Renewable hydrocarbon compositions

Abstract

This specification provides for renewable hydrocarbon compositions comprising n-paraffins and i-paraffins, wherein the total amount of any C8-C16 i-paraffins is 50-94 wt% of the total weight of the hydrocarbon composition, and the kinematic viscosity of the hydrocarbon composition at -20°C is 3.7-8 mm². 2 A renewable hydrocarbon composition is provided, having a temperature of / s and a weighted average number of carbon atoms in the hydrocarbon composition of 12.1 to 14.2.

Description

[Technical Field]

[0001] This disclosure generally relates to hydrocarbon compositions. In particular, this disclosure relates to renewable hydrocarbon compositions that can be used as jet fuel components or jet fuel, but is not limited thereto. Furthermore, this disclosure relates to methods for producing the above hydrocarbon compositions. [Background technology]

[0002] This section provides useful background information for any of the techniques described herein, without considering them representative of the current state of the art.

[0003] In the transportation sector, particularly in aviation, there is a continuing need to reduce greenhouse gas emissions and / or carbon footprint. Therefore, interest in renewable jet fuel and jet fuel components is growing. Methods for producing jet fuel components from renewable raw materials have been proposed. However, the yield of jet fuel components (compared to other fuel components) in these methods has remained relatively low. Furthermore, there is a need and interest in producing jet fuel components that can be used in high proportions in the aviation sector, or even as neat fuel; therefore, specific product characteristics and requirements are becoming increasingly important.

[0004] Jet fuel is subjected to harsh conditions. At high altitudes, ambient temperatures are extremely low, while the operation itself requires high thermal oxidation stability. Furthermore, jet fuel must provide reliable performance.

[0005] Currently, the yield of renewable jet fuel (also known as sustainable aviation fuel, or SAF) is lower than the corresponding yield of renewable diesel, even with the use of advanced hydrotreatment processes used in the production of renewable jet fuel from renewable oils and fats.

[0006] Therefore, there is a need to develop new hydrocarbon compositions that can preferably be used as jet fuel or jet fuel components. Furthermore, there is a need to find a method for producing hydrocarbon compositions that yields good yield and production efficiency. [Overview of the project]

[0007] The attached claims define the scope of protection. Any examples or descriptions of products or methods not covered by the claims in the specification, claims, and / or drawings are provided herein not as embodiments of the invention, but as background art or as examples useful for understanding the invention.

[0008] According to the first embodiment, a hydrocarbon composition comprising n-paraffin and i-paraffin, -The total amount of all C8-C16 i-paraffins is 50-94 wt% of the total weight of the hydrocarbon composition. - The kinematic viscosity of the above hydrocarbon composition at -20°C is 3.7-8 mm² when measured according to ASTM D445-21e2. 2 / s, preferably 3.7-5.5 mm 2 It is within the range of / s. A hydrocarbon composition is provided in which the weighted average number of carbon atoms of the hydrocarbons in the hydrocarbon composition is 12.1 to 14.2.

[0009] The inventors have found that the above hydrocarbon composition is particularly suitable for jet fuel. This hydrocarbon composition also yields a lighter jet fuel than commercially available corresponding jet fuels.

[0010] According to a second aspect, a jet fuel or jet fuel component is provided comprising a fuel or fuel component, preferably a hydrocarbon composition as defined herein. The hydrocarbon composition blends well with aviation fuel components currently on the market. The hydrocarbon composition provides properties particularly beneficial to aviation fuel for such blends.

[0011] According to a third aspect, the use of a hydrocarbon composition as defined herein as a renewable jet fuel or renewable jet fuel component is provided. Surprisingly, the inventors have found that when a hydrocarbon composition as a main product that can be used as a renewable jet fuel or renewable jet fuel component is produced simultaneously with renewable diesel obtained as a co-product, both have improved properties. Accordingly, according to a fourth aspect, a method is provided for compounding a high-quality jet fuel component (which can, in some cases, even be used as neat fuel in the aviation sector) with a high-quality winter renewable diesel. Surprisingly, in the compounding process, after the recovery of the high-quality jet fuel component, the remaining product is still recognized as renewable diesel, which meets the stringent requirements set for high-quality winter renewable diesel fuel. More specifically, the renewable jet fuel or renewable jet fuel component has been shown to have desired light properties along with improved low-temperature properties, and the simultaneously recovered renewable diesel (RD) exhibited excellent winter properties.

[0012] In common to the above embodiments, the hydrocarbon composition yields remarkably attractive thermal oxidation stability, namely, a high JFTOT breakpoint temperature, kinematic viscosity, freezing point, density, and / or biogenic carbon content at -20°C (some of which are also experimentally demonstrated by the results shown in the examples).

[0013] Several exemplary embodiments will be described with reference to the accompanying drawings. [Brief explanation of the drawing]

[0014] [Figure 1] Figure 1 shows the total weight of the analyzed hydrocarbon composition, i.e., the content of n-paraffins, unbranched i-paraffins, various multibranched i-paraffins, naphthenes, and aromatics per carbon number (x axis) in the sample in question, expressed as wt% (y axis). The above content can be measured by GC×GC-FID or GC×GC-MS. [Figure 2] Figure 2 shows the total weight of the analyzed hydrocarbon composition, i.e., the content of n-paraffins, unbranched i-paraffins, various multibranched i-paraffins, naphthenes, and aromatics per carbon number (x axis) in the sample in question, expressed as wt% (y axis). The above content can be measured by GC×GC-FID or GC×GC-MS. [Figure 3] Figure 3 shows the total weight of the analyzed hydrocarbon composition, i.e., the content of n-paraffins, unbranched i-paraffins, various multibranched i-paraffins, naphthenes, and aromatics per carbon number (x axis) in the sample in question, expressed as wt% (y axis). The above content can be measured by GC×GC-FID or GC×GC-MS. [Figure 4] Figure 4 shows the total weight of the analyzed hydrocarbon composition, i.e., the content of n-paraffins, unbranched i-paraffins, various multibranched i-paraffins, naphthenes, and aromatics per carbon number (x axis) in the sample in question, expressed as wt% (y axis). The above content can be measured by GC×GC-FID or GC×GC-MS. [Figure 5] Figure 5 shows the total weight of the analyzed hydrocarbon composition, i.e., the content of n-paraffins, unbranched i-paraffins, various multibranched i-paraffins, naphthenes, and aromatics per carbon number (x axis) in the sample in question, expressed as wt% (y axis). The above content can be measured by GC×GC-FID or GC×GC-MS. [Figure 6] Figure 6 shows the total weight of the analyzed hydrocarbon composition, i.e., the content of n-paraffins, unbranched i-paraffins, various multibranched i-paraffins, naphthenes, and aromatics per carbon number (x axis) in the sample in question, expressed as wt% (y axis). The above content can be measured by GC×GC-FID or GC×GC-MS. [Figure 7]Figure 7 shows the total weight of the analyzed hydrocarbon composition, i.e., the content of n-paraffin, mono-branched i-paraffin, various multi-branched i-paraffins, naphthene, and aromatic for each carbon number (x-axis) with respect to the sample in question, in weight % (wt%, y-axis). The above content can be measured by the GC×GC-FID method or the GC×GC-MS method. [Figure 8] Figure 8 shows the total weight of the analyzed hydrocarbon composition, i.e., the content of n-paraffin, mono-branched i-paraffin, various multi-branched i-paraffins, naphthene, and aromatic for each carbon number (x-axis) with respect to the sample in question, in weight % (wt%, y-axis). The above content can be measured by the GC×GC-FID method or the GC×GC-MS method. [Figure 9] Figure 9 shows the total weight of the analyzed hydrocarbon composition, i.e., the content of n-paraffin, mono-branched i-paraffin, various multi-branched i-paraffins, naphthene, and aromatic for each carbon number (x-axis) with respect to the sample in question, in weight % (wt%, y-axis). The above content can be measured by the GC×GC-FID method or the GC×GC-MS method. [Figure 10] Figure 10 shows the total weight of the analyzed hydrocarbon composition, i.e., the content of n-paraffin, mono-branched i-paraffin, various multi-branched i-paraffins, naphthene, and aromatic for each carbon number (x-axis) with respect to the sample in question, in weight % (wt%, y-axis). The above content can be measured by the GC×GC-FID method or the GC×GC-MS method. [Figure 11] Figure 11 shows the simulated distillation graphs for two middle distillates (DistFeed1 and DistFeed2) used as distillation feeds, the hydrocarbon composition for comparison in Comparative Example 2, and two hydrocarbon compositions (SAF1 from DistFeed1 and SAF2 from DistFeed2) according to the present disclosure obtained from the above distillation and further specified in the examples. **DETAILED DESCRIPTION OF THE INVENTION**

[0015] In the following description, similar reference numerals indicate similar elements or processes. All standards and methods referred to herein are the most recent revisions available as of the filing date unless otherwise specified.

[0016] Unless otherwise specified, EN ISO 3405-2019 is referenced for distillation characteristics, such as the initial boiling point (IBP), final boiling point (FBP), T10 temperature (10 vol% recovery), T90 temperature (90 vol% recovery), and boiling point range. IBP is the temperature at the moment the first drop of condensate falls from the bottom of the condenser, and FBP is the highest thermometer reading obtained during the test, usually occurring after all the liquid has evaporated from the bottom of the flask. For boiling point distribution, refer to ASTM D2887-22, a GC-based method (pseudo-distillation analysis).

[0017] When used in connection with this disclosure, jet fuel components refer to hydrocarbon compositions suitable for use in fuel compositions that meet the standards for aviation fuels, e.g., ASTM D7566-22A. Specific requirements for the above components are described, for example, in ASTM D7566-22A Annex A2. Typically, such jet fuel components boil in the range of about 100°C to about 300°C, e.g., about 150°C to about 300°C, when measured according to EN ISO 3405-2019. That is, they have IBP and FBP within the above range. Typically, various components are blended to obtain the final jet fuel product. In certain cases, the jet fuel components as defined herein may be used as is, as jet fuel, also known as “neat fuel,” without the need to blend with further components.

[0018] As used herein, JFTOT breakpoint refers to the thermal oxidation test of jet fuel and its results. The JFTOT breakpoint is given as a temperature in °C. Improving the breakpoint is understood to mean increasing the temperature. Thermal oxidation stability is measured by the JFTOT procedure (ASTM D3241-20c). In test method D3241, the breakpoint is the highest control temperature at which the fuel satisfies the heater tube evaluation and ΔP standard requirements. In other words, this definition of breakpoint refers to the highest pass temperature of the fuel.

[0019] When used in connection with this disclosure, diesel fuel components refer to hydrocarbon compositions suitable for use in fuel compositions that meet the standards specified in diesel fuel standards, e.g., EN 590:2022 or EN 15940:2016+A1:2018+AC:2019. Typically, such diesel fuel components boil in the range of about 160°C to about 380°C when measured according to EN ISO 3405-2019, i.e., having IBP and FBP within the above range. Diesel is often characterized by its cetane number, which can be measured, for example, EN 15195-2014. The net calorific value of diesel can be measured according to ASTM D4809-18.

[0020] In connection with this disclosure, various properties of the feed, flow, effluent, product, components, or sample in their properly prepared state are measured according to standard methods referenced or disclosed herein. For example, the cloud point is measured from the product, components, or sample according to ASTM D5773-21.

[0021] As used herein, hydrocarbons refer to compounds consisting of carbon and hydrogen. Hydrocarbons of particular interest in connection with the present invention include paraffins, naphthenes (also called cycloparaffins or cycloalkanes), and aromatics. Oxygen-containing hydrocarbons refer herein to hydrocarbons containing covalently bonded oxygen. The products claimed in the present invention are referred to as "hydrocarbon compositions." Preferably, the hydrocarbon compositions are renewable hydrocarbon compositions.

[0022] As used herein, paraffin refers to an acyclic alkane, i.e., an acyclic open-chain saturated hydrocarbon, which is either straight-chain (normal paraffin, i.e., n-paraffin) or branched (isoparaffin, i.e., i-paraffin). In other words, paraffin as used herein refers to n-paraffin and / or i-paraffin. In connection with this disclosure, i-paraffin refers to a branched open-chain alkane, i.e., an acyclic open-chain saturated hydrocarbon having one or more alkyl side chains. As used herein, an i-paraffin having one alkyl substituent, i.e., an alkyl side chain or branch, is called a monobranched i-paraffin. In accordance with this, an i-paraffin having two or more alkyl side chains or branches is called a polybranched i-paraffin as used herein. In other words, i-paraffin as used herein refers to monobranched i-paraffin and / or polybranched i-paraffin. The alkyl side chain may be, for example, a C1-C5 alkyl side chain, preferably a methyl side chain. The amounts of unbranched i-paraffins and multibranched i-paraffins can be given separately. The term "i-paraffin" refers to the total amount of all unbranched and multibranched i-paraffins present, regardless of the number of branches. Correspondingly, "paraffin" refers to the total amount of all n-paraffins, all unbranched i-paraffins, and all multibranched i-paraffins present, if they exist.

[0023] As used herein, cyclic hydrocarbons refer to all hydrocarbons containing a cyclic structure, namely naphthenes and aromatics. Naphthenes, as used herein, refer to cycloalkanes, i.e., saturated hydrocarbons containing at least one cyclic structure, with or without side chains. Naphthenes are compounds that do not contain an aromatic ring structure. Aromatics, as used herein, refer to hydrocarbons containing an aromatic ring structure, i.e., a cyclic structure having alternating π bonds delocalized around the aforementioned cyclic structure.

[0024] In connection with this disclosure, for compositions that boil at 36°C or above (at standard atmospheric pressure), the content of n-paraffins, i-paraffins, unbranched i-paraffins, various polybranched i-paraffins, naphthenes, and aromatics is expressed as weight % (wt%) relative to the degassed weight of the feed, flow, effluent, product, component, or sample in question, or, as defined, as weight % (wt%) relative to the (total) weight of paraffins or i-paraffins in the feed, flow, effluent, product, component, or sample in question.

[0025] The above content per carbon number can be measured by the GC×GC-FID / GC×GC-MS method, which is preferably carried out as follows: The GC×GC (2D GC) method was carried out as generally disclosed in UOP 990-2011, and with the following modifications according to the experimental section of the master's thesis Comprehensive two-dimensional gas chromatography with mass spectrometric and flame ionisation detectors in petroleum chemistry, University of Helsinki, August 2017 by Nousiainen M. GC×GC was performed in reverse using a semipolar column (Rxi17Sil) first, followed by a nonpolar column (Rxi5Sil), and then an FID detector, with the following execution parameters: helium as carrier gas 31.7 cm / sec; split ratio 1:350; injector 280°C; column temperature program 40°C (0 min) - 5°C / min - 250°C (0 min) - 10°C / min - 300°C (5 min), execution time 52 mins; modulation period 10 seconds; detector 300°C, H 240 ml / min, air 400 ml / min; makeup flow helium 30 ml / min; sampling rate 250 Hz, and injection volume 0.2 microliters. Individual compounds were identified using GC×GC-MS with the following MS parameters: ion source 230°C; interface 300°C; scanning range 25-500 amu. For data processing, for example, to identify detected compounds or hydrocarbon groups, and to determine the mass concentration of the compound or hydrocarbon group by applying the response factor for n-heptane to the volume of the detected peak and then normalizing it to 100 wt%, commercially available tools (Shimadzu's LabSolutions, Zoex's GC Image) were used. The limit of quantification for individual compounds using this method is 0.1 wt%.

[0026] In connection with this disclosure, CX+ paraffin, CX+ n-paraffin, CX+ i-paraffin, CX+ unbranched i-paraffin, CX+ polybranched i-paraffin, CX+ hydrocarbon, or CX+ fatty acid means, respectively, a paraffin, n-paraffin, i-paraffin, unbranched i-paraffin, polybranched i-paraffin, hydrocarbon, or fatty acid having at least X carbon atoms, where X is any suitable integer. Fatty acids and / or derivatives thereof, where mentioned, mean fatty acids, esters, e.g., glycerides or alkyl esters, or salts thereof. It is understood that not all compounds falling within the scope of this definition necessarily exist.

[0027] In connection with this disclosure, CXY~CXZ (or CXY to CXZ) paraffins, CXY~CXZ n-paraffins, CXY~CXZ i-paraffins, CXY~CXZ unbranched i-paraffins, CXY~CXZ polybranched i-paraffins, CXY~CXZ hydrocarbons, or CXY~CXZ fatty acids refer to a broad range of paraffins, n-paraffins, i-paraffins, unbranched i-paraffins, polybranched i-paraffins, hydrocarbons, or fatty acids, respectively, where XY and XZ are appropriate integers of terminal values, and the number of carbon atoms within such ranges is as indicated by the integers of terminal values ​​and any integers between the above terminal values, if present. However, all of the above number of carbon atoms within the above ranges, in particular paraffins, n-paraffins, i-paraffins, unbranched i-paraffins, polybranched i-paraffins, hydrocarbons, or fatty acids with carbon atoms at or around the endpoint are not necessarily present unless expressly stated in some cases. On the other hand, isomers, as the name suggests, can include several compounds with the same number of carbon atoms. For example, C15 isomers can include methyltetradecane (methyl branching at different positions), dimethyltridecane (two methyl branchings at different positions), and so on. Here, "C15 isomers" includes the total amount of all such diverse variations.

[0028] As used herein, the total weight of C8-C16 n-paraffins, C8-C16 single-branched i-paraffins, and C8-C16 multi-branched i-paraffins defines the total weight of n-paraffins and i-paraffins (single-branched i-paraffins and multi-branched i-paraffins) having C8, C9, C10, C11, C12, C13, C14, C15, or C16 carbon atoms, where the weight of each individual compound may be 0 (considering the detection limit). Furthermore, an i-paraffin may contain several individual compounds depending on the position, number, and stereochemistry of one branch (single-branched i-paraffin) or multiple branches (multi-branched i-paraffin) within a single carbon atom, and the total weight of these compounds is still added to the above total weight. In other words, if a compound has C8 to C16 carbon atoms and is either an n-paraffin or an i-paraffin, that compound is included in the count, and if the weight of the compound is 0, 0 is added to the total amount. Therefore, it is understood that not all compounds within the range of this definition necessarily exist. Due to choices made regarding the manufacturing method, for example, C16 n-paraffins may not be present in aviation fuel components. Nevertheless, the total amount can still be obtained by adding 0 (indicating the absence of C16 n-paraffins) to the total weight of all other present C8 to C16 n-paraffins and i-paraffins. Isomerization converts at least a certain amount of n-paraffins to i-paraffins, particularly single-branched i-paraffins. By increasing the degree of isomerization, for example by increasing the degree of hydrogen isomerization conditions, more n-paraffins can be converted to i-paraffins, and single-branched i-paraffins can be converted to multi-branched i-paraffins.

[0029] As used herein, the term renewable means a compound or composition obtained, derived, or whole or partially from plants and / or animals, including compounds or compositions obtained, derived, or whole from fungi and / or algae, any of which may be waste or residue. As used herein, renewable compounds or compositions may include genetically modified compounds or compositions. Renewable feeds, components, compounds, or compositions may also be called biological feeds, components, compounds, or compositions, or bio-derived feeds, components, compounds, or compositions.

[0030] As used herein, the term fossil means compounds or compositions obtained, derivable from, or derived from naturally occurring, non-renewable compositions such as crude oil, petroleum / oil gas, shale oil / shale gas, natural gas, or coal deposits, or combinations thereof, and includes any hydrocarbon-rich deposits that can be utilized from above-ground / subterranean resources.

[0031] The term "circular" typically refers to recycled materials derived from non-renewable resources. For example, the term "circular" may refer to recycled materials derived from plastic waste. The above-mentioned renewable, circular, and fossil-derived compounds or compositions are considered distinct from one another based on their origin and their impact on environmental issues. Therefore, these compounds or compositions may be treated differently under legal and regulatory frameworks. Typically, renewable, circular, and fossil-derived compounds or compositions are distinguished based on their origin and the information provided by the manufacturer.

[0032] Chemically, the renewable nature of any organic compound, including hydrocarbons, can be determined by any suitable method for analyzing the carbon content derived from renewable resources, e.g., DIN 51637 (2014), ASTM D6866 (2020), or EN 16640 (2017). These methods are based on the fact that carbon atoms of renewable or biological origin contain a greater number of unstable radiocarbon (¹⁴C) atoms compared to carbon atoms of fossil origin. Therefore, by analyzing the ratio of ¹⁻²C to ¹⁴C isotopes, it is possible to distinguish carbon compounds derived from renewable or biological resources or raw materials from carbon compounds derived from non-renewable or fossil resources or raw materials. Thus, specific ratios between these isotopes can be used as "tags" to identify renewable carbon compounds and distinguish them from non-renewable carbon compounds. Isotope ratios do not change during chemical reactions. Therefore, isotopic ratios can be used to identify renewable compounds, components, and compositions and to distinguish them from non-renewable fossil materials in reactor feed, reactor effluent, separated product fractions, and various blends thereof. Numerically, the biogenic carbon content can be expressed as the amount of biogenic carbon in the material as a weight percentage of the total carbon (TC) in the material (in accordance with ASTM D6866(2020) or EN 16640(2017)). In connection with the present invention, the term renewable preferably refers to a material in which the biogenic carbon content is greater than 50 wt%, particularly 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%, and even more preferably about 100 wt%, relative to the total weight of carbon in the material (EN 16640(2017)).

[0033] According to the first aspect, the herein provides a hydrocarbon composition comprising n-paraffin and i-paraffin, - The total amount of all C8-C16 i-paraffins is 50-94 wt%, for example 86-92 wt%, of the total weight of the hydrocarbon composition. - The kinematic viscosity of the above hydrocarbon composition at -20°C is 3.7-8 mm² when measured according to ASTM D445-21e2. 2 / s, preferably 3.7-5.5 mm 2 It is within the range of / s. A hydrocarbon composition is provided in which the weighted average number of carbon atoms of the hydrocarbons in the hydrocarbon composition is 12.1 to 14.2.

[0034] The inventors have found that the above hydrocarbon composition is suitable as a component for use as an aviation turbine fuel, or particularly suitable for use as renewable jet fuel, i.e., high-quality sustainable aviation fuel (SAF). Such fuel may also be called light paraffinic kerosene (LPK). Although not bound by theory, the hydrocarbon composition results in an attractive paraffin distribution mainly containing C8-C16 i-paraffins, contributing to remarkably low kinematic viscosity at -20°C and -40°C. Prior to the hydrocarbon composition, kinematic viscosity was one of the factors limiting the blending rate of renewable jet fuel in blends with conventional jet fuels. It has been practically necessary for fossil jet fuel components to improve the kinematic viscosity of blended fuels to meet the kinematic viscosity limits at -40°C and -20°C according to Table 1 of ASTM D7566-22A for blends used in aircraft. In at least some embodiments of the hydrocarbon composition, the renewable fuel alone meets these limits.

[0035] Of particular interest to jet fuel is its kinematic viscosity at temperatures below 0°C. Therefore, the kinematic viscosity at -20°C is 3.7–8 mmHg when measured according to ASTM D445-21e2. 2 / s, preferably 3.7-5.5 mm 2 It fluctuates within the range of / s. Experimentally, the kinematic viscosity of this hydrocarbon composition is excellent even at -40°C when measured by the same method, for example, about 9 mm. 2 / s or approximately 10mm 2 These values ​​show / s, and these values ​​even meet the limits shown in Table 1 of ASTM D7566-22A.

[0036] In the hydrocarbon composition, the total amount of all C8-C16 i-paraffins is 50-94 wt%, preferably 86-92 wt%, of the total weight of the hydrocarbon composition. This broad distribution of carbon numbers contributes to the blending properties of the hydrocarbon composition with other possible jet fuel components, resulting in the final jet fuel product.

[0037] Preferably, the i-paraffin in the hydrocarbon composition contains two or more alkyl substituents and is therefore a polybranched i-paraffin. The C8-C16 polybranched i-paraffin may contain 2, 3, 4, 5, 6, or 7 alkyl substituents, typically 2 or 3 alkyl substituents. The most common alkyl substituent is a methyl substituent. Therefore, the total amount of any C8-C16 polybranched i-paraffin is 35-65 wt%, preferably 45-63 wt%, and more preferably 55-60 wt%, of the total weight of the hydrocarbon composition.

[0038] Furthermore, according to one embodiment, the ratio of polybranched i-paraffins to n-paraffins in the hydrocarbon composition is 3.6 to 12.0, preferably 6.5 to 11.4. The presence of polybranched i-paraffins contributes to a specific and broad distribution of carbon numbers, particularly a distribution of carbon numbers above C14. Interestingly, some of the compositions even had a weighted average carbon number exceeding 14. Polybranched i-paraffins with carbon numbers of C15, C16, and even C17 offer advantages over compositions limited to relatively small carbon numbers. Consequently, due to highly isomerized products, the diversity of individual hydrocarbons in the product varies considerably.

[0039] However, the presence of n-paraffins and, optionally, cycloparaffins in the hydrocarbon composition is thought to contribute to the combustion characteristics and usefulness of the fuel in aircraft engines. Therefore, according to some embodiments of this hydrocarbon composition, the total amount of any C8-C16 n-paraffins is 2-12 wt%, preferably 5-11 wt%, and more preferably 6-8 wt%, of the total weight of the hydrocarbon composition. This was surprising because good low-temperature properties, especially those of mainly paraffinic compositions, are typically associated with very high i-paraffin content, and therefore the goal is to minimize the amount of n-paraffins. The freezing point of pure C8-C16 alkanes, i.e., n-paraffins, varies from -57°C to 18°C, and therefore the presence of n-paraffins, especially n-paraffins with a relatively large number of carbon atoms, in this hydrocarbon composition is somewhat unexpected.

[0040] In one embodiment, the total amount of any i-paraffins and n-paraffins is 96-98.5 wt% of the total weight of the hydrocarbon composition.

[0041] This hydrocarbon composition mainly consists of i-paraffins and n-paraffins, but it has been found that when the composition further contains cycloparaffins, these contribute to the fuel properties in the aviation sector. Compositions with low aromatic content generally benefit from cycloparaffins, which act similarly to aromatics at high-temperature surfaces of aircraft engines and fuel systems, when used as jet fuel. Therefore, according to one embodiment, the amount of cycloparaffin in this hydrocarbon composition varies from 1.0 to 5.0 wt%, preferably from 1.8 to 3.1 wt%.

[0042] According to a preferred embodiment, the hydrocarbon composition has a particularly low content of any C17+ hydrocarbon. Thus, the total amount of any C17+ hydrocarbon is less than 1.0 wt%, preferably less than 0.8 wt%, or less than 0.4 wt% of the total weight of the hydrocarbon composition. In one experiment conducted to verify the present invention, the total amount of any C17+ hydrocarbon was 0 wt% within the detection limit (LOD) of the analytical method used.

[0043] As used herein, the hydrocarbon composition is described by its weighted average carbon number. The weighted average carbon number was calculated based on GC×GC analysis by multiplying the weight % of each carbon number present by the carbon number and dividing the sum of the products by 100. The inventors have found that the weighted average carbon number defines the hydrocarbon composition and correlates with the desired product properties when this value is between 12.1 and 14.2. In the experiments conducted, the weighted average carbon numbers calculated for various samples varied from 12.1 to 12.8 and were surprisingly close to each other.

[0044] Certain embodiments according to the present invention may be characterized by even narrower combinations of features, and thus, a preferred hydrocarbon composition containing n-paraffins and i-paraffins is - the total amount of any C8 - C16 i-paraffins is 85 - 94 wt% of the total weight of the hydrocarbon composition, - the kinematic viscosity at -20 °C is in the range of 3.7 - 5.5 mm 2 / s when measured according to ASTM D445-21e2, - the weighted average carbon number of the hydrocarbons in the hydrocarbon composition is between 12.1 and 12.8.

[0045] The inventors have surprisingly found that the hydrocarbon composition with the above narrow limits is particularly suitable for jet fuel.

[0046] In one embodiment, the hydrocarbon composition further has a density measured using standard ASTM D4052-22 of 730 - 772 kg / m 3 , preferably 750.0 - 772.0 kg / m3 More preferably 753.0 to 770.0 kg / m³ 3 More preferably 754.0 to 760.0 kg / m 3 That is the case.

[0047] This hydrocarbon composition exhibited particularly good thermal properties. In the aerospace sector, good thermal properties of fuel contribute to reducing deposits formed in aircraft engine fuel systems when the fuel is heated, improving heat absorption, and enabling more effective heat transfer within the fuel system.

[0048] Furthermore, as can be seen from Figure 11, the carbon number distribution and carbon chain characteristics in this hydrocarbon composition are considered particularly beneficial for fuel combustion in aircraft engine fuel systems. Figure 11 above shows a simulated distillation graph. This graph compares two middle distillates used as distillation feed to obtain high-quality diesel components with the hydrocarbon composition of this disclosure.

[0049] The middle distillates used as paraffinic hydrocarbon feed for distillation are referred to as DistFeed1 and DistFeed2, following the terminology used in the attached example. As can be seen from Figure 11, the T10 temperatures of DistFeed1 and DistFeed2 are relatively high, resulting in a curved graph that then levels off as the temperature rises. This is especially true for DistFeed2. In these samples, the T90 temperature is close to the T50 temperature, and the temperature only rises sharply again towards the end of distillation.

[0050] For the two hydrocarbon compositions described herein, namely SAF1 and SAF2, the simulated distillation curves exhibit a more linear nature from start to finish. The gradient remains substantially constant without any significant curve or slope. Considering combustion in an aircraft engine, such distillation behavior correlates with continuous vaporization during use. Furthermore, the fact that the graph does not become substantially steep at the end indicates that all hydrocarbons in the product burn at aircraft engine temperatures, minimizing deposit formation during use and thus aiding in maintenance.

[0051] In one embodiment, the hydrocarbon composition further has a JFTOT breakpoint of 325°C or higher, preferably 360°C, or more preferably 380°C or higher, as measured according to ASTM D3241-20C. The JFTOT breakpoint indicates particularly good thermal oxidation stability of the hydrocarbon composition. Due to the complex fuel systems of aircraft engines, thermal oxidation stability is important in aviation fuels. Furthermore, thermal stability is directly related to less deposit formation, especially on high-temperature surfaces. This is recognized in the aviation sector and allows for longer maintenance intervals.

[0052] In one embodiment, the hydrocarbon composition further has a freezing point below -50°C, preferably below -60°C, and more preferably below -64°C. This is surprising considering that the freezing point of alkanes (pure) can be above 0°C. Such a low freezing point is unpredictable considering the weighted average carbon number is 12.1 to 14.2.

[0053] In one embodiment, the hydrocarbon composition further has a bio-based carbon content of at least 50 wt%, preferably at least 70 wt%, and more preferably at least 90 wt%, relative to the total weight (TC) of carbon in the jet fuel component, as measured according to EN 16640 (2017). This bio-based carbon content is of particular importance from a regulatory standpoint.

[0054] The hydrocarbon compositions may further characterize typical or general jet fuel qualities. Several samples according to this disclosure were measured for actual gum content. The actual gum content, when measured according to the IP 540 (2008) air evaporation method, was readily less than 7 mg / 100 ml, and even lower, to 1 mg / 100 ml or less.

[0055] According to a second aspect, the Specified herein provides a jet fuel comprising a fuel / fuel component, preferably a hydrocarbon composition as defined herein. This hydrocarbon composition has been found to blend well with currently available aviation fuel components. While not bound by theory, a broad distribution of hydrocarbons with C8 to C16 carbon atoms is thought to contribute to the above-mentioned good blend. In other words, a composition comprising several hydrocarbons with different chain lengths and substituents provides a better blend partner than, for example, an essentially pure compound, such as industrial-grade n-dodecane. The above hydrocarbon composition provides particularly beneficial properties for aviation fuels for such blends, as described in detail with respect to the hydrocarbon composition of the first aspect.

[0056] According to one embodiment, the fuel or fuel component is a jet fuel containing 3 vol% to about 100 vol% of the hydrocarbon component, with the remainder being petroleum-based jet fuel. According to some embodiments, the fuel or fuel component is a jet fuel that may contain at least 3 vol%, at least 36 vol%, at least 50 vol%, at least 56 vol%, at least 75 vol%, or at least 90 vol% of the hydrocarbon component, with the remainder being petroleum-based jet fuel. According to a preferred embodiment, the fuel or fuel component is a jet fuel that may contain about 36 vol% to about 90 vol%, or about 36 vol% to about 56 vol%, of the hydrocarbon component, with the remainder being petroleum-based jet fuel. In a particular embodiment, the fuel or fuel component is a jet fuel that may contain about 100 vol% of the hydrocarbon component. As used herein, "about 100 vol%" refers to a realistic situation in which the fuel or fuel component consists of the hydrocarbon composition, including trace components and additives.

[0057] Additives applicable to this jet fuel or jet fuel components, or applicable when using hydrocarbon compositions in jet fuel compositions, may be selected from the additives approved for jet fuel listed in the DEF STAN 91-091 standard, such as antioxidants or lubricity enhancers.

[0058] According to a third aspect, the use of a hydrocarbon composition as defined herein as a renewable jet fuel or a renewable jet fuel component is provided.

[0059] In the above use, the hydrocarbon composition provides the jet fuel composition with excellent properties including at least one of the following: thermal oxidation stability, JFTOT breakpoint temperature, kinematic viscosity at -20°C, freezing point, density, and / or biogenic carbon content, as well as blendability with currently available aviation fuel components.

[0060] According to one embodiment of the above use, the hydrocarbon compositions defined herein may be used in a jet fuel composition to reduce emissions compared to those from petroleum-based jet fuel, more specifically to reduce NOx gas emissions, CO2 gas emissions, or exhaust particulate matter. The hydrocarbon compositions defined herein may be used in a jet fuel composition to reduce NOx gas emissions by 10-15%, CO2 emissions by 2-5%, or particulate (volume) emissions by 81-98% compared to those from petroleum-based jet fuel. Preferably, at least two of the above emissions are reduced simultaneously, more preferably all three are reduced, i.e., NOx gas emissions are reduced by 10-15%, CO2 emissions by 2-5%, and particulate (volume) emissions by 81-98% compared to those from petroleum-based jet fuel.

[0061] This hydrocarbon composition is a synthetic product and is therefore manufactured in a refinery through several processing steps. In some embodiments, if the raw materials supplied for the above manufacture are of non-fossil origin, the product may be called a renewable product. Preferably, this hydrocarbon composition is a renewable hydrocarbon composition, and the co-product obtained from the above manufacture is renewable diesel.

[0062] Also known as distillation feed (referred to as DistFeed in the example), this is a stream that is distilled to produce diesel, and the hydrocarbon composition according to the present invention can be produced by any suitable method. The description of the production here begins with supplying a paraffinic hydrocarbon feed to the fractionation phase.

[0063] In one embodiment, n-paraffins are produced from renewable raw materials, such as vegetable oils or animal fats. Such raw materials are subjected to a deoxygenation process to remove heteroatoms, mainly oxygen, from the renewable oil, thereby obtaining an n-paraffinic hydrocarbon feed.

[0064] In preferred embodiments, the deoxygenation treatment to which the renewable raw material is supplied is a hydrogenation treatment. Preferably, the renewable raw material is subjected to hydrogenation deoxygenation (HDO), which preferably uses an HDO catalyst. Catalyst HDO is the most common method of removing oxygen and has been widely considered and optimized. However, the present invention is not limited thereto. As the HDO catalyst, an HDO catalyst in which a metal hydride is supported on a support can be used. Examples include HDO catalysts containing a metal hydride selected from the group consisting of Pd, Pt, Ni, Co, Mo, Ru, Rh, W, or combinations thereof. In particular, alumina or silica are suitable as supports. The hydrogenation deoxygenation process may be carried out, for example, at a temperature of 100 to 500°C and a pressure of 10 to 150 bar (absolute).

[0065] In one embodiment, the n-paraffinic hydrocarbon feed is produced by the Fischer-Tropsch process, which begins with the gasification of biomass. This synthesis route is commonly known as BTL or Biomass-to-Liquid. It is well documented in the literature that biomass, such as lignocellulose material, can be gasified at high temperatures using oxygen or air to obtain a gas mixture of hydrogen and carbon monoxide (synthesis gas). After purification of the gas, this synthesis gas can be used as a feedstock for the Fischer-Tropsch synthesis route to produce paraffin from the synthesis gas. The n-paraffin produced by the Fischer-Tropsch method ranges from gaseous components to waxy paraffin, and paraffin within the boiling point range of the middle distillate can be obtained by distillation from the paraffinic hydrocarbon feed.

[0066] n-paraffins formed by either the hydrogenation of renewable oil or the Fischer-Tropsch process require isomerization. Isomerization causes branching of the hydrocarbon chains of the hydrogenated raw material, i.e., isomerization. Branching of the hydrocarbon chains improves the low-temperature properties. That is, the isomerized compositions formed by isomerization have better low-temperature properties compared to the hydrogenated raw material. Better low-temperature properties refer to a lower freezing point temperature in the case of aviation fuels and a lower cloud point temperature in the case of diesel. The isomerized hydrocarbons formed by isomerization, i.e., isomerized paraffins, may have one or more side chains, and therefore each may be monobranched or polybranched.

[0067] The isomerization step may be carried out in the presence of an isomerization catalyst and optionally in the presence of hydrogen added to the isomerization method, and may therefore be carried out by a method called hydrogen isomerization. As used herein, “isomerization” may preferably refer to hydrogen isomerization. A suitable isomerization catalyst comprises a molecular sieve and / or a metal selected from Group VIII of the periodic table, and optionally a support. Preferably, the hydrogen isomerization catalyst comprises SAPO-11, or SAPO-41, or ZSM-22, or ZSM-23, or fernerite, and Pt, Pd, or Ni, and Al2O3 or SiO2. Typical hydrogen isomerization catalysts are, for example, Pt / SAPO-11 / Al2O3, Pt / ZSM-22 / Al2O3, Pt / ZSM-23 / Al2O3, and Pt / SAPO-11 / SiO2. The catalysts may be used alone or in combination. The presence of added hydrogen is particularly preferable in order to reduce catalyst deactivation.

[0068] In preferred embodiments, the hydrogen isomerization catalyst is a noble metal bifunctional catalyst, such as Pt-SAPO and / or Pt-ZSM catalyst, used in combination with hydrogen. The hydrogen isomerization process may be carried out at a temperature of, for example, 200-500°C, preferably 280-400°C, or 300-350°C, and at a pressure of 5-150 bar, preferably 10-130 bar, more preferably 30-100 bar (absolute).

[0069] The isomerization step may include further intermediate steps, such as purification and / or fractionation steps.

[0070] The product obtained there is called the sequential HDO hydrogen isomerization product.

[0071] In a particular embodiment, a paraffinic hydrocarbon feed can be obtained as a product of such hydrogen isomerization, wherein the feed contains at least 90 wt% paraffin by weight of the total paraffinic hydrocarbon feed, and of the paraffin, up to 30 wt% is n-paraffin.

[0072] As an example, the above paraffinic hydrocarbon feed may be characterized by a T10 temperature of 200-270°C and an FBP of 280-320°C.

[0073] In one embodiment of this method, the paraffinic hydrocarbon feed is obtained from sequential HDO hydrogen isomerization, which may be followed by distillation. A commercially proven method for sequential HDO hydrogen isomerization is available. Therefore, according to this embodiment, the method can be easily integrated into the above-described method to produce a high-quality product, for example, the hydrocarbon composition as a renewable aviation fuel component, with the remainder meeting the requirements for renewable diesel.

[0074] In one embodiment of this method, the paraffinic hydrocarbon feed is obtained from sequential HDO-hydrogen isomerization, further comprising decomposition isomerization either before or after isomerization, and optionally followed by distillation. Decomposition isomerization has been found to efficiently increase the degree of isomerization and contribute to the desired product characteristics.

[0075] In one embodiment of this method, the paraffinic hydrocarbon feed is obtained by sequential HDO-hydrogen isomerization, with a decomposition isomerization step performed before hydrogen isomerization. It has been found that the combination of decomposition isomerization and hydrogen isomerization contributes to the yield of the desired number of carbon atoms and branching in the resulting product.

[0076] In one embodiment of this method, a paraffinic hydrocarbon feed is obtained from sequential HDO-hydrogen isomerization, followed by a decomposition isomerization step. It was found that decomposition isomerization contributes to branching, particularly to the formation of highly branched i-paraffins.

[0077] When hydrocracking is applied, it is generally operated so that more cracking reactions, particularly those that enhance the effective cracking of C8-C16 hydrocarbons, occur than in a hydrogen isomerization reactor. Preferably, cracking reactions, especially those that enhance the effective cracking, are the main reactions in the hydrocracking reactor, but generally there is no excessive cracking or excessive fuel gas formation. Typically, hydrocracking is carried out within the following conditions: temperature: 200°C to 450°C, preferably 220°C to 430°C, more preferably 280°C to 350°C; pressure: 0.4 MPa to 8 MPa, preferably 1 MPa to 7 MPa; partial pressure of H2 at the reactor inlet: 0.4 MPa to 8 MPa, preferably 1 MPa to 7 MPa; gravimetric space velocity: within the range of 0.1 to 10 kg per hour per kg of catalyst, preferably 0.2 to 8 kg, more preferably 0.4 to 6 kg, even more preferably 0.5 to 1.5 kg of reactor feed; and H2 to reactor feed ratio: within the range of 10 to 2000 normal liters of H2 per liter of reactor feed, preferably 50 to 1000 normal liters.

[0078] In one embodiment of this method, isomerized paraffin (also called paraffinic hydrocarbon feed) formed by the isomerization method is fractionated in order to obtain the diesel fuel fraction and hydrocarbon composition according to the present invention. Fractionation can be carried out by any suitable method and is not limited to distillation. However, distillation is the most commonly used method for separating various fractions from a hydrocarbon composition and is suitable here as well.

[0079] More specifically, the method for producing the hydrocarbon composition described herein is: - A paraffinic hydrocarbon feed is supplied to the fractionation phase, comprising at least 90 wt% paraffin of the total weight of the paraffinic hydrocarbon feed, with a maximum of 30 wt% of the paraffin being n-paraffin. - Fractionating the paraffinic hydrocarbon feed to recover the previously defined hydrocarbon composition. Includes.

[0080] The paraffinic hydrocarbon feed, which is the raw material for this method, can be obtained by the following process, which has already been described in detail: - A process of preparing renewable feedstock containing fatty acids and / or derivatives thereof, - A process of deoxygenating the supplied raw materials to produce paraffin. - A step of producing isomerized paraffin by subjecting the generated paraffin to an isomerization step and an optional decomposition isomerization step, wherein the decomposition isomerization is performed either before or after the isomerization step, and the isomerization is preferably hydrogen isomerization, and In some cases, the fraction used as paraffinic hydrocarbon feed is recovered by distillation of the product.

[0081] According to a preferred embodiment, the hydrocarbon composition is obtained as a single fraction from the above fraction, which involves one distillation. According to another embodiment, the hydrocarbon composition is obtained as a single fraction from the above fraction, which involves two distillations. The residue is preferably recovered as a diesel fuel fraction.

[0082] Considering the production of the raw materials supplied to this method, according to one embodiment, the total weight of the recovered hydrocarbon composition and the diesel fuel fraction is at least 65 wt%, and at least 70 wt%, of the renewable raw materials supplied for deoxygenation, which include fatty acids and / or their derivatives.

[0083] According to a particular embodiment, a fraction having a T10 temperature of 200-270°C and an FBP of 280-320°C is recovered from distillation and used as paraffinic hydrocarbon feed.

[0084] Conventional manufacturing methods, which have primarily produced products suitable for use as aviation fuel, have been lacking in one or more of the properties, specifically one or more of the properties regulated by standards, and therefore have required additional components to adjust them to meet all requirements.

[0085] Preferably, the hydrocarbon composition, jet fuel component, and / or jet fuel meet the current stringent requirements for the low-temperature properties of a fuel suited to the purpose. One challenge in the sustainable production of jet fuel components has been that, even with advanced hydrotreatment methods, it has been impossible to produce jet fuel components from renewable oils and fats in a yield comparable to the corresponding yield of renewable diesel. Therefore, an advantage of this composite production is that the by-products recoverable from the production of jet fuel / jet fuel components also have good market value.

[0086] In a fourth aspect, the present invention describes a method for compounding a high-quality jet fuel component (which may even be used as neat fuel in the aviation sector) with a high-quality winter renewable diesel.

[0087] As shown in the attached example, this method enables the simultaneous production in high yield of a high-quality hydrocarbon composition suitable as jet fuel or jet fuel component and high-quality renewable diesel fuel or renewable diesel fuel component from fractionation, preferably distillation. Accordingly, according to a preferred embodiment, a diesel fuel fraction, preferably a renewable diesel fuel fraction, is further recovered from the fractionation. It is advantageous to recover the hydrocarbon composition as a single fraction and the diesel fuel as another single fraction directly from the fractionation. Preferably, the diesel fuel fraction is recovered as a residue or bottom product. Even more preferably, the hydrocarbon composition suitable as jet fuel or jet fuel component is recovered as a fraction, and the diesel fuel fraction is recovered as a bottom product from distillation, so that there are essentially no other products or flows recovered from distillation.

[0088] According to one embodiment, the total weight of the recovered hydrocarbon composition and the diesel fuel fraction is at least 80 wt%, preferably at least 90 wt%, and more preferably at least 98 wt%, of the weight of the paraffinic hydrocarbon feed used for fractionation. By recovering the hydrocarbon composition and the diesel fuel fraction in such a way that the total weight is as large as possible, the reduction in recovered material and the generation of other low-value products are minimized.

[0089] The recovered diesel fuel fraction was experimentally characterized in Example 5. In Example 5, the physicochemical properties of the recovered diesel fuel fraction were measured and compared with a control sample. The recovered diesel fuel fraction may be characterized by one or more of the following properties: The cetane number is at least 74, preferably at least 76, more preferably at least 78, or even more than 80, as measured according to EN 15195-2104. The cloud point temperature is less than -28°C, preferably less than -32°C, and more preferably less than -36°C, as measured according to ASTM D5773-21. • Density is at least 780 kg / m³ when measured according to ASTM D4052-22. 3 Preferably at least 783 kg / m³ 3 That is, The true calorific value is at least 33 MJ / l, preferably at least 34 MJ / l, as measured according to ASTM D4809-18. The flash point temperature is at least 95°C, preferably at least 115°C, and more preferably at least 130°C, as measured according to IP170-21.

[0090] Many of the above characteristics are far superior to those of current diesel fuel standards, such as EN15940. When measuring the net calorific value, density is measured at 15°C.

[0091] Next, we will explain the suitability of this hydrocarbon composition for use as a jet fuel component in neat jet fuel, and the diesel fuel obtained as a by-product, through experimental findings and characterization of the samples.

[0092] example The following examples are given to better illustrate the claimed invention. These examples should not be construed as limiting the scope of the invention as determined by the claims. Where specific materials are mentioned, they are merely illustrative and not intended to limit the invention. Those skilled in the art can develop equivalent means or reactants without inventive ability and without departing from the scope of the invention. It should be understood that many modifications can be made to the procedures described herein while remaining within the scope of the invention. All exemplary materials and parameters used in the following examples are compatible with the Method and Products of this invention.

[0093] Example 1: Manufacturing and obtaining this hydrocarbon composition The hydrocarbon compositions discussed herein were recovered from test runs. During the test runs, several different feeds or cuts were distilled to separate them into the hydrocarbon compositions as fractions and diesel components as residues. Surprisingly, both separated products were of high quality and possessed desirable product characteristics for their respective renewable product categories: aviation fuel (SAF) and diesel fuel.

[0094] The distillation feed is obtained by sequential HDO and isomerization, or by sequential HDO, isomerization, and decomposition isomerization, where isomerization is preferably hydrogen isomerization, followed by distillation and optionally a second distillation step.

[0095] Several distilled feeds were obtained by subjecting the fat feed to hydrodeoxygenation (HDO) and gas-liquid separation to obtain a hydrodeoxygenated feed containing more than 95 wt% paraffin relative to the total weight of the paraffinic hydrocarbon feed. The above hydrodeoxygenated feed was further subjected to hydrogen isomerization (HI) and / or partially subjected to decomposition isomerization of varying degrees. If necessary, the fraction of the isomerized effluent or simply the bottom fraction was decomposed, and the effluent from the decomposition was subsequently degassed or degassed and stabilized. From the (liquid) effluent thus obtained, at least the middle distillate was recovered in high yield as the main product. The method for producing the middle distillate is highly optimized and ensures a high yield of the middle distillate relative to the renewable oils and fats used as feedstock. The above middle distillate was separated by distillation into the hydrocarbon composition (SAF1 and SAF2) and the diesel component.

[0096] Several of the distillation feeds (DistFeed1 and DistFeed2) were obtained as the main product from sequential HDO-hydrogen isomerization (in yield of over 80 wt% as a middle fraction from the regenerative oil feed). The middle fraction met the EN 15940 standard, meaning it can be used in paraffinic diesel fuel. This middle fraction was further distilled to obtain two fractions. This fraction, i.e., the hydrocarbon composition, was obtained from the distillation feed in yield of approximately 10 wt%, meeting the requirements of HEFA-SPK (regenerative component) in standard ASTM D7566-22A Annex A2, and exhibiting an extremely low kinematic viscosity (11.77 mm) at -40°C. 2It was found to possess ( / s). This makes the hydrocarbon composition very interesting as a renewable jet fuel component / sustainable aviation fuel component, and it may even be possible to use it alone as SAF in the future. A heavier fraction was obtained from the distillation feed in a yield of about 90 wt%, which also met the EN 15940 standard. Furthermore, based on certain parameters (e.g., energy density), this fraction showed improved quality compared to the middle distillate used as feedstock for distillation. Overall, this means that this method is a way to produce high-quality SAF and renewable diesel in a high total yield (over 80 wt% from renewable oil feed). Both the produced SAF and renewable diesel can be used as fuel components in high blend ratios, and even as neat fuel. Moreover, surprisingly, based on the analysis results of the distillation feed and fraction (i.e., SAF), the low-temperature properties of the distillation residue (i.e., renewable diesel) were found to be much better than expected. This is shown and explained in more detail in Example 7 and Table 10 of this specification.

[0097] The resulting hydrocarbon composition was renewable due to its renewable origin as a starting material (various types of fat-supplying raw materials).

[0098] In these experiments, a "synthetic pilot," or continuous distillation apparatus, was used for distillation. The column used had a diameter of 80 mm, a height of 4 m, and approximately 40-100 theoretical plates. The column also included structured packing. The fractionation rate was approximately 8-80 g / min, depending on the feedstock. The operating temperature of the bottom heater was 320°C. The distillation column is suitable for fractionation up to a true boiling point (Tbp) of approximately 560°C. The operating pressure in the above apparatus can generally range from atmospheric pressure to 1 mbar.

[0099] Example 2: Physicochemical properties of this aviation fuel component The physicochemical properties of two hydrocarbon compositions (=aviation fuel components) obtained as fractions from the middle distillate fraction reported in Example 1 were investigated. Density (kg / m³) 3 ), flash point (°C), kinematic viscosity at -20°C (mm²) 2 kinematic viscosity (mm² / s), kinematic viscosity at -40°C 2 The analytical values ​​for the temperature (°C), freezing point (°C), 10% distillation temperature (°C), 50% distillation temperature (°C), 90% distillation temperature (°C), and distillation FBP (°C) are reported in Tables 1 and 2.

[0100] The hydrocarbon compositions shown in Table 1 were obtained by fractionation after sequential decomposition and isomerization of HDO-hydrogen isomerization products. The hydrocarbon composition (SAF1) is the fraction with an IBP of 265°C, of ​​which the lightest 1 wt% was removed by another distillation to meet the flash point requirements.

[0101] [Table 1]

[0102] In Table 1 and Tables 2, 3, and 6 below, "viscosity" refers to the kinematic viscosity at -20°C and -40°C, as indicated. The weighted average carbon number is calculated based on the carbon number distribution analyzed by GC×GC and the weight percentage of each carbon number measured therein. The hydrocarbon compositions analyzed in Table 2 were obtained by fractionation from DistFeed2.

[0103] [Table 2]

[0104] In addition to the selected properties of ASTM D7566-22A as identified in Tables 1 and 2, both hydrocarbon compositions met all the requirements of ASTM D7566-22A Annex A2 for paraffinic kerosene obtained from hydrogenated fatty acid feedstock. The kinematic viscosity (both -20°C and -40°C) and freezing point of these hydrocarbon compositions were remarkably low. From the distillation properties in Tables 1, 2, and Figure 11, it was also found that these aviation fuel components exhibit relatively linear distillation behavior, which is beneficial, for example, to combustion properties.

[0105] Regarding the hydrocarbon composition of the samples in Table 2, the flash point is clearly higher than the required 38°C, due to the high flash point of the distillation feed (DistFeed2).

[0106] Furthermore, although ASTM D7566-22A Annex A2 for paraffinic kerosene obtained from hydrogenated fat feedstock does not specify viscosity requirements at sub-zero temperatures, each of the aviation fuel components reported in Tables 1 and 2 has a very low kinematic viscosity at -20°C, meeting the requirement in Table 1 of ASTM D7566-22A for Jet A1 aviation fuel composition, namely a maximum of 8.0 mm. 2 The / s requirement was met very clearly. The above results clearly demonstrate that this hydrocarbon composition can be incorporated into aviation fuel compositions at a much higher proportion than typical paraffinic jet fuel components. This hydrocarbon composition can be incorporated into aviation fuel compositions in amounts exceeding 50 vol% of the total volume of the aviation fuel composition. Depending on the development status of jet fuel standards, it can be speculated that this hydrocarbon composition may be usable as a 100 vol% aviation fuel composition in the future.

[0107] The improved properties of this hydrocarbon composition make it advantageous for other applications requiring superior performance in low-temperature environments.

[0108] The hydrocarbon compositions exhibit exceptionally low freezing points and kinematic viscosities compared to typical commercially available renewable aviation fuel components, such as those shown in Comparative Example 2. In particular, the two hydrocarbon compositions of the present invention (SAF1 and SAF2) have viscosities of up to 12 mmHg at -40°C. 2 Since these compositions already meet the requirements of Table 1 of ASTM D7566-22A, which state that the blend ratios are / s, the blend ratios of these compositions are not limited by viscosity. These blend ratios are limited not by viscosity but by the aromatic content of the conventional jet fuel components, and therefore it is easy to achieve a standard-compliant blend using 50 vol% HEFA-SPK, or even up to 68 vol% HEFA-SPK, with appropriate conventional jet fuel, as shown in Example 4 of this application.

[0109] Comparative Example 2: Hydrocarbon composition of commercially available SAF products currently on the market The same renewable paraffinic feed (DistFeed1) as in Example 2 was produced by hydrogenation deoxygenation and isomerization of a feedstock mixture of renewable origins, and then sent to a fractionation unit for distillation. In the fractionation unit, conditions were selected to maximize the weight yield of SAF, and the renewable paraffinic product was separated into multiple fractions. One of these fractions, i.e., the SAF described above, was analyzed using various analytical methods. The results are summarized in Table 3.

[0110] [Table 3]

[0111] The analyzed products in Table 3 meet the requirements for HEFA-SPK according to ASTM D7566-22A Annex A2, although their freezing points are not particularly low. Importantly, even though the products contain virtually no aromatic components, their blending ratios are limited by their kinematic viscosities at -20°C and -40°C.

[0112] Example 3: Hydrocarbon distribution of this hydrocarbon composition Several experimentally obtained hydrocarbon compositions were analyzed for composition by GC×GC-FID / MS. The wt% results for n-paraffins, unbranched i-paraffins, and polybranched i-paraffins (bifibranched and tribranched, respectively, are shown in their respective columns) for each carbon number in each sample, along with the aromatic and naphthene content, are reported in Table 4 for one exemplary hydrocarbon composition. The results in Table 4 correspond to those shown in Figure 3. Correspondingly, several other samples were analyzed, and their results are shown in Figures 1 to 10. To better identify factors that may contribute to superior product properties, several composition-related properties were calculated based on the analytical results reported in the above figures and are reported in Table 5 for the total carbon number range C8 to C16.

[0113] [Table 4]

[0114] [Table 5]

[0115] In Tables 4 and 5, i represents i-paraffin, n represents n-paraffin, poly-i represents polybranched i-paraffin, and i represents monobranched i-paraffin. The ratio of i to n refers to the weight ratio of the sum of any i-paraffin and any n-paraffin, all of which have carbon numbers in the range of C8 to C16. The weighted average carbon number was calculated based on detailed compositional results considering all carbon numbers and types, i.e., carbon numbers 1-7 and 17-30, as well as naphthenes and aromatics, as shown for the exemplary compositions in Table 4.

[0116] From the exemplary compositions in Figures 1-10 and Table 4, it can be seen that all samples are highly paraffinic even with very low naphthene and aromatic content. Table 4 also shows that the most abundant carbon numbers in these samples were C10, C11, C12, and C13. Within the carbon number range (within the detection limit), none contained only n-paraffins; at least one-branched i-paraffin was detected for each carbon number, and polybranched i-paraffin was also detected (or even dominant) for most carbon numbers. This demonstrates a high degree of isomerization across the entire C8-C16 range.

[0117] Generally, a higher i-paraffin content tends to improve the low-temperature properties of paraffinic hydrocarbon compositions, but n-paraffins generally have the opposite effect, and long-chain n-paraffins in particular can even solidify at low temperatures. Table 5 shows that each sample had a very high i-paraffin content of C8-C16, i.e., 86 wt% or more. At the same time, each sample also had a notable n-paraffin content of C8-C16, i.e., 5-10 wt%. Nevertheless, the freezing points of the analyzed samples were still below -64°C.

[0118] Example 4: Blend The blending properties were examined with various variations of the hydrocarbon composition, various variations of conventional fossil jet fuels, and various combinations of commercially available SAF for comparison. To highlight the differences from prior art solutions, conventional fossil jet fuel (CJF) was first blended with both SAF1 (as claimed in this patent) and commercially available SAF(CHC) for comparison. To demonstrate that the compatibility is not limited to one specific fossil jet fuel, after the initial Example 4.1, the example flow was designed to blend the hydrocarbon composition (SAF1) from Example 4.1 with another conventional fossil jet fuel in Example 4.2. Subsequently, yet another variety of variations were introduced one by one, addressing the need for observations on only one variable at a time.

[0119] Example 4.1 Blends compared to commercially available SAF Considering the hydrocarbon compositions of Example 2 and Example 3, and Comparative Example 2, the blending of these compositions with conventional jet fuels is limited by various parameters. Table 6 shows the characteristics of the limitations imposed by standards on the blending of conventional jet fuel (CJF) with the hydrocarbon composition (PHC), on the one hand with commercially available SAF (CHC) for comparison, on the other hand.

[0120] [Table 6]

[0121] As can be seen from Table 6, the blending ratio of this hydrocarbon composition is limited to 56 vol% by the requirements for aromatic content of conventional jet fuels, rather than by its low-temperature viscosity. In other words, with this low-temperature viscosity, it is possible to increase the proportion of this hydrocarbon composition in the blend even further. This is surprising because, in the case of the comparative hydrocarbon composition, even a CHC:CJF blending ratio of 36:64 vol% already fails to meet the viscosity requirement at -40°C.

[0122] Example 4.2 Blending with further diverse variations Further data are provided, using the same method as in Example 4.1, for blends of the hydrocarbon composition (from Example 2) with other conventional jet fuels, for further hydrocarbon compositions whose properties closely match those of the hydrocarbon composition from Examples 2 and 3, and for blends thereof with conventional jet fuels.

[0123] [Table 7]

[0124] These results demonstrate that the blending ratio of this hydrocarbon composition can be increased even beyond the currently approved limit of 50 vol%. For a 75 vol% blend, properties critical to aircraft operation, such as freezing point, flash point, distillation properties, and viscosity, are all within the limits of current standards, although density and aromatic content fall short of the limits. Another specially selected conventional jet fuel may even better meet these limits.

[0125] The conventional jet fuel (CJF2) shown in Table 7 was further used in blends with the hydrocarbon composition (SAF3) according to the present invention, whose properties match those shown in Examples 2 and 3. The results of these blends are shown in Table 8.

[0126] [Table 8]

[0127] These results demonstrate that this hydrocarbon composition can be blended with conventional jet fuel even at a high blending ratio of 90:10 vol%, even if it does not meet the density and aromatic requirements that can be addressed in aircraft design.

[0128] Finally, the SAF3 shown in Table 8 was further blended with another conventional jet fuel (CJF3). The CJF3 was then further blended with another hydrocarbon composition according to the present invention (SAF4) whose properties matched those shown in Examples 2 and 3. These fuels and their results are shown in Table 9.

[0129] Here too, the requirements for this hydrocarbon composition are met, and even at high blending ratios of 50, 75, and even 90 vol%, the requirements for semi-synthetic jet fuel are met in terms of important properties.

[0130] [Table 9]

[0131] Example 5: Physicochemical properties of renewable diesel fuel obtained as a by-product As described, the hydrocarbon composition suitable as an SAF component was recovered from a test run. In the test run, several different feeds or cuts were separated by distillation. The surprisingly good quality of the above hydrocarbon composition as an SAF component is described in Examples 2-4. Furthermore, the diesel oil cuts obtained from the same distillation were also of high quality and possessed desirable product characteristics for diesel fuel, as shown below.

[0132] As reported in Example 1, the physicochemical properties of two renewable diesel fuels / components obtained as residue or bottom fraction from the distillation of the middle distillate were investigated. Density (kg / m³) 3 Table 10 reports the analytical values ​​for ), flash point (°C), cloud point (°C), cetane number, distillation IBP (°C), 50% distillation temperature (°C), 95% distillation temperature (°C), and net calorific value (MJ / l).

[0133] [Table 10]

[0134] The EN 15940 standard covers paraffinic diesel fuels used directly in vehicles and defines their fuel characteristics at the point of retail sale. In this context, paraffinic diesel is defined as hydrogenated paraffinic renewable diesel fuel, as well as GTL, BTL, and CTL (Cultured Coal Oil), which are synthetic products of the Fischer-Tropsch process.

[0135] The control regenerative middle distillate DistFeed2 meets the EN 15940 standard, and therefore, the distillation bottom fraction described in the present invention was also compared to this standard to confirm that the necessary parameters are met.

[0136] The bottom fractions of both renewable diesels exhibit higher densities, cetane numbers, and flash points compared to the control renewable middle distillate. Furthermore, the bottom fraction from DistFeed2 has a higher net calorific value than DistFeed2 when measured in MJ / liter units.

[0137] Example 6: Hydrocarbon composition of renewable diesel fuel obtained as a by-product. Several experimentally obtained renewable diesel fuel samples were analyzed for composition by GC×GC-FID / MS in the same manner as the hydrocarbon composition in Example 3. The wt% results for n-paraffins, unbranched i-paraffins, and multibranched i-paraffins (billy, tribranched, and tetrabranched, respectively, are shown in their respective columns) for each carbon number in each sample, along with the aromatic and naphthene content, are reported in Table 11 for one exemplary renewable diesel fuel sample. Several further samples were analyzed, but the results are not detailed here. To better identify factors that may contribute to the superior product characteristics of the above renewable diesel fuel samples, several composition-related properties were calculated based on the above samples and are reported in Table 12 for the total carbon number range C15–C22.

[0138] [Table 11]

[0139] Table 11 shows that the exemplary renewable diesel compositions primarily consist of highly branched i-paraffins. The most typical carbon number is C18, followed by C16 and C17.

[0140] [Table 12]

[0141] The renewable diesel compositions were highly isomerized, particularly containing high levels of highly branched i-paraffins. The hydrocarbon distribution and composition shown in Tables 11 and 12 are thought to contribute to the physicochemical properties of the renewable diesel fuels / components reported in Table 10.

[0142] Example 7: Low-temperature properties of the hydrocarbon composition and its by-product, renewable diesel. The low-temperature properties of paraffinic compositions can be estimated by calculation. Table 13 shows the analytical and calculated cloud point values ​​of renewable diesel (using linear calculation models for various distillation fractions).

[0143] [Table 13]

[0144] Based on its low-temperature properties, distillation properties, high paraffin concentration, and very high degree of isomerization, this hydrocarbon composition is expected to have desired properties for a wide range of other applications besides aviation fuels. These applications include solvents, carriers, dispersant compositions, deemulsifiers, extractants, detergents, degreasing compositions, cleaning agents, diluents, penetrating oils, corrosion inhibitors, multipurpose oils, metalworking fluids, particularly rolling oils, cutting oils, drilling fluids, lubricants, drawable oils, paint compositions, coating fluids or pastes, adhesives, resins, varnishes, printing pastes or inks, plasticizing oils, turbine oils, hydrophobic compositions, agricultural and crop protection fluids, construction, concrete release compounds, electronic equipment, medical devices, feedstocks for industrial conversion processes, preferably pyrolysis feedstocks and / or catalytic cracking feedstocks, compositions for the automotive, electrical, textile, packaging, paper and / or pharmaceutical industries, and / or intermediates for these.

[0145] Example 5: Analysis of JFTOT and smoke point The JFTOT breakpoint refers to the thermal oxidation test of jet fuel and its results. The JFTOT breakpoint is given as a temperature in °C. Improving the above breakpoint is understood to mean increasing the above temperature. Thermal oxidation stability was experimentally measured according to the JFTOT procedure (ASTM D3241-20c). In test method D3241, the breakpoint is the highest control temperature at which the fuel satisfies the heater tube evaluation and ΔP standard requirements. However, measurements are performed up to a practical upper temperature limit, i.e., 380 °C, the temperature above which the sample vial begins to melt. Therefore, the upper limit is determined independently of the analytical instrument provider.

[0146] JFTOT breakpoint values ​​were measured for two samples (SAF1 and SAF2) reported in the patent application documents, as well as two additional samples (SAF3 and SAF4) (all according to the present invention). The results, along with smoke point measurements for the same samples, are shown in the following table (Table 14).

[0147] [Table 14]

[0148] It can be concluded that all samples of hydrocarbon compositions according to this claim meet the JFTOT breakpoint requirement of 325°C or higher. Even when the temperature was further increased to 340°C, 360°C, and even 380°C, the fuels met the heater tube evaluation and ΔP standard requirements.

[0149] Furthermore, the superior properties are confirmed by smoke point results that exceed the requirements specified herein.

[0150] Various embodiments have been presented. Please understand that in this book, the terms "comprise," "include," and "contain" are used as open-ended expressions, not intended to be exclusive.

[0151] The foregoing description has provided a complete and useful description of the best mode currently intended by the inventors to carry out the invention, as non-limiting examples of specific implementations and embodiments. However, it will be apparent to those skilled in the art that the invention is not limited to the details of the embodiments shown above, and that the invention can be carried out in other embodiments or in different combinations of embodiments using equivalent means without departing from the features of the invention.

[0152] Furthermore, some of the features of the exemplary embodiments disclosed above can be advantageously used without corresponding use of other features. Therefore, the foregoing description should be considered merely illustrative of the principles of the present invention and not limiting the invention. Accordingly, the scope of the present invention is limited only by the appended claims.

Claims

1. A hydrocarbon composition comprising n-paraffin and i-paraffin, - The total amount of all C8-C16 i-paraffins is 50-94 wt% of the total weight of the hydrocarbon composition. - The kinematic viscosity of the hydrocarbon composition at -20°C is 3.7 to 8 mm when measured according to ASTM D445-21e2. ２ / s, preferably 3.7 to 5.5 mm ２ It is within the range of / s, - A hydrocarbon composition in which the weighted average number of carbon atoms of the hydrocarbons in the hydrocarbon composition is 12.1 to 14.

2.

2. The hydrocarbon composition according to claim 1, wherein the JFTOT breakpoint is 325°C or higher, preferably above 360°C, or more preferably above 380°C, when measured according to ASTM D3241-20C.

3. The density of the hydrocarbon composition, as measured using the ASTM D4052-22 standard, is 730 to 772 kg / m³. ３ Preferably 750.0 to 772.0 kg / m ３ More preferably 753.0 to 770.0 kg / m ３ Most preferably 754.0 to 760.0 kg / m ３ The hydrocarbon composition according to claim 1 or 2.

4. The hydrocarbon composition according to any one of claims 1 to 3, wherein the total amount of all C8 to C16 n-paraffins is 2 to 12 wt%, preferably 5 to 11 wt%, of the total weight of the hydrocarbon composition.

5. The hydrocarbon composition according to any one of claims 1 to 4, wherein the total amount of all C8-C16 polybranched i-paraffins is 35-65 wt%, preferably 45-63 wt%, more preferably 55-60 wt%, of the total weight of the hydrocarbon composition.

6. The hydrocarbon composition according to any one of claims 1 to 5, wherein the freezing point is less than -50°C, less than -60°C, preferably less than -64°C, as measured according to IP529-22.

7. The hydrocarbon composition according to any one of claims 1 to 6, wherein the bio-derived carbon content is at least 50 wt%, preferably at least 70 wt%, and more preferably at least 90 wt%, relative to the total weight (TC) of carbon in the jet fuel components, as measured according to EN 16640 (2017).

8. A fuel or fuel component comprising the hydrocarbon composition according to any one of claims 1 to 7, preferably a jet fuel or a jet fuel component.

9. The fuel or fuel component according to claim 8, comprising 3 vol% to about 100 vol%, 3, 36, 50, 56 vol% to 50, 56, 75, 90, or 100 vol%, more preferably 36 vol% to 90 vol%, of the hydrocarbon component according to any one of claims 1 to 7, with the remainder being petroleum-based jet fuel.

10. The fuel or fuel component according to claim 8, comprising about 100 vol% of the hydrocarbon component according to any one of claims 1 to 7.

11. Use of the hydrocarbon composition according to any one of claims 1 to 7 as renewable jet fuel or a renewable jet fuel component.

12. The use of the jet fuel composition according to claim 11 for improving one or more product properties of the jet fuel composition.

13. The use according to claim 12, wherein one or more of the product properties of the jet fuel composition include at least one of the following: thermal oxidation stability, JFTOT breakpoint temperature, kinematic viscosity at -20°C, freezing point, density, and / or biogenic carbon content.

14. Compared to emissions from petroleum-based jet fuel, NOx gas emissions should be reduced by 10-15%, or CO2 emissions should be reduced. ２ The use of a jet fuel composition according to claim 13 for reducing emissions by 2 to 5 percent or reducing particulate (volume) emissions by 81 to 98 percent, or for at least one of these purposes.

15. A method for producing a hydrocarbon composition according to any one of claims 1 to 7, - A paraffinic hydrocarbon feed is supplied to the fractionation phase, comprising at least 90 wt% paraffin of the total weight of the paraffinic hydrocarbon feed, with a maximum of 30 wt% of the paraffin being n-paraffin. - Fractionating the paraffinic hydrocarbon feed to recover the hydrocarbon composition according to any one of claims 1 to 7. Methods that include...

16. The method according to claim 15, wherein the hydrocarbon composition according to any one of claims 1 to 7 is obtained as a single fraction from the fractionation.

17. The method according to claim 15 or 16, wherein the diesel fuel fraction is further recovered from the fraction, preferably as a bottom product.

18. The method according to claim 17, wherein the recovered diesel fuel fraction is characterized by one or more of the following: - The cetane number is at least 74, preferably at least 76, more preferably at least 78, or even more than 80, as measured according to EN 15195-2104. The cloud point temperature is less than -28°C, preferably less than -32°C, and more preferably less than -36°C, as measured according to ASTM D5773-21. - The density is at least 780 kg / m when measured in accordance with ASTM D4052-22 ３ , preferably at least 783 kg / m ３ and is The true calorific value is at least 33 MJ / l, preferably at least 34 MJ / l, when measured according to ASTM D4809-18. The flash point temperature is at least 95°C, preferably at least 115°C, and more preferably at least 130°C, as measured according to IP170-21.

19. The method according to any one of claims 15 to 18, wherein the paraffinic hydrocarbon feed is obtained by the following steps: - A process of preparing renewable feedstock containing fatty acids and / or derivatives thereof, - A step of deoxygenating the supplied raw material to produce paraffin, A step of producing isomerized paraffin by subjecting the generated paraffin to an isomerization step and an optional decomposition isomerization step, wherein the decomposition isomerization is performed either before or after the isomerization step, and - A step of recovering the fraction used as the paraffinic hydrocarbon feed by distillation of the product, if applicable.

20. The method according to any one of claims 17 to 19, wherein the total weight of the recovered hydrocarbon composition and the diesel fuel fraction is at least 80 wt%, preferably at least 90 wt%, more preferably at least 98 wt%, of the weight of the paraffinic hydrocarbon feed supplied to the fractionation, or the method according to claim 19, wherein the total weight of the recovered hydrocarbon composition and the diesel fuel fraction is at least 65 wt%, at least 70 wt%, of the renewable feed material comprising fatty acids and / or derivatives thereof that is subjected to deoxygenation.

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