre-fractionation column and a main distillation column, from which multiple streams or fractions are obtained. Figure 4 In the distillation, the gasoline fuel component 250, the aviation fuel component 260, and / or the diesel fuel component 270 are recovered, and a recycle stream 280 having a T5 boiling point of 270°C or more is further separated. Figure 4 In the embodiment, the recycle stream 280 is fed to the second reactor 290, where it is hydrocracking in the presence of the HC catalyst 300 to obtain the recycle effluent 310. Figure 4 In the embodiment, the circulating effluent 310 is subjected to gas-liquid separation 320 to separate at least the gaseous compounds in the NTP 330 from the circulating effluent 310 to obtain a degassed circulating effluent 340, and then the degassed recycled effluent 340 and the degassed HI effluent 230 are fed as a co-feed to the distillation unit 240 for fractionation. In certain embodiments, a portion of the HI effluent 200, 230 may be fed as a co-feed 500 together with the recycled stream 280 to the second reactor 290 for hydrocracking. Figure 4 In contrast, the HC process 1 in Example 2 does not feed a portion of the HI effluent 200 , 230 to the hydrocracking reactor 290 as a co-feed 500 with the recycle stream 280 .

[0162] Figure 5 Another illustrative process involving hydrocracking is shown schematically. This process is used as HC process 2 in Example 2 without using the recycle feed. Figure 5 In the method, Figure 4 As shown, the degassed HI effluent 230 is obtained. Figure 5In the process, the degassed HI effluent 230 is fed to a second reactor 290, where it is hydrocracking in the presence of an HC catalyst 300 to obtain a hydrocracking effluent 350, and the hydrocracking effluent 350 is subjected to a gas-liquid separation 360 to separate at least gaseous compounds at NTP 370 from the hydrocracking effluent 350 to obtain a degassed hydrocracking effluent 380. Figure 5 In the embodiment of the present invention, the degassed hydrocracking effluent 380 is fed to a distillation unit 240, which may include a column, or a pre-fractionation column and a main distillation column, where it is fractionated into multiple streams or fractions. Figure 5 In the distillation, gasoline fuel component 390, aviation fuel component 400, and diesel fuel component 410 are recovered. Figure 5 In contrast, the HC process 2 in Example 2 does not separate and hydrocrack the recycle stream 420 , nor does it feed a portion of the HI effluent 200 or 230 to the fractionation 240 as a co-feed 500 with the hydrocracking effluent 350 , 380 .

[0163] Example

[0164] Example 1 - Trial run

[0165] Two different test run feeds (Feed A and Feed E) were obtained by subjecting a fat feedstock to hydrodeoxygenation (HDO) and gas-liquid separation to obtain a paraffin feed containing >95 wt% paraffins based on the total weight of the paraffin feed, and subjecting the paraffin feed to initial hydroisomerization (HI) of low severity (Feed A) or medium severity (Feed E). The effluent fractions of the initial HI were obtained by recovering only the bottom fraction (Feed A) from the initial HI, or by degassing and stabilizing to remove gas and light naphtha (Feed E). The detailed information of these Feeds A and E is shown in Table 1.

[0166] Table 1. Details of the trial run feeds.

[0167]

[0168] In the test run, the heavier feed A and the lighter feed E were hydrocracked (HC) according to the present process using an HC catalyst (1.7 g) followed by HI using an HI catalyst (1.7 g) and for comparison with hydroisomerization using only an HI catalyst (3.4 g), hydrocracking using only an HC catalyst (3.4 g), and HI using an HI catalyst (1.7 g) followed by hydrocracking using an HC catalyst (1.7 g). The total / cumulative amount of catalyst for each test run was the same whether the catalyst in the test run was only HI, only HC, HI followed by HC, or HC followed by HI. One HI catalyst and one HC catalyst were used in the test runs, both of which were non-sulfided bifunctional catalysts. The test run conditions and catalysts are reported in Table 2, as well as the cloud point measured for the degassed test run effluent (liquid product).

[0169] Table 2. Method details of the run conditions, catalysts, and run times. In each run, the total amount of catalyst was the same (3.4 g) and the WHSV was 1.5 h. -1 , pressure was 40 bar, and H2 to liquid feed ratio was 500 nL / L.

[0170]

[0171] As can be seen in Table 2, as the reaction temperature increases for each catalyst system tested, a liquid effluent with a lower (better) cloud point is produced. When comparing Runs TR3a-c, which used only the HC catalyst and fed Feed A, to Runs TR1a-c, which used only the HI catalyst and fed Feed A, it can be seen that the operating temperatures using the HC catalyst were significantly lower enough to achieve the same cloud point levels, which represents the cold performance of the degassed run effluent (i.e., the liquid run product).

[0172] An interesting comparison can be made between run TR1a using HI catalyst at 300°C, TR2a using HI-HC catalyst at 300°C / 300°C, TR3a using HC catalyst at 290°C, and TR4a_INV using HC-HI catalyst according to the present method at 290°C / 290°C, each fed with the heavier feed A. Using the same total amount of catalyst and very similar operating conditions, the present method provided the lowest cloud point of -31.4°C, about 8°C lower than the cloud point of -23.2°C provided by TR1a using HI catalyst, and about 8°C lower than the cloud point of -23.8°C provided by TR2a using HI-HC catalyst. The present method provided an improvement of about 6°C in cloud point compared to TR3a using HC catalyst (-25.8°C), which was the second lowest cloud point of these runs.

[0173] Figure 3 The distillation temperature as a function of the distillate recovered (wt %) is presented for runs TR1b (HI only), TR2b (HI-HC), TR3b (HC only), and TR4b_INV (HC-HI). Although TR4b_INV has the lowest cloud point of these runs (-34.8°C), the highest temperature is achieved at, for example, 10 wt % recovery. TR1b (HI only) and TR3b (HC only) have very similar distillation curves in the beginning, but at around 60 wt % recovery, the temperature of TR3b starts to be higher than the other runs, which may explain why the cloud point of TR3b is only -16.7°C. Finally, TR1b (HI only) shows a significant heavy tail that may affect the cloud point, with the cloud point of TR1b being only -23.8°C. On the other hand, TR2b (HI-HC) has the lowest temperature throughout the distillation. Based on the distillation curves alone, one might expect TR2b (HI-HC) to have a higher temperature during the distillation. Figure 3 The run in , however, surprisingly, TR2b had the second lowest cloud point of -28.5°C, while TR4b_INV had a significantly lower cloud point of -34.8°C. These results illustrate the importance of an HC catalyst followed by a HI catalyst, rather than vice versa, to achieve enhanced cold performance.

[0174] The comparison of runs TR5-TR8 with the lighter feed E is less straightforward due to the differences in run temperatures. However, here, runs TR8a_INV and TR8b_INV according to the present method provide approximately the same good cloud points as runs TR 5a and TR5b using only HI catalyst. For the lighter feed E, the lowest performing runs in terms of cloud points achieved are TR3a and TR3b using only HC catalyst. When comparing the results of runs TR1-TR4 with those of runs TR5-TR8, different cloud point behaviors can be seen, obtained with the same catalyst setup at similar temperatures. These are most likely due to differences in feed characteristics: feed A is much heavier, with a C17+ content of about 97 wt.-%, while feed E has a C17+ content of about 60 wt.-%, but feed A also has a lower degree of isomerization, especially in terms of the multi-branched isoparaffin content, which is about 20 wt.-% for feed A and about 50 wt.-% for feed E.

[0175] The degassing test run effluent was fractionated to recover gasoline fuel component, aviation fuel component, and diesel fuel component. The yields of these liquid fuel components, the ratio of the aviation fuel component yield to the diesel fuel component productivity, and vice versa, and the yield of the C1-C4 gaseous fraction are reported in Table 3. In addition, some physicochemical properties of the diesel and aviation fuel components were measured, as shown in Table 4.

[0176] Table 3. For selected test runs, the yields of C1-C4 gaseous fractions, gasoline fuel component (GFC), aviation fuel component (AFC) and diesel fuel component (DFC) (expressed as weight % of hydrocarbons in the test run effluent), as well as the total yield of AFC and DFC are presented. In addition, the ratio of AFC to DFC and the ratio of DFC to AFC are also presented.

[0177]

[0178] Table 4. Cloud points of the diesel fuel components (DFC) and aviation fuel components (AFC), and flash points and densities of the aviation fuel components at 15°C for selected test runs.

[0179]

[0180] As can be seen from Table 3, the trial runs according to the present process produced the lowest amount of light gases, both for the heavier feed A and the lighter feed E, which were about half as much as the trial runs using only HI. In addition, the total yield of the aviation fuel component and the diesel fuel component, which are considered in this context to be the most valuable products of the process, was the highest in the trial runs according to the present process and unexpectedly the lowest in the trial runs using HI-HC (i.e. the same catalyst as in the present process, but in the reverse order). Interestingly, the feed composition did not seem to have much influence on the yield of light gases and the total yield of diesel and aviation fuel components, but in the trial runs fed with the heavier feed A, the share of diesel fuel components produced increased, although the aviation fuel component remained the main product. In the trial runs according to the present process, the heavier feed A, which had a lower content of multi-branched isoparaffins, provided the largest share of the diesel fuel components produced. In other words, by increasing the weight of the first reaction stage feed and / or reducing the content of multi-branched isoparaffins, the process appears to produce a higher share of diesel fuel components compared to other trial run settings. This can be achieved, for example, by blending a recycle stream or side draw from the fractionation into the first reaction stage feed. This provides a valuable and simple way to adjust the share of diesel and aviation fuel components produced, for example in response to fluctuations in market demand for these products.

[0181] As can be seen from Table 4, the diesel fuel component obtained from the test runs according to the present method has the best cold properties, as shown by the lowest cloud point, and the cloud point of the aviation fuel component is the second lowest, only slightly higher than the aviation fuel component in the test runs using only HI. However, as shown in Table 3, the production of the aviation fuel component by the process using only HI has the disadvantage of the highest light gas formation rate. The density of the aviation fuel component in the test runs according to the present method is higher than the upper limit of 772 kg / m set in Annex A2 of ASTM D7566-21 for isoparaffinic kerosene obtained from hydrotreated fatty feedstocks. 3 , but on the other hand, the flash point is much higher than the minimum value of 38°C set in ASTM D7566-21 Annex A2, so the density can be easily adjusted to meet the requirements by optimizing or adjusting the distillation cut-off value and recycling more light fractions into the aviation fuel components.

[0182] Example 2 - Simulation 1

[0183] Simulations were performed using Aspen Plus V10.0 software to illustrate the advantages of the present process compared to a conventional HVO process in which a fat feedstock is subjected to a hydrodeoxygenation (HDO) step and a subsequent HI step (referred to herein as initial HI) as disclosed in FI100248 and EP1396531, followed by fractionation to recover at least one aviation fuel component.

[0184] The oxygenated hydrocarbon feed fed to HDO contained 100% animal fat, and the high paraffin feed (containing about 98% by weight of paraffins) fed to the initial HI contained about 59% by weight of C17-C18 normal paraffins, about 29% by weight of C15-C16 normal paraffins, about 4% by weight of C17-C18 isoparaffins, and about 2% by weight of C15-C16 isoparaffins. About 97% by weight of the paraffin feed fed to the initial HI was C14-C22 hydrocarbons, and about 1% by weight was cyclic hydrocarbons.

[0185] Reference 1 (Tables 5 and 6) shows a typical distribution of products recovered from fractionation of a conventional HVO process operated in winter-grade renewable diesel production mode, i.e. involving an HDO step and a medium severity HI step. Reference 2 (Tables 5 and 6) shows a typical distribution of products recovered from fractionation of an HVO process operated with an HDO step similar to Reference 1, but followed by a high severity HI step using fresh catalyst.

[0186] For HC Method 1 (Tables 5 and 6), the Figure 4The HDO and initial HI steps were run similarly to Reference 1, and then the initial HI effluent and the hydrocracking effluent from the hydrocracking reactor were fractionated to which a recycle stream (a portion of the diesel component recovered from the fractionation) was added. For HC Method 2 (Tables 5 and 6), Figure 5 The process shown (without recycle stream), the HDO and initial HI steps are run similarly to Reference 1, followed by hydrocracking and fractionation of the initial HI effluent.

[0187] The components shown in Table 5 are recovered from the fractionation. Tables 5 and 6 show that HC Process 2 provides similar and very good yields of sustainable / renewable aviation fuel (SAF) components and winter-grade diesel components compared to the process of Reference 2, with only small amounts of light gas components formed. At the same time, the quality of the SAF and winter-grade diesel components is better than that obtained using the process of Reference 2, as can be seen from the very low freezing point of SAF and the cloud point of the winter-grade diesel component. As a significant advantage over the process of Reference 2, the improvement is achieved while avoiding the limitations of the process of Reference 2, namely, the need to use high severity HI, which generally involves high temperature and / or lower WHSV compared to medium severity HI conditions, and / or the use of fresh HI catalyst. Compared to the process of HC Process 1, HC Process 2 provides higher overall yields of the products that are considered to be the most valuable in the current context, namely, SAF and winter-grade diesel components, with less light gas components formed. In addition, based on the freezing point of SAF and the cloud point of the winter-grade diesel component, the quality of the SAF and winter-grade diesel components is better than that obtained using HC Process 1. Although HC Process 2 was operated without a recycle stream in this experiment, HC Process 1 demonstrates that the yield of the SAF component can be easily and significantly increased by recycling at least a portion of the diesel component to the hydrocracking when desired.

[0188] Table 5. Simulation test results, yield based on raw material feed (oxygenated hydrocarbons)

[0189]

[0190] Table 6. Product characteristics. SAF stands for Sustainable / Renewable Aviation Fuel Component.

[0191]

[0192] Although these simulations of HC Process 1 and HC Process 2 were conducted without subjecting the hydrocracking effluent to hydroisomerization prior to recovering the components from fractionation, it is apparent from the test run results shown in Example 1 that improved cold performance, reduced amounts of light gases produced, and increased overall yields of diesel and aviation fuel components similar to those of Example 1 can be obtained by replacing the hydrocracking catalyst with a catalyst system containing the same total amount of catalyst but configured as an HC catalyst and an HI catalyst. Furthermore, based on a comparison of HC Process 1 and HC Process 2, it is apparent that the yield of aviation fuel components can be adjusted or optimized by recovering the recycle stream in the present process and using it as a co-feed, i.e., as part of the feed to the first reaction stage of the hydrocracking.

[0193] Example 3 - Simulation 2

[0194] Further simulations were performed using Aspen Plus V10.0 software to show the effect of varying the weight ratio of the hydrocracking catalyst in the first reaction stage to the hydroisomerization catalyst in the second reaction stage.

[0195] In these simulations, two different feeds were used: a high isoparaffin feed E (as shown in Table 1) and a high normal paraffin feed N containing about 100 wt% paraffins, of which about 5 wt% were isoparaffins. A high normal paraffin feed with a low isoparaffin content can be prepared, for example, by performing HDO on an oxygenated hydrocarbon feed such as animal fat / vegetable oil using appropriate process conditions, cocatalysts and / or product recycle, i.e., a separate isomerization step may not be required to achieve low isoparaffin levels.

[0196] Thus, the overall process setup for the test points was HDO followed by initial HI followed by hydrocracking, hydroisomerization and fractionation in the case of feed E, and HDO, hydrocracking followed by hydroisomerization and fractionation in the case of feed N. In these simulations, there was no recycle from fractionation to hydrocracking. As a reference, a conventional HVO process operating in winter grade renewable diesel production mode was selected, i.e. including an HDO step followed by a medium severity HI step, but without any hydrocracking step.

[0197] In the simulation, the yield of the aviation fuel component (SAF) is calculated at the lowest flash point (38°C), the lowest freezing point (-40.0°C) and the highest density (772.0kg / m 3 As a reference, the hydroisomerization was carried out at 330 °C, 40 bar and WHSV 1.7 h -1 For the other test points, hydrocracking was carried out at 280°C and hydroisomerization was completed at 320°C, both steps were carried out at about 40 bar and WHSV 1.5h -1 Next completed.

[0198] The yields of diesel components, SAF, gasoline fuel components and light gases are shown in Table 7, and certain properties of the fuel components recovered from the fractionation are shown in Table 8.

[0199] Table 7. Calculated yields of liquid products based on HDO. SAF stands for sustainable / renewable aviation fuel component.

[0200]

[0201] Table 8. Product properties. SAF stands for Sustainable / Renewable Aviation Fuel Component.

[0202]

[0203] From the results in Table 7, it can be seen that the weight ratio of the hydrocracking catalyst in the first reaction stage to the hydroisomerization catalyst in the second reaction stage is 5:95, and in the case of high isoparaffin feed E, the SAF yield is significantly improved, the total yield of diesel and SAF is only slightly reduced, or the formation of light gases is reduced while maintaining the total yield of diesel and SAF in the case of high normal paraffin feed N. By further increasing the share of the HC catalyst, the benefit is further improved, that is, in the case of high isoparaffin feed E, the SAF yield is further improved, the total yield of diesel and SAF is only slightly reduced, and in the case of high normal paraffin feed N, a further reduction in light gas formation is achieved, and the total yield of diesel and SAF is increased.

[0204] It can also be seen from Table 7 that when the weight ratio of the hydrocracking catalyst in the first reaction stage to the hydroisomerization catalyst in the second reaction stage is controlled to be less than 80:20, the formation of light gas can be suppressed even in the case of high isoparaffin feed E. At the same time, both high isoparaffin feed E and high normal paraffin feed N obtain a higher total yield of diesel and SAF. In addition, the density of the SAF component remains high, as shown in Table 8, which is conducive to mixing with fossil components to provide the final aviation fuel. Otherwise, the minimum density required for the final aviation fuel (775 kg / m 3 ), but special fossil components may be required. Table 8 also shows that both feeds provide better cloud points (less than -15°C) for diesel components when the HC:HI catalyst weight ratio is limited to less than 80:20.

[0205] Various embodiments have been presented.It should be understood that in this document, the words include, contain and contain are used as open-ended expressions without exclusive meanings.

[0206] The foregoing description has provided, by way of non-limiting examples of specific embodiments and embodiments, a complete and informative description of the best mode presently contemplated by the inventor for carrying out the invention. However, it will be apparent to those skilled in the art that the invention is not limited to the details of the embodiments given above, but may be implemented in other embodiments using equivalent means or in different combinations of embodiments without departing from the features of the invention.

[0207] In addition, some features of the exemplary embodiments disclosed above can be used advantageously without the corresponding use of other features. Therefore, the above description should be considered as merely an illustration of the principles of the present invention, rather than a limitation of the present invention. Therefore, the scope of the present invention is only limited by the attached patent claims.

Claims

1. A method of producing at least one liquid transportation fuel component, the method comprising: providing a paraffin feed comprising at least 60 wt% paraffins based on the total weight of the paraffin feed, wherein at least 5 wt% of the paraffins are isoparaffins; subjecting a first reaction stage feed comprising said paraffinic feed and optionally a recycle stream and / or a side draw to hydrocracking in a first reaction stage in the presence of a hydrocracking catalyst to obtain a hydrocracking effluent; subjecting a second reaction stage feed comprising the hydrocracking effluent to hydroisomerization in a second reaction zone in the presence of a hydroisomerization catalyst to obtain a hydroisomerization effluent; as well as The hydroisomerization effluent is fed to a fractionation and at least one or more liquid transportation fuel components and optionally the recycle stream and / or the side draw are recovered from the fractionation.

2. The process according to claim 1, wherein the paraffinic hydrocarbon feed comprises at least 70 wt %, preferably at least 80 wt %, more preferably at least 90 wt %, even more preferably at least 95 wt % of paraffinic hydrocarbons, based on the total weight of the paraffinic hydrocarbon feed; and / or at least 70 wt %, preferably at least 80 wt %, more preferably at least 90 wt %, even more preferably at least 95 wt % of C12-C30 hydrocarbons, based on the total weight of the paraffinic hydrocarbon feed.

3. The process according to claim 1 or 2, wherein the paraffin feed comprises at least 8 wt%, or at least 10 wt%, preferably at least 20 wt%, further preferably at least 30 wt%, more preferably at least 40 wt%, further more preferably at least 50 wt%, even more preferably at least 60 wt%, most preferably at least 70 wt% or at least 80 wt% of isoparaffins based on the total weight of paraffins in the paraffin feed.

4. The process according to any one of the preceding claims, wherein the paraffin feed comprises at least 3 wt. %, preferably at least 5 wt. %, more preferably at least 10 wt. %, even more preferably at least 15 wt. % of multi-branched isoparaffins, based on the total weight of paraffins in the paraffin feed.

5. The process according to any one of the preceding claims, wherein the first reaction stage feed comprises at least 30 wt. %, preferably at least 40 wt. %, further preferably at least 50 wt. %, more preferably at least 60 wt. %, further more preferably at least 70 wt. %, even more preferably at least 80 wt. % of isoparaffins, based on the total weight of paraffins in the first reaction stage feed; and / or at least 5 wt. %, preferably at least 10 wt. %, more preferably at least 15 wt. %, even more preferably at least 20 wt. % of multi-branched isoparaffins, based on the total weight of paraffins in the first reaction stage feed.

6. The process according to any one of the preceding claims, comprising recovering the recycle stream from the fractionation and feeding the recycle stream to the first reaction stage as part of the first reaction stage feed, and / or recovering the side draw from the fractionation and feeding the side draw to the first reaction stage as part of the first reaction stage feed; and / or feeding a portion of the paraffin feed to the second reaction stage as part of the second reaction stage feed, the portion of the paraffin feed being obtained by distributing the paraffin feed between the first reaction stage and the second reaction stage.

7. A process according to any one of the preceding claims, wherein the recycle stream and / or the side draw comprises at least 50 wt.-%, preferably at least 60 wt.-%, more preferably at least 70 wt.-%, even more preferably at least 80 wt.-% of isoparaffins, based on the total weight of paraffins in the recycle stream or side draw, respectively; and / or at least 10 wt.-%, preferably at least 15 wt.-%, more preferably at least 20 wt.-%, even more preferably at least 30 wt.-% of multi-branched isoparaffins, based on the total weight of paraffins in the recycle stream or side draw, respectively.

8. The process according to any one of the preceding claims, wherein the second reaction stage feed comprises a portion of the paraffin feed, and wherein the paraffin feed is distributed between the first reaction stage feed and the second reaction stage feed in a weight ratio of the first reaction stage feed to the second reaction stage feed in the range of 1:99 to 99:1, preferably 10:90 to 95:5, more preferably 20:80 to 90:10, even more preferably 30:70 to 80:

20.

9. The process according to any one of the preceding claims, wherein the side draw has a T5 and T95 temperature determined according to EN ISO 3405-2019 in the range of 250 to 320°C, preferably in the range of 260 to 310°C, more preferably in the range of 270 to 305°C; and / or a difference between T95 and T5 temperatures (95% and 5% by volume recovered, EN ISO 3405-2019) of below 40°C, preferably below 30°C, more preferably below 20°C.

10. The process according to any one of the preceding claims, wherein the recycle stream has a T5 temperature above 270°C (recovery rate 5 vol-%, EN ISO 3405-2019); and / or a T5 temperature in the range of 270°C to less than 300°C, preferably in the range of 270°C to less than 295°C, more preferably in the range of 270°C to less than 290°C; and / or an initial boiling point (IBP) of less than 290°C, preferably less than 288°C, more preferably less than 285°C.

11. The process according to any one of the preceding claims, wherein the first reaction stage feed comprises the paraffin feed and a recycle stream and / or a side draw, and the weight ratio of the paraffin feed to the total amount of the recycle stream and / or the side draw is in the range of 10:90 to 90:10, preferably in the range of 20:80 to 80:

20.

12. The process according to any one of the preceding claims, wherein the hydrocracking in the first reaction stage is carried out at a temperature in the range of 200 to 500°C, preferably 220 to 430°C, more preferably 280 to 400°C, a pressure in the range of 0.5 to 20 MPa, preferably 1 to 20 MPa, more preferably 3 to 15 MPa, a H partial pressure at the inlet of the first reaction stage in the range of 0.5 to 20 MPa, preferably 1 to 20 MPa, more preferably 3 to 15 MPa, a weight hourly space velocity in the range of 0.1 to 10, preferably 0.2 to 10, more preferably 0.4 to 8, even more preferably 0.5 to 5 kg of first reaction stage feed / kg catalyst / hour, a H in the range of 10 to 2000, preferably 50 to 1000 standard liters of H / liter of first reaction stage feed and a first reaction stage feed ratio.

13. The process according to any one of the preceding claims, wherein the hydroisomerization in the second reaction stage is carried out at a temperature in the range of 200 to 500°C, preferably 230 to 500°C, more preferably 250 to 450°C, even more preferably 280 to 400°C, a pressure in the range of 1 MPa to 20 MPa, preferably 2 MPa to 15 MPa or 3 MPa to 10 MPa, a H partial pressure at the inlet of the second reaction stage in the range of 1 MPa to 20 MPa, preferably 2 MPa to 15 MPa or 3 MPa to 10 MPa, a weight hourly space velocity in the range of 0.1 to 10, preferably 0.2 to 8, more preferably 0.4 to 6 kg second reaction stage feed / kg catalyst / hour, a H and paraffin feed ratio in the range of 10 to 2000, preferably 50 to 1000 standard liters H / liter second reaction stage feed.

14. The process according to any one of the preceding claims, wherein the first reaction stage is operated at a lower temperature than the second reaction stage.

15. The process according to any one of the preceding claims, wherein the hydrocracking catalyst is arranged in one or more catalyst beds in the first reaction section and the hydroisomerization catalyst is arranged in one or more catalyst beds in the second reaction section, and the first reaction section and the second reaction section are arranged in the same reactor or in separate reactors, preferably in separate reactors.

16. Process according to any one of the preceding claims, wherein the weight ratio of hydrocracking catalyst in the first reaction stage to hydroisomerization catalyst in the second reaction stage is in the range of 5:95 to 70:30, preferably 10:90 to 65:35, more preferably 20:80 to 60:

40.

17. 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 Elements, more preferably selected from Pt and / or Pd, and at least one or more acidic porous materials, and preferably each of the first reaction stage feed and the second reaction stage feed comprises less than 50 ppm by weight, preferably less than 30 ppm by weight, more preferably less than 10 ppm by weight of sulfur (ppm by weight, calculated as elemental S) based on the total feed to each reaction stage determined according to ISO 20846-2019.

18. 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 noble metals selected from Group VIII, more preferably selected from Pt and / or Pd; and At least one or more acidic porous materials selected from zeolites and / or zeolite-type materials, wherein preferably at least one and / or more zeolites and / or zeolite-type materials have a framework type selected from AEL, ATO, AFO, MRE, MTT, MTW, TON, MRT, MOR, FER and / or MWW, preferably at least one or more acidic porous materials are 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 are selected from SAPO-11, SAPO-41, ZSM-23 and / or ZSM-48; and Optionally, at least one or more of alumina, silica, amorphous silica-alumina, titanium-alumina, titania and / or zirconia.

19. 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 of the 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 are selected from SAPO-5, SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23, ZSM-43, ZSM-48, IZM-2, mordenite, beta zeolite, Y-type zeolite and / or amorphous silica-alumina, more preferably at least one or more acidic porous materials are selected from SAPO-5, SAPO-11, ZSM-23, beta zeolite, Y-type zeolite and / or amorphous silica-alumina; and Optionally, at least one or more of alumina, silica, titanium alumina, titania and / or zirconia.

20. The method according to any one of claims 17 to 19, wherein: The bifunctional hydrocracking catalyst in the first reaction stage has a greater total number of acid sites as measured by NH3-TPD than the bifunctional hydroisomerization catalyst in the second reaction stage.

21. The method according to any one of the preceding claims, wherein providing the paraffinic feed comprises hydrotreating a hydroprocessing feed, preferably hydrodeoxygenating an oxygenated hydrocarbon feed, optionally followed by initial hydroisomerization, 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 wastes and residues, and / or enzymatically liquefied organic wastes and residues, more preferably the oxygenated 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 (FT) conversion, optionally followed by initial dewaxing, 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.

22. The process according to any one of the preceding claims, wherein the biogenic carbon content (EN 16640 (2017)) of the paraffinic feed is at least 50 wt.-%, preferably at least 70 wt.-%, more preferably at least 90 wt.-%, even more preferably at least 95 wt.-%, or even about 100 wt.-%, based on the total weight of carbon (TC) in the paraffinic feed.

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

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

25. A process according to any one of the preceding claims, comprising recovering an aviation fuel component from the fractionation in a yield of at least 30 wt%, preferably at least 40 wt%, more preferably at least 50 wt%, for example in the range of 30 to 90 wt%, of the total weight of the paraffinic feed.

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