Method for treating a gaseous composition comprising propane

Abstract

A method for processing a gaseous composition is disclosed that includes subjecting a gaseous composition comprising H2, methane, ethane, propane, and hydrocarbons having a carbon number of at least C4 to distillation in a thermally connected distillation system to recover a propane composition.

Description

[Technical field]

[0001] The present disclosure relates generally to methods for processing gaseous compositions and for co-producing propane compositions and fuel components. The present disclosure particularly, but not exclusively, relates to methods for processing gaseous compositions derived from hydroprocessing effluents. [Background technology]

[0002] This section provides useful background information without any admission that any of the technology described herein represents the state of the art.

[0003] Propane is typically used, for example, for home heating and as a transportation fuel.

[0004] Traditionally, propane has been produced from crude mineral oil by established technologies and processes, but efforts have been made to replace propane derived from mineral oil or fossil fuels with more environmentally sustainable propane derived, at least in part, from bio-based renewable materials.

[0005] For example, established processes for obtaining propane from crude mineral oil cannot be easily transferred to renewable materials because renewable materials typically contain significant amounts of oxygen-containing organic compounds and have carbon number distributions that differ significantly from that of crude mineral oil.

[0006] Thus, there is a need for methods for obtaining propane compositions, especially from renewable sources. Summary of the Invention

[0007] The present invention aims to provide an improved method for separating a propane composition from a gaseous composition, to reduce the energy consumption of such a method, and in particular to provide an improved commercial-scale process for the co-production of a fuel component, e.g. aviation fuel, gasoline and / or diesel fuel component, with a high-quality propane composition, which can be used for catalytic upgrading, e.g. catalytic dehydrogenation to produce propene.

[0008] The appended claims define the scope of protection. The examples and technical descriptions of the apparatus, products and / or methods in the specification and / or drawings that are not included in the claims are presented as examples useful for understanding the present invention.

[0009] In a first exemplary aspect, a method for treating a gaseous composition, comprising: (i) providing a gaseous composition comprising H2, methane, ethane, propane and hydrocarbons having a carbon number of at least C4, wherein the total amount of H2, methane, ethane, propane and hydrocarbons having a carbon number of at least C4 is at least 80 wt-%, preferably at least 85 wt-%, more preferably at least 90 wt-% of the total weight of the gaseous composition; and (ii) subjecting the gaseous composition to distillation in a thermally connected distillation system comprising n distillation columns, at least one and up to n-1 condensers, and at least one and up to n-1 reboilers, where n is an integer equal to or greater than 1, to recover a propane composition. A method is provided that includes:

[0010] In a second exemplary aspect, (i) subjecting a hydroprocessing feed comprising vegetable oils, animal fats and / or microbial oils, and optionally a hydrocarbon diluent, to catalytic hydroprocessing, including at least hydrodeoxygenation using a sulfurized hydroprocessing catalyst, to obtain a hydroprocessing effluent: subjecting the hydrotreatment effluent to gas-liquid separation to obtain at least a gaseous stream comprising H, H2S, CO, CO2, HO, methane, ethane, propane and hydrocarbons having a carbon number of at least C4 and a liquid hydrotreatment stream comprising hydrocarbons of C6 to C30; subjecting said gaseous stream to a pretreatment step, including at least purification to remove H2S and CO2, H2 separation, and drying, to obtain a gaseous composition comprising H2, methane, ethane, propane, and hydrocarbons having a carbon number of at least C4, wherein the total amount of H2, methane, ethane, propane, and hydrocarbons having a carbon number of at least C4 is at least 80 wt%, preferably at least 85 wt%, more preferably at least 90 wt% of the total weight of the gaseous composition; and (ii) subjecting the gaseous composition to distillation in a thermally connected distillation system comprising at least a first distillation column connected to a condenser without being connected to a reboiler and a second distillation column connected to a reboiler without being connected to a condenser by feeding the gaseous composition to the first distillation column and recovering a propane composition from the second distillation column; 1. A method for co-producing a propane composition and a fuel component comprising: Provided is a method, wherein the method further comprises subjecting the liquid hydrotreated stream comprising C6 to C30 hydrocarbons to fractionation, optionally after further catalytic hydroprocessing including at least hydroisomerization, to recover one or more of a gasoline fuel component, an aviation fuel component and / or a diesel fuel component.

[0011] Above, various non-binding exemplary aspects and embodiments are illustrated. The above embodiments are merely used to illustrate selected aspects or steps that can be used in various implementations. The embodiments and preferred embodiments disclosed in relation to the present method for processing a gaseous composition are equally applicable to the present method for co-producing a propane composition and a fuel component.

[0012] Several exemplary embodiments will now be described with reference to the accompanying drawings. [Brief description of the drawings]

[0013] [Figure 1] FIG. 1 is a schematic diagram of the thermally coupled distillation of step (ii) according to an exemplary embodiment. [Diagram 2] FIG. 2 is a schematic diagram of an exemplary embodiment of the method of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] In the following description, like reference numbers refer to like elements or steps. All standards referred to herein are the latest editions available as of the filing date.

[0015] C4+ compounds, in the context of this disclosure, refer to compounds having a carbon number of at least C4. C4+ hydrocarbons, in the context of this disclosure, refer to hydrocarbons having a carbon number of at least C4. C4+ hydrocarbon content refers to the wt-% content of C4+ hydrocarbons in the gaseous composition being treated, in other streams in the process, or in the propane composition produced, relative to the weight of the total stream of interest. The C4+ hydrocarbon content is measured as the sum of the individual contents of the components with respect to their respective carbon numbers, for example (C4+C5+...). C5+ hydrocarbon content is used respectively for hydrocarbons with a carbon number of at least C5.

[0016] A C5+ compound, in the context of this disclosure, refers to a compound having a carbon number of at least C5. A C5+ hydrocarbon, in the context of this disclosure, refers to a hydrocarbon having a carbon number of at least C5.

[0017] A thermally connected distillation system in the context of this disclosure refers to a distillation system comprising n distillation columns, at least one and at most n-1 condensers, and at least one and at most n-1 reboilers, where n is an integer equal to or greater than 2. In other words, in a thermally connected distillation system, at least two distillation columns share a condenser and a reboiler, such that for the (at least) two distillation columns, there is only one condenser and one reboiler. In the experimental section, a system comprising two distillation columns, one condenser, and one reboiler is studied as an example of the thermally connected distillation system of the present invention.

[0018] Condenser column means in the context of the present disclosure a distillation column that is (directly) connected to a condenser, preferably at its top, and that is not (directly) connected to a reboiler. Reboiler column means in the context of the present disclosure a distillation column that is (directly) connected to a reboiler, preferably at its bottom, and that is not (directly) connected to a condenser. Thus, for example, the bottom of the condenser column is not equipped with a reboiler, and, for example, the top of the reboiler column is not equipped with a condenser.

[0019] The bottom of the distillation column, in the context of this disclosure, refers to the section of the respective distillation column below the inlet for the gaseous composition and below the outlet for the propane composition, and the top of the distillation column, in the context of this disclosure, refers to the portion of the respective distillation column above the inlet for the gaseous composition and above the outlet for the propane composition.

[0020] A conventional distillation system, in the context of this disclosure, refers to a distillation system that includes n distillation columns, n reboilers, and n condensers, where n is an integer equal to or greater than 1. In other words, a conventional distillation system includes as many reboilers and as many condensers as there are distillation columns included in the system.

[0021] Propane recovery, in the context of this disclosure, is determined by dividing the weight of propane in the recovered propane composition by the weight of propane in the gaseous composition subjected to distillation in step (ii). The quotient may optionally be multiplied by 100% to express the propane recovery in wt-%.

[0022] As used in the context of this disclosure, unless otherwise specified, "content ratio" means the ratio of the contents of particular components on a weight basis (wt-% / wt-%), and unless otherwise specified, "content" is the content on a weight basis and is calculated relative to the total weight of the composition in question, such as, for example, the total weight of a gaseous composition or a propane composition.

[0023] As used in the context of this disclosure, aviation fuel component means a hydrocarbon component suitable for use in a fuel composition that meets a standard specification for aviation fuel, such as the specifications set forth in ASTM D7566-2021. Typically, such aviation fuel components boil within the range of about 100° C. to about 300° C., such as within the range of about 150° C. to about 300° C., measured according to EN ISO 3405-2019.

[0024] As used in the context of this disclosure, a diesel fuel component refers to a hydrocarbon composition suitable for use in a fuel composition that meets standard specifications for diesel fuel, such as those set forth in EN 590-2013+A1-2017. Typically, such diesel fuel components boil within the range of about 160° C. to about 380° C., measured according to EN ISO 3405-2019.

[0025] As used in the context of this disclosure, a gasoline fuel component means a hydrocarbon composition suitable for use in a fuel composition that meets standard specifications for gasoline fuels, such as those set forth in EN 228-2012+A1-2017. Typically, such gasoline fuel components boil within the range of about 25° C. to about 200° C., measured according to EN ISO 3405-2019.

[0026] Boiling temperatures of fuels and fuel components refer to temperatures at normal atmospheric pressure, measured, for example according to EN ISO 3405-2019, unless otherwise specified.

[0027] The terms renewable or bio-based or biogenic refer to the presence of compounds or components derived from renewable sources (biological sources). Renewable or living carbon atoms (biogenic carbon) contain a greater number of unstable radiocarbons ( 14 C) contains atoms. Therefore, 12 C and 14By analyzing the isotope ratio of C, it is possible to distinguish between carbon compounds derived from renewable or biological sources and those derived from fossil sources. Thus, a specific ratio of the isotopes can be used as a "tag" to identify and distinguish renewable carbon compounds from non-renewable carbon compounds. The isotope ratio does not change during the course of a chemical reaction. Examples of suitable methods for analyzing the content of carbon from biological or renewable sources are DIN 51637 (2014), ASTM D6866 (2020) and EN 16640 (2017). In the context of this disclosure, the content of (biogenic) carbon derived from biological or renewable sources is expressed as biogenic carbon content, which means the amount of biogenic carbon in a material as a weight percentage of the total carbon (TC) in the material, measured according to EN 16640 (2017). The biogenic carbon content of the total carbon content in a completely biogenic product can be about 100 wt-%. The biogenic carbon content of the renewable hydroprocessing feed, diluent, gaseous composition, propane composition, and / or fuel components of the present disclosure may be lower when other carbonaceous components than biological or renewable components are used in the methods and / or propane compositions of the present disclosure, but the biogenic carbon content is preferably at least 5 wt-%.

[0028] 1. A method for treating a gaseous composition, comprising: (i) providing a gaseous composition comprising H2, methane, ethane, propane and hydrocarbons having a carbon number of at least C4, wherein the total amount of H2, methane, ethane, propane and hydrocarbons having a carbon number of at least C4 is at least 80 wt-%, preferably at least 85 wt-%, more preferably at least 90 wt-% of the total weight of the gaseous composition; and (ii) subjecting the gaseous composition to distillation in a thermally connected distillation system comprising n distillation columns, at least one and up to n-1 condensers, and at least one and up to n-1 reboilers, where n is an integer equal to or greater than 1, to recover a propane composition. A method is provided that includes:

[0029] The total amount of H2, methane, ethane, propane and hydrocarbons having a carbon number of at least C4 is determined as the sum of the weights of said individual components relative to the total weight of the gaseous composition.

[0030] The present disclosure provides a method for obtaining a propane composition having a high purity, such as at least 95 wt-% propane based on the weight of the total propane composition, from a gaseous composition while maintaining a high propane recovery, even 95 wt-% or more. In particular, the present disclosure provides a method for obtaining a high purity propane composition, even from a gaseous composition containing a higher amount, even about 25 wt-%, of C4+ hydrocarbons. The higher the amount of C4+ hydrocarbons, and especially the amount of C5+ hydrocarbons in the gaseous composition, the more difficult it will be to achieve a high purity propane composition that meets the specifications for high-end applications, such as for catalytic upgrading, e.g., dehydrogenation of propane. Prior art processes have had difficulty reaching purity specifications without sacrificing the propane recovery and the yield of the propane composition. Subjecting the gaseous composition to distillation in a thermally connected distillation system provides good control of the product quality, i.e., the quality of the recovered propane composition, while maintaining a high yield of the propane composition and a high propane recovery. Furthermore, the cooling and reboiling workload is also reduced compared to distillation in a conventional distillation system, such as distillation in a single cryogenic distillation. For example, the recovered propane composition may meet one or more of the EN 589, DIN 51622, BS 4250 or FID-5 propane specifications without further purification. Thus, an on-specification propane composition may be obtained with improved propane recovery or propane composition yield and lower energy consumption, i.e., reduced condenser and reboiler workload, compared to distillation in, for example, a single conventional cryogenic distillation column. Furthermore, the method provides improved control, such that, for example, each of the propane content, C4+ hydrocarbon content and C5+ hydrocarbon content in the propane composition may be provided on-specification or on target without exceeding the specifications or targets for all of them. The method of the present disclosure is particularly advantageous for separating a high purity propane composition from a gaseous composition containing a relatively large amount of C4+ hydrocarbons.Such gaseous compositions may be, but are not limited to, gaseous streams separated from hydroprocessing effluents obtained during the production of renewable fuel components.

[0031] Thus, the method of the present invention using a thermally connected distillation system is suitable for producing high quality propane compositions in a cost-effective manner, including meeting even stringent propane specifications for high-end use, while avoiding over-purification, which would ultimately reduce the yield of the propane composition without adding any value to the propane composition. Prior art methods using conventional distillation, such as distillation in a single cryogenic distillation column, typically allowed the optimization of the level of only one impurity, namely the level of the most important impurity to meet the targeted product specification (often referred to as the limiting specification). This resulted in over-purification with respect to other impurities, or a trade-off in quality by conceding to the limiting specification, which in other respects could still be over-purification (but to a lesser extent). Thus, prior art methods often led to a trade-off in quality and / or a reduced yield of the propane composition.

[0032] The propane composition recovered in the present process may comprise at least 95 wt-%, preferably at least 96 wt-%, propane, and up to 5.0 wt-%, preferably up to 3.0 wt-%, hydrocarbons having a carbon number of at least C4, and up to 0.20 wt-%, preferably up to 0.18 wt-%, more preferably up to 0.13 wt-%, hydrocarbons having a carbon number of at least C5, based on the total weight of the propane composition.

[0033] The gaseous composition may have a biogenic carbon content of at least 50 wt-%, preferably at least 75 wt-%, more preferably at least 90 wt-%, and even more preferably at least 95 wt-%, based on the total weight of carbon (TC) in the gaseous composition. The propane composition recovered in the present method may have a biogenic carbon content of at least 50 wt-%, preferably at least 75 wt-%, more preferably at least 90 wt-%, and even more preferably at least 95 wt-%, based on the total weight of carbon (TC) in the propane composition. In such an embodiment, the gaseous composition or the propane composition may be fully renewable (e.g., having a biogenic carbon content of about 100 wt-%) or may be a blend of renewable and fossil materials.

[0034] In certain embodiments, the propane composition recovered in the process is a propane composition that meets (without further purification) one or more of the EN 589, DIN 51622, BS 4250 or FID-5 propane specifications.

[0035] The content of methane, ethane, propane, hydrocarbons having a carbon number of at least C4, hydrocarbons having a carbon number of at least C5, and / or unsaturated hydrocarbons (if present) in the propane composition may be measured according to ASTM D 2163. The content of CO2 in the propane composition may be measured according to ASTM D 2505. The content of CO in the propane composition may be measured according to ASTM D 2504. The content of sulfur-containing compounds (such as H2S or COS) in the propane composition may be calculated as elemental S and measured according to ASTM D 6667. The content of water in the propane composition may be measured according to ASTM D 5454.

[0036] The propane composition recovered in the process may optionally be compressed during or after the distillation of step (ii) to provide a liquefied propane composition. Compression may be performed after the distillation or during the distillation, for example when the propane composition is in a liquid state under the conditions applied during the distillation, at least at the stage at which the propane composition is removed.

[0037] The recovered propane composition can be formulated into a propane-containing product. The propane-containing product can include an odorant selected from, for example, one or more of tert-butylthiol, tetrahydrothiophene, and ethanethiol. The propane composition or propane-containing product can be used, for example, for heating, vehicle fuel, or cooking.

[0038] The propane composition in gas or liquid form may be subjected to further processing. For example, it may be subjected to a conversion, such as hydroreforming, including catalytic dehydrogenation, to obtain a dehydrogenated product / effluent from which at least a propene-containing fraction is recovered, optionally after purification and / or fractionation, to obtain a propene composition. The propene composition may be used in a polymerization reaction or to form a polymer, with or without a comonomer.

[0039] In certain preferred embodiments, the thermally connected distillation system applied in step (ii) comprises at least a first distillation column connected (directly) to a condenser, preferably at its top, without being connected (directly) to a reboiler, and a second distillation column connected (directly) to a reboiler, preferably at its bottom, without being connected (directly) to a condenser. Hence, in these preferred embodiments, as defined in the present disclosure, the first distillation column is a condenser column and the second distillation column is a reboiler column. Thus, the condenser column may not have a reboiler at its bottom, and the reboiler column may not have a condenser at its top. As a result, the vapor flow between the condenser column and the reboiler column is unidirectional from the reboiler column to the condenser column, and the liquid flow between the condenser column and the reboiler column is unidirectional from the condenser column to the reboiler column. A unidirectional flow is easier to implement and may facilitate the distillation set-up than a bidirectional flow. In these preferred embodiments, the gaseous composition is fed to a first distillation column and the propane composition is recovered from a second distillation column. In certain other embodiments, the gaseous composition can be fed to a reboiler column as a first distillation column and the propane composition can be recovered from a condenser column as a second distillation column.

[0040] The thermally connected distillation system of step (ii) may comprise one or more further distillation columns (in addition to the condenser and reboiler columns), which may or may not be in thermal communication (with each other, with the condenser column, or with the reboiler column).

[0041] In an embodiment, liquid feed and liquid reflux are provided from the condenser column to the reboiler column, and vapor feed and vapor boilup are provided from the reboiler column to the condenser column. In a preferred embodiment, the bottoms of the condenser column are provided as a liquid feed to the bottom of the reboiler column, and the overheads of the reboiler column are provided as a vapor feed to the top of the condenser column. Preferably, liquid reflux is provided from the top of the condenser column below the vapor feed inlet to the top of the reboiler column, and vapor boilup is provided from the bottom of the reboiler column above the liquid feed inlet to the bottom of the condenser column. Any one or any combination of liquid feed or liquid reflux or vapor feed or vapor boilup may be referred to as a connecting stream between columns.

[0042] The reboiler column, the condenser column, and / or any further distillation column may be, independently of each other, a packed column, a tray or plate column, or any other suitable distillation column. Preferably, the reboiler column, the condenser column, and / or any further distillation column are suitable for high pressure distillation (distillation at pressure above atmospheric pressure). In an embodiment, both the condenser column and the reboiler column are provided without a partition wall or multiple partition walls, i.e., without a partition wall or multiple partition walls. Furthermore, the optional further distillation column may be provided without a partition wall or multiple partition walls.

[0043] In certain embodiments, the condenser column is configured to separate compounds lighter than propane, such as ethane, methane, H2, and the reboiler column is configured to separate compounds heavier than propane, such as hydrocarbons having a carbon number of at least C4. Thus, the condenser column may form the rectifying section of a thermally connected distillation system, and the reboiler column may form the stripping section of a thermally connected distillation system.

[0044] Liquid reflux can be provided as one or more liquid reflux streams from the condenser column to the reboiler column, using one or more conduits, respectively, and similarly vapor boilup can be provided as one or more vapor boilup streams from the reboiler column to the condenser column. Preferably, the thermally connected distillation systems are arranged such that one liquid reflux stream is fed from the condenser column to the reboiler column and / or one vapor boilup stream is fed from the reboiler column to the condenser column. In this way, the complexity of the columns is minimized and control becomes simpler.

[0045] The condenser bottoms, or liquid feed to the reboiler column, may contain primarily (e.g., 80 wt-%) propane with C4+ hydrocarbons and at most trace amounts of compounds lighter than propane, such as CO, CO2, CH4, ethane, and / or H2. The vapor boilup to the condenser column may contain primarily propane and small amounts of C4+ hydrocarbons and small amounts of compounds lighter than propane, such as CO, CO2, CH4, ethane, and / or H2. Also, the liquid reflux to the reboiler column may contain propane and C4+ hydrocarbons. The reboiler column overhead, or vapor feed to the condenser column, may contain propane and small amounts of compounds lighter than propane, such as CO, CO2, CH4, ethane, and / or H2, and small amounts of C4+ hydrocarbons.

[0046] The compositions of the liquid streams between the condenser column and the reboiler column, particularly the liquid feed and liquid reflux, and the vapour streams, particularly the vapour feed and vapour boil-up, may vary or vary depending on process conditions such as, for example, flow rate, pressure and temperature, and / or depending on the composition of the gaseous composition subjected to distillation in step (ii).

[0047] The liquid stream may be transported between the condenser and reboiler columns by pumps or by natural convection facilitated, for example, by gravity. The vapor flow between the condenser and reboiler columns may be transported by natural convection facilitated by a pressure difference or using, for example, one or more compressors. In a preferred embodiment, the vapor flow between the condenser and reboiler columns is arranged to be transported by the pressure difference between the condenser and reboiler columns.

[0048] Typically, the pressure in a thermally-communicated distillation system is controlled using an overall pressure control device and is influenced by, for example, pressure drops caused by column internals, valves, etc. The temperature in a thermally-communicated distillation system is influenced, for example, by pressure and by the composition of the streams. The temperature and / or pressure conditions of a thermally-communicated distillation system can also be adjusted by conditioning the communicating streams between the columns, for example, using compressors and / or heat exchangers. For example, by controlling the flow rates of the streams, it is possible to affect the separation and temperature.

[0049] The distillation in step (ii) may be carried out with sufficient theoretical plates in the condenser and reboiler columns so that compounds lighter than propane, e.g., ethane, methane, CO, CO2, H2, and compounds heavier than propane, e.g., C4+ hydrocarbons, may be separated from the propane.

[0050] In a preferred embodiment, the distillation in step (ii) can be carried out under superatmospheric pressure (above 1 atmosphere). The condenser and reboiler columns can be pressurized distillation columns. Typically, there is a vertical pressure gradient in the reboiler column, especially over the combination of the reboiler column and the reboiler, and / or there is a vertical pressure gradient in the condenser column, especially over the combination of the condenser column and the condenser. The pressure gradient can be influenced, for example, by the number of stages or the length of the column.

[0051] In an embodiment, the thermally connected distillation system of step (ii) is operated at a pressure greater than 1500 kPa, preferably greater than 1900 kPa, for example at a pressure in the range of from 1500 kPa to 5000 kPa, or from 1900 kPa to 4500 kPa, or from 2400 kPa to 3900 kPa.

[0052] In an embodiment, the thermally connected distillation system of step (ii) is operated at a temperature above -70°C, such as above -60°C, preferably at a temperature in the range of -70°C to 250°C, more preferably -70°C to 200°C, even more preferably -70°C to 180°C. If the temperature is much lower than -70°C, for example, CO may start to solidify and cause problems in the thermally connected distillation system. The condenser column and condenser combination may be operated at a temperature in the range of -70°C to 120°C, preferably -70°C to 100°C, while the reboiler column and reboiler combination may be operated at a temperature in the range of 0°C to 250°C, preferably 0°C to 200°C, more preferably 0°C to 180°C.

[0053] In a preferred embodiment, the thermally communicated distillation system of step (ii) may be operated at a pressure above 1500 kPa, preferably above 1900 kPa, such as a pressure in the range of 1500 kPa to 5000 kPa, or in the range of 1900 kPa to 4500 kPa, or in the range of 2400 kPa to 3900 kPa, and at a temperature above -70°C, such as a temperature above -60°C, preferably a temperature in the range of -70°C to 250°C, more preferably a temperature in the range of -70°C to 200°C, even more preferably a temperature in the range of -70°C to 180°C.

[0054] In a preferred embodiment, the condenser tower and condenser combination is operated at a pressure in the range of 1500 kPa to 5000 kPa, or 1900 kPa to 4500 kPa, or 2400 kPa to 3900 kPa, and a temperature in the range of -70°C to 120°C, preferably -70°C to 100°C. Preferably, the minimum temperature of the condenser tower and condenser combination is less than 0°C. Operating the condenser tower and condenser combination at low temperature conditions can improve the recovery of propane and the yield of propane compositions.

[0055] In an embodiment, the thermally connected distillation system of step (ii) is operated such that the minimum pressure in the reboiler tower / reboiler combination is higher than the maximum pressure in the condenser tower / condenser combination, and the minimum pressure in the reboiler tower / reboiler combination is preferably 20 kPa to 150 kPa higher, more preferably 30 kPa to 120 kPa higher, than the maximum pressure in the condenser tower / condenser combination. When the pressure in the reboiler tower / reboiler combination is higher than the pressure in the condenser tower / condenser combination, a compressor is not necessarily required, but the vapor flow can be conveyed from the reboiler tower to the condenser tower by natural convection driven by the pressure difference, thereby reducing energy consumption. A moderate pressure difference, e.g., less than 120 kPa or in the range of 30 kPa to 120 kPa, is preferred, since a larger pressure difference between the reboiler tower / reboiler combination and the condenser tower / condenser combination may increase energy consumption and require an increase in the distillation temperature, which may complicate the setup of the thermally connected distillation system. Nevertheless, it is also possible to operate the thermally connected distillation system such that the minimum pressure in the reboiler tower / reboiler combination is not higher than the maximum pressure in the condenser tower / condenser combination, and to transport the vapor stream from the reboiler tower to the condenser tower, e.g., using one or more compressors.

[0056] Both the condenser tower / condenser combination and the reboiler tower / reboiler combination may have relatively high / wide temperature gradients. Typically, the temperature profile is steeper closer to the condenser or reboiler stage, but may not be as steep otherwise, especially when separating primarily C3 from C4 and C2, which have boiling points relatively close to each other.

[0057] In certain embodiments, the thermally connected distillation system is operated with a larger temperature gradient (Tmax-Tmin), and preferably also a larger pressure gradient (pmax-pmin), in the condenser column-condenser combination than in the reboiler column-reboiler combination.

[0058] In an embodiment, the reboiler tower and reboiler combination is operated at a pressure in the range of 1500 kPa to 5000 kPa, or 1900 kPa to 4500 kPa, or 2400 kPa to 3900 kPa, and at a temperature in the range of 0° C. to 250° C., preferably 0° C. to 200° C., more preferably 0° C. to 180° C. Preferably, the lowest temperature in the condenser tower and condenser combination is below 0° C., and the highest temperature in the reboiler tower and reboiler combination is higher than the highest temperature in the condenser tower and condenser combination, preferably 30° C. to 150° C., more preferably 50° C. to 120° C., and preferably the lowest temperature in the reboiler tower and reboiler combination is at most as high as the highest temperature in the condenser tower and condenser combination.

[0059] In addition to the propane composition, other compositions or streams may be recovered from step (ii). In certain embodiments, a stream of light compounds, including, for example, H2, CO, CO2, CH4, and ethane, may be recovered as a condenser column overhead vapor, and a stream of heavy compounds, including C4+ hydrocarbons, may be recovered as a reboiler column bottoms from the thermally connected distillation system of step (ii). The propane composition may be recovered from the reboiler column, for example, from product trays of the reboiler column.

[0060] The light compound stream exiting the thermally connected distillation system of step (ii) typically contains CO, CO2, CH4, ethane and H2, and may contain at least traces of propane. The light compound stream has a high calorific value and can therefore be combusted for energy. Optionally, the light compound stream exiting the thermally connected distillation system of step (ii) may have a relatively high pressure, for example higher than 1500 kPa, preferably higher than 1900 kPa, for example in the range of 1500 kPa to 5000 kPa, or in the range of 1900 kPa to 4500 kPa, or in the range of 2400 kPa to 3900 kPa, so that the light compound stream can be suitably subjected to H2 separation, for example by using membrane separation technology.

[0061] The heavy compounds stream exiting the thermally connected distillation system in step (ii) comprises C4+ hydrocarbons and may also comprise some propane. This heavy compounds stream may be used, for example, as a component in naphtha and / or in the production of H2 by steam reforming.

[0062] In an embodiment, the gaseous composition provided in step (i) and subjected to distillation in step (ii) comprises at least 60 wt-%, preferably at least 65 wt-%, more preferably at least 70 wt-%, for example 60-85 wt-%, or 65-80 wt-%, or 70-75 wt-% propane, based on the total weight of the gaseous composition. Having propane as the major component of the gaseous composition increases the efficiency of the process.

[0063] In an embodiment, the gaseous composition provided in step (i) and subjected to distillation in step (ii) comprises at most 18.5 wt-%, preferably at most 18.0 wt-%, more preferably at most 17.0 wt-%, even more preferably at most 16.0 wt-%, most preferably at most 10.5 wt-%, and / or at least 5.0 wt-%, preferably at least 7.0, more preferably at least 9.0 wt-%, for example 5.0-18.5 wt-%, or 7.0-17.0 wt-%, or 9.0-16.0 wt-%, of hydrocarbons having a carbon number of at least C4, based on the total weight of the gaseous composition. The method is particularly useful for treating gaseous compositions having a high content of heavy tails (C4+) and can achieve a targeted low C4+ content in the recovered propane composition.

[0064] In an embodiment, the gaseous composition provided in step (i) and subjected to distillation in step (ii) has a content ratio of hydrocarbons having a carbon number of at least C4 to propane in the range of at least 0.05, preferably 0.05 to 0.40, more preferably 0.07 to 0.35, even more preferably 0.09 to 0.30, and most preferably 0.10 to 0.20.

[0065] In an embodiment, the gaseous composition provided in step (i) and subjected to distillation in step (ii) comprises hydrocarbons having a carbon number of at least C5, which is at most 15.0 wt-%, preferably at most 10.0 wt-%, more preferably at most 8.0 wt-%, even more preferably at most 6.0 wt-%, and / or at least 1.5 wt-%, preferably at least 2.0 wt-%, more preferably at least 3.0 wt-%, for example 1.5 to 15.0 wt-%, or 2.0 to 10.0 wt-%, or 3.0 to 8.0 wt-%, based on the total weight of the gaseous composition. The method is particularly useful for the treatment of gaseous compositions having a high content of heavy tail (C4+), especially C5+ hydrocarbons, and can achieve the targeted very low C5+ hydrocarbon content in the recovered propane composition. Conventional distillation processes have difficulty obtaining propane compositions with such low C5+ contents.

[0066] In an embodiment, the gaseous composition provided in step (i) and subjected to distillation in step (ii) comprises hydrocarbons having a carbon number of at least C5 and has a content ratio of hydrocarbons having a carbon number of at least C5 to propane in the range of at least 0.01, preferably 0.01-0.35, more preferably 0.02-0.30, even more preferably 0.03-0.25, and most preferably 0.04-0.15.

[0067] In an embodiment, the gaseous composition provided in step (i) and subjected to distillation in step (ii) comprises up to 35 wt-%, preferably 5-30 wt-%, more preferably 10 to 25 wt-%, of compounds lighter than propane, such as H2, methane and ethane, based on the total weight of the gaseous composition, and / or comprises 1-10 wt-%, preferably 2-9 wt-%, more preferably 3-8 wt-% of H2, based on the total weight of the gaseous composition. The method is capable of processing gaseous compositions with a high content of compounds lighter than propane, while a maximum moderate content of compounds lighter than propane ensures a lower workload of the condenser and reboiler, as well as allowing the use of smaller equipment and higher pressures in the thermally connected distillation system.

[0068] In an embodiment, the gaseous composition provided in step (i) and subjected to distillation in step (ii) comprises up to 15 wt-%, preferably 1-15 wt-%, more preferably 2-10 wt-% CO, based on the total weight of the gaseous composition, and / or 0.01-5.0 wt-%, preferably 0.1-3.0 wt-% CO, based on the total weight of the gaseous composition. CO and / or CO are typical impurities in gaseous compositions that can be obtained by hydrotreating renewable hydrotreating feeds, such as vegetable oils, animal fats, microbial oils, etc., because their deoxygenation produces not only H2O, but also various amounts of CO and CO2, depending on the extent to which the hydrotreating conditions promote the decarbonylation / decarboxylation reactions. Sweetening, for example with an amine scrubber, can remove at least a portion of the CO2, but a portion of it, especially CO, typically remains in the gaseous composition. The method can remove both CO and CO2 to levels as low as required by specifications for high-end applications of propane compositions, such as for catalytic upgrading, e.g., dehydrogenation of propane to propylene.

[0069] In a preferred embodiment, (i) providing a gaseous composition comprises subjecting the hydroprocessing effluent to gas-liquid separation to obtain at least a gaseous stream, and optionally subjecting the gaseous stream to pretreatment to obtain a gaseous composition. In an embodiment comprising subjecting the gaseous stream to pretreatment including at least H2 separation to obtain a gaseous composition, the separated H2 or at least a part of it is preferably recycled to hydroprocessing to further improve the cost-effectiveness and sustainability of the process. Furthermore, when H2 is also separated from the light compound stream optionally recovered in step (ii), at least a part of the H2 separated from said light compound stream may be combined with at least a part of the H2 separated in the pretreatment of step (i), and preferably at least a part of the combined H2 stream is recycled to hydroprocessing. Such recycling may help to capture a part of the trace amounts of C4+ hydrocarbons that may be present in the H2 separated from the light compound stream in step (ii) and / or the H2 separated in the pretreatment of step (i).

[0070] Subjecting the gaseous stream to a pre-treatment including at least H2 separation is beneficial since the gaseous stream separated from the hydroprocessing effluent may have a high H2 content, whereas processing in step (ii) a gaseous composition having only a moderate content of compounds lighter than propane provides the advantages as described for steam.

[0071] In an embodiment, (i) providing the gaseous composition includes subjecting a hydrotreating feed comprising vegetable oil, animal fat, microbial oil, crude oil, thermally, e.g., thermally catalytically and / or enzymatically liquefied organic waste and residue, e.g., biomass waste and residue, municipal solid waste and / or waste plastic, or a combination thereof, optionally with a hydrocarbon diluent, to catalytic hydrotreating, including hydrodeoxygenation (HDO), hydrocracking, hydroisomerization, hydropyrolysis, hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodehalogenation (HDX), hydrodearomatization (HDA), hydrodemetalization and / or hydrogenation, to obtain a hydrotreating effluent; subjecting the hydrotreating effluent to gas-liquid separation to obtain at least a gaseous stream; and subjecting the gaseous stream to pretreatment to obtain a gaseous composition. A variety of sustainable and / or renewable materials can be used as the hydrotreating feed, optionally with a hydrocarbon diluent to control the temperature, especially in exothermic hydrotreating. Depending on the composition and / or impurities of the hydrotreating feed, and other products desired to be produced, an appropriate catalytic hydrotreating process and conditions therefor may be selected.In certain preferred embodiments, (i) providing the gaseous composition comprises subjecting a hydroprocessing feed comprising vegetable oils, animal fats, microbial oils, and / or combinations thereof, optionally with a hydrocarbon diluent, to catalytic hydroprocessing including at least hydrodeoxygenation to obtain a hydroprocessed effluent; subjecting the hydroprocessed effluent to gas-liquid separation to obtain at least a gaseous stream and a liquid hydroprocessed stream; subjecting the gaseous stream to pretreatment to obtain the gaseous composition; and subjecting at least a portion of the liquid hydroprocessed stream to at least a portion of the liquid hydroprocessed stream to obtain a further hydroprocessed effluent. subjecting the further hydroprocessing effluent to further gas-liquid separation to obtain at least a further gaseous stream and a further liquid hydroprocessed stream comprising isomerized C6 to C30 hydrocarbons; combining at least a portion of the further gaseous stream with the gaseous stream before or after pretreatment; and subjecting the further liquid hydroprocessed stream comprising isomerized C6 to C30 hydrocarbons to fractionation to recover one or more of a gasoline fuel component, an aviation fuel component, and / or a diesel fuel component.

[0072] In a preferred embodiment, (i) providing the gaseous composition comprises subjecting a hydroprocessing feed comprising a vegetable oil, an animal fat and / or a microbial oil, optionally together with a hydrocarbon diluent, to catalytic hydroprocessing, including at least hydrodeoxygenation using a sulfurized hydroprocessing catalyst, to obtain a hydroprocessing effluent; and subjecting the hydroprocessing effluent to a gaseous stream comprising at least H2S, CO, CO2, HO, methane, ethane, propane and hydrocarbons having a carbon number of at least C4, and a liquid hydroprocessing stream comprising hydrocarbons of C6 to C30. subjecting the gaseous stream to pretreatment including at least purification to remove H2S and CO2, H2 separation, and drying to obtain a dried H2S, CO2 and H2 depleted gaseous stream as the gaseous composition; and the method further includes subjecting the liquid hydrotreated stream comprising C6 to C30 hydrocarbons to fractionation, optionally after further catalytic hydroprocessing including at least hydroisomerization, to recover one or more of a gasoline fuel component, an aviation fuel component, and / or a diesel fuel component.

[0073] The gaseous composition provided in step (i), comprising H2, methane, ethane, propane and hydrocarbons having a carbon number of at least C4, wherein the total amount of H2, methane, ethane, propane and hydrocarbons having a carbon number of at least C4 is at least 80 wt-%, preferably at least 85 wt-%, more preferably at least 90 wt-% of the total weight of the gaseous composition, may be derived from hydrotreating, in particular from hydrotreating vegetable oils, animal fats and / or microbial oils. In particular, the gaseous composition provided in step (i) may be obtained or obtained as a gaseous stream from gas-liquid separation of a hydrotreating effluent, in particular from hydrotreating vegetable oils, animal fats and / or microbial oils. The hydrotreating may be, for example, hydrotreating to produce fuel components, such as gasoline, diesel and / or aviation fuel components, preferably aviation fuel components. For example, gaseous compositions can be used in the manufacture of gaseous compositions as disclosed in Finnish Patent No. 100248, U.S. Pat. No. 8,859,832, U.S. Pat. No. 10,800,976, U.S. Pat. No. 10,800,976, U.S. Pat. No. 10,800,976, European Patent No. 1741,768, U.S. Pat. No. 10,941,349, U.S. Pat. No. 8,742,185, European Patent No. 3517,591, U.S. Pat. No. 10,941,349, U.S. Pat. No. 8,742,185, European Patent No. 3517,591, , EP 1741768, U.S. Patent No. 10941349, U.S. Patent No. 8742185, EP 3517591, EP 1741768, U.S. Patent No. 10941349, U.S. Patent No. 8742185, EP 3517591, EP 2141217, U.S. Patent No. 5705722, CN 107488462, U.S. Patent No. 9567264.

[0074] Since a relatively large amount of C4+ hydrocarbons tends to enter the gaseous stream of the hydroprocessing effluent when producing aviation paraffins by more severe hydroprocessing conditions, the method of the present invention is particularly advantageous for recovering high purity or on-specification propane compositions from such gas fractions. The method allows for recovery of on-specification propane compositions with high propane recovery and yield of propane compositions, and relatively low condenser and reboiler workload, despite the relatively high amount of C4+ hydrocarbons in the gas fraction.

[0075] Hydroprocessing of hydroprocessing feeds, particularly to produce fuel range hydrocarbons, especially when the hydroprocessing feeds contain vegetable oils, animal fats, microbial oils, and / or combinations thereof, can involve the generation of a large amount of gaseous reaction products that enter into the gaseous stream separated from the hydroprocessing effluent. Examples of these reaction products include HO cleaved by hydrotreating (HDO) from organic oxygenates such as fatty acids; CO and CO cleaved by decarbonylation and decarboxylation of organic oxygenates such as fatty acids; propane, for example, from glycerides and / or cracking; various cracking products, including methane, ethane, C4+ hydrocarbons, of organic oxygenates such as fatty acids, or hydrocarbons derived therefrom or used for dilution; H2S cleaved by hydrodesulfurization from organic sulfur-containing compounds present in some hydroprocessing feeds and / or added to maintain activity of hydrosulfurized hydroprocessing catalysts; and NH3 cleaved by hydrodenitrogenation from organic nitrogen-containing compounds typically present in renewable hydroprocessing feeds such as vegetable oils, animal fats, microbial oils, etc. Additionally, the gaseous stream separated from the hydroprocessing effluent may contain a significant amount of unused (unreacted) hydrogen (H2). The gaseous stream may contain at least 70 mol-%, e.g., at least 75 mol-%, at least 80 mol-% hydrogen (H2), based on the total weight of the gaseous stream, and / or the H2 content may be less than 95 mol-%, e.g., less than 90 mol-%.

[0076] Hydrotreating renewable hydroprocessing feeds, such as vegetable oils, animal fats, microbial oils, etc., is of interest not only for producing renewable diesel fuel components, but also for producing renewable aviation fuel components. To increase the yield of typical aviation fuel range hydrocarbons with carbon chain lengths of C8 to C15 from renewable hydroprocessing feeds, such as vegetable oils, animal fats, microbial oils, etc., which typically contain fatty acids with carbon chain lengths of C16 to C20, hydroprocessing can be adjusted so that more cracking is achieved (compared to the production of renewable diesel fuel components). In addition to the desired aviation fuel range C8 to C15 hydrocarbons, shorter chain hydrocarbons (hydrocarbons with carbon numbers up to C7) are also formed, for example, due to increased cracking achieved by using more severe hydroprocessing conditions, such as higher temperatures and / or pressures, or catalysts or cocatalysts with higher cracking activity and / or selectivity.

[0077] Such methods are particularly beneficial for co-producing high quality propane compositions and fuel components from hydroprocessed feeds that contain vegetable oils, animal fats, microbial oils, and / or combinations thereof, since increased cracking during hydroprocessing to obtain more aviation fuel range paraffins (compared to hydroprocessing optimized to produce diesel fuel range hydrocarbons) can increase not only the formation of C4+ hydrocarbons, but also the formation of propane (in addition to the propane derived from the glycerol moieties of the feed), increasing the overall propane yield.

[0078] Furthermore, high quality propane compositions can be produced even from gaseous compositions containing large amounts of entrained C4+ hydrocarbons, especially C4-C6 hydrocarbons, without the need to limit the recycle of gaseous and / or liquid streams in the process.

[0079] The process is particularly well suited to a variety of real-world conditions providing flexibility so that variations in unit configuration, selection of process conditions, and / or feed characteristics do not compromise the quality of the recovered propane composition.

[0080] Preferably, the process comprises the steps of (i) subjecting a hydroprocessing feed comprising vegetable oils, animal fats and / or microbial oils, and optionally a hydrocarbon diluent, to catalytic hydroprocessing, including at least hydrodeoxygenation using a sulfurized hydroprocessing catalyst, to obtain a hydroprocessing effluent; subjecting the hydrotreatment effluent to gas-liquid separation to obtain at least a gaseous stream comprising H, H2S, CO, CO2, HO, methane, ethane, propane and hydrocarbons having a carbon number of at least C4 and a liquid hydrotreatment stream comprising hydrocarbons of C6 to C30; subjecting said gaseous stream to a pretreatment step, including at least purification to remove H2S and CO2, H2 separation, and drying, to obtain a gaseous composition comprising H2, methane, ethane, propane, and hydrocarbons having a carbon number of at least C4, wherein the total amount of H2, methane, ethane, propane, and hydrocarbons having a carbon number of at least C4 is at least 80 wt%, preferably at least 85 wt%, more preferably at least 90 wt% of the total weight of the gaseous composition; and (ii) subjecting the gaseous composition to distillation in a thermally connected distillation system comprising at least a first distillation column connected to a condenser without being connected to a reboiler and a second distillation column connected to a reboiler without being connected to a condenser by supplying the gaseous composition to the first distillation column and recovering a propane composition from the second distillation column; 1. A method for co-producing a propane composition and a fuel component comprising: Provided is a method, wherein the method further comprises subjecting the liquid hydrotreated stream comprising C6 to C30 hydrocarbons to fractionation, optionally after further catalytic hydroprocessing including at least hydroisomerization, to recover one or more of a gasoline fuel component, an aviation fuel component and / or a diesel fuel component.

[0081] In addition to recovering one or more fuel components, particularly one or more of the gasoline fuel component, aviation fuel component, and / or diesel fuel component, other hydrocarbon compositions other than fuel components, such as hydrocarbon compositions for electrotechnical fluids and / or marine fuel components, including various grades of these fuel components, and / or other fuel components other than gasoline fuel components, aviation fuel components, or diesel fuel components may also be recovered from the fractionation of the method according to the present disclosure.

[0082] In an embodiment, subjecting the gaseous stream to pretreatment includes at least purification to remove H2S and CO2, separation of H2, and drying to obtain a dried H2S, CO2 and H2 depleted gaseous stream as a gaseous composition. Conventionally used pretreatment operations and equipment may be used, such as those disclosed in WO 2017 / 045791 or WO 2021 / 110524. Pretreatment of the gaseous stream includes at least purification to remove H2S and CO2, and possibly purification to remove other impurities such as NH3. The presence of acid gases, especially H2S, can be harmful, for example, to membrane materials optionally used in subsequent H2 separation, which may be performed by membrane separation. Furthermore, the presence of H2S in addition to CO2 can result in the formation of COS, which cannot be easily separated from propane by distillation. Since the production of COS is an equilibrium reaction, increasing the content of CO2 and H2S and decreasing the content of H2O shifts it toward the COS side. Therefore, by removing CO2 and H2S prior to drying, the production of COS can be suppressed. The method of the present disclosure can include subjecting the H2S and CO2 depleted gaseous stream to H2 separation and drying to obtain dried H2S, CO2 and H2 depleted gaseous stream, and a H2-rich stream as the separated H2 stream.

[0083] The separation of H2 is preferably carried out using a selective membrane (selective membrane separation). However, other methods for separating H2 (and optionally other gas components at the same time) can be carried out using any other suitable method, such as swing adsorption. The hydrogen-selective membrane is preferably selective for hydrogen over propane in that it preferentially permeates most of the hydrogen and rejects most of the propane and C4+ hydrocarbons in the retentate. Usually, the membrane is operated so that some of the hydrogen (H2) remains in the retentate stream, since this will result in a higher purity of hydrogen (H2) in the permeate stream (stream enriched in H2). H2O, CO2, H2S and NH3 are rejected or partially rejected, depending on the type of membrane and the conditions of the membrane separation (such as temperature and pressure), while CO and hydrocarbons lighter than propane, if present, may also be rejected together with the propane. The driving force for membrane permeation is provided by a higher pressure on the feed side than on the permeate side. For example, the feed side pressure can be 10 bar (gauge) or more, such as 30 bar (gauge) or more, or 50 bar (gauge) or more, and the permeate side pressure can include a pressure at least 1 bar lower than the feed side pressure, such as at least 5 bar lower, or at least 10 bar lower, or at least 30 bar lower.

[0084] Drying may be performed before or after H2 separation. Considering the processing efficiency, drying is preferably performed after H2 separation. In this way, a smaller drying device is required, so that less installation space and lower investment costs are required. Drying can be performed using conventional chemical and / or physical methods, such as adsorbents and / or water absorbents. One particularly preferred embodiment is drying using a molecular sieve dehydrating bed.

[0085] The hydrotreating feed may comprise vegetable oils, animal fats, microbial oils, crude oils, thermally, e.g., thermocatalytically and / or enzymatically liquefied organic wastes and residues, e.g., biomass wastes and residues, municipal solid waste and / or waste plastics, and / or any combination thereof. Preferably, a renewable hydrotreating feed is used. Renewable hydrotreating feed refers in particular to feedstocks derived from biological raw materials that contain oils and / or fats, usually containing free fatty acids and / or glycerides, such as, for example, plant oils / fats, vegetable oils / fats, animal oils / fats, fish oils / fats and / or algae oils / fats, and / or oils / fats from other microbial processes. The oils / fats may comprise, for example, genetically engineered algae oils / fats, genetically engineered oils / fats from other microbial processes, and / or also genetically engineered vegetable oils / fats. Components of such materials may also be used, such as alkyl esters (typically C1C5-alkyl esters, such as methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl esters, etc.) Preferably, renewable hydroprocessing feeds are used that include vegetable oils, animal fats, microbial oils, and / or any combination thereof.

[0086] Examples of vegetable oils that can be used in the renewable hydrotreating feed include, but are not limited to, rapeseed oil, canola oil, soybean oil, coconut oil, sunflower oil, palm oil, palm kernel oil, peanut oil, linseed oil, sesame oil, corn oil, poppy seed oil, cottonseed oil, soybean oil, tall oil, corn oil, castor oil, jatropha oil, jojoba oil, olive oil, linseed oil, camelina oil, safflower oil, babassu oil, rapeseed oil, rice bran oil, as well as fractions and residues of the above mentioned oils, such as, for example, palm olein, palm stearin, palm fatty acid distillate (PFAD), refined tall oil, tall oil fatty acids, tall oil resin acid, tall oil unsaponifiables, tall oil pitch (TOP), and used vegetable edible oils. Examples of animal fats that can be used in the renewable hydrotreating feed include, but are not limited to, tallow, lard, yellow grease, brown grease, fish oil, chicken fat, and used cooking oils of animal origin. Examples of microbial oils that can be used in the renewable hydrotreating feed include algal lipids, fungal lipids, and bacterial lipids.

[0087] Vegetable oils, animal fats, microbial oils, and / or any combination thereof typically contain C10-C24 fatty acids, including esters of fatty acids, glycerides, i.e., glycerol esters of fatty acids, phospholipids, glycolipids, sphingolipids, and the like. Glycerides can specifically include monoglycerides, diglycerides, and triglycerides. Upon hydrogenation, the glycerol backbone of the glycerides is typically converted to renewable propane. Thus, the present disclosure also relates to a method for producing a renewable propane composition from a renewable hydroprocessing feed.

[0088] The present disclosure provides a flexible process that allows for easy adjustment of the hydrotreating feed composition and operating conditions, thereby obtaining gasoline fuel components, aviation fuel components and / or diesel fuel components, and high quality propane compositions in ratios that best suit prevailing or forecasted market demand.

[0089] The hydrotreating feed or any of its constituent feeds, in particular one or more feeds selected from vegetable oils, animal fats, microbial oils, crude oils, thermocatalytically and / or enzymatically liquefied organic wastes and residues, such as biomass wastes and residues, municipal solid waste and / or waste plastics, and any combination thereof, may be subjected to a pre-refining treatment before being subjected to hydrotreating. Such pre-refining treatments may include one or more of washing, degumming, bleaching, evaporation, distillation, fractionation, rendering, heat treatment, filtration, adsorption, partial hydrodeoxygenation, partial hydrogenation, hydrolysis, transesterification, centrifugation, and / or precipitation. These pre-treatment methods are convenient and effective for removing impurities including S, N, P, metals and / or metalloids (such as Si), pitch, solids, and / or compounds containing unsaturated bonds. The presence of high amounts of these impurities in the hydrotreating feed may promote the deactivation of hydrotreating catalysts, and a high content of compounds containing unsaturated bonds may complicate temperature control during hydrotreating.

[0090] The hydroprocessing feed or its constituent feeds can be combined with a hydrocarbon diluent prior to any pre-purification treatment. Alternatively or additionally, the hydroprocessing feed may be combined with a diluent prior to hydroprocessing, or the diluent may be fed directly to hydroprocessing. The hydrocarbon diluent may be, for example, a diluent of mineral origin (fossil diluent), a diluent of biogenic origin (such as renewable paraffins), or preferably, a hydrocarbon separated and recycled from any hydroprocessing product stream or effluent. If increased cracking has occurred in hydroprocessing, the recycle portion of the hydroprocessing effluent may contain increased amounts of, in particular, C4-C6 hydrocarbons. The process of the present invention is beneficial in that, despite such an increase in C4-C6 hydrocarbons in the process feed, high purity propane compositions may be produced with good yield and propane recovery.

[0091] In catalytic hydrotreating, a sulfurized hydrotreating catalyst may be applied. The sulfurized state of the catalyst is preferably maintained by adding a sulfur-containing compound to the hydrotreating feed and / or the hydrocarbon diluent and / or by feeding it together with and / or separately to the hydrotreating reactor with H2 gas. Typically, the sulfur-containing compound is H2S. In an embodiment, the sulfur content of the hydrotreating feed, calculated as elemental S, is 10-10000 w-ppm, preferably 10-1000 w-ppm, more preferably 10-500 w-ppm, even more preferably 10-300 w-ppm, even more preferably 10-200 w-ppm, and most preferably 20-100 w-ppm. By adjusting the sulfur content within this range, the occurrence of decarboxylation reactions can be controlled or suppressed, and a lower sulfur content in the feed is also beneficial for controlling or suppressing the occurrence of COS. That is, in embodiments where a sulfided catalyst is employed in hydrotreating (without requiring high temperatures), a minimum amount of sulfur ensures sufficient catalytic activity, while not exceeding a sulfur content of, for example, 10,000 w-ppm or 1,000 w-ppm can suppress the production of (large amounts of) H2S that can be converted to COS, thereby reducing the effort required to reduce the amount of H2S after hydrotreating. The content of sulfur in the hydrotreating feed, expressed as elemental S, can be measured according to EN ISO 20846. H2S, which may be removed during pretreatment of the gaseous stream in step (i), can be recovered and recycled to the hydrotreating as a source of sulfur to maintain the activity of the sulfided metal catalyst used therein.

[0092] The hydrotreating conditions are preferably selected such that the hydrotreating provides saturated hydrocarbons (paraffins), particularly n-paraffins and / or isoparaffins, preferably having a carbon number within the aviation fuel range.

[0093] Many conditions for hydrotreating, such as hydrodeoxygenation or hydroisomerization, are well known to those skilled in the art. Hydrotreating can be carried out in the presence of a catalyst, such as a sulfide metal catalyst. The catalyst can include one or more group VI metals, such as MO or W, or one or more non-noble group VIII metals, such as Co or Ni. The catalyst can be supported on any convenient support, such as alumina, silica, zirconia, titania, amorphous carbon, molecular sieves, or combinations thereof. Typically, the metal of the catalyst is impregnated or deposited on the support as a metal oxide. If a sulfide metal catalyst is desired, the metal oxide is typically converted to a sulfide.

[0094] Examples of typical catalysts for hydrodeoxygenation are molybdenum-containing catalysts, NiMo, CoMo, and / or NiW catalysts; supported on alumina or silica, although many other hydrodeoxygenation catalysts are known in the art and have been described with or in comparison to NiMo and / or CoMo catalysts. Hydrodeoxygenation is preferably carried out in the presence of hydrogen (H2) gas under the influence of a sulfided hydrotreating catalyst, such as a catalyst containing sulfided NiMo or sulfided CoMo. Examples of typical catalysts for hydroisomerization, if applicable, are catalysts containing SAPO-11 or SAPO-41 or ZSM-22 or ZSM-23 or ferrierite and Pt, Pd or Ni and Al2O3 or SiO2. The hydroisomerization is preferably carried out under the influence of platinum / SAPO-11 / Al2O3, platinum / ZSM-22 / Al2O3, platinum / ZSM-23 / Al2O3 or platinum / SAPO-11 / SiO2.

[0095] The hydrogenation treatment is carried out at a hydrogen pressure selected from the range of 10 to 200 bar, preferably 30 to 100 bar, at a temperature selected from the range of 200°C to 500°C, preferably 250°C to 400°C, and for 0.1 to 10 hours. -1 The reaction may be carried out under conditions of a feed rate (liquid hourly space velocity) of (v / v).

[0096] By supplying hydrogen (H2) to the hydroprocessing to provide a pressure (H2 partial pressure) selected from the range of 1-200 bar (or preferably 10-100 bar, more preferably 30-70 bar), efficient HDO, HDN (hydrodenitrogenation), and HDS (hydrodesulfurization) reactions can be ensured, while decarbonation and / or cracking reactions are controlled to be kept at low levels.

[0097] In an embodiment, when the hydrotreatment includes hydrodeoxygenation and hydroisomerization, the hydrodeoxygenation is carried out under a hydrogen pressure selected from the range of 10 to 100 bar, preferably 30 to 70 bar, at a temperature selected from the range of 200° C. to 400° C., preferably 250° C. to 350° C., more preferably 280° C. to 340° C., and for 0.1 h. -1 ~10h -1 , preferably 0.1h -1 ~3.0h -1 , more preferably 0.2 to 2.0 h -1 and the hydroisomerization can be carried out under a hydrogen pressure selected from the range of 10 to 150 bar, preferably 30 to 100 bar, at a temperature selected from the range of 200° C. to 500° C., preferably 280° C. to 400° C., and for 0.1 h. -1 ~10h -1 The reaction may be carried out at a liquid hourly space velocity of 0.05 to 0.25.

[0098] The process provides flexibility since the severity of the hydroprocessing, e.g., the hydroisomerization severity, can be smoothly adjusted depending on the market demand for the optionally recovered gasoline, aviation fuel and / or diesel fuel components, without having to essentially change or adjust the separation and pretreatment of the gaseous streams, while continuously obtaining high quality propane compositions.

[0099] After subjecting a hydrotreating feed, in particular comprising vegetable oils, animal fats and / or microbial oils, to catalytic hydrotreating, in particular catalytic hydrotreating including at least hydrodeoxygenation, for example as described above, propane is present in the hydrotreating effluent as one of the various gaseous phase components. The hydrotreating effluent is then subjected to gas-liquid separation, for example to obtain at least a gaseous stream comprising H2, H2S, CO, CO2, H2O, methane, ethane, propane and / or hydrocarbons having a carbon number of at least C4, and optionally a liquid hydrotreating stream, typically comprising hydrocarbons from C6 to C30. Advantageously, the gaseous stream is subjected to a pretreatment, for example to separate a stream rich in H2, thereby obtaining a gaseous composition.

[0100] In a preferred embodiment, the gas-liquid separation is carried out at a temperature selected from the range of 0° C. to 500° C., preferably 15° C. to 300° C., more preferably 15° C. to 150° C., even more preferably 15° C. to 65° C., and at a pressure preferably selected from the range of 1 to 200 bar (gauge), more preferably 10 to 100 bar (gauge), or 30 to 70 bar (gauge). The higher the pressure and / or the lower the temperature in the gas-liquid separation step, the lower the amount of heavy components (e.g. C4+ hydrocarbons) in the gaseous stream and gaseous composition.

[0101] Gas-liquid separation can be performed as a separate stage after the hydroprocessing effluent leaves the hydroprocessing reactor or reaction zone and / or as an integral stage within, for example, the hydroprocessing reactor or reaction zone. Although most of the water formed during HDO and that may be carried over from the fresh hydroprocessing feed may be removed, for example, via a water boot in the gas-liquid separation step, trace amounts will typically be entrained in the gaseous stream.

[0102] The gaseous stream obtained by subjecting the hydrotreating effluent to gas-liquid separation may contain hydrotreating reaction products, such as H2O, CO2 and CO from HDO and / or decarboxylation reactions, H2 not consumed in hydrotreating, H2S produced from additives for catalytic sulfidation or sulfur-containing compounds in the hydrotreating feed, NH3 produced from nitrogen-containing compounds in the hydrotreating feed, methane, ethane, propane and C4+ hydrocarbons produced by cracking the hydrotreating feed and any diluent, and propane produced from HDO of glyceride sites present in the hydrotreating feed containing fatty acid glycerides. The propane content in the gaseous stream may be improved, for example, by using a hydrotreating feed containing mainly fatty acid glycerides, by reducing the amount of optional diluent in the hydrotreating feed, by increasing the severity of the hydrotreating conditions, and / or by using a catalyst or cocatalyst with higher cracking activity and / or selectivity.

[0103] The gaseous stream or composition comprises hydrocarbons having a carbon number of at least C4. In certain circumstances, for example, when hydroprocessing includes hydrodeoxygenation and hydroisomerization under conditions optimized for producing an aviation fuel component, or when hydroprocessing includes hydrodeoxygenation utilizing a catalyst or cocatalyst with a high cracking tendency, the gaseous stream or composition may comprise a relatively large amount of C4+ hydrocarbons.

[0104] The C4+ hydrocarbons entrained in the gaseous stream or composition may include, but are not limited to, C4-C6 hydrocarbons, such as: butane, 2-methylpropane, pentane, isopentane, neopentane, hexane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2,2-dimethylbutane, etc. Additionally, the gaseous stream or composition may also include hydrocarbons having seven or more carbon atoms, such as C7-C10 hydrocarbons, although the amounts are typically very small.

[0105] The gaseous stream preferably comprises at least 1 mol-% propane, for example at least 3 mol-% propane, and / or 25 mol-% or less, for example 20 mol-% or less, or 15 mol-% or less, propane, based on the total mass of the gaseous stream. In embodiments, when the gaseous stream is derived from a hydroprocessing feed comprising vegetable oils, animal fats and / or microbial oils and having a glycerol equivalent content of 2 wt-% to 60 wt-% based on the total weight of the hydroprocessing feed, the propane content of the gaseous stream is often 25 mol-% or less. The term "glycerol-equivalent content relative to the total weight of the hydrotreatment feed" means the content of glycerol and / or glycerol-based moieties in the hydrotreatment feed, and is calculated as all glycerol (or glycerol-based) moieties (i.e., in free glycerol, and / or in mono-, di- or triglycerides, and / or glycerol-based moieties, such as, for example, partially deoxygenated glycerol, e.g., 1-propanol, 2-propanol, 1,2-propanediol or 1,3-propanediol and / or esters thereof) present as deprotonated glycerol (M=89.07 g / mol). In other words, the glycerol equivalent content can be calculated as follows: glycerol equivalent content = (molar amount of glycerol-based sites [mol]) x 89.07 g / mol / (total mass [g] of hydrotreating feed).

[0106] The liquid hydroprocessed stream obtained from the gas-liquid separation may contain at least C6-C30 hydrocarbons, typically mainly C6-C30 paraffins. Preferably, the liquid hydroprocessed stream containing C6-C30 hydrocarbons is subjected to further catalytic hydroprocessing, including at least hydroisomerization. In these embodiments, liquid fuel components with excellent low temperature properties may be obtained. The further gaseous stream separated from the further hydroprocessing effluent from the further hydroprocessing may optionally be combined with the gaseous stream from the main (first) hydroprocessing, before or after being subjected to pretreatment.

[0107] Figure 1 is a schematic diagram of the distillation of step (ii) according to an exemplary embodiment. In Figure 1, a gaseous composition 110, such as the dried H2S, CO2, and H2-depleted gaseous stream (432 in Figure 2) described above, is fed to a thermally connected distillation system 100. The gaseous composition 110 is fed to a first distillation column 210 (condenser column) configured to separate compounds lighter than propane, comprising a condenser 211 but no reboiler. Below the inlet of the gaseous composition, the condenser column 210 is referred to as the bottom of the condenser column, and above said feed inlet, the condenser column 210 is referred to as the top of the condenser column. The condenser column bottom is pumped from the condenser column 210 as liquid feed 120 by a first pump 310 to the bottom of a second distillation column 220 (reboiler column) that includes a reboiler 212 but no condenser and is configured to separate compounds heavier than propane. Below the product outlet (propane composition outlet), the reboiler column 220 is referred to as the reboiler column bottom, and above the product outlet, the reboiler column 220 is referred to as the reboiler column top. From the bottom of the reboiler column 220, steam boil-up 130 is led to the bottom of the condenser column 210, preferably driven by the pressure difference between the reboiler column 220 and the condenser column 210. The reboiler column overhead is directed from the reboiler column 220 to the top of the condenser column 210 as vapor feed 150, preferably driven by the pressure difference between the reboiler column 220 and the condenser column 210. From the top of the condenser column, below the inlet of the vapor feed 150, liquid reflux 140 is pumped by a second pump 320 to the top of the reboiler column 220. A stream of light compounds including, for example, H2, CO, CO2, CH4, and ethane is discharged as condenser column overhead vapor 160, and a stream of heavy compounds including C4+ hydrocarbons is discharged from the thermally connected distillation system 100 as reboiler bottoms 170. A propane composition 180 is recovered as a side draw from the product tray of the reboiler column 220.

[0108] FIG. 2 is a schematic diagram of an exemplary embodiment of the method of the present disclosure. In FIG. 2, some optional steps or treatments are indicated by dashed lines. In FIG. 2, a hydrotreated feed 410 of vegetable oil, animal fat and / or microbial oil is provided, as described above in connection with step (i), which is optionally fed to a pre-refining treatment 510. The optionally refined hydrotreated feed 410 is subjected to hydrotreatment 520. The hydrotreated effluent 420 is fed to a gas-liquid separation 530 to obtain a gaseous stream 430 and a liquid hydrotreated stream 440. At least a portion of the liquid hydrotreated stream 440 is subjected to optional further hydrotreatment 540, as described above, and then to fractionation 550 to recover at least an aviation fuel component 650, and optionally a diesel fuel component 660 and / or a gasoline fuel component (not shown in FIG. 2) from fractionation 550. The effluent from the further hydroprocessing step, i.e., the effluent from the hydroprocessing of the liquid hydroprocessed stream 440, can be fed to a gas-liquid separation (not shown in FIG. 2) to obtain a further gaseous stream and a further liquid hydroprocessed stream. A part of the further liquid hydroprocessed stream (not shown in FIG. 2) that was not subjected to fractionation 550 and / or a further fraction 670 of hydrocarbons from fractionation 550 can optionally be recycled to hydroprocessing 520 as a diluent. Optionally, a part of the liquid hydroprocessed stream 440 can be recycled to hydroprocessing 520 without being subjected to further hydroprocessing 540 or fractionation 550. The gaseous stream 430 is fed to a pretreatment including purification 560 to remove at least H2S and CO2 from the gaseous stream 430, thus obtaining a gaseous stream 431 depleted in H2S and CO2. The H2S and CO2 depleted gaseous stream 431 is fed to H2 separation and drying 570 as part of pre-processing to obtain a dried H2S, CO2 and H2 depleted gaseous stream 432 and a H2433 enriched stream. The H2433 enriched stream (or a portion thereof) is optionally recycled to hydroprocessing 520 and / or further hydroprocessing 540.The dried H2S, CO2 and H2 depleted gaseous stream 432 is fed as a gaseous composition to fractionation in a thermally connected distillation system comprising a condenser column 210 and a reboiler column 220 configured to feed a liquid stream 450 (liquid feed 120 and liquid reflux 140) to the reboiler column 220, and configured to provide a vapor stream 460 (vapor boilup 130 and reboiler column overhead (vapor feed) 150) to the condenser column 210. The overhead vapor 160 of the condenser column 210, i.e., a stream of light compounds including, for example, H2, CO, CO2, CH4, and ethane, and the bottoms 170 of the reboiler column 220, i.e., a stream of heavy compounds including C4+ hydrocarbons, are discharged from the thermally connected distillation system. EXAMPLES

[0109] The following examples are provided to better illustrate the claimed invention and are not to be construed as limiting the scope of the invention. To the extent that specific materials are mentioned, they are merely illustrative and are not intended to limit the invention.

[0110] The separation of renewable high purity propane compositions from gas compositions containing various amounts of heavy tails, i.e., hydrocarbons having a carbon number of at least C4 (C4+ hydrocarbons), was investigated.

[0111] A hydrotreating feed containing vegetable oils and animal fats, and a hydrocarbon diluent was subjected to hydrodeoxygenation to obtain a gaseous stream and a liquid hydrotreating stream, and then the hydrotreating effluent was subjected to gas-liquid separation and aqueous phase removal. The gaseous stream contained H2, methane, ethane, propane, H2O, H2S, CO2, CO, NH3, and C4+ hydrocarbons, and was purified by subjecting it to sweetening and ammonia removal, H2 recovery, and drying operations using the respective process steps disclosed in WO2021 / 110524 to provide a gaseous composition having the main components shown in Table 1. The biogenic carbon content of the provided gaseous composition was about 100 wt-% based on the total weight (TC) of carbon in the gaseous composition, measured according to EN 16640 (2017).

[0112] [Table 1]

[0113] The gaseous composition of Table 1 was simulated in ASPEN-PLUS using a feed rate to the distillation of 951 kg / h. At this feed rate, the heavy tail rate of C4+ hydrocarbons in the gaseous composition of Table 1 was about 910 kg / h. The maximum allowable C4+ hydrocarbon content in the product propane composition was set at 0.3 wt-%, and the propane content was targeted to be about 96 wt-%. Propane compositions with such high propane content and low C4+ hydrocarbon content are desired for use in, for example, catalyst upgrading.

[0114] In the simulation, the above gaseous composition as distillation feed was subjected to distillation in a heating integrated or thermally connected distillation system corresponding to the distillation system shown in FIG. 1 having two columns: one condenser tower with one condenser that is not a reboiler, having less than 20 theoretical stages, and a combination of a condenser tower (first distillation column) and a condenser operated with a temperature gradient of about 150° C. selected from −70° C. to 120° C. and a pressure gradient of about 50 kPa selected from 3200 kPa to 3600 kPa; and one reboiler tower (second distillation column) with one reboiler that is not a condenser, having more than 20 theoretical stages, and a combination of a reboiler tower and a reboiler operated with a temperature gradient of about 90° C. selected from 0° C. to 180° C. and a pressure gradient of less than 20 kPa selected from 3300 to 3700 kPa.

[0115] The lowest pressure in the reboiler column and reboiler combination was set to about 50 kPa higher than the highest pressure in the condenser column and condenser combination, and the reboiler power was set to an initial value of .about.702 kW. The vapor flow between the columns was unidirectional from the reboiler column to the condenser column, and the liquid flow between the columns was unidirectional from the condenser column to the reboiler column.

[0116] Further simulations were performed by gradually increasing the amount of heavy tails (C4+), accounting for situations where, for example, hydroprocessing conditions, catalysts and / or feed composition promote cracking of the feed, thereby increasing the amount of heavy tails in the gaseous stream separated from the hydroprocessing effluent. The chemical compositions and yields of the recovered renewable propane compositions, as well as the propane recoveries, are shown in Table 2.

[0117] [Table 2]

[0118] As can be seen in Table 2, the thermally connected distillation system can be operated to obtain a renewable propane composition having a high purity and a high propane content of 95 wt-% or more / around 96 wt-% based on the weight of the total renewable propane composition, regardless of the amount of heavy tail in the distillation feed. Also, the amount of C4+ hydrocarbons remaining in the obtained propane composition can be kept low within the target value. In particular, the amount of hydrocarbons having a carbon number of at least C5 (C5+ hydrocarbons) can be kept low. The yield of the propane composition was also excellent, exceeding 6.0 t / h (corresponding to about 90% or more of the recoverable yield in the absence of additional heavy tail) when the additional heavy tail was added up to about 700 kg / h (corresponding to a C4+ hydrocarbon content in the feed of about 17.0 wt-%). When the amount of additional heavy tail was about 850 kg / h or more (corresponding to a C4+ hydrocarbon content in the feed of more than 18.5 wt-%), the yield of the propane composition dropped to less than 70% of the yield that would be recoverable without the additional heavy tail. When the feed contained more than 883 kg / h of additional heavy tail (corresponding to a C4+ hydrocarbon content in the feed of more than 18.8 wt-%), the reboiler work had to be increased, making the process less energy efficient. To demonstrate this, an additional set of simulations was performed in which the reboiler work was increased by 28.2% (results are shown in Table 3).

[0119] [Table 3]

[0120] From Table 3, it can be seen that even at higher energy consumption (reboiler work), the targeted high propane content and low C4+ hydrocarbon content in the propane composition were achieved regardless of the amount of additional heavy tails in the gaseous composition, even when the C4+ hydrocarbon content in the gaseous composition was as high as about 25 wt-%. However, the yield of the highest propane composition was up to 91% of the yield recoverable without the addition of heavy tails. Thus, there is an optimum value for the heavy tails content (up to 16.0 wt-%) in the gaseous composition (distillation feed), beyond which the propane composition yield decreases, regardless of the increased reboiler work.

[0121] As a comparative simulation test, four of the renewable energy distillation feeds with the lowest heavy tails contents listed in Table 2 above were each fed into a high pressure distillation system disclosed in WO 2017 / 045791 or WO 20211 / 10524 having one low temperature distillation column with both a condenser and a reboiler. The renewable propane compositions recovered from the comparative distillation of each distillation feed and their yields are shown in Table 4.

[0122] [Table 4]

[0123] From Table 4, it can be seen that it is possible to reach the target C4+ hydrocarbon content in the propane composition, but reaching it will also increase the propane content, which, if not required for the target application of the propane composition, will lead to over-quality and a lower yield of the propane composition. The yield of the propane composition recoverable with the comparative distillation is slightly lower than the yield recoverable with a thermally connected distillation system from a feed without the addition of additional heavy tails, and the decrease in yield with the increase in additional heavy tails in the feed is greater than the decrease in the yield recoverable with the thermally connected distillation system. Also, the propane recovery with the comparative distillation is lower than with the thermally connected distillation system. Furthermore, the C5+ hydrocarbon content reached with the comparative distillation is at a higher level compared to Tables 2 and 3, which may give the propane compositions reported in Table 4 that are not suitable for certain applications.

[0124] In addition to improved yields of propane compositions, significant savings in condenser and reboiler work were achieved using the thermally coupled distillation compared to the comparative distillation. The condenser and reboiler work for the distillations reported in Tables 4 and 2, respectively, are shown in Table 5.

[0125] [Table 5]

[0126] As seen in Table 5, the savings in condenser work ranges from approximately 3500 kW to about 4000 kW, and the savings in reboiler work ranges from approximately 3700 kW to about 3800 kW. The savings in condenser and reboiler work increase as the amount of heavy tails in the distillation feed increases.

[0127] Distillation through a thermally connected distillation system including a condenser column and a reboiler column thus provides a high quality, on-spec renewable propane composition with improved propane composition yields and significant savings in reboiler and condenser work compared to obtaining a high quality renewable propane composition by comparative distillation using a single cryogenic distillation column.

[0128] Various embodiments are presented. It is to be understood that, as used herein, the words comprise, include, and contain are each used as open-ended phrases without intent of exclusivity.

[0129] The foregoing description provides a complete and informative description of the best mode currently contemplated by the inventors for carrying out the invention by way of certain embodiments and non-limiting examples of the embodiments. However, it will be apparent to those skilled in the art that the invention is not limited to the details of the embodiments set forth above, but that it may be carried out in other embodiments using equivalent means, or in combinations of different embodiments, without departing from the characteristics of the invention.

[0130] Moreover, some of the features of the above disclosed exemplary embodiments may be used to advantage without the corresponding use of other features. As such, the foregoing description should be considered as merely illustrative of the principles of the invention, and not in limitation thereof. The scope of the invention is therefore limited only by the appended claims.

Claims

1. 1. A method for treating a gaseous composition, comprising: (i) H 2 providing a gaseous composition comprising methane, ethane, propane and hydrocarbons having a carbon number of at least C4, 2 , wherein the total amount of methane, ethane, propane and hydrocarbons having a carbon number of at least C4 is at least 80 wt-%, preferably at least 85 wt-%, more preferably at least 90 wt-% of the total weight of the gaseous composition; and (ii) subjecting the gaseous composition to distillation in a thermally connected distillation system comprising n distillation columns, at least one and up to n-1 condensers, and at least one and up to n-1 reboilers, where n is an integer equal to or greater than 1, to recover a propane composition. A method comprising:

2. 10. The method of claim 1, wherein the thermally connected distillation system comprises at least a first distillation column connected to a condenser without being connected to a reboiler, and a second distillation column connected to a reboiler without being connected to a condenser, and wherein the gaseous composition is fed to the first distillation column and the propane composition is fed to the second distillation column.

3. 3. The method of claim 1, wherein a liquid feed and a liquid reflux are provided to the second distillation column from the first distillation column of the thermally connected distillation system, and a vapor feed and a vapor boil-up are provided to the first distillation column from the second distillation column of the thermally connected distillation system.

4. 4. The method of claim 3, wherein the bottoms of the first distillation column are provided as a liquid feed to the bottom of the second distillation column, and the overhead of the second distillation column is provided as a vapor feed to the top of the first distillation column, and the liquid reflux is provided from the top of the first distillation column below the vapor feed inlet to the top of the second distillation column, and the vapor boilup is provided from the bottom of the second distillation column above the liquid feed inlet to the bottom of the first distillation column.

5. The first distillation column of the thermally connected distillation system is, for example, H 2 3. The method of claim 1, wherein the first distillation column of the thermally connected distillation system is configured to separate compounds lighter than propane, such as methane and ethane, and the second distillation column of the thermally connected distillation system is configured to separate compounds heavier than propane, such as hydrocarbons having a carbon number of at least C4.

6. 3. The method according to claim 1 or 2, wherein the gaseous composition has a content ratio of the hydrocarbons having a carbon number of at least C4 to the propane of at least 0.05, preferably in the range of 0.05 to 0.40, more preferably 0.07 to 0.35, even more preferably 0.09 to 0.30, and most preferably 0.10 to 0.

20.

7. 3. The method according to claim 1 or 2, wherein the gaseous composition comprises hydrocarbons having a carbon number of at least C5 and has a content ratio of the hydrocarbons having a carbon number of at least C5 to the propane of at least 0.01, preferably in the range of 0.01 to 0.35, more preferably 0.02 to 0.30, even more preferably 0.03 to 0.25, and most preferably 0.04 to 0.

15.

8. the gaseous composition comprises at most 18.5 wt-%, preferably at most 18.0 wt-%, more preferably at most 17.0 wt-%, even more preferably at most 16.0 wt-%, most preferably at most 10.5 wt-%, and / or at least 5.0 wt-%, preferably at least 7.0, more preferably at least 9.0 wt-%, for example 5.0 to 18.5 wt-%, or 7.0 to 17.0 wt-%, or 9.0 to 16.0 wt-%, of hydrocarbons having a carbon number of at least C4, based on the total weight of the gaseous composition; and / or 3. The method of claim 1 or 2, wherein the gaseous composition comprises at most 15.0 wt-%, preferably at most 10.0 wt-%, more preferably at most 8.0 wt-%, even more preferably at most 6.0 wt-%, and / or at least 1.5 wt-%, preferably at least 2.0 wt-%, more preferably at least 3.0 wt-%, for example 1.5 to 15.0 wt-%, or 2.0 to 10.0 wt-%, or 3.0 to 8.0 wt-%, based on the total weight of the gaseous composition, of hydrocarbons having a carbon number of at least C5.

9. 3. The method of claim 1 or 2, wherein the gaseous composition comprises at least 60 wt-%, preferably at least 65 wt-%, more preferably at least 70 wt-%, for example 60 to 85 wt-%, or 65 to 80 wt-%, or 70 to 75 wt-% propane, based on the total weight of the gaseous composition.

10. The gaseous composition may contain compounds lighter than propane, such as H 2 , methane and ethane, etc., in an amount of up to 35 wt-%, preferably 5-30 wt-%, more preferably 10 to 25 wt-%, based on the total weight of the gaseous composition; and / or 1-10 wt-%, preferably 2-9 wt-%, more preferably 3-8 wt-%, based on the total weight of the gaseous composition. 2 The method of claim 1 or 2, comprising:

11. 3. The method according to claim 1 or 2, wherein the propane composition comprises at least 95 wt-%, preferably at least 96 wt-%, propane, and at most 5.0 wt-%, preferably at most 3.0 wt-%, of said hydrocarbons having a carbon number of at least C4, and at most 0.20 wt-%, preferably at most 0.18 wt-%, more preferably at most 0.13 wt-%, of said hydrocarbons having a carbon number of at least C5, based on the total weight of the propane composition.

12. 3. The method of claim 1 or 2, wherein the gaseous composition has a biogenic carbon content of at least 50 wt-%, preferably at least 75 wt-%, more preferably at least 90 wt-%, even more preferably at least 95 wt-%, based on the weight of total carbon (TC) in the gaseous composition, and / or the propane composition has a biogenic carbon content of at least 50 wt-%, preferably at least 75 wt-%, more preferably at least 90 wt-%, even more preferably at least 95 wt-%, based on the weight of total carbon (TC) in the propane composition.

13. 3. A process according to claim 1 or 2, wherein the thermally connected distillation system is operated at a pressure above 1500 kPa, preferably above 1900 kPa, for example in the range of 1500 kPa to 5000 kPa, or 1900 kPa to 4500 kPa, or 2400 kPa to 3900 kPa, and / or at a temperature above -70°C, preferably in the range of -70°C to 250°C, more preferably -70°C to 200°C, even more preferably -70°C to 180°C.

14. 3. The process of claim 1 or 2, wherein the combination of the first distillation column and the condenser is operated at a pressure in the range of 1500 kPa to 5000 kPa, or in the range of 1900 kPa to 4500 kPa, or in the range of 2400 kPa to 3900 kPa, and at a temperature in the range of -70°C to 120°C, more preferably in the range of -70°C to 100°C.

15. The method according to claim 1 or 2, wherein the lowest pressure in the combination of the second distillation column and the reboiler is higher than the highest pressure in the combination of the first distillation column and the condenser, and the lowest pressure in the combination of the second distillation column and the reboiler is preferably 20 kPa to 150 kPa higher, more preferably 30 kPa to 120 kPa higher, than the highest pressure in the combination of the first distillation column and the condenser.

16. 3. The method according to claim 1 or 2, wherein the lowest temperature in the combination of the first distillation column and the condenser is below 0°C, and the highest temperature in the combination of the second distillation column and the reboiler is 30°C to 150°C, more preferably 50°C to 120°C higher than the highest temperature in the combination of the first distillation column and the condenser, and preferably the lowest temperature in the combination of the second distillation column and the reboiler is at most as high as the highest temperature in the combination of the first distillation column and the condenser.

17. 3. The method of claim 1 or 2, wherein (i) providing the gaseous composition comprises subjecting a hydroprocessing effluent to gas-liquid separation to obtain at least a gaseous stream, and subjecting the gaseous stream to pretreatment to obtain the gaseous composition.

18. (i) providing the gaseous composition comprises: subjecting a hydrotreatment feed comprising vegetable oils, animal fats, microbial oils, crude oils, thermally and / or enzymatically liquefied organic wastes and residues, such as biomass wastes and residues, municipal solid waste and / or waste plastics, or a combination thereof, optionally together with a hydrocarbon diluent, to catalytic hydrotreatment comprising hydrodeoxygenation, hydrocracking, hydroisomerization, hydropyrolysis, hydrodesulfurization, hydrodenitrogenation, hydrodehalogenation, hydrodearomatization, hydrodemetallization and / or hydrogenation to obtain a hydrotreated effluent; subjecting the hydroprocessing effluent to gas-liquid separation to obtain at least a gaseous stream; subjecting said gaseous stream to a pretreatment to obtain said gaseous composition; The method of claim 1 or 2, comprising:

19. (i) providing the gaseous composition comprises: subjecting a hydrotreatment feed comprising vegetable oils, animal fats and / or microbial oils, optionally together with a hydrocarbon diluent, to catalytic hydrotreatment, including at least hydrodeoxygenation using a sulfided HDO catalyst, to obtain a hydrotreated effluent; At least, H 2 , H 2 S, CO, CO 2 , H 2 subjecting the hydrotreated effluent to gas-liquid separation to obtain a gaseous stream comprising O, methane, ethane, propane and hydrocarbons having a carbon number of at least C4, and a liquid hydrotreated stream comprising hydrocarbons of C6 to C30; The gaseous stream is 2 S and CO 2 a pretreatment including at least purification to remove H 2 The separated and dried H 2 S, CO 2 and H 2 subjecting the depleted gaseous stream to drying to obtain said gaseous composition; and 3. The method of claim 1 or 2, wherein the method further comprises subjecting the liquid hydrotreated stream comprising C6 to C30 hydrocarbons to fractionation, optionally after further catalytic hydroprocessing including at least hydroisomerization, to recover one or more of a gasoline fuel component, an aviation fuel component and / or a diesel fuel component.

20. (i) subjecting a hydrotreatment feed comprising vegetable oils, animal fats and / or microbial oils, and optionally a hydrocarbon diluent, to catalytic hydrotreatment, including at least hydrodeoxygenation using a sulfurized hydrotreating catalyst, to obtain a hydrotreated effluent; H 2 , H 2 S, CO, CO 2 , H 2 subjecting the hydrotreated effluent to gas-liquid separation to obtain at least a gaseous stream comprising O, methane, ethane, propane and hydrocarbons having a carbon number of at least C4 and a liquid hydrotreated stream comprising hydrocarbons of C6 to C30; H 2 , methane, ethane, propane and hydrocarbons having a carbon number of at least C4. 2 S and CO 2 Purification to remove H 2 A pretreatment step including separation and drying, 2 , wherein the total amount of methane, ethane, propane and hydrocarbons having a carbon number of at least C4 is at least 80 wt %, preferably at least 85 wt %, more preferably at least 90 wt % of the total weight of the gaseous composition; and (ii) subjecting the gaseous composition to distillation in a thermally connected distillation system comprising at least a first distillation column connected to a condenser without being connected to a reboiler and a second distillation column connected to a reboiler without being connected to a condenser, by supplying the gaseous composition to the first distillation column and recovering a propane composition from the second distillation column; 1. A method for co-producing a propane composition and a fuel component comprising: The method further comprises subjecting the liquid hydrotreated stream comprising C6 to C30 hydrocarbons to fractionation, optionally after further catalytic hydroprocessing including at least hydroisomerization, to recover one or more of a gasoline fuel component, an aviation fuel component and / or a diesel fuel component.

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