Process for producing liquid transport fuel component

Abstract

A method of producing at least one liquid transport fuel component is provided. In a first operating mode of one of the processes, a hydrocarbon feed comprising nitrogen impurities is hydrotreated in a reactor A in the presence of a hydrotreating catalyst A to obtain a hydrotreated effluent A, the hydrotreated effluent A is catalytically hydrotreated in a reactor B after degassing to obtain a hydrotreated effluent B, optionally after degassing, fractionating the hydrotreated effluent B to obtain at least one liquid transport fuel component, preferably at least an aviation fuel component. In the process, parameters indicative of deactivation of the hydrotreating catalyst A are monitored and when these parameters reach predetermined values, the process switches to a second operating mode in which the order of reactors A and B is changed, thereby feeding the degassed hydrotreating effluent B to reactor A.

Description

Technical Field

[0001] The present disclosure generally relates to a method for producing a renewable fuel component. The present disclosure specifically, but not exclusively, relates to a method for producing at least one or more liquid transportation fuel components, preferably at least an aviation fuel component. In addition, a computer program useful for implementing the method is disclosed. Background Art

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

[0003] In the transportation sector, and in particular in aviation, there is a continuing need to reduce greenhouse gas emissions and / or carbon footprint. As a result, interest in renewable aviation fuels and aviation fuel components is and has been growing.

[0004] Catalytic processes for producing aviation fuel components from renewable raw materials have been proposed. However, in the described processes, the yield of aviation fuel components (compared to other fuel components) is relatively low due to unavoidable catalyst deactivation. In addition, there is a need to reduce the quality degradation of renewable aviation fuel components towards the end of operation. In addition, there is an increasing demand for the production of fuel components from a wide range of renewable raw materials, including raw material qualities with elevated impurity content, without compromising the catalyst life. Summary of the invention

[0005] The present invention aims to solve or alleviate at least some of the problems associated with the prior art. One goal is to improve the quality of aviation fuel components obtainable from renewable sources. Another goal is to be able to increase the yield of aviation fuel components. Yet another goal is to extend the run time or hydroprocessing catalyst life in a process for producing renewable liquid transportation fuel components. Yet another goal is to enable a wide range of renewable raw materials to be used in a process for producing renewable liquid transportation fuel components, particularly aviation fuel components.

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

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

[0008] providing a hydrocarbon feed comprising nitrogen impurities;

[0009] i) subjecting a reactor A feed comprising a hydrocarbon feed to hydrotreating in reactor A in the presence of a hydrotreating catalyst A to obtain a hydrotreating effluent A, and separating compounds that are gaseous at least at NTP from the hydrotreating effluent A to obtain a degassed hydrotreating effluent A;

[0010] ii) hydrotreating a reactor B feed comprising degassed hydroprocessing effluent A in reactor B in the presence of a hydroprocessing catalyst B to obtain hydroprocessing effluent B;

[0011] iii) feeding the hydroprocessing effluent B to a fractionation, optionally after separation of at least the compounds that are gaseous at NTP from the hydroprocessing effluent B, and recovering at least one or more liquid transportation fuel components from the fractionation; and

[0012] monitoring a parameter indicative of deactivation of hydroprocessing catalyst A to receive a value;

[0013] comparing the received value to a predetermined value; and

[0014] When the received value reaches a predetermined value, switch from i), ii), and iii) to:

[0015] I) subjecting a reactor B feed comprising a hydrocarbon feed to hydroprocessing in the presence of a hydroprocessing catalyst B in a reactor B to obtain a hydroprocessing effluent B, and separating compounds that are gaseous at least at NTP from the hydroprocessing effluent B to obtain a degassed hydroprocessing effluent B;

[0016] II) hydrotreating a reactor A feed comprising degassed hydroprocessing effluent B in the presence of a hydroprocessing catalyst A in reactor A to obtain hydroprocessing effluent A;

[0017] III) feeding the hydroprocessing effluent A to a fractionation, optionally after separation of at least the compounds that are gaseous at NTP from the hydroprocessing effluent A, and recovering at least one or more liquid transportation fuel components from the fractionation.

[0018] According to a second exemplary aspect, there is provided a method of producing at least one liquid transportation fuel component, the method comprising:

[0019] providing a hydrocarbon feed comprising nitrogen impurities;

[0020] i) subjecting a reactor A feed comprising a hydrocarbon feed to hydrotreating in reactor A in the presence of a hydrotreating catalyst A to obtain a hydrotreating effluent A, subjecting the hydrotreating effluent A to fractionation and separating from the fractionation at least a recycle stream having a T5 temperature of 270° C. or more (recovery 5 vol%, EN ISO 3405-2019) and optionally comprising C16 n-paraffins;

[0021] ii) hydrotreating the reactor B feed comprising the recycle stream in the presence of a hydrotreating catalyst B in reactor B to obtain a hydrotreating effluent B;

[0022] iii) feeding the hydroprocessing effluent B as a co-feed with the hydroprocessing effluent A to a fractionation and recovering at least one or more liquid transportation fuel components from the fractionation; and

[0023] monitoring a parameter indicative of deactivation of hydroprocessing catalyst A to receive a value;

[0024] comparing the received value to a predetermined value; and

[0025] When the received value reaches a predetermined value, switch from i), ii), and iii) to:

[0026] I) subjecting a reactor B feed comprising a hydrocarbon feed to hydrotreatment in the presence of a hydrotreatment catalyst B in a reactor B to obtain a hydrotreatment effluent B, subjecting the hydrotreatment effluent B to fractionation and separating at least a recycle stream from the fractionation, the recycle stream having a T5 temperature of 270° C. or more (recovery 5 vol%, EN ISO 3405-2019) and optionally comprising C16 n-paraffins;

[0027] II) hydrotreating the reactor A feed comprising the recycle stream in the presence of a hydrotreating catalyst A in reactor A to obtain a hydrotreating effluent A;

[0028] III) feeding the hydroprocessing effluent A as a co-feed with the hydroprocessing effluent B to a fractionation and recovering at least one or more liquid transportation fuel components from the fractionation.

[0029] According to a third exemplary aspect, there is provided a method of producing at least one liquid transportation fuel component, the method comprising:

[0030] i) providing a reactor A feed comprising a hydrocarbon feed containing nitrogen impurities, wherein the reactor A feed comprises at least 0.4 w-ppm nitrogen, expressed as elemental nitrogen (ASTM D4629-17), or at least 0.6 w-ppm, or at least 1.0 w-ppm, or even at least 1.5 w-ppm or at least 2.0 w-ppm nitrogen, based on the total weight of the reactor A feed;

[0031] ii) hydrotreating the reactor A feed in the presence of a hydrotreating catalyst A in reactor A to obtain a hydrotreating effluent A, and optionally separating compounds that are gaseous at least at NTP from the hydrotreating effluent A to obtain a degassed hydrotreating effluent A;

[0032] iii) feeding the hydroprocessing effluent A or the degassed hydroprocessing effluent A to fractionation and recovering at least one or more liquid transportation fuel components from the fractionation; and

[0033] monitoring a parameter indicative of deactivation of hydroprocessing catalyst A to receive a value;

[0034] comparing the received value to a predetermined value; and

[0035] When the received value reaches a predetermined value, switch from i), ii), and iii) to:

[0036] I) providing a reactor A feed comprising a hydrocarbon feed, wherein the reactor A feed is substantially free of nitrogen impurities;

[0037] II) hydrotreating the reactor A feed in the presence of a hydrotreating catalyst A in reactor A to obtain a hydrotreating effluent A, and optionally separating compounds that are gaseous at least at NTP from the hydrotreating effluent A to obtain a degassed hydrotreating effluent A;

[0038] III) feeding the hydroprocessing effluent A or the degassed hydroprocessing effluent A to fractionation and recovering at least one or more liquid transportation fuel components from the fractionation.

[0039] In the present disclosure, reference to a method, the present method or any feature thereof should be understood to be considered any method according to the first, second and / or third exemplary aspects, unless it is specifically stated that only certain exemplary aspects are considered, or unless it is obvious from the context that only certain exemplary aspects are considered.

[0040] In certain preferred embodiments, the hydrocarbon feed contains at least 0.4 w-ppm nitrogen impurity, expressed as elemental nitrogen (ASTM D4629-17), or at least 0.6 w-ppm, or at least 1.0 w-ppm, or even at least 1.5 w-ppm or at least 2.0 w-ppm nitrogen impurity, based on the total weight of the hydrocarbon feed.

[0041] In certain embodiments, in steps iii) and III), at least one or more aviation fuel components, diesel fuel components, gasoline fuel components and / or marine fuel components are recovered from the fractionation, preferably at least an aviation fuel component, more preferably at least an aviation fuel component and a diesel fuel component, or at least an aviation fuel component and a gasoline fuel component.

[0042] In certain preferred embodiments, in steps iii) and III), at least an aviation fuel component having a density at 15°C of 730 to 772 kg / m 3 range (EN ISO 12185-1996), T10 temperature not more than 205 °C (EN ISO 3405-2019), final boiling point not more than 300 °C (EN ISO 3405-2019), flash point at least 38 °C (IP 170-2013, Abel closed cup method) and freezing point not more than -40 °C (IP 529-2016).

[0043] Compared with conventional methods for producing fuel components by hydrodeoxygenation (HDO) and hydroisomerization (HI) of renewable fats and oils, the present invention is particularly useful for producing liquid transportation fuel components from a wider range of feeds, including more impure and optionally heavier feeds, especially feeds containing elevated levels of nitrogen impurities. In addition, compared with the conventional methods mentioned above, the method of the present invention can provide an extended process run time or extend the life of the hydrotreating catalyst. The method of the present invention is particularly suitable for producing aviation fuel components. The method of the present invention enables a higher yield of aviation fuel components to be obtained. In addition, compared with the aviation fuel components produced from the same feed by the conventional methods mentioned above, the method of the present invention enables the production of aviation fuel components with improved quality that are available in aviation fuels in an increased amount, or even when appropriately added.

[0044] According to a fourth exemplary aspect, a computer program product is provided that includes instructions, which, when executed by a processor of a control device in a system for producing at least one liquid transportation fuel component, causes the control device to compare a received value with a predetermined value in a method according to the first, second or third exemplary aspect, and when the received value reaches the predetermined value, switch from i), ii), iii) to I), II), III), and optionally switch from I), II), III) back to i), ii), iii). The computer program product can cause the control device to execute the method according to the first, second or third exemplary aspect, performing at least the following steps: compare the received value with a predetermined value; and switch from i), ii), iii) to I), II), III), and optionally switch from I), II), III) back to i), ii), iii).

[0045] To name just a few of the advantages, the computer program product according to the fourth example aspect enables a more accurate operation of the method according to the first, second and / or third example aspects, monitoring of a greater number of different parameters, comparison of the obtained values ​​with massive data sets, use of the obtained values ​​in complex models, faster adjustment and / or switching of the method based on the comparison, improvement or adjustment of the yield and / or quality of the recovered liquid transportation fuel components as required, and enhanced safety of the method of the invention.

[0046] Different non-combined example aspects and implementations have been described above. The above implementations are only used to explain selected aspects or steps that can be used in different implementations. Some implementations are only provided for certain example aspects. It should be understood that the corresponding implementations can also be applied to other example aspects. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Some example embodiments will be described with reference to the accompanying drawings, in which:

[0048] Figure 1 The method according to the example implementation of the first example aspect is schematically shown before switching from i), ii), iii) to I), II), ie before operating according to the example implementation of i), ii), iii) (first mode).

[0049] Figure 2 The method according to the example implementation of the first example aspect is schematically shown after switching from i), ii), iii) to I), II), III), ie after operating according to the example implementation of I), II), III) (second mode).

[0050] Figure 3The method according to the example implementation of the second example aspect is schematically shown before switching from i), ii), iii) to I), II), III), ie before running (first mode) according to the example implementation of i), ii), iii).

[0051] Figure 4 The method according to the example implementation of the second example aspect is schematically shown after switching from i), ii), iii) to I), II), III), ie after running according to the example implementation of I), II), III) (second mode).

[0052] Figure 5 A method according to an example implementation of the third example aspect is schematically illustrated. DETAILED DESCRIPTION

[0053] In the following description, like reference symbols denote like elements or steps.

[0054] Unless otherwise stated, all standards referred to herein are to the latest revision available on the date of submission.

[0055] Unless otherwise stated, for distillation characteristics such as initial boiling point (IBP), final boiling point (FBP), T5 temperature (5 vol% recovery), T95 temperature (95 vol% recovery) and boiling range, reference is made to EN ISO 3405-2019. IBP is the temperature at which the first drop of condensate falls from the lower end of the condenser tube, and FBP is the maximum thermometer reading obtained during the test, which usually occurs after all the liquid at the bottom of the flask has evaporated. For boiling point distribution, reference may also be made to the GC-based method (simdis) ASTM D2887-19e1, or, for gasoline range hydrocarbons, to ASTM D7096-19.

[0056] As used in the context of this disclosure, aviation fuel components refer to hydrocarbon compositions suitable for use in fuel compositions that meet standard specifications for aviation fuels, such as the specifications specified in ASTM D7566-21. Typically, the boiling points of these aviation fuel components, i.e., IBP and FBP, are in the range of about 100°C to about 300°C, such as in the range of about 150°C to about 300°C, as determined according to EN ISO 3405-2019.

[0057] As used in the context of the present disclosure, a diesel fuel component refers to a hydrocarbon composition suitable for use in a fuel composition that meets a standard specification for diesel fuel, such as the specifications specified in EN 590:2022 or EN 15940:2016+A1:2018+AC:2019. Typically, the boiling points, i.e., IBP and FBP, of these diesel fuel components are in the range of about 160°C to about 380°C, as determined according to EN ISO 3405-2019.

[0058] As used in the context of the present disclosure, gasoline fuel components or naphtha refers to hydrocarbon components suitable for use in fuel compositions that meet standard specifications for gasoline fuels, such as the specifications specified in EN 228-2012+A1-2017. Typically, the boiling points of these gasoline fuel components, i.e., IBP and FBP, are in the range of about 25°C to about 210°C, as determined according to EN ISO 3405-2019.

[0059] As used in the context of this disclosure, a bunker fuel component refers to a hydrocarbon component suitable for use in a fuel composition that meets a standard specification for bunker fuels, such as the specification specified in ISO 8217-2017. Typically, the boiling points of these bunker fuel components, i.e., IBP and FBP, are in the range of about 180°C to about 600°C, such as in the range of about 180°C to about 400°C, as determined according to EN ISO 3405-2019.

[0060] As used herein, hydrocarbon refers to a compound consisting of carbon and hydrogen. Hydrocarbons of particular interest in the context of this article include paraffins, n-paraffins, isoparaffins, mono-branched isoparaffins, multi-branched isoparaffins, olefins, cycloalkanes and aromatics. Oxygenated hydrocarbons refer to hydrocarbons comprising covalently bonded oxygen in this article.

[0061] As used herein, paraffin refers to non-cyclic alkanes, i.e., non-cyclic, open-chain saturated hydrocarbons that are straight (n-paraffin) or branched (isoparaffin). In other words, paraffin refers herein to n-paraffin and / or isoparaffin.

[0062] In the context of the present disclosure, isoparaffin refers to branched open-chain alkanes, i.e., non-cyclic, open-chain saturated hydrocarbons with one or more alkyl side chains. In this article, isoparaffins with one alkyl side chain or branch are referred to as monobranched isoparaffins, and isoparaffins with two or more alkyl side chains or branches are referred to as multi-branched isoparaffins in this article. In other words, isoparaffins refer to monobranched isoparaffins and / or multi-branched isoparaffins in this article. For example, the alkyl side chain of isoparaffins can be a C1-C9 alkyl side chain, preferably a methyl side chain. The amount of monobranched and multi-branched isoparaffins can be given respectively. The term "isoparaffin" refers to the total amount of any monobranched isoparaffins and any multi-branched isoparaffins (if present), which represents the total amount of any isoparaffins present without considering the number of branches. Accordingly, "paraffin" refers to the total amount of any normal paraffins, any monobranched isoparaffins, and any multi-branched isoparaffins (if present).

[0063] In the context of the present disclosure, olefin refers to an unsaturated, linear, branched or cyclic hydrocarbon, excluding aromatic hydrocarbons. In other words, olefin refers to a hydrocarbon having at least one unsaturated bond, excluding unsaturated bonds in aromatic rings.

[0064] As used herein, cyclic hydrocarbons refer to all hydrocarbons containing a ring structure, including cycloolefins, cycloalkanes, and aromatic hydrocarbons. Cycloalkanes (naphthenes) herein refer to cycloalkanes, i.e., saturated hydrocarbons containing at least one ring structure with or without side chains. Since cycloalkanes are saturated compounds, they are compounds without aromatic ring structures. Aromatic hydrocarbons herein refer to hydrocarbons containing at least one aromatic ring structure, i.e., a ring structure with delocalized alternating π bonds around the ring structure.

[0065] In the context of the present disclosure, for compositions boiling at or above 36°C (at standard atmospheric pressure), the content of n-paraffins, isoparaffins, mono-branched isoparaffins, multiple multi-branched isoparaffins, cycloparaffins and aromatics is expressed as weight % (wt %) relative to the degassed weight of the feed, stream, effluent, product, component or sample in question, or, when so defined, as weight % (wt %) relative to the (total) weight of paraffins or the (total) weight of isoparaffins of the feed, stream, effluent, product, component or sample in question. The content can be determined by a GC×GC-FID / GC×GC-MS method, preferably performed as follows: a GC×GC (2D GC) method as generally disclosed in UOP 990-2011 and Nousiainen M. in his master's thesis Comprehensive two-dimensional gas chromatography with mass spectrometric and flame ionization detectors in petroleum chemistry, University of Helsinki, August 2017, with the following modifications. The GC×GC was operated in reverse mode, first using a semipolar column (Rxi17Sil) and then a nonpolar column (Rxi5Sil), followed by a FID detector, using the following operating parameters: carrier gas: helium 31.7 cm / sec (column flow 1.60 ml / min at 40°C); split ratio: 1:350; injector: 280°C; column T program: 40°C (0 min) -5°C / min -250°C (0 min) -10°C / min -300°C (5 min), run time: 52 min; modulation period: 10 s; detector: 300°C, using H2 40 ml / min and air 400 ml / min; makeup gas flow: helium 30 ml / min; sampling rate: 250 Hz, and injection volume: 0.2 μL. Individual compounds were identified using GC×GC-MS, with MS parameters: ion source: 230°C; interface: 300°C; scan range: 25-500 amu; event time (seconds): 0.05; scan speed: 20000. Data processing was performed using commercial tools (Shimadzu's LabSolutions, Zoex's GC Image), including identification of the detected compounds or hydrocarbon groups and determination of their mass concentrations by applying a response factor relative to n-heptane to the volume of the detected peaks and then normalizing to 100 wt%. Unless reported separately, olefins were classified as cycloalkanes and heteroatom-containing substances were classified as aromatics. The quantification limit for individual compounds of this method was 0.1 wt%.

[0066] In the context of the present disclosure, various characteristics of a feed, stream, effluent, product, component or sample are determined according to appropriately prepared standard methods mentioned or disclosed herein. For example, the cloud point is determined from a degassed feed, stream, effluent, product, component or sample according to ASTM D 5771-17.

[0067] Typically, the various hydrocarbon feeds, streams, effluents and fuel components referred to herein as recovered products or fractions thereof may contain, in addition to hydrocarbons, varying trace amounts of, for example, heteroatom-containing hydrocarbons and inorganic compounds as impurities, and the oxygenated hydrocarbon feeds contain varying amounts of, for example, other heteroatom-containing hydrocarbons and inorganic compounds as impurities. Typically, the impurity levels in the main process streams are highest in the first part of the process and subsequently decrease to negligible or even below the detection limit of the recovered liquid transportation fuel component.

[0068] As used herein, the term hydroprocessing refers to a process in the presence of added molecular hydrogen and a solid hydroprocessing catalyst. Typically, the solid hydroprocessing catalyst is selective for the desired reaction under the prevailing reaction conditions. The term hydroprocessing herein includes processes that consume hydrogen, but also processes that do not involve large amounts of hydrogen consumption. Examples of hydroprocessing include hydroisomerization, hydrocracking, hydrodearomatization, and hydrofining, and may include a variety of reactions such as isomerization, cracking, (de)hydrogenation, desulfurization, denitrogenation, deoxygenation, etc., based on the feed composition and impurity species, the selected catalyst, and the reaction conditions.

[0069] Isomerization converts at least a certain amount of normal paraffins into isoparaffins, especially into mono-branched isoparaffins. By (further) increasing the degree of isomerization, for example by increasing the severity of hydroisomerization as described below, more normal paraffins can be converted into isoparaffins, and mono-branched isoparaffins can be converted into multi-branched isoparaffins, such as di-branched and / or tri-branched isoparaffins, even isoparaffins containing more than three branches. As used herein, and particularly in the context of an embodiment in which the hydrotreatment in reactor A and / or B is hydrocracking, the effective cracking degree refers to the cracking of obtaining non-gaseous (NTP) cracking products, and is particularly expressed herein as the ratio of the C8 to C14 hydrocarbon content in the effluent of each reactor to the C8 to C14 hydrocarbon content in the feed of each reactor.

[0070] As used herein, whether a reaction step is defined as occurring in a "reactor", such as reactor A and / or reactor B, the expression is primarily for illustrative purposes. Those skilled in the art recognize that any "reactor" is implemented in practice as a reactor system that can be composed of one or more reactors. Whether the reactor is actually arranged in a single reactor or in several reactors is an engineering issue and may be affected by practical issues such as the maximum height of the field facility, the reactor diameter, the management and maintenance issues at the site, the wind conditions at the site, and / or the available equipment. Similarly, "fractionation" can be carried out in a fractionation system, which typically includes (for example) separation and distillation units, which can be arranged according to conventional engineering practices in the art.

[0071] In the context of the present disclosure, catalyst characteristics, such as the total number of acid sites, refer to the characteristics of the catalyst in its ready-to-use state at the start of the process of the present invention.

[0072] As used herein, the term catalyst deactivation refers to the change in the activity and / or selectivity of the catalyst at a given time point (t0) compared to the activity and / or selectivity of the catalyst at the start of the process (t0). n The term catalyst deactivation is used herein to deactivate the catalyst, which is a decrease in catalyst activity (reflected by an increase in the amount of unconverted feed in the reactor effluent) and / or a decrease in catalyst selectivity (reflected by a decrease in the amount of the desired reaction product in the reactor effluent). As used herein, the term catalyst deactivation is not limited to any particular type or mechanism of deactivation, although catalyst deactivation observed in the process of the present invention is generally believed to be due to poisoning and fouling phenomena, and encompasses both reversible and irreversible deactivation. However, since the process of the present invention uses a hydrocarbon feed containing at least nitrogen impurities, the term catalyst deactivation encompasses at least reversible deactivation herein.

[0073] In the context of the present disclosure, the feed to a reactor, in particular to reactor A and / or reactor B, is defined such that H2 that may be fed to the respective reactor, e.g. H2 fed to a hydroprocessing, is not included in the definition of the feed.

[0074] As used herein, the term renewable refers to a compound or composition that is obtainable, derivable or sourced from plants and / or animals in whole or in part, including a compound or composition that is obtainable, derivable or sourced from fungi and / or algae. As used herein, renewable compounds or compositions may include genetically manipulated compounds or compositions. Renewable feed, component, compound or composition may also be referred to as biofeed, component, compound or composition, or as biogenic feed, component, compound or composition.

[0075] As used herein, the term fossil refers to a compound or composition obtainable, derivable or sourced from a naturally occurring non-renewable composition, such as crude oil, petroleum / petroleum gas, shale oil / shale gas, natural gas or coal deposits, and the like, and combinations thereof, including any hydrocarbon-rich deposits that can be utilized from above-ground / underground sources.

[0076] The term "recycled" refers to recycled materials that are usually derived from non-renewable energy sources. For example, the term "recycled" may refer to recycled materials derived from waste plastics. Based on their sources and impact on environmental issues, the renewable, recycled and fossil compounds or compositions are considered to be different from each other. Therefore, they may be treated differently under regulations and regulatory frameworks. Typically, renewable, recycled and fossil compounds or compositions are distinguished based on their sources and information provided by the producers.

[0077] Chemically, the carbon content of any organic compound, including hydrocarbons of renewable or fossil origin, can be determined by appropriate methods for analyzing the carbon content of renewable origin, for example, DIN 51637 (2014), ASTM D6866 (2020) or EN 16640 (2017). The methods are based on the fact that carbon atoms of renewable or biological origin contain a higher number of unstable radiocarbons ( 14 C) atoms. Therefore, it is possible to analyze 12 C and 14 C isotope ratios are used to distinguish carbon compounds derived from renewable or biological sources or raw materials from carbon compounds derived from non-renewable or fossil sources or raw materials. Therefore, the specific ratio of the isotopes can be used as a "tag" to identify renewable carbon compounds and distinguish them from non-renewable carbon compounds. The isotope ratio does not change during the chemical reaction. Therefore, the isotope ratio can be used to identify renewable compounds, components and compositions and distinguish them from non-renewable, fossil materials in reactor feeds, reactor effluents, separated product fractions and various blends thereof. Numerically, the biochar content can be expressed as the amount of biochar in the material as a weight percentage of the total carbon (TC) in the material (according to ASTM D6866 (2020) or EN 16640 (2017)). In the context of the present invention, the term renewable preferably refers to a material having a biocarbon content of greater than 50 wt%, in particular greater than 60 wt% or greater than 70 wt%, preferably greater than 80 wt%, more preferably greater than 90 wt% or greater than 95 wt%, even more preferably about 100 wt%, based on the total weight of carbon in the material (EN 16640 (2017)).

[0078] According to a first exemplary aspect, provided herein is a method of producing at least one liquid transportation fuel component, the method comprising:

[0079] providing a hydrocarbon feed comprising nitrogen impurities;

[0080] i) subjecting a reactor A feed comprising a hydrocarbon feed to hydrotreating in reactor A in the presence of a hydrotreating catalyst A to obtain a hydrotreating effluent A, and separating compounds that are gaseous at least at NTP from the hydrotreating effluent A to obtain a degassed hydrotreating effluent A;

[0081] ii) hydrotreating a reactor B feed comprising degassed hydroprocessing effluent A in reactor B in the presence of a hydroprocessing catalyst B to obtain hydroprocessing effluent B;

[0082] iii) feeding the hydroprocessing effluent B to a fractionation, optionally after separation of at least the compounds that are gaseous at NTP from the hydroprocessing effluent B, and recovering at least one or more liquid transportation fuel components from the fractionation; and

[0083] monitoring a parameter indicative of deactivation of hydroprocessing catalyst A to receive a value;

[0084] comparing the received value to a predetermined value; and

[0085] When the received value reaches a predetermined value, switch from i), ii), and iii) to:

[0086] I) subjecting a reactor B feed comprising a hydrocarbon feed to hydroprocessing in the presence of a hydroprocessing catalyst B in a reactor B to obtain a hydroprocessing effluent B, and separating compounds that are gaseous at least at NTP from the hydroprocessing effluent B to obtain a degassed hydroprocessing effluent B;

[0087] II) hydrotreating a reactor A feed comprising degassed hydroprocessing effluent B in the presence of a hydroprocessing catalyst A in reactor A to obtain hydroprocessing effluent A;

[0088] III) feeding the hydroprocessing effluent A to a fractionation, optionally after separation of at least the compounds that are gaseous at NTP from the hydroprocessing effluent A, and recovering at least one or more liquid transportation fuel components from the fractionation.

[0089] According to a second exemplary aspect, provided herein is a method of producing at least one liquid transportation fuel component, the method comprising:

[0090] providing a hydrocarbon feed comprising nitrogen impurities;

[0091] i) subjecting a reactor A feed comprising a hydrocarbon feed to hydrotreating in reactor A in the presence of a hydrotreating catalyst A to obtain a hydrotreating effluent A, subjecting the hydrotreating effluent A to fractionation and separating from the fractionation at least a recycle stream having a T5 temperature of 270° C. or more (recovery 5 vol%, EN ISO 3405-2019) and optionally comprising C16 n-paraffins;

[0092] ii) hydrotreating the reactor B feed comprising the recycle stream in the presence of a hydrotreating catalyst B in reactor B to obtain a hydrotreating effluent B;

[0093] iii) feeding the hydroprocessing effluent B as a co-feed with the hydroprocessing effluent A to a fractionation and recovering at least one or more liquid transportation fuel components from the fractionation; and

[0094] monitoring a parameter indicative of deactivation of hydroprocessing catalyst A to receive a value;

[0095] comparing the received value to a predetermined value; and

[0096] When the received value reaches a predetermined value, switch from i), ii), and iii) to:

[0097] I) subjecting a reactor B feed comprising a hydrocarbon feed to hydrotreatment in reactor B in the presence of a hydrotreatment catalyst B to obtain a hydrotreatment effluent B, subjecting the hydrotreatment effluent B to fractionation and separating from the fractionation at least a recycle stream having a T5 temperature of 270° C. or more (recovery 5 vol%, EN ISO 3405-2019) and optionally comprising C16 n-paraffins;

[0098] II) hydrotreating the reactor A feed comprising the recycle stream in the presence of a hydrotreating catalyst A in reactor A to obtain a hydrotreating effluent A;

[0099] III) feeding the hydroprocessing effluent A as a co-feed with the hydroprocessing effluent B to a fractionation and recovering at least one or more liquid transportation fuel components from the fractionation.

[0100] According to a third exemplary aspect, provided herein is a method of producing at least one liquid transportation fuel component, the method comprising:

[0101] i) providing a reactor A feed comprising a hydrocarbon feed containing nitrogen impurities, wherein the reactor A feed comprises at least 0.4 w-ppm nitrogen, expressed as elemental nitrogen (ASTM D4629-17), or at least 0.6 w-ppm, or at least 1.0 w-ppm, or even at least 1.5 w-ppm or at least 2.0 w-ppm nitrogen, based on the total weight of the reactor A feed;

[0102] ii) hydrotreating the reactor A feed in the presence of a hydrotreating catalyst A in reactor A to obtain a hydrotreating effluent A, and optionally separating compounds that are gaseous at least at NTP from the hydrotreating effluent A to obtain a degassed hydrotreating effluent A;

[0103] iii) feeding the hydroprocessing effluent A or the degassed hydroprocessing effluent A to fractionation and recovering at least one or more liquid transportation fuel components from the fractionation; and

[0104] monitoring a parameter indicative of deactivation of hydroprocessing catalyst A to receive a value;

[0105] comparing the received value to a predetermined value; and

[0106] When the received value reaches a predetermined value, switch from i), ii), and iii) to:

[0107] I) providing a reactor A feed comprising a hydrocarbon feed, wherein the reactor A feed is substantially free of nitrogen impurities;

[0108] II) hydrotreating the reactor A feed in the presence of a hydrotreating catalyst A in reactor A to obtain a hydrotreating effluent A, and optionally separating compounds that are gaseous at least at NTP from the hydrotreating effluent A to obtain a degassed hydrotreating effluent A;

[0109] III) feeding the hydroprocessing effluent A or the degassed hydroprocessing effluent A to fractionation and recovering at least one or more liquid transportation fuel components from the fractionation.

[0110] Preferably, the process of the invention according to the first, second and third exemplary aspects is a continuous process.

[0111] The method operating according to steps i), ii), iii) may be referred to as an initial / first mode of the method / operation, whereas the method operating according to steps I), II), III) may be referred to as a switching / second mode of the method / operation.

[0112] During continuous operation of catalytic hydroprocessing, the hydroprocessing catalyst gradually deactivates due to, for example, impurities and coking in the process stream. Catalyst deactivation can be of a reversible or irreversible nature. A typical example of reversible deactivation is the deactivation of the acid sites of the catalyst by nitrogen impurities in the feed. Although the effects can be severe, they are temporary and can usually be eliminated within hours to days, or sometimes within weeks, after the nitrogen source is removed from the feed.

[0113] Nitrogen is a typical impurity in hydrocarbon feeds obtained, for example, by subjecting an oxygenated hydrocarbon feed to catalytic hydrodeoxygenation (HDO). This can be due to the evolution of nitrogen in the oxygenated hydrocarbon feed by the catalytic HDO step, whether it is caused by a particularly high nitrogen content in the feed or a reduction in the activity and efficiency of the (HDO) catalyst in cleaving heteroatoms, which may occur particularly at the end of a run. Other examples of reversibly bound impurities may include some carbon impurities, such as coke, in particular soft coke.

[0114] In the first operating mode, the hydroprocessing catalyst A is subjected to most of the impurities in the hydrocarbon feed, and in multiple embodiments, to all impurities. Switching the method from i), ii), iii) to I), II), III), i.e., switching from the first method mode to the second method mode, results in a stream fed to the hydroprocessing reactor A that is purer (containing less nitrogen impurities) than the hydrocarbon feed fed to it in the first mode. Since the deactivation of the hydroprocessing catalyst A that occurs in the first mode of the method of the present invention is caused at least by the nitrogen impurities present in the hydrocarbon feed, the purer stream fed to the hydroprocessing reactor A in the second mode helps to flush the hydroprocessing catalyst A and release the reversibly bound impurities therefrom, thereby reversing the deactivation at least to some extent. In other words, in this way, the reversibly bound nitrogen can be flushed from the hydroprocessing catalyst A and its deactivation can be at least partially reversed. Nitrogen is released from the hydroprocessing catalyst A as NH3, which is then separated from the hydroprocessing effluent A by degassing or fractionation. The release of nitrogen from the hydroprocessing catalyst A can be enhanced by operating the reactor A at high pressure and / or high temperature.

[0115] In the methods according to the first and second exemplary aspects, in the first operating mode, the hydroprocessing catalyst B in the reactor B is protected by the cleaning effect of the hydroprocessing catalyst A in the reactor A located upstream, so that the deactivation of the hydroprocessing catalyst B is expected to be slower than that of the hydroprocessing catalyst A in the reactor A. The cleaning effect of the catalyst A includes the conversion of impurities into compounds that are gaseous at NTP, in particular the conversion of nitrogen impurities into NH3, and to a lesser extent the binding or deposition of impurities on the hydroprocessing catalyst A. Separating or removing compounds that are gaseous at NTP from the hydroprocessing effluent A removes the converted impurities from the process stream and thus from the reactor B feed (and vice versa in the second operating mode). In a first exemplary aspect, feeding a purer stream to reactor A in a second operating mode is achieved by feeding the hydrocarbon feed to reactor B and, after separation of compounds that are gaseous at NTP, feeding hydroprocessing effluent B to reactor A, i.e., in a sense, changing the order of reactors A and B in the process so that the hydroprocessing catalyst A in reactor A is protected by the cleaning effect of hydroprocessing catalyst B in reactor B, which is now located upstream. In a second exemplary aspect, feeding a purer stream to reactor A in a second mode is similarly achieved by changing the order of reactors A and B in a sense so that the hydrocarbon feed is fed to reactor B and a recycle stream comprising a portion of hydroprocessing effluent B is fed to reactor A. Thus, typically in the first operating mode, reactor A is located upstream of reactor B, while in the second operating mode, reactor B is located upstream of reactor A.

[0116] In a third example aspect, feeding a purer stream to reactor A in the second operating mode is achieved by providing a reactor A feed that is substantially free of nitrogen impurities, for example, by providing a purer hydrocarbon feed (a hydrocarbon feed having less or substantially no nitrogen impurities) and / or by diluting the hydrocarbon feed.

[0117] In the present disclosure, an objective is to improve overall process efficiency by extending the run time of the process, or extending the life of the hydroprocessing catalyst, and / or making the impurity content in the feed to the process higher. In this way, the raw materials can be subjected to less laborious and / or severe pretreatment methods, and the source has greater flexibility in terms of quality. Furthermore, as an additional or alternative objective, embodiments using hydrocarbon feeds obtained by subjecting an oxygenated hydrocarbon feed to HDO allow the catalytic HDO to run longer before changing the HDO catalyst, and thus deactivate the HDO catalyst more than conventionally.

[0118] Thus, in certain preferred embodiments of the methods according to the first and second exemplary aspects, and in certain preferred embodiments of the first method mode according to the third exemplary aspect, the hydrocarbon feed contains nitrogen impurities and contains at least 0.4 w-ppm of nitrogen, expressed as elemental nitrogen (ASTM D4629-17), or at least 0.6 w-ppm, or at least 1.0 w-ppm, or even at least 1.5 w-ppm or at least 2.0 w-ppm of nitrogen, based on the total weight of the hydrocarbon feed. The method of the present invention is particularly suitable for treating hydrocarbon feeds having a high or increased nitrogen content. Preferably, the hydrocarbon feed contains up to 40.0 w-ppm of nitrogen, expressed as elemental nitrogen (ASTM D4629-17). An increase in the amount of nitrogen in the hydrocarbon feed generally accelerates catalyst deactivation. As mentioned above, the deactivation of catalyst acid sites by nitrogen impurities is a reversible deactivation, which can be reversed, at least to some extent, by switching the mode of the method of the present invention.

[0119] When the method according to the third exemplary aspect is operated in the second mode, the reactor A feed is substantially free of nitrogen impurities, i.e. a reactor A feed substantially free of nitrogen impurities is provided. Preferably, this means that the reactor A feed comprises in the second mode at most 0.3 w-ppm, more preferably less than 0.3 w-ppm of nitrogen, expressed as elemental nitrogen (ASTM D4629-17), based on the total weight of the reactor A feed. In the method according to the third exemplary aspect, this is preferably achieved by a hydrocarbon feed comprising at most 0.3 w-ppm, more preferably less than 0.3 w-ppm of nitrogen, expressed as elemental nitrogen (ASTM D4629-17), based on the total weight of the hydrocarbon feed.

[0120] At least one or more liquid transportation fuel components recovered from the fractionation may be one or more of an aviation fuel component, a diesel fuel component, a gasoline fuel component and / or a marine fuel component. Preferably, at least an aviation fuel component is recovered, more preferably at least an aviation fuel component and a diesel fuel component are recovered, or at least an aviation fuel component and a gasoline fuel component are recovered.

[0121] Compared to conventional methods for producing fuel components, for example, by hydrodeoxygenation (HDO) and hydroisomerization (HI) of renewable fats and oils, by the method of the present invention, it is possible to obtain a higher yield of liquid transportation fuel components, in particular aviation fuel components, over the entire process operating time or the life of the hydroprocessing catalyst A without reducing the capacity of the hydroprocessing in the reactor A, and / or it is possible to improve the quality of the aviation fuel component.

[0122] Using the process of the invention, even near the end of a run, it may be possible to produce an aviation fuel component that has excellent low temperature properties and is therefore usable in aviation fuel at high blending ratios or even by itself (i.e., unblended) when properly added. In addition, the process of the invention enables extended hydroprocessing catalyst life and the use of a wider range of feeds, including more impure and even heavier feeds, compared to conventional processes for producing fuel components from HDO and HI of renewable fats and oils.

[0123] Furthermore, even near the end of a run, the inventive process enables flexible adjustment of product selectivity for a variety of liquid transportation fuel components, such as gasoline fuel components, aviation fuel components, diesel fuel components, and / or bunker fuel components, based on, for example, market dynamics.

[0124] The process of the invention is highly flexible and includes a variety of possibilities for adjusting the yield and / or quality of the liquid transportation fuel components recovered, and for extending the process operating time or the life of the hydroprocessing catalyst, in particular the life of the hydroprocessing catalyst A. The various possibilities of the process of the invention for compensating for the deactivation of the hydroprocessing catalyst enable the use of hydrocarbon feeds with a higher impurity content than conventional processes for the production of liquid fuel components by HDO and HI of renewable fats and oils. In addition, when using hydrocarbon feeds obtained by subjecting oxygenated hydrocarbon feeds to catalytic hydrodeoxygenation (HDO), the process of the invention can tolerate some nitrogen evolution through the HDO step, as may occur in particular near the end of the life of the HDO catalyst, and thus the HDO can be operated for a longer time than conventional processes in which, for example, the HDO is followed by HI.

[0125] The method of the present invention includes monitoring a parameter indicative of deactivation of a hydroprocessing catalyst A to receive a value; comparing the received value with a predetermined value; and when the received value reaches or is equal to the predetermined value, switching from i), ii), iii) to I), II), III), i.e., switching from the first method mode to the second method mode. Preferably, the received value is compared with the corresponding predetermined value. Switching from i), ii), iii) to I), II), III) can compensate for the deactivation of the hydroprocessing catalyst (especially the deactivation of the hydroprocessing catalyst A), thereby allowing the recovered at least one liquid transportation fuel component to maintain good yield and quality for a longer time before the hydroprocessing catalyst A needs to be changed or regenerated. In addition, switching from i), ii), iii) to I), II), III) results in feeding a purer stream to the hydroprocessing reactor A than the hydrocarbon feed fed thereto in the first mode, which flushes the hydroprocessing catalyst A, thereby releasing reversibly bound impurities therefrom at least to some extent, i.e., in a sense, results in at least some degree of regeneration of the hydroprocessing catalyst A. Initially, at the beginning of the process operation, the activity of the hydroprocessing catalyst A is usually good or sufficient, and the value received from the monitoring is not equal to the (corresponding) predetermined value. However, at some point during the process operation, the deactivation of the hydroprocessing catalyst A usually reaches a point when the value received from the monitoring reaches the (corresponding) predetermined value, which has been identified as indicating that the performance of the hydroprocessing catalyst A is insufficient or close to insufficient, for example, in terms of the volume (yield) and / or composition and / or physicochemical characteristics of the recovered liquid transportation fuel components. At this point, when the value received from the monitoring reaches the (corresponding) predetermined value, a switch from i), ii), iii) to I), II), III) is usually performed in order to restore and preferably even exceed the target minimum value of the process performance. By switching from i), ii), iii) to I), II), III), the process can be operated for a longer time, thereby producing the desired liquid transportation fuel components in the desired amount and / or the desired quality. Optionally, the method of the present invention may include, while operating according to I), II), III), monitoring a parameter indicative of a reversal of deactivation of the hydroprocessing catalyst A to receive a value, comparing the received value to a predetermined value, and optionally switching from I), II), III) back to i), ii), iii) when the received value reaches a predetermined value. For example, the method may switch from I), II), III) back to i), ii), iii) when sufficient reversal of deactivation of the hydroprocessing catalyst A has been achieved.

[0126] When the process of the present invention is run, reactors A and / or B are typically not bypassed. Typically, the process of the present invention, which includes at least one switch from i), ii), iii) to I), II), III), is run without replacing the hydroprocessing catalyst A and / or the hydroprocessing catalyst B, or without bypassing reactors A and / or B to regenerate the catalyst therein. In other words, reactors A and B are typically kept in operation, i.e., fluidly connected to each other throughout the process run, including during and / or before the switch. Similarly, in the third exemplary aspect, during the process run, the feed to reactor A is typically not interrupted.

[0127] In certain embodiments, in addition to switching from the first mode to the second mode, the method of the present invention may include adjusting one or more operating conditions of reactor A and / or reactor B to achieve, maintain or even exceed the target minimum value of the method performance. In these embodiments, the switch from the first mode to the second mode can be performed at some point after the operating conditions of reactor A and / or reactor B have been adjusted in one or more cases. The operating conditions can be adjusted to their feasible limits and then the switch is performed, or alternatively, the operating conditions can be adjusted to a certain extent and the switch is performed before the limit is reached. The adjustment of one or more operating conditions can be based on the same or different parameters as the switch from i), ii), iii) to I), II), III). Preferably, the reactor A and / or reactor B, in particular one or more operating conditions of reactor A, are first adjusted to compensate for catalyst deactivation, and when it is no longer feasible (or no longer necessary) to compensate for catalyst deactivation by adjusting the operating conditions in reactor A and / or reactor B alone, the switch from i), ii), iii) to I), II), III) is performed. In certain embodiments, after switching from i), ii), iii) to i), II), III), when the switch is substantially complete, the operating conditions of reactor A may be mitigated, and thus the target yield and / or quality of the recovered fuel component may be achieved, for example, at a lower temperature and / or higher WHSV in reactor A than before the switch. In these embodiments, after the switch, it may be beneficial to increase the temperature in reactor B to compensate for the generally increased WHSV therein. During the second operating mode, one or more operating conditions of reactor A and / or reactor B may be (again) adjusted to compensate for further catalyst deactivation, in particular deactivation of the hydroprocessing catalyst A in reactor A.

[0128] When the process has been run for a sufficiently long time and switched between modes, at least from the first mode to the second mode, and the operating conditions in reactor A and / or reactor B have optionally been adjusted to their feasible extremes, the target performance of the process, for example in terms of yield and / or composition and / or physicochemical characteristics of the recovered liquid transport fuel components, can no longer be achieved due to the extent of catalyst deactivation. The catalyst is then usually replaced with a fresh catalyst or regenerated before optionally starting to operate the process in the first mode (starting a new process movement), i.e., operating sequence i), ii), iii), which in the process of the invention usually represents the end of the process run.

[0129] In certain embodiments, the process does not include adjusting the operating conditions to compensate for catalyst deactivation, i.e., is carried out without adjustment, and compensates for the deactivation of the catalyst in reactor A by switching from i), ii), iii) to I), II), III) and optionally switching from I), II), III) back to i), ii), iii). In these embodiments, the total feasible operating time of the process may be shorter than in embodiments in which, in addition to switching between modes, the operating conditions of at least reactor A are adjusted.

[0130] In certain preferred embodiments, the method includes monitoring a parameter indicating reversal of deactivation of hydroprocessing catalyst A to receive a value when operating I), II), III), i.e., operating the method in the second mode, wherein the parameter indicating reversal of deactivation of hydroprocessing catalyst A preferably includes at least two or more parameters selected from items a. to i. as defined below; comparing the received value with a (corresponding) predetermined value; and switching from I), II), III) back to i), ii), iii) when the received value reaches the (corresponding) predetermined value. When monitoring the parameter indicating reversal of deactivation of hydroprocessing catalyst A, the predetermined value may be different from the predetermined value when monitoring deactivation of hydroprocessing catalyst A, although the parameter indicating deactivation of hydroprocessing catalyst A and the parameter indicating reversal of deactivation of hydroprocessing catalyst A may be the same.

[0131] These variants of the process of the invention may include adjusting the operating conditions in reactor A and / or reactor B to compensate for catalyst deactivation after switching from i), II), III) back to i), ii), iii). In addition, the operating conditions may be adjusted to their feasible limits and then switched from i), ii), iii) to I), II), III), or alternatively, the operating conditions may be adjusted to a certain extent and the switch from i), ii), iii) to I), II), III) may be performed before reaching the extreme values.

[0132] An example sequence for applying these variants includes operating the process in a first mode and adjusting the operating conditions of reactor A and / or reactor B up to the feasible limits; thereafter, switching to a second mode and adjusting the operating conditions of reactor A and / or reactor B up to the feasible limits; then switching back, i.e. switching from i), II), III) to i), ii), iii) and operating until the target performance of the process is no longer met despite adjusting the operating conditions, and then switching from i), ii), iii) to i), II), III) and operating until the target performance of the process is no longer met despite adjusting the operating conditions, which results in regeneration or modification of the catalyst.

[0133] The first and second operating modes, combined with appropriate temperatures and other operating conditions in reactor A and reactor B (when applicable), provide the possibility of flexibly adjusting the process to meet and even optimize the target yields and / or qualities of the various recovered components. In the process of the present invention, according to the third exemplary aspect, the operating conditions of reactor A can be adjusted as described above.

[0134] In certain preferred embodiments, when operating i), ii), iii), a portion of the hydrocarbon feed is fed to reactor B for hydrotreatment as a portion of the feed to reactor B; and / or when operating i), II), III), a portion of the hydrocarbon feed is fed to reactor A for hydrotreatment as a portion of the feed to reactor A. In these embodiments, for example, the portion can be obtained by simply splitting the hydrocarbon feed between reactor A and reactor B using, for example, a fixed or preferably gradually adjusted ratio. These embodiments provide further flexibility in the operation of the process of the present invention and provide the possibility of even more precisely adjusting the process to meet the target yield and quality of more than one recovered component at the same time. In this way, it may be possible to avoid a situation in which the target yield and quality of one recovered fuel component is met, but at the expense of producing an excessively high quality of another recovered fuel component (e.g., producing a diesel fuel component with an unnecessarily low cloud point). It may also be beneficial to split the hydrocarbon feed when switching the process from i), ii), iii) to I), II), III) or vice versa, thereby providing a smooth transition between modes.

[0135] In these embodiments, the amount of the portion of the hydrocarbon feed fed to reactor B in the first mode or to reactor A in the second mode may vary, but is typically only a small portion (outside of the switch). For example, the portion of the hydrocarbon feed optionally fed to reactor B in the first mode or to reactor A in the second mode may be less than 50 wt%, preferably less than 30 wt%, and more preferably less than 10 wt% of the total weight of the hydrocarbon feed.

[0136] In certain preferred embodiments of the method according to the first exemplary aspect, the switching includes, when operating i), ii), iii), feeding a gradually decreasing hydrocarbon feed portion and a gradually increasing portion of the degassed hydroprocessing effluent B as part of the reactor A feed to reactor A, and simultaneously feeding a gradually increasing portion of the hydrocarbon feed and a gradually decreasing portion of the degassed hydroprocessing effluent A as part of the reactor B feed to reactor B, until the method is operated according to I), II), III). In certain preferred embodiments of the method according to the second exemplary aspect, the switching includes, when operating i), ii), iii), feeding a gradually decreasing hydrocarbon feed portion and a gradually increasing portion of the recycle stream as part of the reactor A feed to reactor A, and simultaneously feeding a gradually increasing portion of the hydrocarbon feed and a gradually decreasing portion of the recycle stream as part of the reactor B feed to reactor B, until the method is operated according to I), II), III).

[0137] In the process of the present invention, parameters indicative of deactivation of hydroprocessing catalyst A are monitored to receive values, and in addition to the initiation of any switch, comparison of the received values ​​with predetermined values ​​can be used to select appropriate adjustments to operating conditions in reactor A and optionally other process units.

[0138] The parameters indicating the deactivation of the hydroprocessing catalyst A can be freely selected, but preferably at least two monitored parameters belong to one or more of the following items a, b, c, d, e, f, g, h and / or i. For example, two parameters can be selected from one item, and more parameters can be selected from other items, or one parameter can be selected from one item and at least one parameter can be selected from other items. Therefore, in certain preferred embodiments, the parameters indicating the deactivation of the hydroprocessing catalyst A include at least two or more of the following parameters:

[0139] a. The content of nitrogen impurities in the reactor A feed or hydrocarbon feed (evaluated as elemental nitrogen), and optionally the content of at least one or more other impurities selected from S, O, P, Si, Cl, Fe, alkali metals, alkaline earth metals and / or coke-forming compounds in the reactor A feed or hydrocarbon feed; all of the substances or impurities are known catalyst deactivators, in particular deactivators of non-sulfided bifunctional hydroprocessing catalysts containing precious metals. In addition, the substances or impurities are usually present in feeds derived from vegetable oils, animal fats, microbial oils, organic wastes and residues from thermal liquefaction and / or enzymatic liquefaction in varying amounts, as well as in feeds derived from the Fischer-Tropsch process, and therefore can be brought into and present in hydrocarbon feeds in varying amounts in certain embodiments. Typically, elemental impurities themselves are not present in hydrocarbon feeds, but their content indicates the presence of compounds containing them. Elemental impurities and coke-forming compounds are determined by standard laboratory analysis. An increase in the content of any of these impurities may result in an increase in catalyst deactivation.

[0140] b. The content of NH3 and optionally H2S in the gas phase of the hydroprocessing effluent A; Generally, an increase in the content of (for example) NH3 in the gas phase of the hydroprocessing effluent indicates an increase in the exposure of the catalyst to nitrogen impurities and thus may be an indication of increased catalyst deactivation. Similarly, an increase in the content of H2S in the gas phase of the hydroprocessing effluent indicates an increase in the exposure of the catalyst to sulfur and may be an indication of increased catalyst deactivation.

[0141] c. Physical and chemical characteristics of the degassed hydroprocessing effluent A, preferably at least one or more of cloud point, freezing point, pour point, cold filter plugging point, kinematic viscosity, density and / or distillation characteristics; an increase in any of cloud point, freezing point, pour point, cold filter plugging point, kinematic viscosity and / or density can indicate an increase in catalyst deactivation. Distillation characteristics, where an increase can indicate catalyst deactivation, include T5, T50, FBP, etc. As for other distillation characteristics, a change in the boiling point distribution to higher boiling point compounds can indicate catalyst deactivation.

[0142] d. Compositional characteristics of the degassed hydroprocessing effluent A, preferably at least one or more of the isoparaffin content, C8-C14 hydrocarbon content, multi-branched isoparaffin content and / or C1-C4 hydrocarbon content in the degassed hydroprocessing effluent A; a decrease in the isoparaffin content, multi-branched isoparaffin content and / or C8-C14 hydrocarbon content may indicate an increase in catalyst deactivation. The content of C1-C4 hydrocarbons may decrease with increasing catalyst deactivation. However, increasing the operating temperature to compensate for catalyst deactivation may result in an increase in the content of C1-C4 hydrocarbons.

[0143] e. The yield of at least one or more of the recovered liquid transportation fuel components and / or the separated recycle stream, preferably the yield of aviation fuel components; increased yields of high boiling hydrocarbons and increased volumes of recovered recycle streams may indicate increased catalyst deactivation.

[0144] f. At least one or more physicochemical characteristics of the recovered liquid transportation fuel component and / or the separated recycle stream, preferably at least one or more of cloud point, freezing point, pour point, cold filter plugging point, kinematic viscosity, density, research octane number (RON), cetane number and / or distillation characteristics; a decrease in cetane may indicate an increase in catalyst deactivation. In the distillation characteristics, for example, an increase in T5, T50, T95, FBP, etc. may indicate catalyst deactivation. As for other distillation characteristics, a change in the boiling point distribution to higher boiling point compounds may indicate catalyst deactivation. To some extent, the physicochemical characteristics may indicate or be related to the content of isoparaffins or multi-branched isoparaffins in the recovered liquid transportation fuel component and / or the separated recycle stream.

[0145] g. Compositional characteristics of at least one or more of the recovered liquid transportation fuel components and / or the recycle stream, preferably the isoparaffin content and / or the multi-branched isoparaffin content of one or more of the recovered liquid transportation fuel components and / or the separated recycle stream; 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 indicate or be related to the physicochemical characteristics of the recovered liquid transportation fuel components and / or the separated recycle stream.

[0146] h. Temperature differentials across reactor A or one or more catalyst beds therein; such temperature differentials are relatively easy to monitor, and a decrease in the temperature differential may indicate an increase in catalyst deactivation.

[0147] and / or

[0148] i. The operating conditions in reactor A are selected from temperature, pressure, weight hourly space velocity (WHSV), ratio of H2 to reactor A feed and / or H2 partial pressure at the inlet of reactor A. For example, temperature and / or WHSV and / or pressure may have required adjustment during continued operation of the process to compensate for deactivation of the hydroprocessing catalyst, so that increased temperature, decreased WHSV and / or increased pressure may indicate an increase in catalyst deactivation. Conveniently, the temperature in the reactor is measured at the inlet of the reactor.

[0149] The active sites of the hydroprocessing catalyst may be occupied and the catalyst pores may be blocked by impurities and coke, so that these sites are no longer available for catalysis. For example, coke is caused by coke-forming compounds such as olefins, aromatics and cycloalkanes, and when present in the hydrocarbon feed or reactor feed, coke formation can be enhanced by other impurities. For impurities that cause reversible catalyst deactivation, it may be sufficient to monitor the total content of such impurities or such impurities in the feed, because this can give an indication of the expected catalyst deactivation. For some other impurities, especially those that cause irreversible catalyst deactivation, it may be necessary to monitor the content of one or more such impurities in the hydrocarbon feed and calculate it as the received value: the cumulative amount of the hydroprocessing catalyst that has been encountered at a given time point from the start of operation, and the received value is compared with a value that has been predetermined based on (for example) historical data or a model based on historical data to reflect excessive hydroprocessing catalyst deactivation, so that it is no longer possible to foresee the satisfaction of the target yield and / or quality of the desired fuel component.

[0150] In certain preferred embodiments, the method includes monitoring at least two or at least three of the above parameters indicating deactivation of the hydroprocessing catalyst A. For example, when the hydroprocessing in reactor A is HI, the increase in the amount of shorter carbon chains caused by the increased cracking occurring in reactor A, rather than a sufficient degree of isomerization, can achieve good low temperature properties (e.g., cloud point, pour point, sub-zero viscosity) of the degassed hydroprocessing effluent A. Therefore, in order to better understand the state of HI catalyst deactivation, it may be beneficial to monitor at least two or three or even more parameters. For example, it is convenient to monitor one or more operating conditions in reactor A and one or more physicochemical characteristics and / or yields of the recovered liquid transportation fuel components, and it enhances the understanding of the deactivation state of the hydroprocessing catalyst A. In certain exemplary embodiments, the monitoring parameters indicating the deactivation of the hydroprocessing catalyst A include the temperature in reactor A, and optionally WHSV, and for the recovered diesel fuel component yield, at least one or more distillation characteristics and / or cloud point, and / or for the recovered aviation fuel component yield, at least one or more distillation characteristics and / or freezing point.

[0151] The monitoring of the parameter indicating the deactivation of the hydroprocessing catalyst or the parameter indicating the reversal of the deactivation of the hydroprocessing catalyst can be performed continuously, repeatedly, continuously, periodically, intermittently, discontinuously, or the monitoring can be a one-time monitoring. The monitoring of the parameter indicating the deactivation of the hydroprocessing catalyst or the parameter indicating the reversal of the deactivation of the hydroprocessing catalyst can be performed online, for example, using one or more sensors located in any one of the process stream, feed tank and / or product tank, including slip-stream arrangements, or can be performed offline based on samples collected from any one of the process stream, feed tank and / or product tank. The frequency and manner of monitoring one or more parameters can be performed independently of other monitored parameters, that is, some parameters can be (for example) continuously monitored online, while other parameters can be (for example) regularly monitored offline.

[0152] By considering the selected hydroprocessing catalyst, reactor feed composition, target hydroprocessing type, such as hydroisomerization, hydrocracking, hydrodearomatization and / or hydrofining, the skilled person is familiar with how to select hydroprocessing conditions. To some extent, catalyst life or catalyst deactivation may also be considered when selecting or adjusting the operating conditions in reactors A and B (when applicable). Similarly, this applies to the operating conditions in reactor A of the third exemplary aspect. During continuous operation, the hydroprocessing catalyst (for example) gradually deactivates due to impurities and coking in the process stream. Due to catalyst deactivation, catalyst activity decreases and affects selectivity, and typically at some point, the desired properties of the hydroprocessing effluent and / or the recovered liquid transportation fuel component are no longer achieved. When this occurs, at least one or more operating conditions of reactor A and / or reactor B, including (for example) temperature, pressure, WHSV and / or H2 partial pressure at the inlet of reactor A and / or reactor B, can be adjusted, for example, within the range of operating conditions specified below, to compensate for catalyst deactivation so that the desired properties of the hydroprocessing effluent and / or the recovered liquid transportation fuel component can be achieved again. Typically, this means increasing the temperature and / or reducing the WHSV and / or adjusting the ratio of H2 to the hydrocarbon feed or reactor feed and / or increasing the pressure. However, there are limits, beyond which, for example, the temperature cannot be increased and / or the WHSV cannot be reduced without compromising the yield and / or quality of the recovered liquid transportation fuel component. For example, when the operating temperature is increased to a sufficiently high value, thermal cracking side reactions increase, which increases the formation of gaseous hydrocarbons and thus reduces the yield of liquid products. Therefore, it is generally advantageous to start operating the reactor at low temperature at the beginning of the run, using (for example) the lowest feasible temperature within the specified range, because this provides the widest window for increasing the temperature when the catalyst gradually deactivates. In addition, in the first process mode according to the first and second exemplary aspects, the hydroprocessing catalyst B gradually deactivates during the continuous operation, although generally at a lower rate than the hydroprocessing catalyst A subjected to a higher impurity content. In the second process mode according to the first and second exemplary aspects, during the continuous operation, it is the hydroprocessing catalyst B that is subjected to a higher impurity content, and the hydroprocessing catalyst A that is generally deactivated at a lower rate than the hydroprocessing catalyst B. Therefore, similar considerations apply to adjusting the operating conditions of the reactor B.

[0153] In certain preferred embodiments, the process of the present invention comprises feeding a portion of the hydrocarbon feed to the hydroprocessing in reactor B as part of the feed to reactor B when operating i), ii), iii); and / or feeding a portion of the hydrocarbon feed to the hydroprocessing in reactor A as part of the feed to reactor A when operating I), II), III); and / or separating a side cut from the fractionation and feeding the side cut as part of the feed to each reactor to reactor A and / or B when operating i), ii), iii) or I), II), III). In addition to the possibility of adjusting the operating conditions in reactor A and / or reactor B, these embodiments provide further increased flexibility in operating the process, including, for example, the possibility of adjusting the process according to fluctuations in the characteristics of the hydrocarbon feed, according to the demand and / or quality of one or more liquid transportation fuel components recovered, and / or according to the changing activity and / or selectivity of the hydroprocessing catalyst throughout its lifetime.

[0154] The desired properties of the hydroprocessing effluent, the recovered liquid transportation fuel component and / or the separated recycle stream include composition and / or physicochemical characteristics, for example, at least one or more of the wt% of isoparaffins, the wt% of multi-branched isoparaffins, the wt% of hydrocarbons within a specific carbon number range, cloud point, freezing point, pour point, cold filter plugging point, kinematic viscosity, density and / or distillation characteristics. The properties of the hydroprocessing effluent, the recovered liquid transportation fuel component and / or the separated recycle stream can be changed during the operation of the method due to the deactivation of the hydroprocessing catalyst, but also due to other reasons, such as changes in the composition of the hydrocarbon feed. Therefore, one or more parameters indicating the deactivation of the hydroprocessing catalyst and / or indicating the properties of the hydrocarbon feed can be monitored to receive one or more values, and the received values ​​are compared with a predetermined adjustment value. The predetermined adjustment value is usually closer to the initial process setting than the predetermined value for triggering the switch from the first mode to the second mode.

[0155] Thus, according to certain embodiments, the method includes monitoring at least one or more parameters indicative of deactivation of hydroprocessing catalyst A to receive at least one or more values; and / or monitoring at least one or more parameters indicative of deactivation of hydroprocessing catalyst B to receive at least one or more values; and / or monitoring at least one or more parameters indicative of hydrocarbon feed properties to receive at least one or more values; comparing the received values ​​to predetermined adjustment values, and based on the comparison, adjusting at least one or more operating conditions in reactor A and / or reactor B, and / or adjusting the composition of the reactor A feed and / or the reactor B feed, preferably adjusting at least one of the following: One or more of the following: temperature, pressure and / or weight hourly space velocity (WHSV) in reactor A and / or reactor B, the ratio of H2 to reactor A feed and / or reactor B feed, and / or the H2 partial pressure at the inlet of reactor A and / or reactor B, the split ratio of the hydrocarbon feed between reactor A and reactor B, and / or the weight ratio of the side stream optionally separated from the fractionation in the reactor A feed and / or reactor B feed, more preferably increasing the temperature and / or pressure in reactor A and / or reactor B, and / or reducing the WHSV in reactor A and / or reactor B, and / or adjusting the split ratio of the hydrocarbon feed between reactor A and reactor B.

[0156] For example, adjustments to operating conditions to obtain or maintain desired properties of the hydroprocessing effluent, the recovered liquid transportation fuel component, and / or the separated recycle stream may be made based on historical process data, models (e.g., theoretical models or models based on historical process data), and / or one or more parameters related to or indicative of properties of one or more of hydroprocessing effluent A, hydroprocessing effluent B, the recovered liquid transportation fuel component, and / or the separated recycle stream. For example, the adjustments may be based on historical process data from an earlier process run using a similar feed and similar qualitative and quantitative expectations of the recovered liquid transportation fuel component, such as using a model based on historical process data and / or an operating condition profile.

[0157] Except for the hydrocarbon feed used in the second process mode according to certain embodiments of the third exemplary aspect, the hydrocarbon feed used in the process of the present invention contains nitrogen impurities.

[0158] The hydrocarbon feed used in the second method mode according to the third exemplary aspect is preferably a hydrocarbon feed that is substantially free of nitrogen impurities (substantially free of nitrogen impurities). Alternatively, the hydrocarbon feed used in the second method mode according to the third exemplary aspect may include nitrogen impurities, and the low nitrogen content of the reactor A feed in the second method mode according to the third exemplary aspect is achieved by (for example) diluting the hydrocarbon feed with a side stream or a recycle stream from a fractionation. Preferably, in the method according to the third exemplary aspect, the reactor A feed essentially consists of a first mode of a hydrocarbon feed containing nitrogen impurities and a second mode of a hydrocarbon feed that is substantially free of nitrogen impurities. Except for nitrogen impurities, the hydrocarbon feed used in the second method mode according to the third exemplary aspect is a hydrocarbon feed as described herein.

[0159] It is known that nitrogen impurities deactivate the acid sites of the catalyst in a reversible manner. In addition to nitrogen and possible other impurities, the hydrocarbon feed may contain paraffins, cycloalkanes, aromatics and / or olefins. Typically, the hydrocarbon feed contains at least 90wt% of the total weight of the hydrocarbon feed, preferably at least 95wt%, more preferably at least 98wt%, and even more preferably at least 99wt% of hydrocarbons. Preferably, the hydrocarbon feed contains up to 1.0wt% of the total weight of the hydrocarbon feed, preferably up to 0.8wt%, more preferably up to 0.5wt% of oxygen, expressed as elemental oxygen (ASTM D5622-2017). In certain preferred embodiments, the hydrocarbon feed contains at least 60wt% of the total weight of the hydrocarbon feed, and the paraffin is at most 30wt% isoparaffin. This means that when the hydrocarbon feed contains 60wt% of the total weight of the hydrocarbon feed, at most 30wt% of the total weight of the paraffin in the hydrocarbon feed, i.e., at most 18wt% of the total weight of the hydrocarbon feed is isoparaffin. The hydrocarbon feed can be a high paraffin feed. The hydrocarbon feed can comprise at least 60wt% of the hydrocarbon feed gross weight, preferably at least 70wt%, more preferably at least 80wt%, even more preferably at least 90wt% paraffin. The hydrocarbon feed of the present disclosure can comprise at least 95wt% paraffin of the hydrocarbon feed gross weight or consist essentially of paraffin. The hydrocarbon feed of the present disclosure can contain olefins, preferably less than 5wt% of the gross weight based on the hydrocarbon feed, more preferably less than 1wt% olefins, and aromatics and / or cycloalkanes, preferably with their less amount.

[0160] An advantage of using a highly paraffinic feed in the process of the present invention is that paraffins are relatively easy to hydrotreat, such as isomerization or hydrocracking, and are subjected to milder conditions than, for example, cyclic hydrocarbons.

[0161] Of the paraffinic hydrocarbons in the hydrocarbon feed of the present disclosure, preferably up to 30 wt%, further preferably up to 25 wt%, more preferably up to 20 wt%, and even more preferably up to 15 wt% are isoparaffinic hydrocarbons. For example, 1 wt% to 30 wt%, or 1 wt% to 20 wt%, or 2 wt% to 30 wt%, or 2 wt% to 20 wt% of the paraffinic hydrocarbons in the hydrocarbon feed may be isoparaffinic hydrocarbons.

[0162] A high weight ratio (wt%:wt%) of normal paraffins to isoparaffins in the hydrocarbon feed can, for example, help limit cracking side reactions during HI due to hydroprocessing in the reactor feeding the hydrocarbon feed, i.e., Reactor A or Reactor B, based on the modes and exemplary aspects of the method of operation thereof, because normal paraffins are less susceptible to cracking than isoparaffins of the same carbon number. However, the presence of a certain amount of isoparaffins in the hydrocarbon feed may still be beneficial. A hydrocarbon feed containing a certain amount of isoparaffins can produce a liquid transportation fuel component having a higher content of multi-branched isoparaffins compared to an otherwise similar feed that does not contain isoparaffins.

[0163] Preferably, the hydrocarbon feed of the present disclosure comprises hydrocarbons having a carbon number 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 hydrocarbon feed. In certain particularly preferred embodiments, the hydrocarbon feed comprises hydrocarbons having a carbon number 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 hydrocarbon feed. Hydrocarbon feeds having a high C12 to C30 hydrocarbon content are preferred because they allow good yields of two or more different types of liquid transportation fuel components. For the same reason, C14 to C22 hydrocarbons are particularly preferred, and also because they are easily obtained, for example, from conventional HDO of vegetable oils, animal fats and / or microbial oils containing fatty acids.

[0164] In order to improve the yield of aviation fuel components and / or diesel fuel components, it is particularly preferred that the hydrocarbon feed comprises at least 50wt% of the total weight of paraffins in the hydrocarbon feed, preferably at least 60wt%, more preferably at least 70wt%, even more preferably at least 80wt% or at least 90wt% of C16+ paraffins (paraffins with a carbon number of at least C16). In certain embodiments, the hydrocarbon feed comprises at least 50wt% of the total weight of paraffins in the hydrocarbon feed C17+ paraffins (paraffins with a carbon number of at least C17). Such compositions are obtainable by appropriately selecting heavy hydrocarbon feeds, in particular by appropriately selecting raw materials for producing them, such as oxygenated hydrocarbons. Examples of suitable heavy oxygenated hydrocarbon feeds include oils from energy crops, such as Brassica species, algae oils, crude tall oil (CTO), tall oil fatty acids (TOFA), tall oil pitch (TOP) and / or feeds derived from lignocellulose. C17+ paraffins are also obtainable by Fischer-Tropsch conversion of synthesis gas.

[0165] The hydrocarbon feed may comprise any suitable hydrocarbon composition or combination thereof. Preferably, in the process of the present invention, the step of providing a hydrocarbon feed comprises catalytically hydrotreating a hydrotreated feed, preferably catalytically hydrodeoxygenating an oxidized hydrocarbon feed, to obtain a 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 residue and / or enzymatically liquefied organic waste and residue, and / or subjecting the synthesis gas to Fischer-Tropsch (FT) conversion to obtain an FT effluent; subjecting the hydrotreated effluent and / or the FT effluent to gas-liquid separation, and optionally subjecting the hydrocarbon feed to fractionation to provide a hydrocarbon feed. Gas-liquid separation refers to the removal of compounds that are gaseous at least at NTP. Examples of thermally liquefied organic waste and residue and / or enzymatically liquefied organic waste and residue include thermally liquefied and / or enzymatically liquefied biomass waste and residue, municipal solid waste and / or waste plastics.

[0166] Although (for example) FT effluents of fossil origin are readily available (in addition to FT effluents of renewable origin), it is preferred that the hydrocarbon feed of the present disclosure is at least partially renewable, i.e. comprises components of biological origin. In certain preferred embodiments, the hydrocarbon feed has a biogenic carbon content of at least 50 wt%, preferably at least 70 wt%, more preferably at least 90 wt%, further preferably at least 95 wt%, or even about 100 wt%, based on the total carbon weight (TC) of the hydrocarbon feed, preferably as determined according to EN 16640 (2017).

[0167] In certain embodiments, the hydrocarbon feed comprises a degassed Fischer-Tropsch effluent or a fraction thereof or consists essentially of it. The Fischer-Tropsch process comprises a synthesis gas comprising carbon monoxide and hydrogen, which is generally catalytically converted into a substantially Gaussian distributed hydrocarbon chain, mainly normal paraffins, which have a wide carbon chain length distribution, such as from C2 to C100+, generally from about C5 to about C50. The FT effluent is generally highly paraffinic, comprising mainly normal paraffins. The catalytic FT conversion of the synthesis gas can result in a lesser degree of isomerization, and the FT effluent generally comprises about 10wt% or less of the total weight of the FT effluent of isoparaffins. The synthesis gas used in the FT process can be produced by renewable materials, natural gas, coal or a combination thereof.

[0168] Preferably, the hydrocarbon feed of the present disclosure comprises or consists essentially of a degassed hydroprocessing effluent or a fraction thereof, particularly as obtained by catalytic hydroprocessing of a hydroprocessing feed comprising at least one or more of vegetable oils, animal fats, microbial oils, thermally liquefied organic waste and residues and / or enzymatically liquefied organic waste and residues, more preferably at least one or more of vegetable oils, animal fats and / or microbial oils, to obtain a hydroprocessing effluent, followed by gas-liquid separation of the hydroprocessing effluent and optionally fractionation of the hydrocarbon feed to provide a degassed hydroprocessing effluent or a fraction thereof. Nitrogen impurities are typically present in hydroprocessing feeds comprising vegetable oils, animal fats, microbial oils, thermally liquefied organic waste and residues and / or enzymatically liquefied organic waste and residues in varying amounts, and may be carried into and present in the degassed hydroprocessing effluent or a fraction thereof in varying amounts.

[0169] The term "catalytic hydroprocessing" refers to a catalytic process for treating organic materials by molecular hydrogen. Preferably, the catalytic hydroprocessing removes oxygen from organic oxygen compounds in the form of water, i.e., hydrodeoxygenation (HDO), removes sulfur from organic sulfur compounds in the form of dihydrosulfide (H2S), i.e., hydrodesulfurization (HDS), removes nitrogen from organic nitrogen compounds in the form of ammonia (NH3), i.e., hydrodenitrogenation (HDN), removes halogens, for example, removes chlorine from organic chlorine compounds in the form of hydrochloric acid (HCl), i.e., hydrodechlorination (HDCl), and / or removes metals by hydrodemetallization, and / or hydrogenates olefinic bonds if present in the hydroprocessing feed. Depending on the composition of the hydroprocessing feed, different reactions may occur and / or proceed.

[0170] Preferably, the hydrocarbon feed of the present disclosure comprises or consists essentially of a degassed hydrodeoxygenation (HDO) effluent or a fraction thereof, in particular as obtained by catalytic HDO of an oxidized hydrocarbon feed comprising at least one or more of vegetable oil, animal fat and / or microbial oil to obtain an HDO effluent, followed by gas-liquid separation of the HDO effluent and optionally fractionation of the hydrocarbon feed to provide a degassed HDO effluent or a fraction thereof. Nitrogen impurities are typically present in varying amounts in an oxidized hydrocarbon feed comprising vegetable oil, animal fat and / or microbial oil, and may be carried over and present in the degassed HDO effluent or a fraction thereof in varying amounts.

[0171] In certain embodiments, providing a hydrocarbon feed comprises subjecting the oxygenated hydrocarbon feed, preferably to hydrodeoxygenation (HDO) in a hydrodeoxygenation (HDO) reactor in the presence of a hydrodeoxygenation catalyst to obtain a hydrodeoxygenation effluent, and subjecting the hydrodeoxygenation effluent to gas-liquid separation and optionally hydrocarbon feed fractionation to obtain a degassed hydrodeoxygenation effluent or a fraction thereof as a hydrocarbon feed, wherein the hydrodeoxygenation is preferably carried out under the following conditions: a temperature in the range of 200° C. to 500° C., a pressure in the range of 1 MPa to 20 MPa, a H2 partial pressure at the reactor inlet in the range of 1 MPa to 20 MPa, a weight hourly space velocity in the range of 0.1 to 10 kg oxygenated hydrocarbon feed / kg catalyst / hour, and a ratio of H2 to oxygenated hydrocarbon feed in the range of 50 to 2000 standard liters of H2 / liter of oxygenated hydrocarbon feed. Preferably, the oxygenated hydrocarbon feed comprises at least one or more of vegetable oil, animal fat and / or microbial oil. The hydrodeoxygenation is preferably carried out as described in prior art publications, such as FI100248B, EP1741768A1, EP2155838B1 or FI129220 B1.

[0172] The optional hydrocarbon feed fractionation is typically carried out in a fractionation unit different from the fractionation unit used to recover liquid transportation fuel components and / or separate recycle streams. The optional hydrocarbon feed fractionation can be considered separate from the fractionation of the process of the present invention, which refers to or includes fractionation to recover liquid transportation fuel components and / or separate recycle streams.

[0173] Preferably, the HDO catalyst is a sulphurized catalyst comprising at least one or more metals from Group VIII of the Periodic Table and / or Group VIB of the Periodic Table, preferably at least one or more of Ni, Mo, W and / or Co, even more preferably at least one or more of Ni, and / or Co and Mo, and / or W, such as NiMo, CoMo, NiCoMo, NiW, NiMoW. These catalysts are effective, readily available and well tolerate typical impurities of fatty feedstocks. If a catalyst having hydrodewaxing properties, such as a catalyst containing NiW, is used in the hydrodeoxygenation as a hydrodeoxygenation catalyst or as a co-catalyst, an HDO effluent having a slightly increased isoparaffin content can be obtained.

[0174] Preferably, in the first mode of the process of the invention, the reactor A feed consists essentially of a hydrocarbon feed and optionally one or more streams from the process. In the context of the present disclosure, molecular hydrogen (H2) fed to the reactor for hydroprocessing is not included in the definition of reactor feed, i.e. it is not considered herein to be part of the reactor A feed or the reactor B feed.

[0175] Preferably, in a first process mode according to the first exemplary aspect, the reactor B feed consists essentially of the degassed hydrotreatment effluent A and optionally one or more other streams from a portion of the process and / or the hydrocarbon feed. Preferably, in a first process mode according to the second exemplary aspect, the reactor B feed consists essentially of the recycle stream and optionally one or more other streams from a portion of the process and / or the hydrocarbon feed.

[0176] Preferably, in the second process mode according to the first exemplary aspect and in the second process mode according to the second exemplary aspect, the reactor B feed consists essentially of the hydrocarbon feed and optionally one or more streams from the process.

[0177] Preferably, in the second process mode according to the first exemplary aspect, the reactor A feed consists essentially of the degassed hydrotreatment effluent B and optionally one or more other streams from the process and / or a portion of the hydrocarbon feed. Preferably, in the second process mode according to the second exemplary aspect, the reactor A feed consists essentially of the recycle stream and optionally one or more other streams from the process and / or a portion of the hydrocarbon feed.

[0178] Based on the process modes and exemplary aspects, the one or more (other) streams from the process may for example be a side draw and / or a recycle stream from a fractionation, and / or a part of the degassed hydrotreatment effluent A and / or B. Preferably, in the process according to the first and / or second exemplary aspect, the feed to the first reactor in the process modes (reactor A in the first mode and reactor B in the second mode) comprises at least 0.4 w-ppm nitrogen, expressed as elemental nitrogen (ASTM D4629-17), or at least 0.6 w-ppm, or at least 1.0 w-ppm, or even at least 1.5 w-ppm or at least 2.0 w-ppm nitrogen, based on the total weight of the reactor feed.

[0179] In certain embodiments, hydrotreatment is selected from at least one or more of hydroisomerization, hydrocracking, hydrodearomatization and / or hydrofining in reactor A and reactor B independently of each other; preferably, the hydrotreatment in reactor A and reactor B is hydroisomerization, or the hydrotreatment in reactor A and reactor B is hydrocracking, or the hydrotreatment in reactor A is hydroisomerization and the hydrotreatment in reactor B is hydrocracking, or the hydrotreatment in reactor A is hydrocracking and the hydrotreatment in reactor B is hydroisomerization; more preferably, the hydrotreatment in reactor A and reactor B is hydroisomerization. In other words, preferably, the hydrotreatment in reactor A and reactor B is independently selected from at least one or more of hydroisomerization and / or hydrocracking.

[0180] Similarly, in certain embodiments of the method according to the third exemplary aspect, the hydroprocessing in reactor A is selected from at least one or more of hydroisomerization, hydrocracking, hydrodearomatization and / or hydrofinishing, preferably the hydroprocessing in reactor A is hydroisomerization or hydrocracking, more preferably the hydroprocessing in reactor A is hydroisomerization. The hydroprocessing in reactor A in the method according to the third exemplary aspect may be as described herein for reactor A and / or reactor B.

[0181] When the hydroprocessing in reactor A and reactor B are of the same type, the change in the quality and / or yield of the liquid transportation fuel components recovered after the switch can be of less magnitude (compared to embodiments in which the hydroprocessing in reactor A and reactor B are of different types) or even insignificant. When the hydroprocessing in reactor A and reactor B is hydrocracking, enhanced aviation and gasoline fuel component yields can be obtained, even near the end of the life of the hydroprocessing catalyst. When the hydroprocessing in reactor A and reactor B is hydroisomerization, enhanced aviation and diesel fuel component quality and yields can be obtained, even near the end of the life of the hydroprocessing catalyst. When the hydroprocessing in reactor A is hydroisomerization and the hydroprocessing in reactor B is hydrocracking (or vice versa), enhanced aviation and diesel fuel component quality and enhanced aviation and gasoline fuel component yields can be obtained, even near the end of the life of the hydroprocessing catalyst.

[0182] In certain preferred embodiments, the hydrotreatment in reactor A and / or reactor B is hydroisomerization. Preferably, the hydrotreatment in reactor A and / or reactor B is hydroisomerization carried out under the following conditions: a temperature of 200°C to 500°C, preferably 230°C to 500°C, more preferably 250°C to 450°C, even more preferably 280°C to 400°C, a pressure of 1 MPa to 10 MPa, preferably 2 MPa to 8 MPa or 3 MPa to 10 MPa, a H2 partial pressure at the reactor inlet of 1 MPa to 10 MPa, preferably 2 MPa to 8 MPa, a weight hourly space velocity of 0.1 to 10, preferably 0.2 to 8, more preferably 0.4 to 6 kg reactor feed / kg catalyst / hour, and a ratio of H2 to reactor feed of 10 to 2000, preferably 50 to 1000 standard liters of H2 / liter of reactor feed.

[0183] According to certain embodiments, the hydrotreatment in reactor A and / or reactor B is hydroisomerization performed under the following conditions: a temperature in the range of 200° C. to 500° C., a pressure in the range of 1 MPa to 10 MPa, a H2 partial pressure at the reactor inlet in the range of 1 MPa to 10 MPa, a weight hourly space velocity in the range of 0.1 to 10 kg reactor feed / kg catalyst / hour, and a ratio of H2 to reactor feed in the range of 10 to 2000 standard liters of H2 / liter of reactor feed. These conditions are particularly beneficial for hydroisomerization.

[0184] According to certain particularly preferred embodiments, the hydrotreatment in reactor A and / or reactor B is hydroisomerization carried out under the following conditions: a temperature in the range of 230° C. to 500° C., a pressure in the range of 2 to 8 MPa, a H2 partial pressure at the reactor inlet in the range of 2 to 8 MPa, a weight hourly space velocity in the range of 0.2 to 8 kg reactor feed / kg catalyst / hour, and a ratio of H2 to reactor feed in the range of 50 to 1000 standard liters of H2 / liter of reactor feed. These conditions are particularly beneficial for hydroisomerization.

[0185] The degree of isomerization of the hydroprocessing effluent can be improved by increasing the severity of the HI, for example by at least one or more of: reducing the WHSV, increasing the temperature, and / or increasing the pressure. When using a fresh hydroprocessing catalyst, high severity HI conditions can be achieved at lower temperatures, and / or lower pressures, and / or using higher WHSVs (compared to later in the run, when the hydroprocessing catalyst has been at least somewhat deactivated). Towards the end of the life of the hydroprocessing catalyst, higher temperatures and / or higher pressures and / or lower WHSVs may be required to achieve even moderately severe HIs. In the context of the present invention, HI producing a liquid effluent having, as the wt% of paraffins in the liquid effluent, a total isoparaffin content in the range of 50 wt% to 85 wt% and a hyperbranched isoparaffin content of up to 25 wt%, or a total isoparaffin content in the range of 85 wt% to 95 wt% and a hyperbranched isoparaffin content in the range of 25 wt% to 55 wt%, or at least 95 wt% total isoparaffin content and greater than 55 wt% hyperbranched isoparaffin content, is generally considered to be a low severity, medium severity or high severity HI, respectively, although these content ranges are merely for illustrative purposes and may overlap to some extent and vary depending on the circumstances.

[0186] Preferably, when the hydrotreatment in reactor A and / or reactor B is hydroisomerization, each reactor is operated so that the ratio of the amount of wt% isoparaffins based on the total weight of paraffins in each hydrotreatment effluent to the amount of wt% isoparaffins based on the total weight of paraffins in the feed to each reactor 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 so that the ratio of the amount of wt% of multi-branched isoparaffins based on the total weight of paraffins in each hydrotreatment effluent to the amount of wt% of multi-branched isoparaffins based on the total weight of paraffins in the feed to each reactor 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 so that (total) each hydrotreatment effluent contains less than 20 wt%, or less than 10 wt%, preferably less than 5 wt%, more preferably less than 3 wt% of C1 to C4 hydrocarbons, based on the total weight of each hydrotreatment effluent. This can be achieved especially when operating the respective reactor within HI operating conditions and / or using a HI catalyst and / or hydrocarbon feed as defined herein.

[0187] When, based on the method modes and exemplary aspects, the hydroprocessing effluent (or a portion of the hydroprocessing effluent) A and / or B is fed to a subsequent hydroprocessing, i.e., contacted with a subsequent hydroprocessing catalyst, the compounds that are gaseous at least at NTP are separated or removed from the respective hydroprocessing effluent. This can be done, for example, as a gas-liquid separation, which can be performed as an integrated step within each reactor or in a separate gas-liquid separation unit or as part of a fractionation. In particular, in conjunction with the method according to the second exemplary aspect, the separation of compounds that are gaseous at least at NTP can be considered as part of a fractionation.

[0188] For example, degassing removes gaseous impurities from the hydroprocessing effluent. This can protect the subsequent reactor against impurities in the hydrocarbon feed and extend the life of the catalyst in the subsequent reactor. Preferably, at least the separation or removal of gaseous compounds at NTP includes separating or removing NH3 from the hydroprocessing effluent A and / or B. The degassed hydroprocessing effluent A and / or B may contain a small amount or trace amount of gaseous compounds at NTP, because the separation does not necessarily achieve complete removal of all gaseous compounds at NTP. Degassing also increases the hydrogen partial pressure in the subsequent reactor, and when the reactor feed is not too uniform, the operating conditions in the subsequent reactor are easier to optimize.

[0189] When a high paraffin feed is used, the hydroprocessing effluent A and / or B may contain at least 60 wt%, preferably at least 70 wt%, more preferably at least 80 wt%, even more preferably at least 90 wt% or at least 95 wt% paraffins based on the total weight of the hydroprocessing effluent A and / or B. In certain embodiments, the hydroprocessing effluent A and / or B may even consist essentially of paraffins.

[0190] Typically, when the hydrotreatment in reactor A and / or reactor B is hydroisomerization, each hydrotreatment effluent may contain at least 50 wt%, preferably at least 60 wt%, more preferably at least 70 wt%, even more preferably at least 80 wt% of isoparaffins, and optionally at least 5 wt%, more preferably at least 10 wt%, even more preferably at least 15 wt%, or at least 20 wt% of multi-branched isoparaffins, based on the total weight of paraffins in each hydrotreatment effluent. Typically, when the hydrotreatment in reactor A and / or B is hydroisomerization, each hydrotreatment effluent may contain up to 75 wt%, or up to 70 wt%, or up to 60 wt%, such as up to 50 wt%, or up to 40 wt%, sometimes up to 30 wt%, or even up to 20 wt% of multi-branched isoparaffins, based on the total weight of paraffins in each hydrotreatment effluent. Typically, when the hydroprocessing in reactor A and / or reactor B is hydroisomerization, each hydroprocessing effluent may have a cloud point (ASTM D 5771-17) of less than 0°C, preferably less than -5°C, more preferably less than -8°C, even more preferably less than -10°C, or less than -15°C.

[0191] In the process mode, in the first obtained hydroprocessing effluent, the presence of multi-branched isoparaffins can be considered beneficial, for example, when the subsequent hydroprocessing is hydrocracking, because it can advantageously contribute to the effective cracking degree in the hydroprocessing in the subsequent reactor. When the desired degree of effective cracking is achieved in the hydroprocessing in the subsequent reactor under milder operating conditions, especially for C8 to C14 hydrocarbons and for the effective cracking of lighter non-gaseous hydrocarbons, excessive cracking can be avoided and the formation of gaseous hydrocarbons is reduced. Without being bound by any theory, it is believed that multi-branched isoparaffins are more likely to form two branched paraffin molecules rather than one branched paraffin and one normal paraffin when cracking in the hydroprocessing in the subsequent reactor, which therefore increases the isoparaffin content of the second obtained hydroprocessing effluent. An increase in the polybranched isoparaffin content in hydroprocessing effluents A and / or B can be considered beneficial because it can improve the low temperature properties of the recovered liquid transportation fuel components, especially the low temperature properties of aviation fuel components and / or diesel fuel components and / or the RON of gasoline fuel components.

[0192] In certain embodiments, the hydroprocessing in reactor A and / or reactor B is hydrocracking. Preferably, the hydroprocessing in reactor A and / or reactor B is hydrocracking performed at a temperature in the range of 200°C to 450°C, preferably 220°C to 430°C, more preferably 280°C to 350°C, a pressure in the range of 0.4 MPa to 8 MPa, preferably 1 MPa to 7 MPa, more preferably 2.5 MPa to 7 MPa, a H2 partial pressure at the reactor inlet in the range of 0.4 MPa to 8 MPa, preferably 1 MPa to 7 MPa, more preferably 2.5 MPa to 7 MPa, a weight hourly space velocity of 0.1 to 10, preferably 0.2 to 8, more preferably 0.4 to 6, even more preferably 0.5 to 1.5 kg reactor feed / kg catalyst / hour, and a ratio of H2 to reactor feed in the range of 10 to 2000, preferably 50 to 1000 standard liters of H2 / liter of reactor feed.

[0193] According to certain embodiments, the hydroprocessing in reactor A and / or reactor B is hydrocracking performed under the following conditions: temperature in the range of 220°C to 430°C, pressure in the range of 1MPa to 7MPa, weight hourly space velocity in the range of 0.2 to 8kg reactor feed / kg catalyst / hour, and the ratio of H2 to reactor feed in the range of 50 to 1000 standard liters of H2 / liter of reactor B feed. In certain preferred embodiments, the hydroprocessing in reactor A and / or reactor B is hydrocracking performed under the following conditions: temperature in the range of 280 to 350°C, pressure in the range of 2.5 to 7MPa, H2 partial pressure at the reactor inlet in the range of 2.5 to 7MPa, weight hourly space velocity in the range of 0.4 to 6kg reactor feed / kg catalyst / hour, and the ratio of H2 to reactor B feed in the range of 50 to 1000 standard liters of H2 / liter of reactor feed. These conditions are particularly beneficial for hydrocracking.

[0194] When operating the hydroprocessing at lower temperatures and sufficiently high pressures, aromatization side reactions can be better suppressed or even dearomatization can be enhanced.

[0195] Preferably, when the hydrotreatment in reactor A and / or reactor B is hydrocracking, each reactor is operated so that the ratio of the wt% of isoparaffins based on the total weight of paraffins in each hydrotreatment effluent to the wt% of isoparaffins based on the total weight of paraffins in the feed to each reactor is at least 0.5, or at least 0.7, or at least 0.8, or at least 0.9, or at least 1.0; and / or so that the ratio of the C8-C14 hydrocarbon content in each hydrotreatment effluent to the C8-C14 hydrocarbon content in the feed to each reactor is at least 1.1, preferably at least 1.3, more preferably at least 1.5, even more preferably at least 1.8 or at least 2.0.

[0196] In certain preferred embodiments, when the hydroprocessing in reactor A and / or reactor B is hydrocracking, each reactor is operated so that the ratio of the amount of wt% of C1-C4 hydrocarbons formed during hydrocracking in the (total) each hydroprocessing effluent to the amount of wt% of C1-C4 hydrocarbons in the (total) each reactor feed is in the range of 1.1 to 5.0, preferably in the range of 1.1 to 4.0, more preferably in the range of 1.2 to 3.0; and / or so that the (total) each hydroprocessing effluent contains less than 20 wt%, or less than 10 wt%, or less than 5 wt% of C1-C4 hydrocarbons based on the total weight of each hydroprocessing effluent.

[0197] This can be achieved in particular when using a reactor feed as described above, and / or operating the reactor under the hydrocracking operating conditions as described above, and / or in the presence of a HC catalyst as defined below, in particular in the presence of a non-sulphided bifunctional HC catalyst as defined below, preferably in the presence of a non-sulphided bifunctional HC catalyst comprising at least one or more Group VIII noble metals, more preferably Pt and / or Pd.

[0198] When a high paraffinic feed is used, in embodiments in which the hydroprocessing in reactor A and / or reactor B is hydrocracking, each hydroprocessing effluent may comprise at least 60 wt%, preferably at least 70 wt%, more preferably at least 80 wt%, even more preferably at least 90 wt% or at least 95 wt% paraffinic hydrocarbons based on the total weight of each hydroprocessing effluent, or the hydroprocessing effluent may even consist essentially of paraffinic hydrocarbons.

[0199] In step iii) and / or III), a preferred feed for fractionation may contain at least 50 wt%, preferably at least 60 wt%, more preferably at least 70 wt%, even more preferably at least 80 wt% of isoparaffins, and / or at least 3 wt%, or at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt% of multi-branched isoparaffins, based on the total weight of the fractionation feed. For example, such feeds for fractionation may be achieved when the hydrotreatment in reactor A is HI and the hydrotreatment in reactor B is HC, or when the hydrotreatment in reactor A is HC and the hydrotreatment in reactor B is HI.

[0200] Preferably, when comparing the temperatures at the reactor inlets, reactor A is operated at a higher temperature than reactor B. The temperatures compared are the temperatures at the reactor A inlet and at the reactor B inlet, respectively, at a given point in time, including short time intervals. In other words, in this context, the comparison is not between the highest temperatures during the entire run from the start of the process to the termination of the process. It is particularly preferred that reactor A is operated at a higher temperature than reactor B and that reactor A and reactor B are operated within the range of operating conditions specified herein for the hydroprocessing discussed.

[0201] By operating reactor A at a higher temperature than reactor B, and particularly operating reactor A within the range of operating conditions specified herein, deactivation of hydroprocessing catalyst A can be better compensated. This is beneficial because hydroprocessing catalyst A is subject to higher impurity levels, particularly higher nitrogen impurity levels, in the first mode, and may also remain more deactivated during the second mode, compared to hydroprocessing catalyst B. Additionally, operating reactor A in the second mode at an elevated temperature may enhance the release of reversibly bound impurities from hydroprocessing catalyst A.

[0202] In certain embodiments, the hydroprocessing in reactor A and / or reactor B can be hydrodearomatization. This can be beneficial, for example, when the hydrocarbon feed has an elevated aromatic content, and / or when aromatics are formed during the hydroprocessing and / or if ultra-low aromatic content is desired for all or some of the recovered liquid transportation fuel components or for other product fractions that may be recovered from the process. Examples of such other product fractions include product fractions intended for use in cosmetics, pharmaceuticals, and / or other applications involving close contact with humans. In embodiments where the hydroprocessing in reactor A and / or reactor B is HDA, the aromatic level can be reduced, for example, to less than 5000 w-ppm, or less than 300 w-ppm, preferably to less than 100 w-ppm, or less than 50 w-ppm, preferably as determined according to UOP 495-03.

[0203] Preferably, the temperature is in the range of 80°C to 350°C, the pressure is in the range of 3MPa to 16MPa, and the temperature is in the range of 0.2 to 8hr. -1 HDA was performed at a liquid hourly space velocity in the range of 100 Å and a ratio of H2 to reactor feed in the range of 50 to 2000 standard liters of H2 / liter of reactor feed.

[0204] In certain embodiments, the hydroprocessing in reactor A and / or reactor B may be hydrofinishing. For example, this may be beneficial when the hydrocarbon feed contains at least one or more of organic oxygen impurities, organic sulfur impurities, olefins, and / or metal impurities in addition to nitrogen impurities, and / or if, for example, ultra-low levels of nitrogen, oxygen, sulfur, olefins, and / or metals, or even their removal, are desired for all or some of the recovered liquid transportation fuel components or for other product fractions that may be recovered from the process. In embodiments where the hydroprocessing in reactor A and / or B is hydrofinishing, the levels of these impurities in the respective hydroprocessing effluents may be reduced, for example, to less than 50% of their content, or even completely eliminated, i.e., below the detection limit of the respective analytical methods, prior to hydrofinishing.

[0205] Preferably, the temperature is in the range of about 150°C to 400°C, the pressure is in the range of 0.5MPa to 15MPa, and the reaction mixture is heated for 0.5 to 3 hours. -1 The hydrotreating is carried out at a liquid hourly space velocity in the range of and a ratio of H2 to reactor feed in the range of 50 to 2000 standard liters of H2 / liter of reactor feed.

[0206] In particular, when operating according to the second exemplary aspect, the process of the present invention may include subjecting the hydroprocessing effluent A (in the first mode) and / or the hydroprocessing effluent B (in the second mode) to fractionation to separate at least a recycle stream having a T5 temperature (recovery 5 vol%, EN ISO 3405-2019) of 270° C. or higher from the hydroprocessing effluent. In the second exemplary aspect, the total feed initially subjected to fractionation is the hydroprocessing effluent A (in the first mode) or the hydroprocessing effluent B (in the second mode), optionally after gas-liquid separation is performed integrally in the reactor A or B, and since the process remains in operation, the total feed subjected to fractionation comprises the hydroprocessing effluent A and the hydroprocessing effluent B, which effluents are preferably combined.

[0207] In addition, the method variants or embodiments according to the first and third exemplary aspects benefit from separating the recycle stream as disclosed herein from the fractionation, while operating the method in the first mode or in the second mode, or in both the first and second modes. When the method is operated in the second mode, this can be particularly beneficial because separating the recycle stream and hydrotreating it again helps to further compensate for the deactivation of the hydrotreating catalyst at least to some extent. In the embodiments of the first and third exemplary aspects, when the reactor A and / or B feed contains a recycle stream or a portion thereof, the amount of the portion or stream can vary, but is generally only a small portion of the feed to each reactor. In the embodiments according to the first and third exemplary aspects, the reactor A and / or B feed may contain less than 50wt%, preferably less than 30wt%, and more preferably less than 10wt% of the recycle stream based on the total weight of the feed to each reactor. In other words, in the embodiments according to the first and third exemplary aspects, the recycle stream or a portion thereof may account for less than 50wt%, preferably less than 30wt%, and more preferably less than 10wt% of the total weight of the feed to each reactor.

[0208] Preferably, the recycle stream has a T5 temperature of 275°C or higher. In certain preferred embodiments, the T5 temperature of the recycle stream is in the range of 270°C to less than 300°C, preferably in the range of 270°C to less than 295°C, more preferably in the range of 270°C to less than 290°C; and / or the initial boiling point (IBP, EN ISO 3405-2019) is less than 290°C, preferably less than 288°C, more preferably less than 285°C, or less than 280°C. The recycle stream may have the FBP of the total feed to be fractionated, i.e., the recycle stream may comprise the bottom heavy product of the total feed to be fractionated.

[0209] Preferably, the T5 temperature of the recycle stream is selected so that at least a portion of the C16 normal paraffins (if any) present in the total feed to be fractionated are recovered in the recycle stream. Recovery of the C16 normal paraffins in the recycle stream can be achieved by appropriately selecting the T5 temperature and / or IBP of the recycle stream. The boiling point of C16 normal paraffins is 287°C (at atmospheric pressure), but since fractionation (such as distillation separation) is not very precise, it is possible to recover C16 normal paraffins within a temperature range near this boiling point. Preferably, the recycle stream contains C16 normal paraffins.

[0210] It is beneficial to recycle at least some of the C16 normal paraffins to reactor A and / or B for hydrotreating again because the C16 normal paraffins have a relatively high melting point. Therefore, any large presence of C16 normal paraffins (for example) in the recovered aviation fuel component may even make the aviation fuel component unusable in the aviation fuel composition due to poor low temperature properties, especially poor freezing points, and / or poor, i.e. high, kinematic viscosity at sub-zero temperatures, such as -20°C or -40°C. In any case, the C16 normal paraffins in the recovered aviation fuel component impair its low temperature properties, i.e., increase one or more of the cloud point, freezing point, pour point, cold filter plugging point and / or sub-zero kinematic viscosity compared to aviation fuel components with less or no C16 normal paraffin content. Preferably, the recycle stream comprises at least 20wt% or at least 30wt%, more preferably at least 40wt% or at least 50wt% of the C16 normal paraffins in the total feed for fractionation. In the total feed to be fractionated, the amount of n-paraffins, including C16 n-paraffins, may increase upon deactivation of the hydrotreating catalyst and may also be formed by cracking in reactors A and / or B.

[0211] In some particularly preferred embodiments, the recycle stream comprises at least 85wt%, preferably at least 90wt%, more preferably at least 95wt% C16+ paraffins of the total weight of paraffins in the recycle stream. It is beneficial to hydrotreat the C16+ paraffins again in reactor A and / or B because it can increase the yield and / or improve the quality of aviation fuel components. C16+ normal paraffins (normal paraffins with a carbon number of at least C16) have poor low temperature properties, while C18+ normal paraffins (normal paraffins with a carbon number of at least C18) usually boil outside the aviation fuel boiling range.

[0212] Typically, the recycle stream comprises at least 60wt% of the total weight of the recycle stream, preferably at least 70wt%, more preferably at least 80wt%, even more preferably at least 90wt% or at least 95wt% paraffin, or the recycle stream can even be substantially composed of paraffin. Especially when using a high paraffin feed, this situation can be achieved. In some particularly preferred embodiments, the recycle stream comprises at least 50wt% of the total weight of paraffin in the recycle stream, preferably at least 60wt%, more preferably at least 70wt% or at least 80wt%, and / or up to 100wt%, or 98wt% isoparaffin at the most, and / or at least 5wt% of the total weight of paraffin in the recycle stream, or at least 10wt%, preferably at least 15wt% or at least 20wt% of multi-branched isoparaffin. Typically, the recycle stream comprises up to 95 wt% or up to 90 wt%, or up to 80 wt%, or up to 70 wt%, such as up to 60 wt%, or up to 50 wt%, or up to 40 wt%, sometimes up to 30 wt%, or even up to 20 wt% of hyperbranched isoparaffins, typically in the range of 5 wt% to 95 wt%, preferably 5 wt% to 80 wt%, or 5 wt% to 70 wt%, such as 10 wt% to 70 wt%, or 15 wt% to 65 wt% of hyperbranched isoparaffins, based on the total weight of paraffins in the recycle stream. Typically, the cloud point of the recycle stream is less than 0°C, preferably less than -5°C, more preferably less than -10°C, even more preferably less than -20°C, further preferably less than -30°C (ASTM D 5771-17).

[0213] Such a recycle stream has a beneficial composition in view of the effective degree of cracking and / or degree of isomerization, thereby forming more hydrocarbons boiling in the aviation fuel range and also in the gasoline boiling range, because paraffinic hydrocarbons are generally easier to crack and isomerize than cyclic hydrocarbons, longer paraffinic hydrocarbons are easier to crack than shorter paraffinic hydrocarbons and have room to accommodate more branched chains, and isoparaffinic hydrocarbons are expected to be easier to crack than normal paraffinic hydrocarbons, and the relative uniformity of the composition of the recycle stream can make subsequent hydroprocessing conditions easier to optimize. In addition, these embodiments facilitate the easy separation of (for example) diesel fuel components, marine fuel components, base oil components and / or transformer oil components by only diverting from the recycle stream, and the above only illustrates the components that can be separated from such recycle streams and recovered as product streams. In these embodiments, a portion of the recycle stream is fed to reactor A and / or B for hydroprocessing as described above, and another portion of the recycle stream is recovered, preferably the recycle stream is diverted into a portion fed to reactor A and / or B for hydroprocessing and a portion recovered.

[0214] Both the hydrotreating catalyst A and the hydrotreating catalyst B can be arranged in one or more catalyst beds within each reactor. The hydrotreating catalyst A and the hydrotreating catalyst B can be arranged in at least one or more fixed beds, respectively. The method according to the third exemplary aspect generally does not include a reactor B or a hydrotreating catalyst B, but the hydrotreating catalyst A in the reactor A of the method according to the third exemplary aspect can be arranged as described herein and as described herein. Preferably, the hydrotreating catalyst A in the reactor A and the hydrotreating catalyst B in the reactor B are bifunctional hydrotreating catalysts, more preferably non-sulfurized bifunctional hydrotreating catalysts. In certain preferred embodiments, the hydrotreating catalyst A and the hydrotreating catalyst B are selected independently of each other from any commonly used bifunctional HI catalyst and any commonly used bifunctional HC catalyst.

[0215] The HI catalyst is selective for isomerization, i.e., is capable of converting at least a certain amount of normal paraffins into isoparaffins, in particular into monobranched isoparaffins, and / or converting monobranched isoparaffins into multibranched isoparaffins, such as dibranched and / or tribranched isoparaffins, even isoparaffins containing more than three branches. The HC catalyst is capable of cracking hydrocarbon molecules. In the process of the present invention, it is particularly desirable to have an HC catalyst capable of cracking effectively, i.e., obtaining non-gaseous (NTP) cracked products, in particular as expressed herein as the ratio of the C8 to C14 hydrocarbon content in the reactor effluent to the C8 to C14 hydrocarbon content in the corresponding reactor feed.

[0216] Bifunctional hydroprocessing catalysts, such as bifunctional HI and HC catalysts, contain metal sites for catalyzing (de)hydrogenation reactions and acid sites for catalyzing isomerization and cracking reactions. Bifunctional hydroprocessing catalysts, such as bifunctional HI catalysts and bifunctional HC catalysts, are well known in the field of oil refining and in the field of renewable fuel production. Bifunctional hydroprocessing catalysts are preferred because they have excellent catalytic performance, thereby providing a synergistic effect between metal sites and acid sites. Bifunctional hydroprocessing catalysts are also beneficial because the entry and diffusion of molecules to the catalytic sites can be controlled by appropriately selecting the pore characteristics of the catalyst, especially the pore size, pore size and / or pore connectivity in the catalyst.

[0217] In certain particularly preferred embodiments, hydroprocessing catalyst A and hydroprocessing catalyst B are independently selected from a non-sulfided bifunctional hydroprocessing catalyst comprising at least one or more noble metals from Group VIII of the Periodic Table of Elements, more preferably Pt and / or Pd, and at least one or more acidic porous materials, and wherein the reactor A feed and the reactor B feed, respectively, contain less than 50 wt-ppm, preferably less than 30 wt-ppm, more preferably less than 10 wt-ppm sulfur (ppm by weight, calculated as elemental S), based on the respective total feeds, as determined according to ISO 20846-2019.

[0218] Sulfur content can be determined from liquids according to ISO 20846-2019 or from gas fractions according to ASTM-D6667.

[0219] Non-sulfided bifunctional catalysts are preferred because they do not require sulfidation to maintain their activity during operation, and thus the sulfur content of the various process streams can be kept lower and less efficient HS separation and recovery from the various process streams is required. In particular, non-sulfided bifunctional catalysts containing noble metals can be active at lower temperatures and show higher selectivity for isomerization reactions than sulfided catalysts, but are sensitive to deactivation by HS.

[0220] Preferably, the Reactor A feed and the Reactor B feed each contain less than 50 wt-ppm, preferably less than 30 wt-ppm, more preferably less than 10 wt-ppm sulfur (ppm by weight, calculated as elemental S), as determined according to ISO 20846-2019.

[0221] Similarly, the Reactor A feed of the process according to the third example aspect may be a low sulfur feed as described above.

[0222] The very low sulfur content in the stream entering reactor A is beneficial because in most catalytic processes involving metal catalysts, sulfur impurities are known to be adsorbed over large areas essentially irreversibly, leading to a variety of problems. In these embodiments, there is greater freedom in catalyst selection, and liquid transportation fuel components with ultra-low sulfur content are available. In addition, since less H2S will be present, less corrosion is also expected in the long term, and potentially for some equipment materials, even less stringent corrosion resistance requirements may apply.

[0223] A variety of different types of bifunctional hydroprocessing catalysts, such as 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.

[0224] Bifunctional hydroprocessing catalysts, including bifunctional HC catalysts and bifunctional HI catalysts, are similar in that they all contain metal sites capable of catalyzing the hydrogenation (dehydrogenation) of normal / isoparaffins to corresponding normal / isoolefins, and acid sites capable of catalyzing the protonation of normal / isoolefins to normal / isocarbocations, further isomerization of normal / isocarbocations or isocarbocations, and / or cracking of normal / isocarbocations to lighter normal / isoolefins and lighter normal / isocarbocations, and deprotonation of normal / isocarbocations to normal / isoolefins. The hydrogenation of various normal / isoolefins is catalyzed again by the metal sites of these bifunctional catalysts to form normal / isoparaffins. For example, under given operating conditions and given feed composition, which isomerization reaction or cracking reaction is dominant can be particularly affected by the characteristics of the bifunctional catalyst in contact with the feed. These characteristics of the bifunctional catalyst include, for example, the total acidity of the catalyst, the number of Bronsted acid sites, the strength and / or density of the acid sites, and the content of metal in the catalyst.

[0225] Preferably, hydroprocessing catalyst A and hydroprocessing catalyst B independently of each other comprise at least one or more metals selected from Group VIII of the periodic table, preferably metals selected from noble metals of Group VIII, more preferably metals selected from Pt and / or Pd. Noble metals are preferred because they can provide higher selectivity for the desired reaction under operating conditions compared to catalysts comprising only non-noble metals, and have high activity at lower operating temperatures. High activity at lower temperatures provides a wider temperature range, within which the temperature can be adjusted during operation, usually increasing the temperature. The gradual deactivation of the catalyst that occurs when the method is operated for a longer period of time can be compensated to a certain extent by increasing the temperature in the reactor.

[0226] Preferably, hydroprocessing catalyst A and hydroprocessing catalyst B independently of each other comprise at least one or more porous acidic materials having a microporous, mesoporous or hierarchical (microporous-mesoporous) structure. Various zeolite-type materials, such as SAPO and zeolite, are available for providing the desired acidity and pore characteristics.

[0227] According to certain preferred embodiments, the hydrotreatment in reactor A and / or reactor B is hydroisomerization, and the hydrotreatment catalyst A and / or the hydrotreatment catalyst B (when the hydrotreatment in each reactor is HI) are independently selected from bifunctional hydroisomerization catalysts, preferably non-sulfided bifunctional hydroisomerization catalysts, which include

[0228] At least one or more metals selected from Group VIII of the Periodic Table of Elements, preferably selected from noble metals of Group VIII, more preferably selected from metals of Pt and / or Pd; and

[0229] at least one or more acidic porous materials selected from zeolites and / or zeolite-type materials, wherein preferably at least one or more zeolites and / or zeolite-type materials have a framework type selected from the following: AEL, ATO, AFO, MRE, MTT, MTW, TON, MRT, MOR, FER and / or MWW, preferably at least one or more acidic porous materials selected from SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23, ZSM-48, NU-10, ZBM-30, IZM-2, EU-2 and / or mordenite, more preferably at least one or more acidic porous materials selected from SAPO-11, SAPO-41, ZSM-23 and / or ZSM-48; and

[0230] Optionally at least one or more of alumina, silica, amorphous silica-alumina, titania, titania and / or zirconia.

[0231] It has been found that this catalyst selection provides a higher isomerization selectivity, which further helps to achieve even higher amounts of isoparaffins, especially multi-branched isoparaffins, which are very beneficial for the properties of liquid transportation fuel components. The SAPOs and zeolites mentioned are commercially available and have acidic and pore characteristics that allow isomerization of n-paraffins, even long chain n-paraffins, such as C16+ paraffins, including multi-branching.

[0232] According to certain embodiments, the hydroprocessing in reactor A and / or reactor B is hydrocracking, and the hydroprocessing catalyst A and / or the hydroprocessing catalyst B (when the hydroprocessing in each reactor is HC) are independently selected from bifunctional hydrocracking catalysts, preferably from non-sulfided bifunctional hydrocracking catalysts, which include

[0233] 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

[0234] At least one or more acidic porous materials selected from zeolites, zeolite-type materials and / or amorphous silica-alumina, wherein preferably at least one or more zeolites or zeolite-type materials have a framework type selected from MFI, BEA, FAU, MOR, FER, AEL, AFI, ATO, AFO, MRE, MTT, MTW, TON and / or MRT, preferably at least one or more acidic porous materials selected from SAPO-5, SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23, ZSM-43, ZSM-48, IZM-2, mordenite, β-zeolite, Y-type zeolite and / or amorphous silica-alumina, more preferably at least one or more acidic porous materials selected from SAPO-5, SAPO-11, ZSM-23, β-zeolite, Y-type zeolite and / or amorphous silica-alumina; and

[0235] Optionally, at least one or more of alumina, silica, titanium alumina, titania and / or zirconium oxide.

[0236] This catalyst selection has been found to be highly beneficial, since, in addition to the cracking activity, they also have a certain isomerization activity and can be particularly effective in effective cracking. As a further advantage, it has been found that bifunctional HC catalysts comprising at least one or more metals selected from Group VIII noble metals, preferably selected from Pt and / or Pd, provide high activity at relatively low temperatures and thus even better control of thermal cracking compared to HC catalysts comprising non-noble metals. At low temperatures, the thermodynamic equilibrium tends to shift towards dearomatization, thus reducing the formation of aromatics by side reactions. Providing a bifunctional HC catalyst to the reactor makes it possible to achieve excellent isoparaffin contents (wt% of isoparaffins on the total weight of paraffins) in the reactor effluent, even approaching isoparaffin contents obtainable by bifunctional HI catalysts.

[0237] In the process of the present invention, a hydrocarbon feed is hydrotreated in the presence of a hydrotreating catalyst A, and optionally a hydrotreating effluent A or a recycle stream is hydrotreated in the presence of a hydrotreating catalyst B. The hydrotreating catalyst A and the hydrotreating catalyst B may have similar or identical components. According to a preferred embodiment, the hydrotreating catalyst A and the hydrotreating catalyst B are different from each other. The hydrotreating catalyst A and the hydrotreating catalyst B may differ from each other in, for example, the selection of at least one or more of the catalyst components, acidity and / or metal loading, to name just a few examples, but it is also possible to use the same catalyst as the hydrotreating catalyst A in reactor A and the hydrotreating catalyst B in reactor B. Not only the catalyst, but also the operating conditions and the feed composition play a role in which reaction is dominant. When the hydroprocessing effluent A or the recycle stream is contacted with the hydroprocessing catalyst B under hydroprocessing conditions in reactor B (according to the first process mode of the first and second exemplary aspects, respectively), it can be expected that the hydroprocessing effluent B has a different composition and properties compared to the composition and properties of the hydroprocessing effluent A obtained by contacting the hydrocarbon feed with the hydroprocessing catalyst A under hydroprocessing conditions in reactor A, even if the catalyst is the same.

[0238] In certain embodiments, the hydroprocessing catalyst A in reactor A and the hydroprocessing catalyst B in reactor B have different acidity-related characteristics. The acidity-related characteristics of acidic porous materials, such as zeolites, can include the nature, number and distribution of acidic sites in terms of relative strength, and can be determined by well-known methods, such as by adsorption-desorption methods, in which the release of adsorbed basic substances, such as ammonia or pyridine at higher temperatures indicates the presence of strong acidic sites. As an example of a useful adsorption-desorption method, the temperature-programmed desorption of ammonia can be mentioned, for example, according to the procedure described in Niwa et al. (Niwa, M., Katada, N. Measurements of acidic property of zeolites by temperature programmed desorption of ammonia. Catalysis Surveys from Asia1, 215–226 (1997)). Another well-known method for determining the acidity of zeolites, including acid strength, is 1 H-NMR method, for example, as described in Heeribout et al. (Heeribout L., Semmer V., Batamack P., Dorémieux-Morin C., Fraissard J. Brønsted acid strength of zeolites studied by1 H NMR: scaling, influence of defects. Microporous and Mesoporous Materials, Vol. 21, No. 4–6, May 1998, pp. 565–570).

[0239] In certain embodiments, particularly when the hydroprocessing in reactor A is HI and the hydroprocessing in reactor B is HC, the bifunctional hydroprocessing catalyst B of reactor B has a higher number of Bronsted acid sites as determined by NH3-TPD compared to the bifunctional hydroprocessing catalyst A of reactor A. In certain embodiments, particularly when the hydroprocessing in reactor A is HI and the hydroprocessing in reactor B is HC, the bifunctional hydroprocessing catalyst B has a higher total number of acid sites as determined by NH3-TPD compared to the bifunctional hydroprocessing catalyst A.

[0240] The hydroprocessing catalysts A and B may be in a ready-to-use state as such, or they may be treated in any conventional manner to adjust their properties, such as selectivity and / or activity, before or during startup, by subjecting them to reduction, sulfidation and / or passivation, for example, with nitrogen-containing compounds such as amines or ammonia, to obtain ready-to-use fresh or regenerated hydroprocessing catalysts A and / or B. As used herein, hydroprocessing catalyst A, hydroprocessing catalyst B, fresh catalyst and regenerated catalyst generally refer to the catalysts in their ready-to-use state.

[0241] In certain embodiments, the hydroprocessing catalyst A in reactor A and the hydroprocessing catalyst B in reactor B comprise a hydrocracking catalyst and a hydroisomerization catalyst arranged in series, particularly in at least one or more separate beds. In these embodiments, it is preferred to use a bifunctional HC and HI catalyst, more preferably a non-sulfided bifunctional HC and HI catalyst.

[0242] In embodiments where the hydroprocessing in reactors A and / or B is hydrodearomatization, the respective hydroprocessing catalysts may be any catalyst commonly used for hydrodearomatization. Preferably, non-sulfided catalysts comprising precious metals are used, more preferably non-sulfided bifunctional catalysts comprising precious metals, because these catalysts are already active in HDA at lower temperatures, which is beneficial because the thermodynamic equilibrium tends to shift in the direction of dearomatization at low temperatures. In addition, in embodiments where both reactors A and B are operated using non-sulfided precious metal catalysts, no sulfur addition is required to maintain catalyst activity, and less or no work is required to separate sulfur-containing compounds, especially H2S, from the gaseous portion of the reactor effluent, and recovered liquid transportation fuel components and optional other product fractions having both ultra-low aromatics and sulfur contents are available.

[0243] In embodiments where the hydroprocessing in reactors A and / or B is hydrofinishing, the respective hydroprocessing catalysts may be any catalyst commonly used for hydrofinishing. Preferably, non-sulfided catalysts comprising noble metals are used, more preferably non-sulfided bifunctional catalysts comprising noble metals, since these catalysts are already active at lower temperatures and thus provide the widest window for increasing the temperature during continued operation to compensate for catalyst deactivation.

[0244] The process of the present invention comprises fractionation, wherein at least one or more liquid transportation fuel components are recovered and a recycle stream can be separated. In embodiments or aspects in which a recycle stream is separated, the amount of the recycle stream separated and the amount of the recycle stream fed to reactor A and / or B can vary over a wide range. Other liquid streams or fractions, such as side streams, can optionally be separated and / or recovered from the fractionation and optionally recycled back into the process.

[0245] Preferably, in the method of the second exemplary aspect, the weight ratio of the hydroprocessing effluent B subjected to fractionation to the hydroprocessing effluent A is 1: 10 to 10: 1, such as 1: 5 to 5: 1. When operating i), ii), iii), that is, in the first method mode, when a hydrocarbon feed boiling at a lower temperature is processed, a ratio close to the lower limit may be preferred, and when a hydrocarbon feed boiling at a lower altitude (such as a feed containing paraffin hydrocarbons heavier than C18) is processed, a ratio close to the upper limit may be preferred.

[0246] In certain embodiments, the reactor A feed and / or the reactor B feed may include a side cut separated from the fractionation of the inventive method. The side cut is preferably included in the reactor A feed and / or the reactor B feed as a minor component. The side cut is preferably a cut rich in C14-18 hydrocarbons, more preferably a cut rich in C15-C17 hydrocarbons. The side cut is preferably a relatively narrow cut to allow accurate changes in the boiling point distribution of the total feed of the fractionation. The introduction of this side cut in the reactor A feed and / or the reactor B feed can improve the quality of the recovered liquid transportation fuel component or at least some of the recovered liquid transportation fuel components, particularly the aviation fuel component. The side cut may have an elevated isoparaffin content. Therefore, the inclusion of the side cut in the reactor A feed and / or the reactor B feed can increase the isoparaffin content of each feed. In addition, hydrotreating generally has an impurity removal effect on the treated stream, especially when it is followed by gas-liquid separation. Thus, incorporating even a small amount of the side draw into the Reactor A feed and / or the Reactor B feed can reduce or dilute the impurity content of each feed, thereby reducing the rate of deactivation of the hydroprocessing catalyst in each reactor.

[0247] The fractionation of the inventive method may comprise any commonly used fractionation technique. Preferably, the fractionation comprises distillation, such as atmospheric distillation or vacuum distillation. The fractionation may be preceded by a gas-liquid separation, for example, as described below.

[0248] The fractionation can be performed in a fractionation system comprising one or more fractionation units. For example, the gas and light naphtha can be separated in a pre-fractionation unit, while the liquid transportation fuel components and the recycle stream can be recovered and separated from the main distillation unit downstream of the pre-fractionation unit. In an alternative example, a single fractionation unit can be used.

[0249] In the method according to the first exemplary aspect, the hydroprocessing effluent from the reactors arranged in the first mode in each mode (reactor A in the first mode and reactor B in the second mode) is subjected to separation of compounds that are gaseous at NTP, for example, by gas-liquid separation, and then the degassed hydroprocessing effluent is fed to the reactors arranged in the second mode in each mode (reactor B in the first mode and reactor A in the second mode), while the hydroprocessing effluent from the reactors arranged in the second mode in each mode can be subjected to separation of compounds that are gaseous at NTP, for example, by gas-liquid separation in fractionation. In the methods according to the second and third exemplary aspects, the hydroprocessing effluent can be subjected to separation of compounds that are gaseous at NTP, for example, by gas-liquid separation in fractionation. In all exemplary aspects and operating modes, the separation of compounds that are gaseous at NTP can be performed as a gas-liquid separation, for example, in each reactor, or as an integrated step in a separate gas-liquid separation unit that can follow each reactor.

[0250] Typically, the gas-liquid separation is carried out at a temperature in the range of 0°C to 500°C, such as 15°C to 300°C, or 15°C to 150°C, preferably 15°C to 65°C, such as 20°C to 60°C, and preferably at the same pressure as the reactor from which the effluent originates. Typically, the pressure during gas-liquid separation may be in the range of 0.1 MPa to 20 MPa, preferably in the range of 1 MPa to 10 MPa, or in the range of 3 MPa to 7 MPa.

[0251] According to certain embodiments of the process of the present invention, different liquid transportation fuel components and other products may be recovered from fractionation based on, for example, the type of hydroprocessing in reactors A and B (or reactor A in the process according to the third exemplary aspect), the selected operating conditions, the composition of the hydrocarbon feed used, the primary operating mode (first or second), the then-recognized performance of hydroprocessing catalysts A and B (or hydroprocessing catalyst A in the process of the third exemplary aspect), and / or existing or anticipated market demand. In this context, different liquid transportation fuel components and other products means that sometimes different product fraction selections can be recovered, and / or sometimes the recovered product fractions can have different chemical compositions and / or properties.

[0252] The liquid transportation fuel components and optional other products separated and / or recovered from the fractionation may, for example, include a gasoline fuel component boiling in the range of about 25°C to about 200°C, an aviation fuel component boiling in the range of about 100°C to about 300°C, such as in the range of about 150°C to about 300°C, a recycle stream having a T5 temperature of at least 270°C, a diesel fuel component boiling in the range of about 160°C to about 380°C and / or a marine fuel component boiling in the range of about 180°C to about 600°C, such as in the range of about 180°C to about 400°C (boiling in the range as determined according to EN ISO 3405-2019). In certain embodiments, a gasoline fuel component boiling in the range of about 25°C to about 200°C, an aviation fuel component boiling in the range of about 100°C to about 300°C, such as about 150°C to about 300°C, and a recycle stream having a T5 temperature of at least 270°C are first recovered and / or separated from the fractionation, and a diesel fuel component boiling in the range of about 160°C to about 380°C and / or a marine fuel component boiling in the range of about 180°C to about 600°C (boiling in the range as determined according to EN ISO 3405-2019) are recovered from the separated recycle stream. Other products may be recovered from the fractionation, such as the split stream, or further separated from the gasoline fuel component, the aviation fuel component, the diesel fuel component, the marine fuel component, and / or the recycle stream. Examples of these other products include components for solvents, electrical fluids, and base oils.

[0253] Using the process of the present invention, it is possible to produce a low viscosity aviation fuel component having a lower freezing point, especially a lower kinematic viscosity at -20°C, compared to an aviation fuel component having similar IBP and FBP and recovered at the same operating time, but produced by conventional HDO of a fat feedstock followed by HI (i.e., without switching from the first mode to the second mode as in the process of the present invention).

[0254] Therefore, in a preferred embodiment of the process of the present invention, in steps iii) and III), the at least one liquid transportation fuel component recovered from the fractionation is an aviation fuel component having a density at 15°C in the range of 730 to 772 kg / m 3 In some embodiments, the recovered aviation fuel component has a T10 temperature of at most 205°C (EN ISO 3405-2019), a T10 temperature of at most 205°C (EN ISO 3405-2019), a final boiling point of at most 300°C (EN ISO 3405-2019), a flash point of at least 38°C (IP 170-2013, Abel closed cup method) and a freezing point of at most -40°C (IP 529-2016). In these embodiments, the recovered aviation fuel component has a high quality and can be blended into the aviation fuel composition in an increased amount. Typically, the T10 and T90 temperatures of the recovered aviation fuel component are in the range of 120°C to 295°C, preferably in the range of 130°C to 295°C, as determined according to EN ISO 3405-2019.

[0255] The process of the present invention is capable of recovering at least aviation fuel components at surprisingly high yields, even near the end of the life of the hydroprocessing catalyst A. In certain preferred embodiments of the process of the present invention, aviation fuel components are recovered at a yield of 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 hydrocarbon feed. In certain preferred embodiments, the difference between the T90 and T10 temperatures of the aviation fuel component as determined according to EN ISO 3405-2019 is at least 70 ° C, preferably at least 75 ° C, more preferably at least 80 ° C, even more preferably at least 85 ° C, typically up to 180 ° C, such as in the range of 80 ° C to 150 ° C, preferably in the range of 80 ° C to 130 ° C. In these embodiments, aviation fuel components can be recovered at improved yields while achieving desired low temperature properties, density and flash point characteristics. Poor quality of the total feed to the fractionation would require severe limitation of the FBP to meet the low temperature property requirements, which would also limit the T90 temperature and narrow the T90-T10 difference. However, in this context, even near the end of the life of the hydroprocessing catalyst A, the process of the present invention is able to provide superior characteristics such as a high degree of isomerization, especially a high multi-branched isoparaffin content, and an altered distillation profile because the amount of carbon number can be more uniformly distributed, especially in the range of C6-C18.

[0256] Typically, in the process of the present invention, in steps iii) and III), at least one or more aviation fuel components, diesel fuel components, gasoline fuel components and / or marine fuel components are recovered from fractionation, preferably at least aviation fuel components are recovered from fractionation, more preferably at least aviation fuel components and diesel fuel components, or at least aviation fuel components and gasoline fuel components, even more preferably at least aviation fuel components, diesel fuel components and gasoline fuel components. Typically, in embodiments or aspects involving separation and recycling of recycle streams, preferably at least regularly recover at least one heavy product from fractionation, such as diesel fuel components, marine fuel components and / or base oil components. In this way, the heaviest components can be removed from the recycle loop.

[0257] In certain preferred embodiments, the recovered liquid transportation fuel component has a biogenic carbon content of at least 50 wt%, preferably at least 70 wt%, more preferably at least 90 wt%, further preferably at least 95 wt%, or even about 100 wt%, based on the total weight of carbon (TC) in the corresponding recovered liquid transportation fuel component (EN 16640 (2017)). The biogenic carbon content in the recovered liquid transportation fuel component is mainly affected by the biogenic carbon content in the hydrocarbon feed, and in certain preferred embodiments, mainly by the oxygenated hydrocarbon feed subjected to HDO. However, for example, any amount of fossil hydrocarbon diluent fed to the HDO reactor may affect the biogenic carbon content of the recovered liquid transportation fuel component.

[0258] The liquid transportation fuel component recovered in the process of the present invention may have an improved (increased) isoparaffin content, particularly a multi-branched isoparaffin content, an increased C8-C14 hydrocarbon content and / or a reduced aromatic content, compared to the corresponding component obtained by conventional HDO of a fat feedstock followed by HI. The aviation fuel component recovered from the process of the present invention may contain at least 85 wt%, preferably at least 87 wt%, more preferably at least 90 wt%, even more preferably at least 92 wt% of C6 to C18 isoparaffins, based on the total weight of the aviation fuel component; and / or at least 58 wt%, preferably at least 60 wt%, more preferably at least 62 wt% of C6-C18 multi-branched isoparaffins, based on the total weight of the aviation fuel component. The diesel fuel component recovered from the method of the present invention may contain at least 70wt% of the diesel fuel component weight, preferably at least 75wt%, more preferably at least 80wt%, even more preferably at least 90wt% of C15-C22 isoparaffins; and / or at least 60wt% of the diesel fuel component weight, preferably at least 63wt%, more preferably at least 65wt% of C15-C22 multi-branched isoparaffins. The gasoline fuel component recovered from the method of the present invention may contain at least 50wt% of the gasoline fuel component weight, preferably at least 55wt%, more preferably at least 60wt%, even more preferably at least 65wt% of C4-C9 isoparaffins; and / or at least 5wt% of the gasoline fuel component weight, preferably at least 6wt%, more preferably at least 7wt%, even more preferably at least 10wt%, or at least 11wt% of C6-C9 multi-branched isoparaffins.

[0259] Even though each of the gasoline fuel component, aviation fuel component and diesel fuel component can be recovered simultaneously in the process of the present invention, they can be recovered as reasonably broad fractions. When optimizing the yield of the aviation fuel component, the diesel fuel component can be recovered as a narrower fraction, or not recovered at all.

[0260] The products recovered from the process of the invention have excellent characteristics. The recovered liquid transportation fuel component is suitable for use as a blending component in a fuel composition and, when appropriately added, can even be used as a fuel itself, ie as an unblended component. The recovered liquid transportation fuel components and optional other products are suitable for a wide variety of other uses, such as in feedstocks for industrial conversion processes, preferably in thermal cracking feedstocks, such as steam cracking feedstocks and / or catalytic cracking feedstocks, in the production of transformer oils, heat transfer media, switchgear oils, shock absorber oils, insulating oils, hydraulic fluids, gear oils, transmission fluids, degreasing compositions, penetrating oils, anti-corrosion compositions, multi-purpose oils, metalworking fluids, rolling oils, especially for aluminum, cutting oils, drilling fluids, solvents, lubricants, extender oils, carriers, dispersant compositions, demulsifiers, extractants, paint compositions, coating fluids or pastes, adhesives, resins, varnishes, printing pastes or inks, detergents, cleaning agents, plasticizing oils, turbine oils, hydrophobic compositions, agriculture, crop protection fluids, construction, concrete release formulations, electronic equipment, medical devices, compositions for the automotive, electrical, textile, packaging, paper, cosmetic and / or pharmaceutical industries, and / or intermediates therefor. It is foreseen that the relatively high degree of isomerization and the increase in the shorter carbon chain fractions obtainable by the process of the present invention improve the flowability, pumping and mixing characteristics and miscibility of the recovered components and / or fractions. These are generally desirable and beneficial properties for a wide range of uses, particularly those involving spraying, injection and / or mixing with other ingredients.

[0261] Process diagram

[0262] Figure 1 The method according to the example implementation of the first example aspect is schematically shown before switching from i), ii), iii) to I), II), III), that is, before running (first mode) according to the example implementation of i), ii), iii). Figure 1 In the embodiment, an oxygenated hydrocarbon feed 110 is fed into an HDO reactor 120, wherein it is hydrodeoxygenated in the presence of an HDO catalyst 130 to obtain a hydrodeoxygenated effluent (HDO effluent) 140, and the obtained HDO effluent 140 is subjected to a gas-liquid separation 150 to separate a compound 160 that is gaseous at least at NTP from the HDO effluent to obtain a degassed HDO effluent 170, which in this example embodiment is a paraffinic hydrocarbon feed as defined herein. Then, Figure 1The degassed HDO effluent 170 in the reactor is fed to the reactor A 180, wherein the degassed HDO effluent 170 is hydrotreated in the presence of a hydrotreating catalyst A 190 to obtain a hydrotreated effluent A 200, and the obtained hydrotreated effluent A 200 is subjected to a gas-liquid separation 210 to separate a compound 220 that is gaseous at least at NTP from the hydrotreated effluent A 200 to obtain a degassed hydrotreated effluent A 230. Figure 1 In the reactor, the degassed hydroprocessing effluent A 230 is fed to the reactor B 240, where it is hydroprocessed in the presence of a hydroprocessing catalyst B 250 to obtain a hydroprocessing effluent B 260. Figure 1 In the process, the hydroprocessing effluent B 260 is subjected to a gas-liquid separation 270 to separate the compounds 280 that are gaseous at least at NTP from the hydroprocessing effluent B 260 to obtain a degassed hydroprocessing effluent B 290. Figure 1 In the embodiment of the present invention, the degassed hydroprocessing effluent B 290 is fed to a distillation unit 300, which may include a single column or a pre-fractionation column and a main distillation column, from which several streams or fractions may be obtained. Figure 1 In the distillation of , gasoline fuel component 310, aviation fuel component 320 and diesel fuel component 330 are recovered. In addition, a recycle stream 340, preferably having a T5 boiling point of 270°C or higher, may be optionally separated, in which case a fuel component, such as diesel fuel component 330, may be recovered by separation therefrom as a part. Figure 1 In the embodiment of the present invention, the recycle stream 340 can be fed as a co-feed with the degassed hydroprocessing effluent A 230 to the reactor B 240 for hydroprocessing.

[0263] Figure 2 Schematically shows the method according to the example implementation of the first example aspect after switching from i), ii), iii) to I), II), III), i.e. after running according to the example implementation of I), II), III) (second mode). Figure 2 In Figure 1 The process is performed as schematically shown in to obtain a degassed HDO effluent 170, which in this example embodiment is a paraffinic hydrocarbon feed as defined herein. Figure 2In the present invention, the degassed HDO effluent 170 is fed to the reactor B 240, wherein the degassed HDO effluent 170 is hydrotreated in the presence of a hydrotreating catalyst B 250 to obtain a hydrotreated effluent B 260, and the obtained hydrotreated effluent B 260 is subjected to a gas-liquid separation 270 to separate a compound 280 that is gaseous at least at NTP from the hydrotreated effluent B 260 to obtain a degassed hydrotreated effluent B 290. Figure 2 In the reactor A 180, the degassed hydroprocessing effluent B 290 is fed to the reactor A 180, wherein it is hydroprocessed in the presence of the hydroprocessing catalyst A 190 to obtain the hydroprocessing effluent A 200. Figure 2 In the process, the hydroprocessing effluent A 200 is subjected to gas-liquid separation 210 to separate the compound 220 which is gaseous at least at NTP from the hydroprocessing effluent A 200 to obtain the degassed hydroprocessing effluent A 230. Figure 2 In the embodiment of the present invention, the degassed hydroprocessing effluent A 230 is fed to a distillation unit 300 where it can be fractionated into several streams or fractions. Figure 2 Gasoline fuel component 310, aviation fuel component 320 and diesel fuel component 330 are recovered from the distillation in the reactor. In addition, a recycle stream 340, preferably having a T5 boiling point of 270° C. or higher, may be optionally separated, in which case a fuel component, such as diesel fuel component 330, may be recovered by separation therefrom as a part. Figure 2 In the embodiment of the present invention, the recycle stream 340 can be fed as a co-feed with the degassed HDO effluent 170 to the reactor B 240 for hydroprocessing.

[0264] Figure 3 The method according to the example implementation of the second example aspect is schematically shown before switching from i), ii), iii) to I), II), III), i.e. before running according to the example implementation of i), ii), iii) (first mode). Figure 3 In the example, an oxygenated hydrocarbon feed 510 is fed into an HDO reactor 520, wherein it 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 560 that is gaseous at least at NTP from the HDO effluent to obtain a degassed HDO effluent 570, which in this example embodiment is a paraffinic hydrocarbon feed as defined herein. Then, in Figure 3In the reactor A 580, the degassed HDO effluent 570 is fed to the reactor A 580, wherein the degassed HDO effluent 570 is hydrotreated in the presence of a hydrotreating catalyst A 590 to obtain a hydrotreated effluent A 600, and the obtained hydrotreated effluent A 600 is subjected to a gas-liquid separation 610 to separate a compound 620 that is gaseous at least at NTP from the hydrotreated effluent A 600 to obtain a degassed hydrotreated effluent A 630. Figure 3 In the embodiment of the present invention, the degassed hydroprocessing effluent A 630 is fed to a distillation unit 640, which may include a single column or a pre-fractionation column and a main distillation column, from which several streams or fractions may be obtained. Figure 3 The gasoline fuel component 650, the aviation fuel component 660 and / or the diesel fuel component 670 are recovered from the distillation in the reactor and further separated, preferably, a recycle stream 680 having a T5 boiling point of 270°C or higher. Figure 3 In the reactor B 690, the recycle stream 680 is fed to the reactor B 690, where it is hydrotreated in the presence of a hydrotreating catalyst B 700 to obtain a hydrotreating effluent B 710. Figure 3 In the embodiment, the hydroprocessing effluent B 710 is subjected to gas-liquid separation 720 to separate the compounds 730 which are gaseous at least at NTP from the hydroprocessing effluent B 710 to obtain the degassed hydroprocessing effluent B 740. Then, in Figure 3 In the embodiment of the present invention, degassed hydroprocessing effluent B 740 is fed as a co-feed with degassed hydroprocessing effluent A 630 to a distillation unit 640, from which several streams or fractions may be obtained, as described above.

[0265] Figure 4 The method according to the example implementation of the second example aspect is schematically shown after switching from i), ii), iii) to I), II), III), i.e. after running according to the example implementation of I), II), III) (second mode). Figure 4 In Figure 3 The process is performed as schematically shown in to obtain a degassed HDO effluent 570, which in this example embodiment is a paraffinic hydrocarbon feed as defined herein. Figure 4 In the present invention, the degassed HDO effluent 570 is fed to the reactor B 690, wherein the degassed HDO effluent 570 is hydrotreated in the presence of a hydrotreating catalyst B 700 to obtain a hydrotreated effluent B 710, and the obtained hydrotreated effluent B 710 is subjected to a gas-liquid separation 720 to separate a compound 730 that is gaseous at least at NTP from the hydrotreated effluent B 710 to obtain a degassed hydrotreated effluent B 740. Figure 4In the embodiment of the present invention, the degassed hydroprocessing effluent B 740 is fed to a distillation unit 640, from which several streams or fractions can be obtained. Figure 4 The gasoline fuel component 650, the aviation fuel component 660 and / or the diesel fuel component 670 are recovered from the distillation in the reactor and further separated, preferably, a recycle stream 680 having a T5 boiling point of 270°C or higher. Figure 4 In the reactor A 580, the recycle stream 680 is fed to the reactor A 580, where it is hydrotreated in the presence of a hydrotreating catalyst A 590 to obtain a hydrotreating effluent A 600. Figure 4 In the process, the hydroprocessing effluent A 600 is subjected to a gas-liquid separation 610 to separate compounds 620 that are gaseous at least at NTP from the hydroprocessing effluent A 600 to obtain a degassed hydroprocessing effluent A 630, and then the degassed hydroprocessing effluent A 630 is fed to a distillation unit 640 as a co-feed with the degassed hydroprocessing effluent B 740, as described above, and some streams or fractions can be obtained therefrom.

[0266] Figure 5 A method according to an example implementation of the third example aspect is schematically shown. Figure 5 In the embodiment, before switching from i), ii), iii) to I), II), III), i.e., when operating according to the exemplary embodiment of i), ii), iii) (first mode), an oxygenated hydrocarbon feed 810 is fed to an HDO reactor 820, wherein it is hydrodeoxygenated in the presence of an HDO catalyst 830 to obtain a hydrodeoxygenated effluent (HDO effluent) 840, and the obtained HDO effluent 840 is subjected to a gas-liquid separation 850 to separate compounds 860 that are gaseous at least at NTP from the HDO effluent to obtain a degassed HDO effluent 870, which in this exemplary embodiment is a paraffinic hydrocarbon feed containing nitrogen impurities as defined herein, and the degassed HDO effluent 870 is provided as a feed to the reactor A. Figure 5 In the reactor A 880, the degassed HDO effluent 870 is then fed to the reactor A 880, wherein the degassed HDO effluent 870 is hydrotreated in the presence of a hydrotreating catalyst A 890 to obtain a hydrotreated effluent A900. Figure 4 In the process, the obtained hydroprocessing effluent A 900 is subjected to gas-liquid separation 910 to separate the compound 920 which is gaseous at least at NTP from the hydroprocessing effluent A 900 to obtain the degassed hydroprocessing effluent A 930. Figure 5 In the embodiment of the present invention, the degassed hydroprocessing effluent A 930 is fed to a distillation unit 940, which may include a single column or a pre-fractionation column and a main distillation column, from which several streams or fractions may be obtained. Figure 5The distillation in the reactor A 880 recovers the gasoline fuel component 950, the aviation fuel component 960 and / or the diesel fuel component 970. In addition, the recycle stream 980 can be optionally separated and fed to the reactor A 880 as a co-feed with the degassed HDO effluent 870 for hydroprocessing. Preferably, the recycle stream 980 has a T5 boiling point of 270° C. or higher, at which time the diesel fuel component 970 can be recovered by separation therefrom as a part. Figure 5 In the example embodiment, after switching from i), ii), iii) to I), II), III), that is, when operating according to I), II), III) (second mode), the following can be done: Figure 5 The process is performed as schematically shown in and explained above for the first mode, except that this time a reactor A feed (ASTM D4629-17) 870' substantially free of nitrogen impurities is fed to reactor A 880 and hydrotreated in the presence of hydrotreating catalyst A 890. For example, the reactor A feed (ASTM D4629-17) 870' substantially free of nitrogen impurities can be obtained by selecting an oxygenated hydrocarbon feed 810' having a lower nitrogen impurity content than the oxygenated hydrocarbon feed 810 used in the first mode and / or by diluting the degassed HDO effluent 870 with an appropriate amount of a recycle stream 980 separated from fractionation 940 to achieve a target nitrogen impurity level. Although separating the recycle stream 980 is also an option in the first mode of the third exemplary aspect described above, it is a preferred option in the second mode because it provides a simple way to optimize the nitrogen impurity level in the feed fed to reactor A. Preferably, the recycle stream 980 has a T5 boiling point of 270°C or higher, and in the case of recovering the diesel fuel component 970, the diesel fuel component 970 can be separated from the recycle stream as a part, and the heavy hydrocarbon molecules present in the recycle stream can be repeatedly hydrotreated in reactor A in the presence of hydrotreating catalyst A, thereby compensating for the deactivation level of hydrotreating catalyst A at least to some extent.

[0267] Without being limited by the example embodiments presented in the accompanying drawings, in certain preferred embodiments of the process of the present invention in which at least an aviation fuel component is recovered from fractionation, when operating in the first mode, the monitored parameters indicative of deactivation of the hydroprocessing catalyst A include two or more of the following parameters: temperature, for example, WHSV in reactor A as monitored at the inlet of reactor A, temperature difference across reactor A or across a bed of hydroprocessing catalyst A, cloud point and / or pour point of the degassed hydroprocessing effluent A, cloud point and / or pour point of a recycle stream or diesel fuel component, freezing point of an aviation fuel component, and / or one or more distillation characteristics, the respective received values ​​of these parameters being compared with predetermined values. When the monitored parameter is temperature, for example, as monitored at the inlet of reactor A, the predetermined value may be, for example, a maximum of 450°C; for the WHSV in reactor A, the predetermined value may be, for example, 6 kg hydrocarbon feed / kg catalyst / hour; for the cloud point of the deaerated hydroprocessing effluent A, the predetermined value may be, for example, a maximum of -5°C; for the cloud point of the recycle stream or diesel fuel component, the predetermined value may be, for example, a maximum of -15°C (ASTM D 5771-2017); for the freezing point of the aviation fuel component, the predetermined value may be, for example, a maximum of -40°C (IP 529-201); for the distillation characteristics of the aviation fuel component, the predetermined value may be, for example, for T10, a maximum of 205°C, or for the T90-T10 difference, for example, a minimum of 22°C (EN ISO 3405-2019); for the distillation characteristics of the diesel fuel component, the predetermined value may be, for example, a maximum of 360°C for T95 (EN ISO 3405-2019). When the received value for the monitored parameter reaches the corresponding predetermined value, the process is switched to and operated in the second mode. After switching, the monitored parameters and predetermined values ​​may be the same as in the first mode, or different parameters may be monitored, and / or different predetermined values ​​may be selected, depending on, for example, whether the same product and its quality are still targeted.

[0268] The method as described herein can be controlled by prior art means, in particular by computer implementation. In certain exemplary embodiments, the method of the present invention further comprises causing the control device to perform at least the following steps: comparing the received value with a predetermined value; and switching from i), ii), iii) to I), II), III). In certain exemplary embodiments, the method of the present invention is controlled by a computer program product, as defined as a fourth exemplary aspect, which comprises instructions, when executed by a processor of a control device in a system for producing at least one liquid transportation fuel component, the instructions cause the control device to at least compare the received value with a predetermined value, and when the received value reaches a predetermined value, switch from i), ii), iii) of the method according to any of the exemplary aspects to I), II), III), and optionally switch back from I), ii), iii) of the method according to any of the exemplary aspects. The control device that executes the instructions of the computer program product can be (for example) a general-purpose computer or some other electronic data processing device including a processor and a (non-transitory) memory. The instructions of the computer program product can be stored in a memory for execution by a processor to cause the operation of the control device.

[0269] A number of embodiments have been provided.It should be understood that herein, the words "comprise", "include", and "contain" are each used as open expressions and are not intended to be exclusive.

[0270] The above description provides a comprehensive and informative description of the best mode currently considered by the inventors for implementing the present invention through non-limiting examples of specific implementations and embodiments. However, it is clear to those skilled in the art that the present invention is not limited to the detailed information of the embodiments present in the above, but in other embodiments, it can be implemented in an equivalent manner or in a combination of different embodiments without departing from the characteristics of the present invention.

[0271] In addition, some features of the example embodiments disclosed above can be used advantageously without the corresponding use of other features. Thus, the above description should be considered as merely an illustration of the principles of the present invention, rather than a limitation thereof. Therefore, the scope of the present invention is limited only by the attached patent claims.

Claims

1. A method for producing at least one liquid transportation fuel component, the method comprising: providing a hydrocarbon feed comprising nitrogen impurities; i) subjecting a reactor A feed comprising said hydrocarbon feed to hydrotreatment in the presence of a hydrotreatment catalyst A in a reactor A to obtain a hydrotreatment effluent A, and separating compounds that are gaseous at least at NTP from said hydrotreatment effluent A to obtain a degassed hydrotreatment effluent A; ii) hydrotreating a reactor B feed comprising said degassed hydroprocessing effluent A in the presence of a hydroprocessing catalyst B in reactor B to obtain hydroprocessing effluent B; iii) feeding said hydroprocessing effluent B to a fractionation, optionally after separation of at least compounds that are gaseous at NTP from said hydroprocessing effluent B, and recovering at least one or more liquid transportation fuel components from said fractionation; and monitoring a parameter indicative of deactivation of the hydroprocessing catalyst A to receive a value; comparing the received value to a predetermined value; and When the received value reaches the predetermined value, switch from i), ii), and iii) to: I) subjecting a reactor B feed comprising the hydrocarbon feed to hydrotreatment in the presence of the hydrotreatment catalyst B in a reactor B to obtain a hydrotreatment effluent B, and separating compounds that are gaseous at least at NTP from the hydrotreatment effluent B to obtain a degassed hydrotreatment effluent B; II) hydrotreating a reactor A feed comprising said degassed hydroprocessing effluent B in the presence of said hydroprocessing catalyst A in reactor A to obtain hydroprocessing effluent A; III) feeding said hydroprocessing effluent A to a fractionation, optionally after separation of at least compounds that are gaseous at NTP from said hydroprocessing effluent A, and recovering at least one or more liquid transportation fuel components from said fractionation.

2. A method for producing at least one liquid transportation fuel component, the method comprising: providing a hydrocarbon feed comprising nitrogen impurities; i) subjecting a reactor A feed comprising said hydrocarbon feed to hydrotreatment in reactor A in the presence of a hydrotreatment catalyst A to obtain a hydrotreatment effluent A, subjecting said hydrotreatment effluent A to fractionation and separating at least a recycle stream from said fractionation, said recycle stream having a T5 temperature of 270° C. or more (recovery 5 vol%, EN ISO 3405-2019) and optionally comprising C16 n-paraffins; ii) hydrotreating the reactor B feed comprising the recycle stream in the presence of a hydrotreating catalyst B in reactor B to obtain a hydrotreating effluent B; iii) feeding said hydroprocessing effluent B as a co-feed with said hydroprocessing effluent A to said fractionation and recovering at least one or more liquid transportation fuel components from said fractionation; and monitoring a parameter indicative of deactivation of the hydroprocessing catalyst A to receive a value; comparing the received value to a predetermined value; and When the received value reaches the predetermined value, switch from i), ii), and iii) to: I) subjecting a reactor B feed comprising said hydrocarbon feed to hydrotreatment in the presence of said hydrotreating catalyst B in a reactor B to obtain a hydrotreatment effluent B, subjecting said hydrotreatment effluent B to fractionation and separating at least a recycle stream from said fractionation, said recycle stream having a T5 temperature of 270° C. or more (recovery 5 vol%, EN ISO 3405-2019) and optionally comprising C16 n-paraffins; II) hydrotreating the reactor A feed comprising the recycle stream in the presence of the hydrotreating catalyst A in the reactor A to obtain a hydrotreating effluent A; III) feeding said hydroprocessing effluent A as a co-feed with said hydroprocessing effluent B to said fractionation and recovering at least one or more liquid transportation fuel components from said fractionation.

3. A process according to claim 1 or 2, wherein the hydrocarbon feed comprises at least 0.4 w-ppm nitrogen, expressed as elemental nitrogen (ASTM D4629-17), based on the total weight of the hydrocarbon feed, or at least 0.6 w-ppm, or at least 1.0 w-ppm, or even at least 1.5 w-ppm, or at least 2.0 w-ppm nitrogen, based on the total weight of the hydrocarbon feed, and optionally at most 1.0 wt%, preferably at most 0.8 wt%, more preferably at most 0.5 wt% oxygen, expressed as elemental oxygen (ASTM D5622-2017).

4. The method according to any one of the preceding claims, wherein the parameters indicative of deactivation of the hydroprocessing catalyst A include at least two or more of the following parameters: a. the nitrogen impurity content in the reactor A feed or the hydrocarbon feed, and optionally the content of at least one or more other impurities selected from S, O, P, Si, Cl, Fe, alkali metals, alkaline earth metals and / or coke-forming compounds in the reactor A feed or the hydrocarbon feed; b. the content of NH3 and optionally H2S in the gas phase of the hydroprocessing effluent A; c. the physicochemical characteristics of the degassed hydroprocessing effluent A, preferably at least one or more of cloud point, freezing point, pour point, cold filter plugging point, kinematic viscosity, density and / or distillation characteristics; d. the composition characteristics of the degassed hydroprocessing effluent A, preferably at least one or more of the isoparaffin content, C8-C14 hydrocarbon content, multi-branched isoparaffin content and / or C1-C4 hydrocarbon content in the degassed hydroprocessing effluent A; e. the yield of at least one or more of the recovered liquid transportation fuel components and / or the separated recycle stream, preferably the yield of aviation fuel components; f. at least one or more physicochemical characteristics of the recovered liquid transportation fuel component and / or the separated recycle stream, preferably at least one or more of cloud point, freezing point, pour point, cold filter plugging point, kinematic viscosity, density, research octane number (RON), cetane number and / or distillation characteristics; g. the compositional characteristics of at least one or more of the recovered liquid transportation fuel components and / or the recycle stream, preferably the isoparaffin content and / or the multi-branched isoparaffin content of one or more of the recovered liquid transportation fuel components and / or the separated recycle stream; h. the temperature difference in the reactor A or one or more catalyst beds; and / or i. The operating conditions in the reactor A are selected from the group consisting of temperature, pressure, weight hourly space velocity (WHSV), ratio of H2 to reactor A feed and / or H2 partial pressure at the reactor A inlet.

5. The method according to any one of the preceding claims, wherein the hydrotreatment in reactor A and reactor B is independently selected from at least one or more of hydroisomerization, hydrocracking, hydrodearomatization and / or hydrofinishing, preferably the hydrotreatment in reactor A and reactor B is hydroisomerization, or the hydrotreatment in reactor A and reactor B is hydrocracking, or the hydrotreatment in reactor A is hydroisomerization and the hydrotreatment in reactor B is hydrocracking, or the hydrotreatment in reactor A is hydrocracking and the hydrotreatment in reactor B is hydroisomerization; more preferably, the hydrotreatment in reactor A and reactor B is hydroisomerization.

6. The method of claim 1 or any one of claims 3 to 5 when dependent on claim 1, wherein the switching comprises, when operating i), ii), iii), feeding a gradually decreasing portion of the hydrocarbon feed and a gradually increasing portion of the degassed hydroprocessing effluent B as part of the reactor A feed to reactor A, and simultaneously feeding a gradually increasing portion of the hydrocarbon feed and a gradually decreasing portion of the degassed hydroprocessing effluent A as part of the reactor B feed to reactor B until the method is operated according to i), II), III); or A method according to claim 2 or any one of claims 3 to 5 when dependent on claim 2, wherein the switching comprises, when operating i), ii), iii), feeding a gradually decreasing portion of the hydrocarbon feed and a gradually increasing portion of the recycle stream as part of the reactor A feed to reactor A, and simultaneously feeding a gradually increasing portion of the hydrocarbon feed and a gradually decreasing portion of the recycle stream as part of the reactor B feed to reactor B, until the method is operated according to i), II), III).

7. The process according to any one of the preceding claims, wherein the hydrotreatment in reactor A and / or reactor B is carried out as hydroisomerization under the following conditions: a temperature in the range of 200°C to 500°C, preferably 230°C to 500°C, more preferably 250°C to 450°C, even more preferably 280°C to 400°C, a pressure in the range of 1 MPa to 10 MPa, preferably 2 MPa to 8 MPa or 3 MPa to 10 MPa, a H2 partial pressure at the reactor inlet in the range of 1 MPa to 10 MPa, preferably 2 MPa to 8 MPa, a weight hourly space velocity in the range of 0.1 to 10, preferably 0.2 to 8, more preferably 0.4 to 6 kg reactor feed / kg catalyst / hour, and a ratio of H2 to reactor feed in the range of 10 to 2000, preferably 50 to 1000 standard liters of H2 / liter of reactor feed.

8. The process according to any one of the preceding claims, wherein the hydrotreatment in reactor A and / or reactor B is carried out as hydrocracking under the following conditions: a temperature in the range of 200°C to 450°C, preferably 220°C to 430°C, more preferably 280°C to 350°C, a pressure in the range of 0.4 MPa to 8 MPa, preferably 1 MPa to 7 MPa, more preferably 2.5 MPa to 7 MPa, a H2 partial pressure at the reactor inlet in the range of 0.4 MPa to 8 MPa, preferably 1 MPa to 7 MPa, more preferably 2.5 MPa to 7 MPa, a weight hourly space velocity in the range of 0.1 to 10, preferably 0.2 to 8, more preferably 0.4 to 6, even more preferably 0.5 to 1.5 kg reactor feed / kg catalyst / hour, and a ratio of H2 to reactor feed in the range of 10 to 2000, preferably 50 to 1000 standard liters of H2 / liter of reactor feed.

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

10. The process according to any one of the preceding claims, wherein the hydroprocessing catalyst A and / or the hydroprocessing catalyst B are independently selected from a non-sulfided bifunctional hydroprocessing catalyst comprising at least one or more noble metals from Group VIII of the Periodic Table, more preferably Pt and / or Pd, and at least one or more acidic porous materials, and wherein the reactor A feed and the reactor B feed each contain less than 50 wt-ppm, preferably less than 30 wt-ppm, more preferably less than 10 wt-ppm sulfur (ppm by weight, calculated as element S) of the respective total feed as determined according to ISO 20846-2019.

11. The process according to any one of the preceding claims, wherein the hydrotreatment in reactor A and / or reactor B is hydrocracking and the respective hydrotreatment catalysts are independently selected from bifunctional hydrocracking catalysts, preferably from non-sulfided bifunctional hydrocracking catalysts, comprising At least one or more metals selected from Group VIII of the Periodic Table of Elements, Mo, Co and / or W, preferably selected from Ni, Mo, Co, W, Pt and / or Pd, more preferably selected from Pt and / or Pd; and At least one or more acidic porous materials selected from zeolites, zeolite-type materials and / or amorphous silica-alumina, wherein preferably at least one or more zeolites or zeolite-type materials have a framework type selected from the following: MFI, BEA, FAU, MOR, FER, AEL, AFI, ATO, AFO, MRE, MTT, MTW, TON and / or MRT, preferably at least one or more selected from SAPO-5, SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23, ZSM-43, ZSM-48, IZM-2, mordenite, β-zeolite, Y-type zeolite and / or amorphous silica-alumina acidic porous materials, more preferably at least one or more selected from SAPO-5, SAPO-11, ZSM-23, β-zeolite, Y-type zeolite and / or amorphous silica-alumina acidic porous materials; and Optionally, at least one or more of alumina, silica, titanium alumina, titania and / or zirconium oxide.

12. The process according to any one of the preceding claims, wherein the hydrotreatment in reactor A and / or reactor B is hydroisomerization and the respective hydrotreatment catalysts are independently selected from bifunctional hydroisomerization catalysts, preferably from non-sulfided bifunctional hydroisomerization catalysts, comprising At least one or more metals selected from Group VIII of the Periodic Table of Elements, preferably selected from noble metals of Group VIII, more preferably selected from Pt and / or Pd; and at least one or more acidic porous materials selected from zeolites and / or zeolite-type materials, wherein preferably at least one or more zeolites and / or zeolite-type materials have a framework type selected from the following: AEL, ATO, AFO, MRE, MTT, MTW, TON, MRT, MOR, FER and / or MWW, preferably at least one or more acidic porous materials selected from SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23, ZSM-48, NU-10, ZBM-30, IZM-2, EU-2 and / or mordenite, more preferably at least one or more acidic porous materials selected from SAPO-11, SAPO-41, ZSM-23 and / or ZSM-48; and Optionally at least one or more of alumina, silica, amorphous silica-alumina, titania, titania and / or zirconia.

13. The process according to any one of the preceding claims, wherein the hydroprocessing catalyst A and the hydroprocessing catalyst B are different from each other.

14. The process according to any one of the preceding claims, wherein the hydrocarbon feed comprises at least 90 wt%, preferably at least 95 wt%, more preferably at least 98 wt%, even more preferably at least 99 wt% of hydrocarbons, based on the total weight of the hydrocarbon feed, and / or at least 60 wt%, preferably at least 70 wt%, more preferably at least 80 wt%, even more preferably at least 90 wt% of paraffinic hydrocarbons, based on the total weight of the hydrocarbon feed; and / or at most 30 wt%, preferably at most 25 wt%, more preferably at most 20 wt%, even more preferably at most 15 wt% of isoparaffinic hydrocarbons, based on the total weight of paraffinic hydrocarbons in the 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 hydrocarbon feed; and / or at least 70 wt%, preferably at least 80 wt%, more preferably at least 90 wt%, even more preferably at least 95 wt% of C14-C22 hydrocarbons, based on the total weight of the hydrocarbon feed.

15. A method according to any one of the preceding claims, wherein the step of providing the hydrocarbon feed comprises catalytically hydrotreating, preferably catalytically hydrodeoxygenating, an oxygenated hydrocarbon feedstock to obtain a hydrotreated effluent, wherein the oxygenated hydrocarbon feedstock preferably comprises at least one or more of vegetable oil, animal fat and / or microbial oil, and / or subjecting the synthesis gas to a Fischer-Tropsch (FT) conversion to obtain a FT effluent, The hydrotreating effluent and / or the FT effluent is subjected to gas-liquid separation and optionally hydrocarbon feed fractionation to provide the hydrocarbon feed.

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

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

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

19. A method for producing at least one liquid transportation fuel component, the method comprising: i) providing a reactor A feed comprising a hydrocarbon feed containing nitrogen impurities, wherein the reactor A feed comprises at least 0.4 w-ppm nitrogen, expressed as elemental nitrogen (ASTM D4629-17), or at least 0.6 w-ppm, or at least 1.0 w-ppm, or even at least 1.5 w-ppm or at least 2.0 w-ppm nitrogen, based on the total weight of the reactor A feed; ii) hydrotreating the reactor A feed in the presence of a hydrotreating catalyst A in a reactor A to obtain a hydrotreating effluent A, and optionally separating compounds that are gaseous at least at NTP from the hydrotreating effluent A to obtain a degassed hydrotreating effluent A; iii) feeding said hydroprocessing effluent A or said degassed hydroprocessing effluent A to fractionation and recovering at least one or more liquid transportation fuel components from said fractionation; and monitoring a parameter indicative of deactivation of the hydroprocessing catalyst A to receive a value; comparing the received value to a predetermined value; and When the received value reaches the predetermined value, switch from i), ii), and iii) to: I) providing a reactor A feed comprising a hydrocarbon feed, wherein the reactor A feed is substantially free of nitrogen impurities; II) hydrotreating the reactor A feed in the presence of a hydrotreating catalyst A in a reactor A to obtain a hydrotreating effluent A, and optionally separating compounds that are gaseous at least at NTP from the hydrotreating effluent A to obtain a degassed hydrotreating effluent A; III) feeding said hydroprocessing effluent A or said degassed hydroprocessing effluent A to fractionation and recovering at least one or more liquid transportation fuel components from said fractionation.

20. The process according to claim 19, wherein in step I), the Reactor A feed comprises at most 0.3 w-ppm, preferably less than 0.3 w-ppm, nitrogen, expressed as elemental nitrogen (ASTM D4629-17), based on the total weight of the Reactor A feed.

21. The method according to claim 19 or 20, wherein In step i) and / or step I), the hydrocarbon feed is as further defined in claim 14 or 16; and / or In step i) and / or step I), the step of providing the hydrocarbon feed is as further defined in claim 15; and / or The parameter indicating the deactivation of the hydroprocessing catalyst A is further defined in claim 4; and / or The hydroprocessing in reactor A is as further defined in claim 5; and / or Carrying out the hydrotreatment in reactor A is further defined in claim 7 or 8; and / or The hydroprocessing in reactor A and the hydroprocessing catalyst A are as further defined in claim 11 or 12; and / or The recovered liquid transportation fuel component is as further defined in claim 17 or 18.

22. The method according to any one of the preceding claims, wherein the method further comprises, when operating I), II), III), monitoring a parameter indicating the reversal of deactivation of the hydroprocessing catalyst A to receive a value, wherein the parameter indicating the reversal of deactivation of the hydroprocessing catalyst A preferably comprises at least two or more parameters selected from a. to i. as defined in claim 4; comparing the received value with a predetermined value; and optionally switching from I), II), III) back to i), ii), iii) when the received value reaches the predetermined value.

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

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