Method for Converting Carbon Oxides into Sustainable Aviation Fuel (SAF)

Abstract

A reforming system for the dedicated steam reforming of a paraffin- and / or olefin-rich stream of a jet fuel synthesis plant incorporating a reforming system is provided. The present invention provides an overall more efficient feed-jet fuel system and method.

Description

Technical Field

[0001] The present invention relates to a more efficient system (plant) and method for producing transport fuels such as synthetic kerosene, e.g., jet fuel or sustainable aviation fuel (SAF), and optionally also diesel, from carbon oxide-containing fuels, e.g., a carbon dioxide-rich feed or a carbon monoxide-rich feed. The plant or method includes methanol synthesis, methanol-jet synthesis, and optionally an upgrade section. Aspects of the present invention include feeding by-products rich in paraffins and / or olefins, optionally and off-gas streams produced in a jet fuel synthesis plant, to a dedicated reformer to provide steam reforming in the dedicated reformer in order to improve the overall carbon and hydrogen efficiency.

Background Art

[0002] Methods for converting sustainable feedstocks such as CO2 and biomass into gasoline or jet fuel via methanol are known. First, biomass can be converted to syngas via gasification, and then the syngas can be converted to methanol, for example, in a methanol synthesis loop (hereinafter also referred to as the "methanol loop"), and finally the methanol can be converted to olefins. This olefin can then be oligomerized and hydrogenated to form jet fuel, which is a hydrocarbon in the range of C8 - C19, for example, in the range of C8 - C16 or C8 - C18. A CO2 feedstock can be converted to methanol together with an H2 feedstock, and then this methanol can be converted to jet fuel. Independently of the main feedstock, several by-products are present with the jet fuel. One of the by-products from such a process is a fraction containing hydrocarbons lighter than the range corresponding to jet fuel (C8 - 18), in particular, a by-product stream rich in paraffins and / or olefins, for example, light paraffins in the range of C3 - C7 starting with propane and / or butane (C3 and / or C4), as well as olefins. This C3 and / or C4 fraction is known as liquefied petroleum gas (LPG). Off-gas streams containing CO2, H2, CH4, higher hydrocarbons, etc. are also typically produced and taken out as an exhaust gas stream.

[0003] Lighter hydrocarbons, such as light paraffins, by themselves often have low commercial value. Further, in many cases, the offgas stream has no effective use other than using it in a combustion device that emits CO2. Therefore, it would be of interest to recycle these streams as part of the jet fuel synthesis process itself to at least improve the overall carbon efficiency (C-efficiency) of this process. Further, a by-product stream containing lighter hydrocarbons that is rich in paraffins and / or olefins (hereinafter also referred to as "by-product stream rich in paraffins and / or olefins") and / or an offgas stream generated in the plant or process (hereinafter also referred to as "offgas stream") are recycled into a syngas stream through dedicated steam reforming, for example, in a methanol plant based on CO2 and H2, which enhances the performance of methanol synthesis (e.g., methanol loop) as will become apparent from one or more of the following aspects of the present invention.

[0004] EP3730473A1 (Patent Document 1) discloses the use of renewable energy in a methanol synthesis plant. Steam reforming of a series of hydrocarbon feedstocks including LPG is provided to a syngas generation section upstream of methanol synthesis to provide methanol synthesis gas, and this is further configured such that more of the net energy required, among other things, by the methanol synthesis plant is provided by a non-carbon-based energy source, a renewable energy source and / or electricity.

[0005] WO2010143980 (Patent Document 2) discloses a system for producing hydrocarbon products by integrating methanol production and hydroprocessing of an oil feedstock. A steam reformer processes a first feedstock, and C1-C4 hydrocarbons can be separated from the hydrocarbon product and recycled to the first feedstock. Therefore, the steam reformer is provided upstream of methanol synthesis to provide a main methanol synthesis gas feed, and a hydroprocessing plant having its own feedstock oil is integrated by obtaining benefits from the hydrogen generated in methanol synthesis.

[0006] The European Patent Application No. 22166260.4 (Patent Document 3) of the present applicant, which is currently ongoing, discloses the conversion of carbon dioxide to gasoline using the electro-steam methane reforming (e-SMR) of recycled liquefied petroleum gas (LPG) streams.

[0007] WO2007108014A1 (Patent Document 4) discloses a method and system for producing gasoline or diesel from carbon dioxide and water. A reforming unit downstream of and in fluid communication with the gasoline or diesel production unit is arranged to steam reform a recycle stream having, for example, a significant portion of LPG and fuel gas, i.e., 15 - 40 wt% of the liquid product.

[0008] US20160168476 (Patent Document 5) discloses a methanol - to - gasoline plant by combining the use of ZSM - 5 with Y - zeolite, in which a by - product stream is withdrawn and converted to syngas in a reformer. This syngas is combined with the main syngas and fed to a first reactor for conversion to methanol. LPG and similar off - gases are discharged from the reformer.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

[0010] [Non-Patent Document 1] “Tubular reforming and autothermal reforming of natural gas - an overview of available processes”, Ib Dybkjaer, Fuel Processing Technology 42(1995)85-107 [Non-Patent Document 2] Studies in Surface Science and Catalysis, Vol.152, ”Synthesis gas production for FT synthesis”; Chapter 4, p.258-352, 2004 [Summary of the Invention] [Problems to be Solved by the Invention]

[0011] Therefore, in order to improve the overall C efficiency and hydrogen efficiency (H-efficiency), paraffin- and / or olefin-rich by-product streams, optionally off-gas streams, and hydrogen-rich streams from a sustainable feed-jet fuel synthesis plant are utilized, but the drawbacks can be avoided. In particular, additional CO2 emissions are avoided, and the methanol loop performance is improved, including smaller-scale methanol loops. An efficient method and system are desired.

Means for Solving the Problem

[0012] When the reformed syngas from the by - product stream rich in paraffin and / or olefin, optionally and from the off - gas stream, is added to, for example, methanol synthesis based on H2 and CO2, such as in a methanol loop (MeOH loop), as will become apparent from the following description, the formation of water (a precursor of methanol catalyst sintering) is reduced, and the volume of the methanol synthesis catalyst in the methanol synthesis reactor for the same production is, therefore, reduced, and the CO / CO2 molar ratio at its inlet is guaranteed, thus making the methanol synthesis unit, such as the MeOH loop, smaller.

[0013] Therefore, a jet fuel synthesis plant, - a first syngas feed containing CO2 - rich CO2 to the plant, a first H2 - rich H2 feed to the plant, or a first syngas feed combining these streams; or a second syngas feed containing carbon oxides and hydrogen to the plant; - a methanol synthesis unit - a methanol - to - jet fuel (MTJ) synthesis section including an oxygenate - to - olefin conversion (MTO), such as methanol - to - olefin conversion, at least partial oligomerization (OLI) of at least a part of the olefins to provide an oligomerized crude product stream, and at least partial hydrogenation (HYDRO) of the oligomerized crude product stream to provide a crude product containing hydrocarbons boiling in the jet fuel range; - an upgrade section optionally including a hydrocracking (HCR) reactor and / or a separation unit; A jet fuel synthesis plant is provided that includes a reforming system for reforming a paraffin and / or olefin-rich byproduct stream and optionally an offgas stream from the MTJ synthesis section and / or the upgrading section to provide a reformer-based syngas stream; and the jet fuel synthesis plant further includes at least a portion of the reformer-based syngas stream being arranged to be supplied to an inlet of the methanol synthesis unit.

[0014] Also provided is a method for synthesizing jet fuel from sustainable feedstocks in such a plant.

[0015] Further details of the technology are set forth in the appended claims and drawings.

[0016] The technology will be described with reference to the following schematic illustrations.

Brief Description of the Drawings

[0017]

Figure 1

Figure 2

Figure 3

Figure 4

[0018] The term "synthesis gas" (abbreviated "syngas") refers to a gas that includes hydrogen and carbon oxides, optionally and in minor amounts other gases such as argon, nitrogen, methane, etc.

[0019] The term "carbon oxide" means CO and / or CO2.

[0020] The term "first syngas feed" means a syngas rich in H2 and CO2 resulting from a combination of a first H2-rich stream and a first CO2 stream. For example, the first syngas feed contains about 75% H2, about 25% CO2, and less than 1% CO.

[0021] The term "second syngas feed" means a separate syngas feed produced upstream of the methanol synthesis unit of a jet fuel synthesis plant. For example, the second syngas feed contains H2 and carbon oxide(s) in a molar ratio of at least 3:1.

[0022] A "sustainable feed" can be a CO2 feed, an H2 feed, or a combination thereof; or a biomass feed, or a syngas feed produced at least partially from electrolysis.

[0023] The term "first, second, third, or fourth syngas stream" is also referred to as a "reformer-based syngas stream" and means a syngas stream taken from a dedicated reforming system that includes a reforming unit (reformer) for treating a by-product stream rich in paraffin and / or olefin. For example, when the reformer is an e-SMR, its reformer-based syngas stream is an e-SMR-based syngas stream.

[0024] The terms "reforming" and "steam reforming" are used interchangeably.

[0025] The description "at least a portion" of a given stream means the entire stream or a part thereof.

[0026] The term "MTO" means methanol-to-olefin conversion or oxygenate-to-olefin conversion. Oxygenates include methanol and / or dimethyl ether (DME).

[0027] The term "OLI" means the oligomerization of olefins.

[0028] The term "HYDRO" means the hydrogenation of the oligomerized olefins.

[0029] The term "MTJ section" means a methanol-to-jet fuel section or an oxygenate-to-jet fuel section. The oxygenates include methanol and / or dimethyl ether (DME). The MTJ section includes an MTO reactor, an OLI reactor, or a HYDRO reactor.

[0030] The terms "system", "plant", i.e., a process plant, are used interchangeably. Throughout this specification, the term "system" is used with respect to reforming, i.e., the term "reforming system".

[0031] The terms "section" and "unit" are usually, in this specification, subsets of a plant or a system.

[0032] The use of a singular term in relation to an item such as a unit means "one or more". For example, the description "electrically heated steam methane reformer (e-SMR)" means one or more, for example, a plurality of e-SMRs arranged in parallel. For example, the description "separation unit" means one or more separation units.

[0033] Expressions such as "as appropriate" can be described with the same meaning as "optional", i.e., an optional aspect.

[0034] Other definitions are provided throughout this application in relation to the detailed description of the aspects.

[0035] Therefore, the jet fuel synthesis plant generally is - A first CO2-rich feed to the plant, a first H2-rich feed to the plant, or a first syngas feed combining these streams; or - A second syngas feed containing carbon oxides and hydrogen to the plant; and - A methanol synthesis unit not equipped with an upstream steam reforming unit for supplying a syngas feed; - An MTJ synthesis section; - An upgrade section optionally including a hydrocracking (HCR) reactor and / or a fractionation unit; and - A reforming system including a reforming unit (reformer); including.

[0036] The jet fuel synthesis plant does not include a reforming unit for steam reforming of a hydrocarbon feed gas disposed upstream of the methanol synthesis unit for supplying the first or second syngas feed.

[0037] Here, more specifically, in a first aspect, a jet fuel synthesis plant, - A CO2-containing first CO2-rich feed (201) to the plant, a first H2-rich feed to the plant, or a first syngas feed (209) combining the first CO2-rich feed (201) and the first H2-rich feed (202); or a second syngas feed (205) containing carbon oxides and hydrogen to the plant; - A methanol synthesis unit 220 arranged to receive the first CO2-rich feed 201 and the first H2-rich feed 202, or arranged to receive the first syngas feed 209, or arranged to receive the second syngas feed 205, and providing a methanol-containing effluent stream 221; - A methanol-jet fuel (MTJ) synthesis section 230 arranged to receive at least a portion of the methanol-containing effluent stream 211 and providing a hydrocarbon crude product 231 boiling in the jet fuel range; - An upgrading section 240, optionally arranged to receive at least a portion of the crude product 231 from the MTJ synthesis section 230 and to provide a jet fuel product stream 241; wherein said optional upgrading section 240 includes a hydrocracking (HCR) reactor and / or a fractionation unit, thereby providing said jet fuel product stream 241; including; - Said MTJ synthesis section 230 and / or said upgrading section 240 are arranged to provide a co-product stream 242, 242' rich in paraffins and / or olefins; - Said jet fuel synthesis plant 200 further includes a reforming system 100 for reforming said first co-product stream 242, 242' rich in paraffins and / or olefins, said reforming system 100 including a reformer unit (reformer, 40) arranged to receive said co-product stream 242, 242' rich in paraffins as a first reforming feed stream 1, to receive said co-product stream 1, 242, 242' rich in paraffins and / or olefins and perform a steam reforming step and provide reformer-based syngas streams 41, 51, 53, 62; - Said jet fuel synthesis plant (200) is further arranged to supply at least a portion of said reformer-based syngas stream to the inlet of said methanol synthesis unit 220; - Said jet fuel synthesis plant 200 does not include a reforming unit arranged upstream of said methanol synthesis unit 220 for providing said first 209 and second 205 syngas feeds; A jet fuel synthesis plant is provided.

[0038] A much simpler plant with a much lower carbon footprint is thereby provided, since the reforming is only carried out for a small internal reforming feed stream, i.e. a paraffin-rich by-product stream, optionally and for the off-gas stream. Furthermore, the reformer-based syngas to the methanol synthesis unit (e.g. MeOH loop) ensures a CO / CO2 molar ratio required for a smaller catalyst volume and thereby a smaller methanol synthesis unit, e.g. a smaller MeOH loop.

[0039] In one embodiment, the reformer-based syngas stream is a first, second or third reformer-based syngas stream 41, 51, 53.

[0040] In one embodiment, the reformer (40) in the reforming system 100 may be any of a steam methane reformer (SMR), i.e. a tubular reformer, an electric steam methane reformer (e-SMR), an autothermal reformer (ATR), a convection heated reformer, e.g. a heat exchange reformer (HER), and combinations thereof.

[0041] Therefore, in a reforming system that receives a by-product stream rich in paraffins and / or olefins, a main reformer such as an SMR may be arranged together with, for example, an ATR; or a convection heated reformer (convection reformer), e.g. a heat exchange reformer (HER), may be arranged together with an ATR. Also, for example, an ATR and an e-SMR (see below) may be provided together. The arrangement may be in series or in parallel.

[0042] In one embodiment, the reformer is either an e-SMR alone or a combination of an e-SMR and an ATR, optionally arranged alone or together with an upstream pre-reformer, and the reformer is arranged to receive the first reforming feed stream as the paraffin-rich by-product stream and to provide one product stream in the form of the reformer-based syngas stream.

[0043] Therefore, the outlet of the reforming system is one product stream in the form of the reformer-based syngas stream containing CO.

[0044] The reformer-based syngas stream containing CO is advantageous for methanol synthesis. As described above, the conversion of syngas through reforming of the first reforming feed stream increases the CO content in the syngas to the methanol synthesis unit. This is advantageous for enhancing the performance of the methanol synthesis unit, for example, when this unit is provided as a smaller-scale MeOH loop compared to when the unit is a methanol synthesis loop, i.e., when the main feeds to the methanol synthesis unit are H2 and CO2.

[0045] The convective reformer may include, for example, one or more bayonet-type reforming tubes, for example, an HTCR reformer, i.e., a Topsøe bayonet reformer, in which case the heat for reforming is transferred by convection along with radiation. In a steam methane reformer (SMR), i.e., a tubular reformer, the heat for reforming is mainly transferred by radiation in a radiant furnace. In an autothermal reformer (ATR), partial oxidation of the hydrocarbon feed by oxygen and steam occurs, followed by reforming by catalysis. In an electrically heated steam methane reformer (e-SMR), electrical resistance is used to generate heat for catalytic reforming.

[0046] For further information on these reformers, here the details are provided by direct reference to the applicant's patents and / or literature. For example, for tubular and autothermal reforming, an overview is given in “Tubular reforming and autothermal reforming of natural gas - an overview of available processes”, Ib Dybkjaer, Fuel Processing Technology 42 (1995) 85 - 107 (Non-Patent Document 1); and the description of HTCR is in EP0535505 (Patent Document 6). For the description of ATR, see further below. For the description of the more recent technology e-SMR, reference is made in particular to WO2019 / 228797A1 (Patent Document 7).

[0047] In one aspect, the catalyst in the steam reforming unit is a reforming catalyst, such as a nickel-based catalyst. In one aspect, this is active in the water gas shift reaction. Examples of reforming catalysts are Ni / MgAl2O4, Ni / Al2O3, Ni / CaAl2O4, Ru / MgAl2O4, Rh / MgAl2O4, Ir / MgAl2O4, Mo2C, Wo2C, CeO2, Ni / ZrO2, Ni / MgAl2O3, Ni / CaAl2O3, Ru / MgAl2O3, or Rh / MgAl2O3, noble metals supported on an Al2O3 carrier, although other catalysts suitable for reforming are also conceivable. The catalytic active material can be Ni, Ru, Rh, Ir, or combinations thereof, while the ceramic coating can be Al2O3, ZrO2, MgAl2O3, CaAl2O3, or combinations thereof, and potentially mixed with oxides of Y, Ti, La, or Ce. The maximum temperature of the reactor can be between 850 and 1300 °C. The pressure of the feed gas can be from 15 to 180 bar, preferably about 25 bar. The steam reforming catalyst is also referred to as a steam methane reforming catalyst or a methane reforming catalyst.

[0048] In one of the other aspects, the reformer (40) in the reforming system 100 is: - An electric steam methane reformer (e-SMR) arranged alone or together with an upstream pre-reformer; Or - An autothermal reformer (ATR) arranged alone or together with an upstream pre-reformer; That is.

[0049] Therefore, for example, there is no main reformer arranged together with the e-SMR in the reforming system, such as a steam methane reformer (SMR) arranged upstream of the e-SMR, or a convective heating reformer arranged directly or in parallel with the e-SMR, such as a heat exchange reformer. However, a pre-reformer (pre-reforming unit) is appropriately arranged upstream of the e-SMR. Therefore, the e-SMR is arranged alone or together with an upstream pre-reformer. Such an arrangement is also referred to as a stand-alone e-SMR. See the attached Figure 1.

[0050] Similarly, for example, there is no main reformer arranged together with the ATR in the reforming system, such as a steam methane reformer (SMR) arranged upstream of the e-ATR, or a convective heating reforming device arranged in series or in parallel with the ATR, such as a heat exchange reformer. However, a pre-reformer (pre-reforming unit) is appropriately arranged upstream of the ATR. Therefore, the ATR is arranged alone or together with an upstream pre-reformer. Such an arrangement is also referred to as a stand-alone ATR.

[0051] An even simpler plant with only a single reformer, optionally including a pre-reformer, can thereby be obtained, and in particular when the reformer is an e-SMR, an even lower carbon footprint can be obtained, since this can be powered by wind, solar, hydro, geothermal, or power from renewable resources such as, for example, nuclear fusion reactions. For the purposes of the present application, the latter resources are considered renewable.

[0052] It has been confirmed that the by-product stream rich in paraffin and / or olefin, optionally and the recycled off-gas stream, can be made to provide a higher efficiency of sustainable feedstock for jet fuel conversion. By using the proposed plant layout, this can be achieved with no CO2 emissions or with significantly less CO2 emissions compared to the conventional processes for the same purpose. Furthermore, the proposed layout also offers the possibility of reducing the consumption of the hydrogen feedstock, thereby enhancing the hydrogen efficiency. The production of hydrogen is power-consuming and capital-cost-intensive, for example when an electrolysis unit is used for hydrogen production. Therefore, when the electrolysis for hydrogen production is omitted, the reduction of the power consumption in the electrolysis unit not only outweighs the power consumption in the e-SMR, but also results in a reduction of the overall power consumption of the system. The outlet of the e-SMR is one product stream, i.e., one syngas stream, which is inherent in the e-SMR. The one syngas stream is, for example, the first syngas stream 41 in the attached FIG. 1.

[0053] Further details about the e-SMR and the ATR are shown below.

[0054] In this reforming system, the reforming unit is, in one aspect, an electro-steam methane reformer (e-SMR). Therefore, this e-SMR is arranged to receive the first reforming feed stream and perform an electro-steam methane reforming (e-SMR) step to provide an e-SMR-based syngas stream.

[0055] By using the e-SMR in this way, it becomes possible to recycle a by-product stream rich in paraffins and / or olefins and optionally an off-gas stream, so that additional CO2 emissions can be avoided or significantly minimized.

[0056] The e-SMR requires a supply of steam. This e-SMR receives the first reforming feed stream, performs an electro-steam methane reforming (e-SMR) step, and thereby provides a first syngas stream. The e-SMR uses electrical resistance heating to provide sufficient heating of the reactant stream and catalyst for an effective reforming reaction. The e-SMR preferably comprises a pressure shell containing a structured catalyst, the structured catalyst comprising a macrostructure of an electrically conductive material. The macrostructure supports a ceramic coating, and the ceramic coating supports a catalytically active material. The reforming step includes supplying power through a conductor connecting a power source installed outside the pressure shell to the structured catalyst to pass an electric current through the macrostructure material, thereby heating at least a part of the structured catalyst to a temperature of at least 500 °C.

[0057] The power supplied to the e-SMR is appropriately generated using a renewable energy source. Suitable e-SMRs for use in the reforming system of the present invention are those described in co-pending applications WO2019 / 228797 (Patent Document 7) and WO2019 / 228798 (Patent Document 8).

[0058] In a steam reforming process, a stream of hydrocarbon and steam is typically catalytically reformed by the following reactions into a product stream of hydrogen and carbon oxides:

[0059] [Chem.] The water-gas shift (WGS) reaction can also occur:

[0060] [Chem.] These reactions are in equilibrium at the reactor outlet conditions.

[0061] In the reforming system, the reforming unit is, in one of other embodiments, an ATR. Therefore, this ATR receives a first reforming feed stream together with an oxidant stream containing oxygen from an electrolysis unit and is arranged to perform an autothermal reforming step to provide, for example, the first ATR-based syngas stream.

[0062] Using the ATR in this way also enables, for example, recycling the by-product stream rich in paraffins and / or olefins and optionally the off-gas stream, thereby avoiding or significantly minimizing additional CO2 emissions.

[0063] The main components of the ATR reactor are a burner, a combustion chamber, and a catalyst bed housed within a heat-resistant lined pressure shell. In the ATR reactor, following the partial oxidation or combustion of the hydrocarbon feed with less than stoichiometric oxygen, steam reforming of the partially combusted hydrocarbon feed stream occurs in a fixed bed of steam reforming catalyst. To some extent, steam reforming also occurs in the combustion chamber due to the high temperature. This steam reforming reaction is accompanied by the water gas shift reaction. Typically, for the steam reforming and water gas shift reactions, the gas is in or near equilibrium at the outlet of the ATR reactor. The temperature of the outlet gas typically ranges between 850 °C and 1100 °C. Further details and a complete description of the ATR can be found in the art, such as "Studies in Surface Science and Catalysis, Vol. 152," Synthesis gas production for FT synthesis"; Chapter 4, p. 258 - 352, 2004 (Non-Patent Document 2)".

[0064] Suitable process conditions (temperature, pressure, flow rate, etc.) and suitable catalysts for such steam reforming processes are known in the art.

[0065] The jet fuel synthesis plant does not include steam reforming for preparing the first or second syngas feed. However, optionally, the jet fuel synthesis plant may be provided with a reverse water gas shift unit (rWGS unit) disposed upstream of the methanol synthesis unit for preparing the second syngas feed, as will become apparent from the following aspects.

[0066] Conventionally, in order to supply methanol synthesis gas as a singas feed, steam reforming of a main hydrocarbon feed gas such as natural gas is required upstream of the methanol synthesis unit. The steam reforming unit is typically very costly in terms of capital and operating expenses, and moreover, it also involves a significant carbon footprint. This application avoids this and instead integrates a reforming system that focuses only on steam reforming a small proportion of hydrocarbon streams, namely, a by-product stream rich in paraffins and / or olefins from the MTJ synthesis section or the upgrading section of the plant, and optionally an offgas stream. The sum of these streams is still a small proportion of the stream supplied to the reforming system. For example, as will also become apparent from the following aspects, up to 50% (volume basis), for example 5 - 45%, is derived from the reformer-based singas stream of the reforming system of the jet fuel synthesis plant. In addition to the advantages associated with enabling a smaller-scale methanol synthesis unit, such as a methanol loop, only a much smaller reformer is required, and thus the plant plot size and the associated capital and operating expenses are reduced. Furthermore, for example, by utilizing electric steam reforming (e-SMR), the unit can be made even more compact, and importantly, the carbon emissions are dramatically reduced because the electric heating can be powered by renewable resources such as wind, solar, or hydro power.

[0067] In one aspect, the reforming system 100 is further arranged for the first reforming feeds 1, 242, 242' that are less than 15 wt% of the crude product 231 containing hydrocarbons boiling in the jet fuel range or less than 15 wt% of the jet fuel product stream 241.

[0068] The generation of by-products and off-gas, i.e., the light hydrocarbon stream in the jet fuel synthesis plant, is less than 15 wt%, for example 10 wt% or less, for example 5 wt% of the jet fuel produced, and the jet fuel produced is a crude product containing hydrocarbons boiling in the jet fuel range, or a jet fuel product stream. Despite the by-products and off-gas(es) being only up to 15 wt% or less, for example about 10 wt% or 5 wt% of the hydrocarbon product, instead of discharging these streams for use as fuel gas, they are advantageously reused in the plant or process to enhance its overall efficiency, i.e., carbon efficiency (C-efficiency) and hydrogen efficiency (H-efficiency). For example, instead of utilizing these streams as the fuel gas, despite the low percentage of the by-products and off-gas, e.g., of the first reforming feed 1, 242, 242', a dedicated reforming unit for reforming such by-products and off-gas into syngas is advantageously provided.

[0069] More generally, the attendant improvement in C-efficiency or overall plant / process efficiency is not only equal to, but greater than, the percentage of said by-products and / or off-gas stream relative to the hydrocarbon product: for example, 10%, 20%, 30% or 40% of the hydrocarbon product (jet fuel) produced, regardless of the percentage of, for example, recycled LPG and / or off-gas relative to the hydrocarbon product. For example, if the production of the by-product and / or off-gas stream fed to the reforming system in the jet fuel synthesis plant is 10 wt%, the improvement in overall plant / process efficiency is not just 10%, but more than 10% when e-SMR is provided. Instead of a reforming system that, as is customary when operating with other types of reformers, such as autothermal reformers, requires at least a portion of a gas, such as LPG, to be used for the purpose of combustion, i.e., as fuel gas, in the e-SMR of the reforming system, all of the carbon fed is utilized in the production of syngas and the CO is fed to the inlet of the methanol synthesis unit. Therefore, there is not only an advantage associated with the installation of e-SMR in terms of the dramatic reduction or elimination of the carbon intensity of the plant by e-SMR rather than releasing CO2, but also the C-efficiency and H-efficiency are improved, in particular, the performance of methanol synthesis, such as the performance of the MeOH loop, is improved, whereby CO in the syngas from the reforming system is fed to methanol synthesis, enabling a smaller methanol synthesis unit.

[0070] The first CO2-rich feed is provided to a methanol synthesis unit (as described above, this may be, as appropriate, a methanol synthesis loop or simply a methanol loop, i.e., a MeOH loop). In one particular embodiment, the first CO2-rich feed contains more than 75% CO2, such as more than 90% CO2, such as more than 95% CO2 or more than 99% CO2. The first CO2-rich feed may contain, in addition to CO2, small proportions of, for example, steam, oxygen, nitrogen, oxygen-containing compounds, amines, ammonia, carbon monoxide and / or hydrocarbons. The first CO2-rich feed contains, as appropriate, only small amounts of hydrocarbons, such as less than 5% hydrocarbons or less than 3% hydrocarbons or less than 1% hydrocarbons.

[0071] The first H2-rich feed is provided to a methanol synthesis unit. The first H2-rich feed consists essentially of hydrogen, as appropriate. The first H2-rich feed of hydrogen is, as appropriate, "hydrogen-rich", which means that the major part of this feed is hydrogen; i.e., more than 75% of this feed, such as more than 85%, preferably more than 90%, more preferably more than 95%, even more preferably more than 99% is hydrogen.

[0072] One source of the first H2-rich feed of hydrogen can be one or more electrolyzer units.

[0073] Accordingly, in one embodiment, the jet fuel synthesis plant further comprises: - an electrolysis section, an electrolysis unit 260 arranged to receive a water feedstock 203, i.e., steam and / or water, and optionally to provide a H2-containing second H2-rich feed 202' or a part thereof as the H2-containing first H2-rich feed 202, or the first H2-rich feed 202; and / or an electrolysis unit 250 arranged to receive a second first CO2-rich feed 201' or the CO2-containing first CO2-rich feed 201 or a part thereof and to provide a CO-enriched feed 204; Means such as a mixing unit or a junction (i.e., a junction) for combining the H2-containing first or second H2-rich feed 202' with the CO-enriched feed 204 and feeding the second syngas feed 205; including an electrolysis section including.

[0074] In one aspect, the reformer in the reforming system includes an ATR, for example, a stand-alone ATR, the electrolysis unit arranged to receive a water feedstock supplies a first oxygen stream 206, and the jet fuel synthesis plant further includes means such as a mixing unit or a junction for combining the steam stream 207 with the first oxygen stream 206 to supply an oxidant stream (208); the ATR is arranged to receive the oxidant stream.

[0075] Optionally, an electrolysis unit arranged to receive a second CO2-rich feed 201' or the CO2-containing first CO2-rich feed 201 or a portion thereof supplies a second oxygen stream 206', and the jet fuel synthesis plant further includes means such as a mixing unit or a junction for combining the first 206 and / or second 206' oxygen streams with the steam stream 207 to supply the oxidant stream 208.

[0076] Thereby, a high degree of integration of process streams is provided in the jet fuel synthesis unit, while at the same time eliminating the need to provide a large and expensive air separation unit (ASU) typically required for the generation of oxygen required when the reformer is an ATR.

[0077] Optionally, a portion of the second CO2-rich feed 201’ or a portion of the first CO-rich feed 201 may bypass the electrolysis unit 250 and be combined with the CO-enriched feed stream 204. Some CO2 is required in the syngas feed, here the second syngas feed, and thus the bypass allows adjustment of the syngas feed module and the CO2 content for optimal performance of the methanol synthesis unit. In one particular embodiment, up to 10% of the first or second CO2-rich feed bypasses the electrolysis unit.

[0078] In addition to hydrogen, the first or second H2-rich feed may contain, for example, steam, nitrogen, argon, carbon monoxide, carbon dioxide, and / or hydrocarbons. In some cases, a small proportion of oxygen, typically less than 100 ppm of oxygen, may be present in this first or second H2-rich feed. The first or second H2-rich feed may optionally contain only a small amount of hydrocarbons, such as less than 5% or less than 3% or less than 1% hydrocarbons.

[0079] Optionally, a purification section is also provided to remove impurities such as oxygen and hydrocarbons from the first or second H2-rich feed. Optionally, there is also a purification section to remove impurities such as sulfur-containing compounds, such as COS, from, for example, the first CO2-rich feed.

[0080] In one aspect, the first CO2-rich feed and the first H2-rich feed are combined to form the first syngas feed before being supplied to the methanol synthesis unit.

[0081] In this embodiment, the jet fuel synthesis plant includes a methanol synthesis unit arranged to receive the first CO2-rich feed and the first H2-rich feed, or the first syngas feed which is a combination of the first CO2-rich feed and the first H2-rich feed, and reformer-based syngas from a reforming system, and optionally second reformer-based syngas therefrom. A methanol-containing effluent stream is obtained. The process of converting the first CO2-rich and first H2-rich streams may occur, for example, by compressing them in a first syngas compressor and passing the compressed and combined gas as the first syngas feed, for example, to a boiling water methanol reactor as one embodiment of a methanol reactor in the methanol synthesis unit, where at least a portion of CO, CO2, and H2 is converted to methanol, and then a purge gas stream is separated from the liquid-phase methanol by a condensation section.

[0082] The crude methanol stream (i.e., the methanol-containing effluent stream) contains methanol in a major proportion; that is, more than 50 wt%, for example more than 75 wt%, preferably more than 85 wt%, more preferably more than 90 wt% of this feed is methanol. Other minor proportion components of this stream include, but are not limited to, higher alcohols, ketones, aldehydes, DME, organic acids, and dissolved gases. The crude methanol also contains water, which usually needs to be removed, for example, by distillation, to purify this stream to a stream containing more than 90 wt% methanol. For example, crude methanol from pure H2 and CO2 will contain about 50 wt% water. Therefore, a water separation section is optionally installed between the methanol synthesis unit (220) and the gasoline synthesis section (230) and is installed to remove water from the methanol-containing effluent stream (221).

[0083] Therefore, a second syngas feed containing carbon oxides and hydrogen may also be provided to the methanol synthesis unit. This second syngas feed is optionally provided by combining the second H2-rich feed and the CO-enriched feed generated in the electrolysis section.

[0084] This ensures a higher CO / CO2 molar ratio to the methanol synthesis unit, and such a molar ratio is superior in that it allows for a smaller catalyst volume, less water purification and thus less need for downstream purification to remove it, and thereby a smaller methanol synthesis unit, e.g., a smaller scale MeOH loop, compared to the case of feeding a CO2-rich feed. More specifically, providing a significantly higher content of CO relative to CO2 in the syngas feed at a CO / CO2 molar ratio greater than 1, e.g., greater than 2, e.g., 10 or more, means that the syngas is more reactive, since this allows the methanol reaction to proceed with less water formation. Since methanol synthesis mainly follows the reaction: CO + 2H2 = CH3OH rather than typically 3H2 + CO2 = CH3OH + H2O, less hydrogen consumption is also achieved due to the dramatic reduction from 3 moles of H2 to 2 moles of H2 required per mole of methanol produced. The water produced also has an adverse effect on the performance of the methanol synthesis catalyst, and when the CO2 concentration in the syngas feed is too high, e.g., 90%, the catalyst volume can increase beyond 100%. Considerably more energy is also required for downstream purification of the methanol, since all of the water is removed by distillation. In particular, the output of the methanol produced increases, which is evident from the higher yield of the target jet fuel product.

[0085] In one aspect, the jet fuel synthesis plant further: - a pyrolysis unit such as a gasification unit arranged to receive a biomass feedstock and provide a raw syngas feed, and a raw syngas purification section arranged to receive the raw syngas feed and provide the second syngas feed 205, including.

[0086] At least a part of said first and / or second oxygen stream from the electrolysis section is suitably supplied to a hot gasification unit, for example a gasification unit.

[0087] The pyrolysis unit is not a primary reforming unit. The latter, for example an SMR (tubular reformer), or a convective heating reformer, for example a heat exchange reformer, is understood to include a catalyst arranged as a fixed bed for converting a hydrocarbon feed gas into syngas.

[0088] Typically, when gasification is carried out to produce a syngas feed for downstream methanol production, said syngas feed is subjected to a shift step, a water gas shift step (WGS step) in a WGS section in order to change the composition of this syngas according to the reaction CO + H2O = CO2 + H2. Said WGS may be either sweet (sulfur-free in the syngas) or sour (sulfur-containing in the syngas). Finally, a part of the CO2 is removed in a CO2 removal section. Such a section is a large unit with high capital and operating expenses. Furthermore, as a result, CO2 is exhausted from the process. In order to adjust the module M = (H2 - CO2) / (CO + CO2) of the syngas feed to an intended level of about 2.0 for downstream methanol synthesis, typically a part of the syngas bypasses the WGS step and the CO2 removal.

[0089] According to the invention, a second syngas feed can be combined with a reformer-based syngas stream, for example a first, second or third reformer-based syngas stream of a reforming system, to adjust the feed to the methanol synthesis unit. Therefore, the need for a WGS section and a CO2 removal section for the second syngas feed can be eliminated.

[0090] The term "pyrolysis" means any decomposition process in which a material is partially decomposed at elevated temperatures, typically from 250 °C to 800 °C or perhaps up to 1000 °C, in the presence of less than stoichiometric amounts of oxygen (including the case of oxygen absence). The products are typically a mixed stream of liquids and gases, as well as some amount of solid carbon. The term is interpreted to include processes known as gasification, pyrolysis, partial combustion or hydrothermal liquefaction.

[0091] In one particular embodiment, pyrolysis is gasification. Therefore, the pyrolysis unit is a gasification unit. Gasification is appropriately carried out in the presence of a gasifying agent such as oxygen, steam, carbon dioxide or a combination thereof. Also appropriately, the gasifying agent is produced in the process; for example, oxygen is provided by electrolysis and steam from the methanol conversion step in a methanol synthesis unit.

[0092] In the raw syngas purification section, impurities such as heavy metals, silica, sulfur, etc. that can be harmful to downstream units and corresponding process steps are removed with the addition of water.

[0093] The term "biomass feedstock" means a renewable feed, particularly a solid renewable feed. The solid renewable feed is - lignocellulosic biomass such as wood, forestry waste, and agricultural waste, among others; and / or - municipal waste, i.e., refuse-derived fuel (RDF) such as municipal solid waste, particularly its organic part, among others. That is.

[0094] The term "lignocellulosic biomass" means biomass containing cellulose, hemicellulose, and optionally lignin. Lignin or a substantial portion thereof may be removed, for example, by a prior bleaching step. Lignocellulosic biomass is forestry waste and / or agricultural waste and includes biomass derived from plants such as turfgrass, e.g., natural turf (turf derived from natural landscapes), wheat, e.g., straw, oats, rye, reedgrass, bamboo, sugarcane or sugarcane derivatives, e.g., bagasse, corn, and other grains.

[0095] The term "Refuse Derived Fuel (RDF)" means a fuel produced from various types of waste, such as Municipal Solid Waste (MSW), industrial waste, or commercial waste. According to the definition provided by Wikipedia after April 25, 2022, RDF consists mostly of combustible components of waste such as non-recyclable plastics (excluding PVC), cardboard, labels, and other corrugated materials. These fractions are separated by various processing steps, such as screening, air classification, ballistic separation, separation of ferrous and non-ferrous materials, glass, stone, and other foreign materials, and crushing to a uniform particle size, or pelletized to produce a uniform material that can be used, for example, as a fossil fuel substitute in cement factories, lime factories, coal-fired power plants, or as a reducing agent in steel furnaces.

[0096] The term "Municipal Solid Waste (MSW)" means garbage or refuse discarded as household items from homes, schools, hospitals, or businesses. Municipal solid waste includes packaging materials, newspapers, clothing, household appliances, and leftover food. For the purposes of this application, the term "Municipal Solid Waste" can be defined as a feedstock including materials of articles discarded by the public, such as mixed municipal waste assigned waste code 200301 (EWC code 20 03 01) in the European Waste Catalog.

[0097] The second syngas feed is rich in CO: for example (on a molar or volume basis, dry basis) from 40 to 70%, for example 60% CO, from 1 to 10%, for example 5% CO2, from 20 to 40%, for example 30% H2, and as the remainder, inerts: N2 + Ar and H2S. Thus, this high CO / CO2 molar ratio in the second syngas feed provides the same advantages as having the high CO / CO2 molar ratio described above.

[0098] The reformer-based syngas generated by reforming a paraffin- and / or olefin-rich stream contains CO, CO2 and H2 and has a composition that also ensures the CO / CO2 molar ratio required for a smaller methanol catalyst volume and thereby a smaller methanol synthesis unit, for example a smaller scale MeOH loop. For example, the composition of the first e-SMR syngas stream, which is the syngas withdrawn from the e-SMR in the reforming system, is (on a volume basis, dry basis) 40 - 70% H2, 10 - 30% CO, 2 - 20% CO2, 0.5 - 5% CH4.

[0099] To obtain an optimized yield in methanol production, it is necessary to consider the stoichiometric amounts of H2, CO and CO2. Thus, in one aspect, the first or second syngas feed has a CO / CO2 molar ratio greater than 1, for example greater than 2, for example 10 or more. Optionally, the first or second syngas feed has a module M = (H2 - CO2) / (CO + CO2) in the range from 1.80 to 2.20, for example from 1.95 to 2.10, defined in terms of molar content. Similarly, the reformer-based syngas, for example the first and second reformer-based syngas streams, can have a CO / CO2 molar ratio greater than 2, for example 10 or more. Optionally, the reformer-based syngas has a module M = (H2 - CO2) / (CO + CO2) in the range from 1.80 to 2.40, for example from 1.95 to 2.10.

[0100] In one aspect, the jet fuel synthesis plant (200) is - A reverse water-gas shift (rWGS) unit, preferably an electric rWGS (e-rWGS) unit, arranged to receive a part of the CO2-rich first CO2-containing feed 201 and a part of the H2-rich first H2-containing feed 202 to provide an rWGS syngas feed, and means such as a mixing unit or a confluence point to combine the rWGS syngas feed with the remainder of the CO2-rich first CO2-containing feed 201 and the H2-rich first H2-containing feed 202 and to provide the second syngas feed (205). In one of the specific embodiments, the rWGS is also arranged to receive a part of the by-product streams 242, 242' rich in paraffin and / or olefin.

[0101] The rWGS reaction CO2 + H2 = CO + H2O is endothermic and requires a significant heat input. Therefore, the rWGS unit is preferably electrically heated (e-rWGS unit). In this case, optionally, a part of the by-product stream rich in paraffin and / or olefin and optionally a part of the off-gas stream are sent to the e-rWGS unit. This is because the e-rWGS unit can also steam reform these streams to some extent.

[0102] For details of e-rWGS, reference may be made to the applicant's WO2022079098 (Patent Document 9) (its e-rWGS section).

[0103] The first or second syngas feed, and the reformer-based syngas may be combined and supplied to a methanol synthesis unit.

[0104] Therefore, in one embodiment, at least a part of the reformer-based syngas streams 41, 51, 53, 62, for example, at least a part of the first, second or third syngas streams 51, 53, 62, is arranged to be mixed with the CO2-rich feed 201 and / or the H2-rich feed 202, or with the first syngas feed 209, or with the second syngas feed 205 and supplied to the inlet of the methanol synthesis unit 220.

[0105] In one aspect, in order to store at least a portion of the methanol-containing effluent stream 221, a methanol storage tank is disposed between the methanol synthesis unit 220 and the MTJ section 230, i.e., downstream of the methanol synthesis unit and upstream of the MTJ section.

[0106] This is a simple solution, for example, to address an intermittent source required to produce the power needed for upstream electrolysis. The methanol storage tank may be disposed downstream of the water separation section for removing water. The water separation section is, for example, a distillation column. The methanol storage tank accumulates methanol, for example, from the overhead section of the distillation column, at a low pressure, for example, at a pressure of less than 5 barg, for example, under atmospheric pressure, thus enabling the use of inexpensive materials for such a tank and also serving as a buffer for sudden fluctuations in power due to the intermittent nature of sources for producing power, such as wind and solar energy.

[0107] Therefore, the plant (and method) according to the present invention improves performance, thereby not only improving the hydrogen (H) and carbon (C) efficiency of the plant while scaling down the methanol synthesis unit, for example, the MeOH loop, but also providing a robust plant that can cope with sudden and often large fluctuations in the power supply (for example, for electrolyzing water or steam into the hydrogen required for the syngas feed for methanol production).

[0108] In one aspect, the methanol synthesis unit 220 is arranged for a reformer-based syngas stream 41, 51, 53, 62 that is up to 50 volume %, for example, from 5 to 45%, for example, from 15 to 45%, for example, from 10 to 40% or from 20 to 40% of the inlet inflow of the methanol synthesis unit 220.

[0109] Thereby, 5 to 50%, for example 10 to 40%, for example 15 to 30% of the methanol-containing effluent stream 221 is obtained from the recycle stream, i.e., from the by-product stream rich in paraffin and / or olefin, optionally and from the offgas stream(s). Therefore, the reformer-based syngas stream can be 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 volume % of the inlet inflow of the methanol synthesis unit.

[0110] The specific supply point of the reformer-based syngas to the inlet of the methanol synthesis unit is, for example, downstream of the mixing point of the CO2-rich feed and / or the H2-rich feed and upstream of the first syngas feed compressor disposed therein, and therefore, is mixed with the first syngas feed or the second syngas feed. For example, the H2-rich feed from the electrolysis of water is provided by a dedicated H2 compressor. The CO2-rich feed is combined with the H2-rich feed after appropriate CO2 gas scrubbing to form the first syngas feed and is fed to the methanol reactor of the methanol synthesis unit by the first syngas feed compressor.

[0111] In one of the other embodiments, the specific supply point of the reformer-based syngas to the inlet of the methanol synthesis unit may be together with the overhead recycle stream of the methanol synthesis unit as described below.

[0112] In one embodiment, the methanol synthesis unit is a methanol synthesis loop (MeOH loop).

[0113] Therefore, the methanol synthesis unit - Optionally, a cleaning section, for example a desulfurization section, which is arranged to receive the CO2-rich feed (201) and / or the H2-rich feed (202), or the first syngas feed (209); or the second syngas feed (205), and thus provide a cleaned methanol syngas feed, for example a desulfurized methanol syngas feed; - A methanol reactor arranged to receive the washed methanol syngas feed, e.g., the desulfurized methanol syngas feed, and to produce a crude methanol effluent stream; - A first separator arranged to receive the crude methanol effluent stream and to produce a bottom stream as the methanol-containing effluent stream and an overhead recycle stream (optionally, after being fed to a second separator such as a low-pressure separator that generates offgas); - A recycle compressor arranged to recycle the overhead recycle stream to the methanol reactor; comprising.

[0114] In one aspect, the methanol synthesis unit further - Means such as a mixing unit or a junction (i.e., the overhead recycle is fed after being mixed with any of the above streams) for combining the overhead recycle stream with the CO2-rich feed and / or the H2-rich feed, or the first syngas feed, or the second syngas feed; comprising.

[0115] In one aspect, the methanol synthesis unit further - Means such as a mixing unit or a junction, optionally installed downstream of the recycle compressor, for combining a reformer-based syngas stream, e.g., a first, second, or third reformer-based syngas stream, with the overhead recycle stream; may include.

[0116] It will be understood that the term "junction" may be used interchangeably with the term "juncture". This represents a mixing point.

[0117] Upstream of the methanol reactor, as described above, a desulfurization section, such as a cleaning section including a sulfur absorber and a sulfur guard, may be provided as appropriate as part of the methanol synthesis unit to remove sulfur from the syngas feed. This is because sulfur is harmful to the downstream methanol reactor catalyst. Instead of combining the reformer-based syngas with, for example, the first syngas feed directly, by combining it with the overhead recycle, the volumetric flow rate to the desulfurization section becomes constant, thereby avoiding the disadvantage of increased sulfur removal capacity by providing a correspondingly larger desulfurization section. After being combined with the overhead recycle, the reformer-based syngas is fed after being mixed with the CO2-rich feed and / or the H2-rich feed, or mixed with the first syngas feed, or mixed with the second syngas feed.

[0118] From the overhead recycle stream of the methanol synthesis unit, an optional fuel gas stream is taken out, appropriately upstream of the recycle compressor, from which a hydrogen stream is recovered. Here, this hydrogen stream is referred to as the excess hydrogen stream from the methanol synthesis unit; and this is, for example, the hydrogen stream of a hydrogen recovery unit such as a pressure swing adsorption unit (PSA unit), or the hydrogen stream of a purge gas scrubber (appropriately arranged upstream of a hydrogen recovery unit such as a PSA unit). Thereby, additional hydrogen is internally produced in the plant or process. The hydrogen stream of a hydrogen recovery unit such as a PSA unit is fed, for example, to a hydrogenation reactor (HYDRO reactor) downstream of an oligomerization reactor (OLI reactor) in the MTJ synthesis section of the plant; and / or to an HCR reactor in the upgrade section of the plant as appropriate. The hydrogen stream of the purge gas scrubber is fed as appropriate to the hydrogenation section of the reforming system of the plant. The hydrogenation section serves, inter alia, to remove olefins supplied to the reforming system.

[0119] Accordingly, in one aspect, the methanol synthesis unit 220 is arranged to supply an excess hydrogen stream, i.e., an excess hydrogen stream from the methanol synthesis unit 220; the plant 200 further includes a hydrogenation section 10 in the reforming system 100, and the hydrogenation section is arranged to receive the excess hydrogen stream from the methanol synthesis unit.

[0120] The provision of the excess hydrogen stream from the methanol synthesis unit eliminates, for example, the need for a hydrogen recovery section (e.g., the membrane unit 60 in the attached FIG. 1) for supplying a hydrogen-rich stream in the reforming system of the plant, and thereby enables a simpler layout in the reforming system by eliminating the need for a hydrogen compressor for sending a hydrogen-rich stream to the hydrogenation section of the reforming system.

[0121] In one aspect, the MTJ synthesis section 200 includes a methanol-olefin reactor (MTO reactor) for supplying an olefin stream, an oligomerization reactor (OLI reactor) for supplying an oligomerized crude product stream, and a hydroprocessing reactor for supplying a crude product 231 containing hydrocarbons boiling in the jet fuel range.

[0122] The term "hydroprocessing" means hydrotreatment and includes any of hydrogenation (HYDRO) in a HYDRO reactor, hydrocracking (HCR) in a HCR reactor, hydroisomerization (HDI) in a HDI reactor, or combinations thereof. These are techniques well known in the art. For example, the applicant's WO2021180805 (Patent Document 10) discloses related catalysts and operating conditions. The applicant's WO2022063992 (Patent Document 11) discloses, among other things, related catalysts and operating conditions for hydrogenation.

[0123] For the purposes of the present application, any upgrade section includes a hydrocracking (HCR) reactor and / or a fractionation unit. Thus, in one aspect, any upgrade section includes a fractionation unit. Any upgrade section may further include a HYDRO reactor, e.g., upstream or downstream of the fractionation unit. Preferably, any upgrade section includes an HCR reactor and a fractionation unit.

[0124] Thus, for example, it will be understood that the HYDRO reactor may be provided in the MTJ section of the plant and / or in the upgrade section of the plant. Also for example, the HYDRO reactor may be provided in the MTJ synthesis section of the plant, and the HCR reactor may be provided in the upgrade section of the plant.

[0125] In one aspect, the hydroprocessing reactor in the MTJ section is a hydrogenation (HYDRO) reactor.

[0126] In one aspect, the MTJ synthesis section 230 includes a methanol-to-olefin reactor (MTO reactor), an oligomerization reactor (OLI reactor), and a hydrogenation reactor (HYDRO reactor), and the MJT synthesis section may further include a separator between the OLI reactor and the HYDRO reactor and / or downstream of the HYDRO reactor to provide a by-product stream rich in paraffins and / or olefins. Thus, more specifically, in one aspect, the MTJ synthesis section 230 includes a methanol-to-olefin reactor (MTO reactor) for providing an olefin stream, an oligomerization reactor (OLI reactor) for providing an oligomerized crude product stream, and a hydrogenation reactor (HYDRO reactor) for providing a crude product 231 containing hydrocarbons boiling in the jet fuel range; and the MTJ synthesis section 230 - A separator between the OLI reactor and the HYDRO reactor, which receives at least a portion of the oligomerized crude product stream and then separates at least a portion of the by-product stream 242 rich in paraffin and / or olefin; and / or - A separator downstream of the HYDRO reactor, which receives at least one of the crude products 231 containing hydrocarbons boiling in the jet fuel range and then separates at least a portion of the by-product stream 242 rich in paraffin and / or olefin; further includes.

[0127] Therefore, it will be understood that the MTJ synthesis section may also include a separator such as a fractionation unit.

[0128] In the MTJ section of the plant, oxygen-containing compounds such as methanol are converted to olefins in a methanol-to-olefin reactor (MTO reactor). As is well known in the art, in the MTJ section, methanol can first be converted to dimethyl ether (DME), and then an oxygen-containing compound stream containing methanol and / or DME is converted to olefins in the MTO reactor. The olefin stream from the MTO reactor, which contains C4-C8 olefins, optionally and higher olefins already in the jet fuel range, is oligomerized and hydrogenated in the OLI reactor and the HYDRO reactor to form the relevant fractions for jet fuel, i.e., C8-C19, for example, C8-C16 paraffins.

[0129] In one aspect, the MTO reactor in the MTJ section of the plant is provided with a conversion catalyst containing a zeolite having a framework with a 10-membered ring pore structure, and the 10-membered ring pore structure is a one-dimensional (1D) pore structure; the 1D pore structure is any one of MRE (ZSM-48), MTT (ZSM-23), TON (ZSM-22), or a combination thereof.

[0130] 1D zeolites such as ZSM-48 already enable the production of a high proportion of olefins that are already in the jet fuel range, thus reducing the burden on the downstream OLI reactor. Optionally, the conversion catalyst is provided in a fixed bed.

[0131] The by-product stream separated between the OLI reactor and the HYDRO reactor is rich in olefins. Thus, in one aspect, the by-product stream rich in paraffins and / or olefins is a stream containing at least 50 wt%, such as at least 60 wt%, or at least 75 wt%, or at least 90 wt% olefins. For example, this stream contains 60 to 80 wt% olefins and 20 to 40 wt% paraffins.

[0132] Downstream of the hydroprocessing reactor, such as the HYDRO reactor, a separator may be provided that receives the crude product containing hydrocarbons boiling in the jet fuel range and then separates the by-product stream rich in paraffins and / or olefins. Thus, this stream mainly contains paraffins in the range C8 to less than C19, such as C3 to C7 paraffins.

[0133] Accordingly, in one aspect, the by-product stream rich in paraffins and / or olefins is a stream containing at least 50 wt%, such as at least 60 wt%, or at least 75 wt%, or at least 90 wt% paraffins, including n- and i-paraffins, optionally and olefins. For example, this stream may contain about 90 wt% paraffins, including n- and i-paraffins, and about 10 wt% naphthenes. In one of the specific aspects, the by-product rich in paraffins and / or olefins is a stream rich in C3 to C7 paraffins, including n- and i-paraffins, optionally and olefins. In one of the other specific aspects, the by-product stream rich in paraffins and / or olefins is a naphtha stream. As used herein, "naphtha stream" means C5 to C9 hydrocarbons, such as C5 to C8 hydrocarbons, such as C5 to C8 olefins, boiling in the range of 30 to 160 °C.

[0134] A by-product stream rich in paraffin and / or olefin can also be fed to the upgrading section of the plant, for example by a hydrocracking reactor (HCR reactor) and / or a fractionation unit arranged therein. For example, the by-product stream rich in paraffin and / or olefin may be a stream rich in propane and / or butane, for example a liquefied petroleum gas (LPG) stream. Also for example, the by-product stream rich in paraffin and / or olefin may be a naphtha stream as described above.

[0135] The description "rich in C3-C7 paraffin" means that at least 50%, for example at least 60%, preferably at least 75% of this by-product stream is C3-C7 paraffin. C8 or higher (C8+) paraffins, especially C8-C19, for example C8-C16 paraffins, are instead taken out as the main hydrocarbon component of jet fuel. The description "rich in propane and / or butane" means that at least 50%, for example at least 60%, preferably at least 75% of this by-product stream is propane and / or butane. Typically, LGP contains 70 to 80 volume% of butane, 20 to 30 volume% of propane, and some other hydrocarbons. Therefore, in one aspect, the by-product stream rich in paraffin and / or olefin is an LPG stream (LPG feed). LPG is typically a mixture of relatively light hydrocarbons, such as propane and butane. Propylene, butylenes and various other hydrocarbons, such as C2H6, CH4, etc. are also present in LPG at low concentrations. The LPG stream may also contain olefins.

[0136] In one aspect, the jet fuel synthesis plant is further arranged to feed one or more off-gas streams, and the one or more off-gas streams 253, 253' are one or more exhaust gas streams rich in CO2, H2, CH4, and the reforming system is arranged to receive at least a part of the one or more off-gas streams (plural available) 253, 253'.

[0137] For the purposes of the present application, the offgas stream is considered separate from the by-products rich in paraffins and / or olefins. The latter are considered the by-product stream and the former is considered the exhaust gas stream.

[0138] Therefore, for the purposes of the present invention, the offgas stream(s) is an exhaust gas stream containing CO2, H2, CH4, optionally and higher hydrocarbons etc. which are also produced in the jet fuel synthesis plant. For example, the offgas stream can be from a methanol synthesis unit (e.g., methanol loop); for example, the offgas stream can be from a separation unit such as a low-pressure separation unit arranged in the methanol synthesis unit. Other offgas streams can result from the upgrade section of the jet fuel synthesis plant. Other offgas streams can result from the MTJ section of the jet fuel synthesis plant, e.g., the MTO reactor (methanol-olefin reactor) therein. As already described, offgas streams often have no useful application other than using them in combustion devices such as combustion heaters that emit CO2. Now, these offgas streams are recycled as part of the jet fuel synthesis process itself, among other things, to improve the overall C-efficiency and / or H-efficiency of the plant and method.

[0139] In particular, using e-SMR alone or in combination with an upstream pre-reformer allows for the recycling of the by-product stream rich in paraffins and / or olefins, e.g., the LPG and / or naphtha stream, optionally and the offgas stream, such that additional CO2 emissions can be avoided or significantly minimized.

[0140] One or more additional offgas streams in the plant are arranged to be fed to the reforming system, optionally in combination with the by-product stream rich in paraffins and / or olefins.

[0141] In one aspect, the reforming system of the plant further includes a separation section arranged to receive at least a portion of the first reformer-based syngas stream and separate it into at least the second reformer-based syngas stream and process condensate. This separation section advantageously separates water, which is harmful for use in methanol synthesis, from the first syngas stream.

[0142] The reforming system may include the hydrogenation section arranged to receive the first reforming feed stream, i.e., the by-product stream rich in paraffin and / or olefin, optionally and the off-gas stream, and provide the hydrogenated first reforming feed stream. In the hydrogenation section, the first reforming feed stream is mixed, as described above, with a hydrogen feed, suitably an excess hydrogen stream from the methanol synthesis unit of the plant, and passed over a hydrogenation active catalyst. Also in this case, the provision of an excess hydrogen stream from the methanol synthesis unit enables a simpler layout that does not require a hydrogen recovery section in the reformer-based syngas for providing a hydrogen-rich stream, as shown, for example, in the attached FIG. 1, and hence a hydrogen compressor for sending this hydrogen-rich stream to the hydrogenation section. The hydrogenation section can include one or more hydrogenation reactors in series. Hydrogenation converts unsaturated hydrocarbon components, such as olefins, such as propylene or butylene, into the corresponding saturated hydrocarbons, which can reduce or avoid carbon formation (in the reforming step) by the conversion of olefins to alkanes. Hydrogenation catalysts and reactors suitable for such processes are commercially available and known to those skilled in the art.

[0143] The reforming system may also include a desulfurization section arranged to receive the hydrogenated first reforming feed stream and to provide the desulfurized first and / or second reforming feed streams. Typically, this desulfurization section includes one or more hydrodesulfurization (HDS) reactors. Desulfurization converts sulfur-containing compounds in the first stream into hydrocarbons (typically saturated hydrocarbons) and sulfur-containing compounds as by-products (e.g., H2S). This can reduce catalyst poisoning in subsequent conversion steps. Desulfurization catalysts and reactors suitable for such processes are commercially available and are known to those skilled in the art. Substances other than sulfur that may need to be removed in such purification steps include chlorine, dust, and heavy metals.

[0144] A pre-reforming section, i.e., a pre-reformer (or alternatively, a pre-reforming unit), may be arranged to receive the first reforming feed stream and to perform a pre-reforming step. A pre-reformed stream is provided. Pre-reforming is an additional reforming step that enables the ultimate production of syngas having the desired composition, i.e., a composition in which higher hydrocarbons have been converted to methane. Pre-reforming is suitably carried out at a temperature from about 350 °C to 700 °C in order to convert higher hydrocarbons as an initial step. Pre-reforming catalysts and reactors suitable for such processes are commercially available and are known to those skilled in the art. The pre-reformer unit used in the present invention is a reaction vessel containing a catalyst and is typically adiabatic. In the pre-reforming unit, the relatively heavy hydrocarbon components in the hydrocarbon feedstock are steam reformed and the products of this heavy hydrocarbon reforming are methanated. Those skilled in the art can construct and operate a suitable pre-reformer unit as required. Pre-reformer units suitable for use in the system / method of the present invention are provided in the applicant's co-pending applications EP20201822 (Patent Document 12) and EP21153815 (Patent Document 13). The pre-reformed stream contains methane, hydrogen, carbon monoxide, and carbon dioxide. The pre-reformed stream at the outlet of the pre-reformer can be in the temperature range from 400 °C to 500 °C.

[0145] The first reformer-based syngas stream is at an elevated temperature (e.g., from 900 °C to 1100 °C) at the outlet of the reformer, so it can advantageously heat exchange with upstream components in the system for efficient energy utilization in the reforming system. Therefore, the reforming system may include one or more heat exchangers arranged to provide heat exchange between the first syngas stream and one or more of the first reforming feed stream, the desulfurized first reforming feed stream, and the boiler feed water stream. Optionally, the first reformer-based syngas stream first heat exchanges with the desulfurized first reforming feed stream, then with the boiler feed water stream, and then with the first reforming feed stream. Alternatively or additionally, one or more electrical heaters may be used to increase the temperature of one or more of the first reforming feed stream, the hydrogenated first reforming feed stream, the desulfurized first reforming feed stream, and the boiler feed water stream.

[0146] As previously explained, the reforming system may further include a second reforming feed stream that is an offgas stream containing CO2, H2, and CH4, and the second stream is suitably arranged to be mixed with the first reforming feed stream upstream of the inlet of the reformer, e.g., upstream of the inlet of e-SMR or ATR.

[0147] In one aspect, the reforming system includes a hydrogen recovery section, the hydrogen recovery section being arranged to receive at least a portion of the second reformer-based syngas stream and provide at least a hydrogen-rich stream and a fourth reformer-based syngas stream; and at least a portion of the second reformer-based syngas stream and at least a portion of the fourth reformer-based syngas stream are arranged to be combined into a combined syngas stream as the third reformer-based syngas stream. The hydrogen recovery section may include a membrane hydrogen separation unit or a PSA (pressure swing adsorption) unit or both.

[0148] At least a portion of the hydrogen-rich stream obtained from the hydrogen recovery section and / or a portion of the second syngas stream from the separation section can be used in the hydrogenation section of the reforming system. Therefore, at least a portion of the hydrogen-rich stream may be combined, for example, with the first reforming feed stream upstream of the hydrogenation section. Alternatively or additionally, the recovered H2 can also be used in the hydrogenation processing reactor of the MTJ synthesis section, such as the hydrogenation reactor (HYDRO reactor).

[0149] Thereby, further integration (by internal hydrogen procurement) and improved hydrogen efficiency of the jet fuel synthesis plant are also achieved.

[0150] As described above, the methanol synthesis unit is appropriately arranged to supply an excess hydrogen stream.

[0151] Accordingly, in one aspect, the methanol synthesis unit 220 is arranged to supply an excess hydrogen stream, i.e., an excess hydrogen stream from the methanol synthesis unit 220; the MTJ synthesis section includes a methanol-to-olefins reactor (MTO reactor), an olefins reactor (OLI reactor), and a hydrogenation reactor (HYDRO reactor); and the HYDRO reactor is arranged to receive a portion of the H2-containing first or second H2-rich feed and / or a portion of the excess hydrogen stream from the methanol synthesis unit 220, for example, a portion of the excess hydrogen stream from the methanol synthesis unit 220, optionally and a portion of the hydrogen-rich stream from the hydrogen recovery section 60 of the reforming system 100; and / or The optional upgrade section 240 includes an HCR reactor, and this HCR reactor is arranged to receive a portion of the H2-containing first or second H2-rich feed 202, 202' and / or a portion of the excess hydrogen stream from the methanol synthesis unit 220, for example, a portion of the excess hydrogen stream from the methanol synthesis unit 220; The reforming system 100 is arranged to receive the excess hydrogen stream from the methanol synthesis unit 220, for example, a part of the excess hydrogen stream from the methanol synthesis unit 220; the reforming system 100 includes a hydrogenation section 10, and the hydrogenation section 10 is arranged to receive the excess hydrogen stream 255 from the methanol synthesis unit 220.

[0152] More generally, the methanol synthesis unit is arranged to provide an excess hydrogen stream, i.e., an excess hydrogen stream from the methanol synthesis unit; the MTJ synthesis section includes a methanol-olefin reactor (MTO reactor), an olefin reactor (OLI reactor), and a hydrogenation processing reactor, such as a hydrogenation reactor (HYDRO reactor); and the hydrogenation processing reactor, such as the HDYRO reactor, includes a part of the H2-containing first or second H2-rich feed; and / or a part of the excess hydrogen stream from the methanol synthesis unit, for example, a part of the excess hydrogen stream from the methanol synthesis unit; optionally and is arranged to receive a part of the hydrogen-rich stream from the hydrogen recovery section of the reforming system. See the attached FIGS. 6 and 1.

[0153] Thereby, for example, the hydrogen required for the HYDRO reactor is also internally sourced rather than relying on costly external sourcing outside the battery limit of the plant. The excess hydrogen stream from the methanol synthesis unit is appropriately generated from the overhead recycle stream by providing a pressure swing adsorption (PSA) unit arranged to receive a part of the overhead recycle stream, for example, the hydrogen recovery unit.

[0154] The MTJ synthesis section is, for example, as disclosed in the applicant's WO2022063992 (Patent Document 11). Thereby, the jet fuel production stream meets the requirements for being qualified as sustainable aviation fuel (SAF) in accordance with ASTM D7566 and ASTM D4054.

[0155] Furthermore, the present invention relates to a method for the synthesis of jet fuel from a CO2-rich first CO2-containing feed 201 and an H2-rich first H2-containing feed 202, or a first syngas feed 209 combining the first CO2-rich feed 201 and the first H2-rich feed 202; or a second syngas feed 205 containing carbon oxides and hydrogen, comprising the following steps: - providing a jet fuel synthesis plant 200 according to any one of the above aspects; - feeding the CO2-rich feed 201 and the H2-rich feed 202, or the first syngas feed; or the second syngas feed 205 to a methanol synthesis unit 220 and providing a methanol-containing effluent stream 221; - feeding at least a portion of the methanol-containing effluent stream 221 from the methanol synthesis unit 220 to a methanol-jet fuel (MTJ) synthesis section 230 and providing a crude product 231 containing hydrocarbons boiling in the jet fuel range; - feeding at least a portion of the crude product 231 from the MTJ synthesis section 230 to an optional upgrade section 240 and providing a jet fuel product stream 241, wherein the optional upgrade section 240 includes a hydrocracking (HCR) reactor and / or a fractionation unit to provide the jet fuel product stream 241; - withdrawing from the MTJ section 230 and / or the upgrade section 240 a by-product stream 242, 242' rich in paraffins and / or olefins, optionally and one or more offgas streams 253, 253', for example a second stream 253 from the methanol synthesis unit 220 and / or a second stream 253' from the optional upgrade section 240; - At least a part of the first reforming feed stream 1 as the secondary product stream 242, 242' rich in paraffin and / or olefin, optionally and at least a part of the one or more off-gas streams, are supplied to the reforming system 100, a reforming step is carried out in a reforming unit (reformer, 40), and a reformer-based syngas stream 41, 51, 53, 62, for example a first, second or third reformer-based syngas stream 41, 51, 53, is provided; - At least a part of the reformer-based syngas streams 41, 51, 53, 62 is mixed at the inlet of the methanol synthesis unit 220, preferably with the CO2-rich feed 201 and / or the H2-rich feed 202, or with the first syngas feed 209; or is mixed with the second syngas feed 205 and supplied; comprising, and - The method does not include steam reforming of a hydrocarbon feed gas for providing the first 209 or the second syngas feed 205, the method is also provided.

[0156] For a plant (MTJ plant), in one aspect for a reforming system, the reforming step may be steam methane reforming in a steam methane reformer (SMR), i.e., a tubular reformer, electrical steam reforming (electrically heated reforming) in an electrical steam methane reformer (e-SMR), autothermal reforming in an autothermal reformer (ATR), convective heating reforming in a convective heating reformer, for example a heat exchange reformer (HER), and any combination thereof.

[0157] In one aspect, the reforming step of the reforming system is - Electrical steam reforming in an electrical steam methane reformer (e-SMR) arranged alone or together with an upstream pre-reformer; or - Autothermal reforming in an autothermal reformer (ATR) arranged alone or together with an upstream pre-reformer; is.

[0158] Therefore, in one particular embodiment, in relation to the plant (MTJ synthesis plant), the process does not include a primary reforming step in relation to the e-SMR reforming step or the autothermal reforming step, for example steam methane reforming (SMR) upstream of the e-SMR step or the autothermal reforming step; or for example convective heating reforming in a heat exchange reformer operating in parallel or directly with e-SMR is not included. Therefore, also in this case, in the reforming system, in addition to pre-reforming, there is only e-SMR or autothermal reforming.

[0159] In one embodiment, the methanol synthesis unit 220 provides an excess hydrogen stream 255, and the method further includes supplying at least a portion of the excess hydrogen stream 255 to the reforming system 100. In one particular embodiment, the reforming system 100 includes a hydrogenation section 10, and the method further includes supplying at least a portion of the excess hydrogen stream 255 to the hydrogenation section 10.

[0160] In one embodiment, the first reforming feed 1, 242, 242' is less than 15 wt% of the crude product 231 comprising hydrocarbons boiling in the jet fuel range or less than 15 wt% of the jet fuel product stream 241.

[0161] In one embodiment, the method further includes - Optionally, an electrolysis step of the water feedstock 203 to provide a second H2-rich feed 202' containing H2 as the first H2-rich feed 202 containing H2; And / or an electrolysis step of the second CO2-rich feed 201' containing CO2 to provide a CO-enriched feed 204; and combining the first or second H2-rich feed 202' containing H2 and the CO-enriched feed (204) to provide the second syngas feed 205; Or - A pyrolysis step of the biomass feedstock to provide a crude syngas feed, for example a gasification step, and a purification step of the crude syngas feed to provide the second syngas feed 205; Or - A reverse water gas shift (rWGS) step of a part of the first CO2-rich feed (201) containing CO2 and a part of the first H2-rich feed 202 containing H2 for providing an rWGS syngas feed, preferably the same step in an electro-reverse water gas shift (e-rWGS) unit; then combining the rWGS syngas feed with the remainder of the first CO2-rich feed 201 containing CO2 and the first H2-rich feed 202 containing H2 to provide the second syngas feed 205; and optionally, supplying a part of the by-product streams 242, 242' rich in paraffin and / or olefin to the rWGS unit; comprises.

[0162] Therefore, the method does not include steam reforming for preparing the first or second syngas feed. Further, the method may be provided with a reverse water gas shift step in a reverse water gas shift unit (rWGS unit) for preparing the first or second syngas feed.

[0163] In one embodiment, up to 50% by volume, for example from 5 to 45%, for example from 15 to 45%, for example from 10 to 40% or from 20 to 40% of the inlet inflow of the methanol synthesis unit (220) is derived from the reformer-based syngas 41, 51, 53, 62. Thereby, in relation to the jet fuel synthesis plant embodiment, from 5 to 50%, for example from 5 to 45%, for example from 10 to 40%; or from 20 to 40%, or for example from 15 to 30% of the methanol-containing effluent stream 221 is obtained from the recycle stream, that is, from the by-product stream rich in paraffin and / or olefin and optionally from the offgas stream(s).

[0164] In one embodiment, the method further includes supplying at least a part of the methanol-containing effluent stream 221 to a methanol storage tank, and the methanol storage tank is installed between the methanol synthesis unit 220 and the MTJ synthesis section 230.

[0165] In one aspect, the MTJ synthesis section includes an MTO reactor provided with a conversion catalyst including a zeolite having a framework with a 10-membered ring pore structure, and the 10-membered ring pore structure is a one-dimensional (1D) pore structure. In one of the specific aspects, the 1D pore structure is any one of MRE (ZSM-48), MTT (ZSM-23), TON (ZSM-22), or a combination thereof.

[0166] In one aspect, the reformer-based syngas streams 41, 51, 53, 62 are the first, second, or third reformer-based syngas streams 41, 51, 53.

[0167] In one aspect, the method further - In the reforming section 100, at least a part of the reformer-based syngas stream as the first syngas stream 41 is supplied to the separation section 50 and separated into at least the second syngas stream 51 and the process condensate 52. including this.

[0168] In one aspect, at least a part of the by-product stream 1, 242, 232' rich in paraffin and / or olefin, optionally and at least a part of the one or more off-gas streams are supplied to the reforming system 100, and the step of subjecting to the reformer-based syngas streams 41, 51, 53, 62, for example, the first, second, or third syngas streams 41, 51, 53, is - Optionally, hydrogenating the first reforming feed stream 1 in the hydrogenation section 10 to provide a hydrogenated first reforming feed 11; - Optionally, desulfurizing the hydrogenated first reforming feed stream 11 in the desulfurization section 20 to provide a desulfurized first reforming feed stream 21; - Pre-reforming the first reforming feed stream 21 in the pre-reforming section 30 to provide a pre-reformed first reforming feed stream 31; - Performing the reforming step on the first reforming feed streams 1, 11, 21, 31 to provide the first syngas stream 41; including this.

[0169] In one aspect, the MTJ synthesis section 230 includes a methanol - to - olefins step (MTO step) in an MTO reactor, a subsequent oligomerization step (OLI step) in an OLI reactor, and a hydroprocessing step in a hydroprocessing reactor, such as a hydrogenation (HYDRO) step in a HYDRO reactor.

[0170] In one aspect, the MTJ synthesis section 230 includes a methanol - to - olefins step (MTO step) in an MTO reactor, a subsequent oligomerization step (OLI step) in an OLI reactor, and a hydrogenation step (HYDRO step) in a HYDRO reactor, and the method further - supplies a portion of the H2 - containing first H2 - rich feed 202 to the HYDRO step; and / or supplies an excess hydrogen stream from the methanol synthesis unit 220 to the HYDRO step; optionally and supplies a portion of the hydrogen - rich stream 61 from the hydrogen recovery section 60 of the reforming system 100 to the HYDRO step, including.

[0171] More specifically, in one embodiment, - the MTJ synthesis section 230 includes a methanol - to - olefins step (MTO step) in an MTO reactor, a subsequent oligomerization step (OLI step) in an OLI reactor, and a hydrogenation step (HYDRO step) in a HYDRO reactor, and the method further includes supplying a portion of the H2 - containing first H2 - rich feed 202 to the HYDRO step; and / or supplying an excess hydrogen stream 255 from the methanol synthesis unit 220, such as a portion of the excess hydrogen stream 255 from the methanol synthesis unit 220, to the HYDRO step; and / or - The upgrade section 240 includes a hydrocracking (HCR) step in the HCR reactor, and the method further includes supplying a portion of the H2-containing first H2-rich feed 202 to the HYDRO step and / or supplying a portion of the excess hydrogen stream 255 from the methanol synthesis unit 220, e.g., the excess hydrogen stream 255 from the methanol synthesis unit 220, to the HYDRO step.

[0172] In one embodiment, the paraffin- and / or olefin-rich by-product streams 242, 242' are streams containing at least 50%, e.g., at least 60%, or at least 75%, or at least 90% paraffins, including n- and i-paraffins, and any olefins; or the paraffin- and / or olefin-rich by-product streams 242, 242' are streams containing at least 50 wt%, e.g., at least 60 wt%, or at least 75 wt%, or at least 90 wt% olefins.

[0173] In one embodiment, the one or more offgas streams 253, 253' are one or more exhaust gas streams rich in CO2, H2, and CH4, and the method further includes supplying at least a portion of the one or more offgas streams 253, 253' to the reforming system 100.

[0174] In one embodiment, the methanol synthesis unit 220 provides an excess hydrogen stream 255, where the MTJ synthesis section 230 includes a methanol-to-olefins reactor (MTO reactor), an olefin reactor (OLI reactor), and a hydrogenation reactor (HYDRO reactor); and a portion of the H2-containing first or second H2-rich feed 202, 202'; and / or a portion of the excess hydrogen stream from the methanol synthesis unit 220, e.g., the excess hydrogen stream 255 from the methanol synthesis unit 220, is supplied to the HYDRO reactor.

[0175] More generally, in one aspect, the methanol synthesis unit 220 provides an excess hydrogen stream 255, where the MTJ synthesis section 230 includes a methanol-to-olefins reactor (MTO reactor), an olefins reactor (OLI reactor), and a hydroprocessing reactor (HYDRO reactor); and a portion of the H2-containing first or second H2-rich feed 202, 202'; and / or a portion of the excess hydrogen stream from the methanol synthesis unit 220, such as a portion of the excess hydrogen stream 255 from the methanol synthesis unit 220, is supplied to the HYDRO reactor.

[0176] In one aspect, the methanol synthesis unit 220 provides an excess hydrogen stream 255, and the optional upgrade section 240 includes an HCR reactor, where a portion of the H2-containing first or second H2-rich feed 202, 202'; and / or a portion of the excess hydrogen stream from the methanol synthesis unit 220, such as a portion of the excess hydrogen stream from the methanol synthesis unit 220, is supplied to the HCR reactor.

[0177] In one aspect, the methanol synthesis unit 220 provides an excess hydrogen stream (255), where a portion of the excess hydrogen stream from the methanol synthesis unit 220, such as a portion of the excess hydrogen stream 255 from the methanol synthesis unit 220, is supplied to the reforming system 100, preferably the reforming system 100 including the hydrogenation section 10; where the excess hydrogen stream 255 is supplied to the hydrogenation section 10.

[0178] It will be understood that all of the above aspects and attendant advantages associated with the jet fuel synthesis plant apply equally to the method and, accordingly, can also be used in connection with the corresponding aspects of the method, and vice versa. DETAILED DESCRIPTION OF THE INVENTION

[0179] Specific Embodiments FIG. 1 shows one layout of the reforming system 100. The first reforming feed stream 1 corresponding to the paraffin- and / or olefin-rich by-product streams 242, 242' in FIG. 2 is compressed in the first pump 69. It will also be understood that the first reforming feed stream 1 can also be provided as one or more offgas streams 253, 253'. The compressed first reforming feed stream is, in this layout, mixed with the hydrogen-rich stream 61 in the mixer 68 and then passes through the heat exchangers 64, 63 to exchange heat with the first syngas stream 41. The heated first reforming feed stream 1 is hydrogenated in the hydrogenation section 10 to provide the hydrogenated first reforming feed stream 11, which is then desulfurized in the desulfurization section 20 to provide the desulfurized first reforming feed stream 21. This desulfurized first reforming feed stream 21 may be mixed with the process steam 22, and this mixed stream is heat-exchanged with the first syngas stream 41 again. The desulfurized first reforming feed stream 21 is pre-reformed in the pre-reforming section 30 to provide the pre-reformed stream 31. The pre-reformed stream 31 is subjected to electro-steam methane reforming (e-SMR) in an electro-steam methane reformer (e-SMR, 40) to provide an e-SMR-based syngas stream, for example the first syngas stream 41. The power for the electro-steam methane reforming (e-SMR) is indicated by the "lightning" symbol. Next, the first syngas stream 41 is heat-exchanged with the boiler feed water 90 in the waste heat boiler 62 to provide the export stream 91. Thereafter, the first syngas stream 41 passes through the heat exchangers 64, 63 (as described above) and then is heat-exchanged with the boiler feed water 90 again in the heat exchanger 65. Additional cooling is performed in the cooling unit 66. The first e-SMR-based syngas stream 41 is sent to the separation section 50, where it is separated into at least a second e-SMR-based syngas stream 51 and a process condensate 52.

[0180] A portion of the second syngas stream 51 is optionally sent to a hydrogen recovery section 60 where a hydrogen-rich stream 61 is separated and a fourth e-SMR based syngas stream 62 is provided. A portion of the second e-SMR based syngas stream 51 and a portion of the third e-SMR based syngas stream 62 are combined to form an e-SMR based combined syngas stream, namely the third e-SMR based syngas stream 53. The hydrogen-rich stream 61 is compressed by a compressor 67 and then combined upstream of the hydrogenation section 10 with the first reforming feed stream 1 as described above.

[0181] Overall, in the system shown in FIG. 1, the paraffin-rich first feed, optionally and offgas stream to the reforming plant are hydrogenated, desulfurized and pre-reformed before being sent to the e-SMR. The effluent stream from the e-SMR (the first e-SMR based syngas stream) is cooled in a series of heat exchangers by preheating the pre-reformer feed, generating steam in the waste heat boiler, the feed preheater, the first feed vaporizer, preheating the boiler feed water, etc. The water in the effluent stream is condensed and then separated to provide the second e-SMR based syngas stream. Then, a portion of the e-SMR based syngas is used for H2 recovery for internal use for hydrogenation and pre-reforming or is used for the HYDRO reactor in the MTJ synthesis section. The remainder of the e-SMR based syngas is sent as the third e-SMR based syngas stream to the methanol synthesis unit as shown in FIG. 2.

[0182] Figure 2 shows a jet fuel synthesis plant 200 according to the present invention. The system 100 according to FIG. 1 is provided to enable recycling of the first reformed feed stream 1. In the plant 200 of FIG. 2, it will be understood that the streams 242, 242' correspond to the first reformed feed stream 1 in FIG. 1. It will also be understood that the first reformed feed stream 1 may also be provided as one or more offgas streams 253, 253'. The CO2-containing first CO2-rich feed 201 and the H2-containing first H2-rich feed 202 are combined together as the first syngas feed 209 as appropriate and then sent to the methanol synthesis unit 220 (methanol loop 220), from which a methanol-containing effluent stream 221 is provided. From the methanol loop 220, an offgas stream 253 is generated from a low-pressure separation unit (not shown) disposed therein as appropriate and supplied to the reforming system 100. This is the same for the other offgas stream 253' from the upgrade section 240. The methanol-containing effluent stream 221 is supplied to an MTJ synthesis section 230 including a methanol-to-olefin reactor (MTO reactor), an olefin reactor (OLI reactor), and a hydrogenation reactor (HYDRO reactor) (not shown), and a crude product 231 boiling in the jet fuel range, i.e., containing C8 to C19, for example C8 to C16, is provided. Optionally, a byproduct stream 242 rich in paraffin and / or olefin 242 is supplied from this MTJ section 230 between the OLI reactor and the HYDRO reactor and / or downstream of the HYDRO reactor to the reforming section 100. The upgrade section 240 may also provide a byproduct stream 242' rich in paraffin and / or olefin. The crude product 231, i.e., the crude jet fuel product, is supplied to the upgrade section 240, where it is upgraded to the jet fuel product stream 241 while optionally generating an offgas stream 253'. The byproduct streams 242, 242' rich in paraffin and / or olefin are supplied to the system 100 as described above and provided with a reformer-based stream, such as the third e-SMR-based syngas stream 53, which is then recycled to the methanol synthesis unit 220.From the reforming system 100, the first or second reformer-based stream, for example the first or second e-SMR-based syngas streams 41, 51, can also be recycled to the methanol synthesis unit 220 (not shown).

[0183] Reformer-based syngas, for example here the e-SMR-based syngas 41, 51, 53, is a minor syngas stream to the gasoline synthesis plant 200, more specifically the methanol synthesis unit 220, compared to the main syngas stream, i.e. the first syngas feed (resulting from the first CO2-rich feed 201 and the first H2-rich feed 202), or compared to a second syngas feed resulting from the combination of electrolysis of CO2 and water / steam as shown in FIG. 3, or for example compared to a second syngas feed also resulting from the pyrolysis of a biomass feedstock, i.e. a solid renewable feed. The reformer-based syngas 41, 51, 52, 53, 62 is in the range of less than 50% (volume-based), for example from 15 to 45%, for example from 20 to 40% of the first syngas feed. Compared to the prior art where the reforming system is provided with the main syngas stream to the gasoline synthesis plant and thus the syngas stream corresponding to the first or second syngas feed to the methanol synthesis unit, the present invention enables a significantly smaller reforming system 100 with significantly reduced plot size and associated capital and operating expenditures.

[0184] Figure 3 shows the gasoline synthesis plant 200 of FIG. 2, where a second syngas feed 205 is supplied to the methanol synthesis unit 220. The plant 200 includes an electrolysis unit 260 arranged to receive a water feedstock 203, i.e., steam and / or water, and a second H2-rich feed 202' containing H2 (optionally as the first H2-rich feed 202), as well as a first oxygen stream 206. The plant 200 further includes an electrolysis unit 250 arranged to receive a second CO2-rich feed 201' or the first CO2-rich feed 201 of FIG. 2 containing CO2 or a portion thereof, and to supply a CO-enriched feed stream 204 and a second oxygen stream 206'. Optionally, a portion of the second CO2-rich feed 201' may bypass the electrolysis unit 250 and be combined with the CO-enriched feed stream 204 (not shown). A mixing unit or a confluence point (not shown) combines the streams 202' and 204 to form a second syngas feed 205, which has a CO / CO2 molar ratio greater than 1, for example, a CO / CO2 molar ratio of 10 or more, enabling a more reactive syngas for methanol synthesis in the methanol synthesis unit 220. A mixing unit or a confluence point (not shown) combines a steam stream 207 with the first oxygen stream 206 and / or the second oxygen stream 206' to supply an oxidant stream 208, which may be supplied to the reforming system 100, where the reformer 40 is optionally an autothermal reformer (ATR). A third reformer-based syngas 53 is optionally mixed with the second syngas feed 205 to supply a more reactive methanol feed gas as an inlet to the methanol synthesis unit 220.

[0185] Figure 4 shows the jet fuel synthesis plant 200 of FIG. 2, further including an excess hydrogen stream 255. Therefore, the methanol synthesis unit 220 is arranged to supply the excess hydrogen stream 255, while the reforming system 100 appropriately includes the hydrogenation section 10 as shown in FIG. 1 and is further arranged to receive the excess hydrogen stream 255; therefore, the excess hydrogen stream 255 or a part thereof is supplied to the hydrogenation section 50. The excess hydrogen stream 255 may be supplied to the hydrogenation reactors in the plant, for example, the HYDRO reactor in the MTJ synthesis section 230 and / or the HCR reactor in the upgrade section 240 and / or the HYDRO reactor in the upgrade section 240 (not shown).

[0186] The present invention has been described with reference to several embodiments and figures. However, those skilled in the art can select and combine various embodiments within the scope of the present invention defined by the appended claims. All documents cited herein are assumed to have their contents as published herein.

Claims

Claim 1 A jet fuel synthesis plant (200), - The CO-containing to the plant ２ First CO ２ rich feed (201), the H-containing to the plant ２ First H ２ rich feed (202), or the first CO ２ rich feed (201) and the first H ２ rich feed (202) combined first single gas feed (209); or to the plant, a second single gas feed (205) containing carbon oxides and hydrogen; - the first CO ２ rich feed (201) and the first H ２ rich feed (202), or receives the first single gas feed (209), or receives the second single gas feed (205), and is arranged to provide a methanol-containing effluent stream (221), a methanol synthesis unit (220); - A methanol-jet fuel (MTJ) synthesis section (230) arranged to receive at least a portion of the methanol-containing effluent stream (221) and provide a crude product (231) containing hydrocarbons boiling in the jet fuel range; - Optionally, an upgrade section (240) arranged to receive at least a portion of the crude product (231) from the MTJ synthesis section (230) and provide a jet fuel product stream (241); provided that the optional upgrade section (240) includes a hydrocracking (HCR) reactor and / or a fractionation unit, thereby providing the jet fuel product stream (241); comprising - The MTJ synthesis section (230) and / or the optional upgrade section (240) are arranged to provide a by-product stream (242, 242') rich in paraffins and / or olefins; - The jet fuel synthesis plant (200) further includes a reforming system (100) for reforming the first by-product stream (242, 242') rich in paraffins and / or olefins, the reforming system (100) including a first reforming feed stream (1) as the by-product stream (242, 242') rich in paraffins and / or olefins; a reforming unit (reformer, 40) arranged to receive the by-product stream (1, 242, 242') rich in paraffins and / or olefins, perform a steam reforming step, and provide a reformer-based syngas stream (41, 51, 53, 62); - The jet fuel synthesis plant (200) is further arranged to supply at least a portion of the reformer-based syngas stream to the inlet of the methanol synthesis unit (220); - The jet fuel synthesis plant (200) does not include a reforming unit arranged upstream of the methanol synthesis unit (220) for providing the first (209) or second (205) syngas feed; the jet fuel synthesis plant (200). Claim 2 Is the reformer (40) in the reforming system (100) any one of a steam methane reformer (SMR), i.e., a tubular reformer, an electric steam methane reformer (e-SMR), an autothermal reformer (ATR), a convection heating reformer, and combinations thereof? Or is the reformer (40) in the reforming system (100) - An electric steam methane reformer (e-SMR) arranged alone or together with an upstream pre-reformer? Or is the reformer (40) in the reforming system (100) An autothermal reformer (ATR) arranged alone or together with an upstream pre-reformer, The jet fuel synthesis plant (200) according to claim 1.

3. The reforming system (100) is further arranged for the first reforming feed (1, 242, 242') of less than 15% by weight of the crude product (231) containing hydrocarbons boiling in the jet fuel range or less than 15% by weight of the jet fuel product stream (241). The jet fuel synthesis plant (200) according to claim 1 or 2.

4. The jet fuel synthesis plant (200) according to any one of claims 1 to 3, - An electrolysis section, A water supply raw material (203), i.e., steam and / or water, is received and (optionally, as the first H ２ first H ２ rich feed (202)) H ２ second H ２ rich feed (202'), or the electrolysis unit (260) arranged to supply a part of it as the first H ２ rich feed (202); and / or Second First CO ２ Rich feed (201'), or said CO-containing ２ First CO ２ An electrolysis unit (250) arranged to receive a rich feed (201), or a portion thereof, and to provide a CO-enriched feed (204); An electrolysis section including; - the H-containing ２ first or second H ２ means such as a mixing unit or a confluence point for supplying the second syngas feed (205) by combining the H-rich feed (202') with the CO-rich feed (204); Or - A pyrolysis unit arranged to receive a biomass feedstock and supply a crude syngas feed, and a crude syngas purification section arranged to receive the crude syngas feed and supply the second syngas feed (205); Or - the CO-containing ２ First CO ２ a portion of the rich feed (201) and the H-containing ２ First H ２ a reverse water gas shift (rWGS) unit, preferably an electric rWGS unit (e-rWGS), arranged to receive a portion of the rich feed (202) and to provide an rWGS singas feed; and means, such as a mixing unit or a confluence point, for combining the rWGS singas feed with the remainder of the CO-containing ２ First CO ２ rich feed (201) and the H-containing ２ First H ２ rich feed (202) to provide the second singas feed (205). The jet fuel synthesis plant (200) further comprising.

5. The jet fuel synthesis plant (200) according to claim 6, wherein the rWGS is also arranged to receive a part of the by-product stream (242, 242') rich in paraffin and / or olefin.

6. At least a part of the reformer base singas stream (41, 51, 53, 62) is the CO ２ rich feed (201) and / or the H ２ rich feed (202) and is mixed or is mixed with the first singas feed (209) or is mixed with the second (205) singas feed and is arranged to be supplied to the inlet of the methanol synthesis unit (220), the jet fuel synthesis plant (200) according to any one of claims 1 to 5.

7. A methanol storage tank is arranged between the methanol synthesis unit (220) and the MTJ synthesis section (230) to store at least a part of the methanol-containing effluent stream (221). The jet fuel synthesis plant (200) according to any one of claims 1 to 6.

8. The jet fuel synthesis plant (200) according to any one of claims 1 to 7, wherein the methanol synthesis unit (220) is arranged for a reformer-based syngas stream (41, 51, 53, 62) up to 50 volume-% at the inlet of the methanol synthesis unit (220), for example from 5 to 45%, for example from 15 to 45%, for example from 10 to 40% or from 20 to 40%.

9. The jet fuel synthesis plant (200) according to any one of claims 1 to 8, wherein the MTJ synthesis section (230) comprises a methanol-olefin reactor (MTO reactor) for supplying an olefin stream, an oligomerization reactor (OLI reactor) for supplying an oligomerized crude product stream, and a hydroprocessing reactor for supplying a crude product (231) containing hydrocarbons boiling in the jet fuel range.

10. The MTJ synthesis section (230) comprises a methanol-olefin reactor (MTO reactor) for supplying an olefin stream, an oligomerization reactor (OLI reactor) for supplying an oligomerized crude product stream, and a hydrogenation reactor (HYDR reactor) for supplying a crude product (231) containing hydrocarbons boiling in the jet fuel range; The MTJ synthesis section (230) further comprises - a separator arranged between the OLI reactor and the HYDRO reactor, which receives at least a part of the oligomerized crude product stream and then separates at least a part of the by-product stream (242) rich in paraffins and / or olefins; and / or a separator downstream of the HYDRO reactor, which receives at least a part of the crude product (231) containing hydrocarbons boiling in the jet fuel range and then separates at least a part of the by-product stream (242) rich in paraffins and / or olefins; The jet fuel synthesis plant (200) according to any one of claims 1 to 8, comprising.

11. The MTJ reactor of the MTJ section of the plant is provided with a conversion catalyst containing a zeolite having a framework with a 10-membered ring pore structure, the 10-membered ring pore structure being a one-dimensional (1D) pore structure; the 1D pore structure being any one of MRE (ZSM-48), MTT (ZSM-23), TON (ZSM-22), or a combination thereof, the jet fuel synthesis plant (200) according to any one of claims 1 to 10.

12. The by-product stream (242, 242') rich in paraffin and / or olefin is a stream containing at least 50%, such as at least 60%, or at least 75%, or at least 90% of paraffin, optionally including n- and i-paraffin, and optionally olefin; or the by-product stream (242, 242') rich in paraffin and / or olefin is a stream containing at least 50% by weight, such as at least 60% by weight, or at least 75% by weight, or at least 90% by weight of olefin, the jet fuel synthesis plant (200) according to any one of claims 1 to 11.

13. A jet fuel synthesis plant (200) according to any one of claims 1 to 12, arranged to supply one or more off-gas streams (253, 253'), wherein the one or more off-gas streams (253, 253') are CO ２ , H ２ , CH ４ -rich one or more exhaust gas streams, and the reforming system (100) is arranged to receive at least a portion of the one or more off-gas streams (253, 253'), said jet fuel synthesis plant (200).

14. The methanol synthesis unit (220) is arranged to supply an excess hydrogen stream (255), i.e., an excess hydrogen stream from the methanol synthesis unit (220); - The MTJ synthesis section (230) includes a methanol-to-olefins reactor (MTO reactor), an olefin reactor (OLI reactor), and a hydrogenation reactor (HYDRO reactor); and the HYDRO reactor receives a part of the H ２ rich feed (202, 202') of the first or second H ２ ; and / or is arranged to receive a part of the excess hydrogen stream from the methanol synthesis unit (220), for example, a part of the excess hydrogen stream (255) from the methanol synthesis unit (220); and / or - said at least one upgrade section (240) comprises an HCR reactor, and said HCR reactor receives a part of said first or second H-rich feed (202, 202') and / or a part of said excess hydrogen stream from said methanol synthesis unit (220), for example a part of said excess hydrogen stream (255) from said methanol synthesis unit (220); ２ first or second H ２ rich feed (202, 202') and / or a part of said excess hydrogen stream from said methanol synthesis unit (220), for example a part of said excess hydrogen stream (255) from said methanol synthesis unit (220); and / or the reforming system (100) is arranged to receive a part of the excess hydrogen stream from the methanol synthesis unit (220), for example, the excess hydrogen stream (255) from the methanol synthesis unit (220); preferably, the reforming system (100) includes a hydrogenation section (10), and the hydrogenation section (10) is arranged to receive the excess hydrogen stream (255). The jet fuel synthesis plant (200) according to any one of claims 1 to 13.

15. CO-containing ２ First CO ２ Rich feed (201) and H-containing ２ First H ２ Of the rich feed (202), or of the first syngas feed (209) combining the rich feed (201) and the first H ２ Rich feed (202); or a method for jet fuel synthesis of a second syngas feed (205) containing carbon oxides and hydrogen, the following steps: ２ ​ - A step of providing a jet fuel synthesis plant (200) according to any one of claims 1 to 14; -CO ２ Rich feed (201) and H ２ Supplying the rich feed (202), or the first single gas feed (209); or the second single gas feed (205) to a methanol synthesis unit (220), and providing a methanol-containing effluent stream (221); - A step of supplying at least a part of the methanol-containing effluent stream (221) from the methanol synthesis unit (220) to the methanol-jet fuel (MTJ) synthesis section (230) and providing a crude product (231) containing hydrocarbons boiling in the jet fuel range; - Feed at least a portion of the crude product (231) from the MTJ synthesis section (230) to an optional upgrading section (240) and subject it to a jet fuel product stream (241); the optional upgrading section (240) includes a hydrocracking (HCR) reactor and / or a fractionation unit, thereby subjecting the jet fuel product stream (241), step; - From the MTJ synthesis section (230) and / or an optional upgrading section (240), a by-product stream (242, 242') rich in paraffin and / or olefin; Optionally and one or more off-gas streams (253, 253'), for example, a second stream (253) from the methanol synthesis unit (220) and / or a second stream (253') from the optional upgrading section (240), step of taking out; - Feed at least a portion of the first reforming feed stream (1) as the by-product stream (242, 242') rich in paraffin and / or olefin, optionally and at least a portion of the one or more off-gas streams to a reforming system (100), perform a reforming step in a reforming unit (reformer, 40), and subject it to a reformer-based syngas stream (41, 51, 53, 62), for example, a first, second or third reformer-based syngas stream (41, 51, 53), step; - At least a part of the reformer-based singas stream (41, 51, 53, 62) is fed to the inlet of the methanol synthesis unit (220), preferably the CO ２ rich feed (201) and / or the H ２ rich feed (202) and mixed therewith, or mixed with the first singas feed; or mixed with the second singas feed (205) and supplied; comprising - The method does not include steam reforming of the hydrocarbon feed gas to provide the first (209) or the second syngas feed (205). The method.

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