WO2025170652A1 - Co-production de carburants à faible teneur en carbone durables à partir de co2 et h2 - Google Patents

Co-production de carburants à faible teneur en carbone durables à partir de co2 et h2

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Publication number
WO2025170652A1
WO2025170652A1 PCT/US2024/054060 US2024054060W WO2025170652A1 WO 2025170652 A1 WO2025170652 A1 WO 2025170652A1 US 2024054060 W US2024054060 W US 2024054060W WO 2025170652 A1 WO2025170652 A1 WO 2025170652A1
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WO
WIPO (PCT)
Prior art keywords
methanol
carbon
low
stream
fcc
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2024/054060
Other languages
English (en)
Inventor
Ahmad Khan
Vishvedeep Bhat
Tamour Javed
Md Ashraful Islam
Rashed Mohammad Aleisa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saudi Arabian Oil Co
Aramco Services Co
Original Assignee
Saudi Arabian Oil Co
Aramco Services Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US18/882,444 external-priority patent/US20250257018A1/en
Application filed by Saudi Arabian Oil Co, Aramco Services Co filed Critical Saudi Arabian Oil Co
Publication of WO2025170652A1 publication Critical patent/WO2025170652A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Processes with two or more reaction steps, of which at least one is catalytic, e.g. steam reforming and partial oxidation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/061—Methanol production
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series

Definitions

  • the present disclosure relates to processes and systems for producing low-carbon fuels and chemicals, and more specifically processes and systems for producing sustainable low-carbon methanol, fuels, and chemicals using co-feeds of low-carbon hydrogen (H2), captured carbon dioxide (CO2), or both to existing refinery processes.
  • H2 low-carbon hydrogen
  • CO2 captured carbon dioxide
  • E-fuel refers to a type of synthetic fuel made from renewable energy sources such as but not limited to wind, solar, hydropower, or combinations of these energy sources.
  • E-fuels, synthetic fuels, or both can be produced from carbon provided by carbon dioxide (CO2) or carbon monoxide (CO) captured from the atmosphere, biogenic, or point sources and hydrogen (H2) generated from renewable energy or low-carbon sources.
  • CO2 carbon dioxide
  • CO carbon monoxide
  • H2 hydrogen
  • low-carbon gasoline such as e-gasoline
  • CCh-to-Methanol and Methanol-to-Gasoline reactions Another route is CCh-to-Syngas followed by the Fischer-Tropsch reaction to produce low-carbon middle distillates, such as e-middle distillates.
  • CCh-to-Syngas followed by the Fischer-Tropsch reaction to produce low-carbon middle distillates, such as e-middle distillates.
  • Targeted low-carbon fuels and chemicals production is scalable, but economically challenging, as these processes require significant capital investment and high operational costs due to the handling requirements associated with the unconventional feedstocks.
  • H2 produced using low-carbon sources e.g., sources having low carbon number
  • renewable sources e.g., sources having low carbon number
  • captured CO2 e.g., captured CO2
  • H2 produced using low-carbon sources e.g., sources having low carbon number
  • renewable sources e.g., sources having low carbon number
  • captured CO2 e.g., captured CO2
  • sustainability credit from these alternative feedstocks will propagate further through the sequential products such as low-carbon methanol to low-carbon fuels and chemicals.
  • This novel pathway for the production of sustainable low-carbon fuels requires minimal investment to produce large volumes of products and achieves certifiable low-carbon fuels and chemicals without large capital investment.
  • a process for producing low-carbon methanol may comprise upgrading a natural gas stream in a methanol production unit to produce a methanol reactor effluent, wherein the methanol production unit comprises a syngas synthesis section and a methanol synthesis section downstream of the syngas synthesis section; and introducing a captured CO2 feed stream, a low-carbon hydrogen feed stream, or both to the syngas synthesis section or to a syngas stream downstream of the syngas synthesis section and upstream of a methanol reactor of the methanol synthesis section. At least a portion of the methanol reactor effluent comprises low-carbon methanol.
  • the low-carbon methanol comprises a portion of total methanol in the methanol reactor effluent that is attributed to the introducing the captured CO2 feed stream, the low-carbon hydrogen feed stream, or both to the methanol production unit based on a mass balance certification basis, an energy balance certification basis, or a trace-the-atom certification basis.
  • FIG. 2 schematically depicts a process for generating low-carbon methanol with cofeeding of low-carbon hydrogen and captured CO2 to a syngas synthesis section of the process of FIG. 1, according to embodiments shown and described in the present disclosure
  • FIG. 3 schematically depicts a process for generating low-carbon methanol with introduction of low-carbon hydrogen and captured CO2 to a syngas at a point upstream of a methanol reactor of the process of FIG. 1, according to embodiments shown and described in the present disclosure;
  • arrows in the drawings refer to process streams. However, the arrows may equivalently refer to transfer lines that may serve to transfer process steams between two or more system components. Additionally, arrows that connect to system components define inlets or outlets in each given system component. The arrow direction corresponds generally with the major direction of movement of the materials of the stream contained within the physical transfer line signified by the arrow. Furthermore, arrows that do not connect two or more system components signify a product stream which exits the depicted system or a system inlet stream which enters the depicted system. Product streams may be further processed in accompanying chemical processing systems or may be commercialized as end products.
  • System inlet streams may be streams transferred from accompanying chemical processing systems or may be non-processed feedstock streams. Some arrows may represent recycle streams, which are effluent streams of system components that are recycled back into the system. However, it should be understood that any represented recycle stream, in some embodiments, may be replaced by a system inlet stream of the same material, and that a portion of a recycle stream may exit the system as a system product.
  • the methods may further include recovering the FCC effluent 414 and certifying at least a portion of the FCC effluent 414 as low-carbon fuel and chemical components, wherein the low-carbon fuel and chemical components are the fuel and chemical components attributed to injection of the low-carbon oxygenate stream 402 to the FCC reactor 410 based on a mass balance certification basis, an energy balance certification basis, or a trace-the-atom certification basis.
  • the low-carbon oxygenate stream 402 may include the low-carbon methanol stream produced from the methanol production unit 10.
  • indication that one stream or effluent is passed or provided from one unit to another unit includes embodiments where the stream or effluent is passed directly from one unit to another unit as well as embodiments where there is an intervening system or unit which may substantially change the composition of the stream or effluent between the units.
  • passing a stream or effluent from one unit "directly” to another unit refers to passing the stream or effluent from the first unit to the second unit without passing the stream or effluent through an intervening reaction system or separation system that substantially changes the composition of the stream or effluent.
  • indication that two systems are "fluidly connected" indicates that streams may be passed directly between the systems.
  • streams may be named for the components of the stream, and the component for which the stream is named may be the major component of the stream (such as a component comprising from 50 weight percent (wt.%), from 70 wt.%, from 90 wt.%, from 95 wt.%, from 99 wt.%, from 99.5 wt.%, or even from 99.9 wt.% of the contents of the stream to 100 wt.% of the contents of the stream, notwithstanding any inert gases, carrier gases, or diluents purposely added to the stream).
  • components of a stream are disclosed as passing from one system component to another when a stream comprising that component is disclosed as passing from that system component to another.
  • a disclosed "hydrogen stream” passing to a first system component or from a first system component to a second system component should be understood to equivalently disclose “syngas” passing to the first system component or passing from a first system component to a second system component.
  • CI carbon intensity
  • the term “low-carbon” does not refer to the number of carbon atoms in a compound. When the number of carbon atoms is material to features herein, the actual number of carbon atoms will be explicitly stated, such as by stating that light olefins refer to olefins having 2-4 carbon atoms.
  • the term “e-fuel” refers to fuels or fuel components that are produced from reacting CO2 and green H2 produced from water electrolysis powered by renewable energy.
  • e-methanol refers to methanol that is produced from reacting CO2 and green H2 produced from water electrolysis powered by renewable energy. It is noted that all e-methanol is low-carbon methanol, but not all low-carbon methanol is e-methanol.
  • the modifier "low-carbon” in front of a species indicates that the species is produced from raw materials or by a process that represents a savings in greenhouse gas emissions over conventional fossil fuel sources and fossil fuel refining methods, whether or not the low-carbon species meets the specifications of certain sustainability standards.
  • the term “light olefins” refers to olefins having from 2-4 carbon atoms, such as ethylene, propylene, mixed butenes, and combinations thereof.
  • middle distillates refers to hydrocarbons having atmospheric boiling point temperatures of from 221 °C to 343 °C.
  • the processes and systems of the present disclosure provide a chemical process scheme for generating low-carbon fuels and chemicals.
  • the processes and systems of the present disclosure include introducing captured CO2, low-carbon H2, or both into existing methanol production units to produce low-carbon methanol, with further processing of this low-carbon methanol or other low-carbon oxygenates to produce more complex low-carbon fuels and chemicals such as gasoline, light olefins, or other compounds.
  • low-carbon methanol is produced in an existing conventional methanol production unit by introducing low-carbon H2, captured CO2, or both to the methanol production unit.
  • a natural gas (NG) stream 102 which is comprised of mainly methane, is passed as a feedstock to a syngas synthesis section 200 to produce a syngas 250 (e.g., a mixture of CO, CO2, H2, H2O, or combinations thereof) through various processes.
  • the syngas 250 is then passed to a methanol synthesis section 300 to produce conventional methanol 334.
  • the systems 100 and processes of the present disclosure include introducing a low carbon H2 feed stream 110, a captured CO2 feed stream 120, or both to the methanol production unit 10.
  • the low-carbon H2 feed stream 110 and the captured CO2 feed stream 120 may both be introduced to the methanol production unit 10 in a specific molar ratio of the low-carbon hydrogen to the captured CO2.
  • H2S hydrogen production from H2S splitting may be utilized to generate the low-carbon H2 in the low-carbon H2 feed stream 110.
  • H2S is generally a waste stream produced from different processes including oil and gas treatment. H2S can be efficiently conserved through the splitting of H2S to produce H2 and sulfur solid. The low-carbon nature of this hydrogen derived from splitting H2S is dependent on powering the H2S splitting process with clean energy and storing the physical sulfur generated.
  • Production of low-carbon methanol in accordance with the various systems and processes of the present disclosure may allow for utilization of existing methanol production units, which can be based on a variety of different processes.
  • conventional methanol production may be achieved in processing plants which utilize different reaction routes.
  • natural gas is processed to generate syngas which then may be synthesized into methanol in a methanol synthesis reactor, which is typically a fixed catalyst bed type of reactor.
  • the systems and process of the present disclosure include introducing the low-carbon H2 in the low-carbon H2 feed stream 110, the captured CO2 in the captured CO2 feed stream 120, or both as co-feeds to an existing feedstock, such as a natural gas stream, at various locations of an existing conventional methanol production unit.
  • an existing feedstock such as a natural gas stream
  • different locations to cofeed the low-carbon H2 and captured CO2 are envisioned within the scope of the present disclosure and the various embodiments.
  • the choice of the feeding location into the conventional methanol production process may depend on the original configuration of the plant, existing feedstock composition, the chosen operating conditions of the process units, or any combination of these considerations.
  • Any existing methanol production unit within a hydrocarbon production facility may be leveraged within the various embodiments of the processes and systems of the present disclosure for generating low-carbon methanol.
  • the systems and processes of the present disclosure will be described in the context of the existing methanol production unit 10 illustrated in FIG. 1.
  • the methanol production unit illustrated in FIG. 1 serves as the base methanol production unit which is leveraged and built upon in FIGS. 2, 3, and 4, but it will be appreciated that other types of methanol production units within a hydrocarbon production facility may be leveraged within the various embodiments by providing co-feeds in a substantially similar matter as disclosed in FIGS. 2, 3, and 4.
  • the natural gas stream 102 may also include small amounts of light hydrocarbon gases (ethane, propane, butane and other light hydrocarbon gases), light oxygenates such as methanol, carbon dioxide, nitrogen, hydrogen sulfide, helium, hydrogen, or other light gases that are naturally-occurring in subterranean natural gas sources.
  • light hydrocarbon gases ethane, propane, butane and other light hydrocarbon gases
  • light oxygenates such as methanol, carbon dioxide, nitrogen, hydrogen sulfide, helium, hydrogen, or other light gases that are naturally-occurring in subterranean natural gas sources.
  • the syngas stream 250 may then be passed from the secondary reformer 230 to the heat recovery unit 240 disposed downstream of the secondary reformer 230.
  • the heat recovery unit 240 may include one or more heat transfer devices configured to capture thermal energy from the syngas stream 250 exiting the secondary reformer 230 for beneficial energy reutilization.
  • the heat recovery unit 240 may recover heat from the syngas stream 250 before passing the syngas stream 250 downstream to the methanol synthesis section 300.
  • CO may react with water (H2O) in the methanol reactor 320 to produce CO2 and H2 according to Reaction 3.
  • the methanol reactor 320 may produce a methanol reactor effluent 322 comprising the methanol produced in the methanol reactor 320 along with any of the unreacted CO, CO2, and H2; water produced in the methanol reactor 320; and any constituents from the pressurized syngas stream 312 passing through the methanol reactor 320.
  • the methanol reactor effluent 322 may be passed from the methanol reactor 320 to the methanol purification unit 330 disposed downstream from the methanol reactor 320.
  • the methanol purification unit 330 may be configured to separate methanol from other products, unreacted species, or combinations thereof to produce a methanol product stream 331 and other constituents 336.
  • the other constituents 336 may be further separated into different streams, which may be either recycled back to the syngas synthesis section 200, recycled back to the methanol synthesis section 300, or otherwise processed outside of the methanol production unit 10.
  • each of the syngas compression unit 310, the methanol synthesis unit 320, and the methanol purification unit 330 are not discussed in significant detail as they represent units which one skilled in the art has extensive familiarity. Specifically, the generation of methanol from a feed of syngas may be in accordance with any processing scheme known to one skilled in the art and provided as existing units within a hydrocarbon processing facility.
  • the methanol production unit 10 of FIG. 1 may be used in a process to upgrade the natural gas stream 102 to methanol.
  • the process may include hydrodesulfurizing the natural gas stream 102 in the hydrodesulfurization unit 210 to produce the desulfurized natural gas stream 212; reforming the desulfurized natural gas stream 212 in the presence of steam 222 in the primary reformer 220 downstream of the hydrodesulfurization unit 210 to produce the primary reformer outlet stream 224; reforming the primary reformer outlet stream 224 in the presence of oxygen in the secondary reformer 230 downstream of the primary reformer 220 to produce the syngas stream 250 comprising at least CO2, CO, and H2; and converting the syngas stream 250 in the methanol reactor 320 disposed downstream of the secondary reformer 230 to produce the methanol reactor effluent 322.
  • the processes may further include compressing the syngas stream 250 in the syngas compression unit 310 upstream of the methanol reactor 320 to produce the pressurized syngas stream 312 and passing the press
  • low- carbon methanol 332 can be produced in the existing methanol production unit 10 by introducing the low-carbon H2 feed stream 110, the captured CO2 feed stream 120, or both to the existing methanol production unit 10 upstream of the methanol reactor 320.
  • the processes disclosed herein may include introducing the low-carbon H2 feed stream 110, the captured CO2 feed stream 120, or both to the syngas synthesis section 200 or to the syngas stream 250 downstream of the syngas synthesis section 200 and upstream of the methanol reactor 320 of the methanol synthesis section 300.
  • a portion of total methanol in the methanol reactor effluent 322 can be certified as low- carbon methanol 332.
  • the low-carbon H2 in the low-carbon H2 feed stream 110 and the carbon dioxide in the captured CO2 feed stream 120 may be fed into a reformer in the syngas synthesis section 200.
  • the low-carbon H2 in the low- carbon H2 feed stream 110 and the carbon dioxide in the captured CO2 feed stream 120 may be combined with the primary reformer outlet stream 224 of the primary reformer 220 and fed into the secondary reformer 230.
  • the low-carbon H2 feed stream 110 and the captured CO2 feed stream 120 may be passed separately and independently to the secondary reformer 230.
  • Feeding the low-carbon H2 and the captured CO2 into the secondary reformer 230 may generate CO and H2O through reaction of the H2 from the low-carbon H2 feed stream 110 and CO2 from the captured CO2 feed stream 120. Accordingly, the composition of the syngas stream 250 may be controlled by controlling the flow rates of the low-carbon H2 feed stream 110, the captured CO2 feed stream 120, or both. The syngas stream 250 may then be processed in the methanol synthesis section 300 to produce methanol.
  • the methanol stream 331 produced from the methanol synthesis section 300 includes both conventional methanol 334 and low-carbon methanol 332.
  • the low-carbon H2 feed stream 110 may be green hydrogen
  • the low-carbon methanol 332 may be certified as e- methanol.
  • the methanol reactor effluent 322 from the methanol reactor 320 may then be directed to the methanol purification unit 330 to separate the methanol product stream 331 from other constituents 336 of the methanol reactor effluent 322.
  • the methanol product stream 331 generated in the methanol synthesis section 300 includes both conventional methanol 334 and low-carbon methanol 332. At least a portion of the methanol product stream 331 may be certified as low-carbon methanol 332.
  • the process may include combining the low-carbon H2 feed stream 110, the captured CO2 feed stream 120, or both with the syngas stream 250 downstream of the secondary reformer 230 to produce a combined syngas stream 130; compressing the combined syngas stream 130 in the syngas compression unit 310 to produce a pressurized combined syngas stream; and passing the compressed combined syngas stream to the methanol synthesis reactor 320.
  • the low-carbon H2 feed stream 110 and the captured CO2 feed stream 120 may be introduced to the methanol production unit 10 at a molar ratio of the low-carbon H2 to the captured CO2 of from 2 to 5, from 2 to 4, from 2 to 3.5, from 2.5 to 5, from 2.5 to 4, from 2.5 to 3.5, from 3 to 5, from 3 to 4, from 3 to 3.5, or from 3.5 to 5.
  • the molar ratio of low-carbon H2 to captured CO2 is equal to the molar flow rate of low-carbon H2 from the low-carbon H2 feed stream 110 divided by the molar flow rate of captured CO2 from the captured CO2 feed stream 120.
  • the molar ratio of low-carbon H2 to captured CO2 in this paragraph does not include any of the H2 and CO2 in the primary reformer outlet stream 224 or syngas stream 250 that was present in the natural gas stream 102 or derived from constituents in the natural gas stream 102.
  • the low-carbon H2 feed stream 110 and the captured CO2 feed stream 120 may be introduced to the methanol production unit 10 at molar flow rates resulting in a mole percentage of the low-carbon feed components of from 0.01 mol% to 40 mol%, where the weight percentage of the low-carbon feed components is equal to the sum of the molar flow rates of the low-carbon H2 feed stream 110 and the captured CO2 feeds stream 120 divided by the total molar flow rate of the pressurized syngas stream 312 introduced to the methanol reactor 320.
  • the mole percentage of the low-carbon feed components (low-carbon H2 feed stream 110, the captured CO2 feeds stream 120, or both) introduced to the methanol production unit 10 may be from 0.01 mol% to 30 mol%, from 0.01 mol% to 20 mol%, from 0.01 mol% to 10 mol%, from 0.01 mol% to 5 mol%, from 0.1 mol% to 40 mol%, from 0.1 mol% to 30 mol%, from 0.1 mol% to 20 mol%, from 0.1 mol% to 10 mol%, from 0.1 mol% to 5 mol%, from 1 mol% to 40 mol%, from 1 mol% to 30 mol%, from 1 mol% to 20 mol%, from 1 mol% to 10 mol%, from 1 mol% to 5 mol%, from 5 mol% to 40 mol%, from 5 mol% to 30 mol%, from 5 mol% to 20 mol%, or from 5 mol% to 10 mol%
  • the captured CO2 feed stream 120 may be introduced to the methanol production unit 10, and a weight ratio of the natural gas stream 102 to the captured CO2 feed stream 120 introduced to the methanol production unit 10 may be from 0.01 to 40, such as from 0.1 to 30, from 1 to 20, from 10 to 15, or about 14.4.
  • the low-carbon H2 feed stream 110 may be introduced to the methanol production unit 10, and a weight ratio of the natural gas stream 102 to the low-carbon H2 feed stream 110 introduced to the methanol production unit 10 may be from 1 to 200, such as from 10 to 150, from 50 to 150, from 75 to 125, or about 105.
  • the low-carbon H2 in the low-carbon H2 feed stream 110 may be combined with the syngas stream 250 produced according to any scheme within the existing methanol production unit 10. It is noted that in accordance with the embodiments in FIG. 4, no captured CO2 feed stream 120 is provided to the methanol production unit 10. As previously discussed, the low-carbon H2 feed stream 110 may include green H2, blue H2, pink H2, turquoise H2, reduced carbon sustainable H2, H2 produced from H2S splitting, or combinations of these.
  • the low-carbon H2 in the low-carbon H2 feed stream 110 may be combined with the syngas stream 250 downstream of the heat recovery unit 240 and upstream of the syngas compression unit 310.
  • the combined stream 130 formed from the syngas stream 250 and the low-carbon H2 feed stream 110 may then be fed to the methanol synthesis section 300 of the existing methanol production unit 10.
  • the combined stream 130 may be fed into the syngas compression unit 310 to be pressurized to produce the pressurized syngas stream 312, which may be passed to the methanol reactor 320 to produce methanol.
  • the low-carbon H2 feed stream 110 may be combined with the pressurized syngas stream 312 downstream of the syngas compression unit 310 and upstream of the methanol reactor 320 to produce a pressurized combined stream.
  • the composition of the syngas stream 250 may be controlled.
  • the syngas stream 250 may then be processed in the methanol synthesis section 300 to generate methanol.
  • the low-carbon H2 in the low-carbon H2 feed stream 110 represents a sustainable feed which was utilized to produce a portion of the syngas stream 250 fed to the methanol synthesis section 300
  • the methanol generated in the methanol synthesis section 300 includes both conventional methanol 334 and low-carbon methanol 332, such as e-methanol.
  • the low-carbon H2 feed stream 110 may be introduced to the methanol production unit 10 in multiple locations.
  • a first portion of the low-carbon H2 feed stream 110 may be combined with the primary reformer outlet stream 224 upstream of the secondary reformer 230, and a second portion of the low-carbon H2 feed stream 110 may be combined with the syngas stream 250 downstream of the secondary reformer 230 and upstream of the methanol reactor 320, either before or after the syngas compression unit 310.
  • the methanol reactor 320 may produce the methanol reactor effluent 322, which may be separated in the methanol purification unit 330 to produce a methanol product stream 331 and a stream containing other constituents 336.
  • the methanol product stream 331 may include low-carbon methanol 332 and conventional methanol 334.
  • the low-carbon methanol 332 is the portion of the total methanol that is attributable to introduction of the low-carbon H2 feed stream 110, the captured CO2 feed stream 120, or both to the existing methanol production unit 10.
  • the conventional methanol 334 is the rest of the methanol presumed to be derived from the natural gas stream 102.
  • the low-carbon methanol 332 is the portion of the total methanol in the methanol product stream 331 that is attributed to introducing the captured CO2 feed stream 120, the low-carbon H2 feed stream 110, or both to the methanol production unit 10 based on a mass balance certification basis, an energy balance certification basis, a trace-the-atom certification basis, or other certification basis.
  • the low-carbon H2 feed stream 110 may be green H2 and the low-carbon methanol
  • heavy hydrocarbon fractions such as heavy gas oils, vacuum gas oils, atmospheric residues, or other heavy fractions are heated to operating temperatures greater than or equal to 315°C (600 °F), such as from 315 °C to 800 °C, from 400 °C to 700 °C, or from 480 °C to 550 °C, and then mixed with a catalyst in a fluidized catalytic cracking reactor.
  • the catalyst and heat break apart the larger hydrocarbon molecules into smaller hydrocarbon molecules, such as those that make up gasoline, middle distillates, olefins, and other greater-value products.
  • a low-carbon oxygenate stream such as the low-carbon methanol 332 produced from the methanol production unit 10, can be co-fed with a conventional FCC feed to an existing FCC unit to produce fuels and chemicals, at least a portion of which can be certified as low-carbon fuels and chemical based on a mass certification basis, an energy certification basis, a trace-the-atom certification basis, other certification basis, or combinations thereof.
  • the FCC unit 400 may include an FCC reactor 410, a catalyst separation section 413 at a downstream end of the FCC reactor 410, an FCC effluent separation unit 420, and a catalyst regenerator 430.
  • the FCC reactor 410 may be a riser reactor, as shown in FIG. 5.
  • the FCC reactor 410 may be a downer reactor.
  • the conventional FCC feed 405 may be introduced to the inlet end 411 of the FCC reactor 410 along with an FCC catalyst, such as the regenerated FCC catalyst 434.
  • the FCC catalyst may include fresh FCC catalyst in addition to or in place of the regenerated FCC catalyst 434.
  • a fluidization gas 406 may be introduced to the inlet end 411 of the FCC reactor 410 to facilitate fluidization of the FCC catalyst.
  • the FCC catalyst and the conventional FCC feed 405 may intermix at the inlet end 411 of the FCC reactor 410 and may flow together through the FCC reactor 410 from the inlet end 411 to the outlet end 412 of the FCC reactor 410.
  • the FCC reactor 410 may be operated at a temperature sufficient to cause catalytic cracking of hydrocarbons from the conventional FCC feed 405 to produce fuels and chemicals.
  • the FCC reactor 410 may be operated at a temperature of from 315 °C to 800 °C, such as from 400 °C to 750 °C, from 400 °C to 700 °C, from 450 °C to 700 °C, from 500 °C to 650 °C, from 480 °C to 550 °C, or any range or subrange therein.
  • Fuels may refer to hydrocarbons that are useful as fuel blending components. Chemicals may refer to chemical intermediates having value as intermediates in the production of other chemical products or plastics. Chemicals may include but are not limited to light olefins (C2-C4 olefins), light aromatic compounds (C6-C8 aromatic compounds such as but not limited to benzene, toluene, xylenes, or others), or other chemicals, or combinations thereof.
  • C2-C4 olefins light aromatic compounds
  • C6-C8 aromatic compounds such as but not limited to benzene, toluene, xylenes, or others
  • the greater value fuels, chemicals, or both may include fuel gas (methane), light petroleum gases (propane, butane, isobutane, etc.), light olefins (propylene, ethylene, mixed butenes), light aromatic compounds (benzene, toluene, xylenes, ethylbenzene, or other C6-C8 aromatic compounds), gasoline (boiling point temperatures of from 30 °C to 225 °C), cycle oils (boiling point temperature range of from 225 °C to 400 °C), or combinations thereof.
  • fuel gas methane
  • light petroleum gases propane, butane, isobutane, etc.
  • light olefins propylene, ethylene, mixed butenes
  • light aromatic compounds benzene, toluene, xylenes, ethylbenzene, or other C6-C8 aromatic compounds
  • gasoline boiling point temperatures of from 30 °C to
  • the used FCC catalyst 416 may be passed to the catalyst regenerator 430, which may be operable to regenerate the used FCC catalyst 416 to produce the regenerated catalyst 434.
  • the processes disclosed herein may include regenerating the used FCC catalyst 416 in the catalyst regenerator 430 to produce the regenerated FCC catalyst 434.
  • the used FCC catalyst 416 may be regenerated in the catalyst regenerator 430 according to any method and system known to those skilled in the art. Regenerating the used FCC catalyst 416 may include removing coke deposits from the used FCC catalyst 416, heating the used FCC catalyst 416 to a temperature greater than or equal to the operating temperature of the FCC reactor 410, or combinations thereof.
  • the FCC catalyst may include any known or future developed FCC catalyst suitable for use in the FCC reactor 410.
  • the catalyst may be a heat carrier and may provide heat transfer to the hydrocarbons in the FCC reactor 410.
  • the catalyst may also have a plurality of catalytically active sites, such as acidic sites for example, that promote cracking reactions.
  • Examples of FCC catalysts suitable for use in the FCC reactor 410 may include, without limitation, zeolites, silica- alumina catalysts, carbon monoxide burning promoter additives, bottoms cracking additives, light olefin-producing additives, other catalyst additives, or combinations of these components.
  • Zeolites may include, but are not limited to, Y zeolite, REY zeolites, USY zeolites, RE-USY zeolites, beta zeolites, or combinations of these.
  • the FCC catalyst may also include a shape- selective catalyst additive, such as but not limited to ZSM-5 zeolites or other pentasil-type catalyst structures, which are often used in FCC processes to produce light olefins and/or increase FCC gasoline octane.
  • the FCC catalyst may include one or more zeolite components in combination with clays, alumina, binders, or combinations of these.
  • the FCC catalysts may be formed into pellets through extrusion, calcining, and sizing.
  • the FCC effluent 414 may be passed from the catalyst separation section 413 to the FCC effluent separation unit 420.
  • the FCC effluent separation unit 420 may include one or a plurality of separation units operable to separate the FCC effluent 414 into one or more product streams 421 comprising the greater value fuels and chemicals.
  • the FCC effluent separation unit 420 may be operable to further produce a light gas stream 426, a bottom stream 428, or both.
  • the light gas stream 426 may include methane, ethane, hydrogen, or other light gases produced in the FCC reactor 410 and may be a fuel gas stream, which can be combusted to produce heat in one or more other refinery systems.
  • a low-carbon oxygenate stream 402 may be co-fed to the FCC reactor 410 along with the conventional FCC feed 405.
  • the low-carbon oxygenate stream 402 may include the low-carbon methanol 332 produced from the methanol production unit 10 through introduction of the low-carbon H2 feed stream 110, the captured CO2 stream 120, or both to the methanol production unit 10.
  • the low-carbon oxygenate stream 402 may include low-carbon oxygenates produced from other sources, such as but not limited to biogenic oxygenates.
  • biogenic oxygenates refer to oxygenates produced from biological materials, such as plant matter or waste organic matter.
  • the biogenic oxygenates can include but are not limited to bio-methanol, bioethanol, bio-dimethyl ether, other bio oxygenate, or combinations of these bio-oxygenates.
  • the low-carbon oxygenate stream 402 may include a combination of the low-carbon methanol 332 and one or more biogenic oxygenate streams.
  • the processes disclosed herein may include co-feeding of biogenic oxygenates, such as but not limited to bio-methanol, bio-ethanol, bio-dimethyl ether, or combinations of these, with the conventional FCC feeds 405 in the FCC unit 400 to produce low-carbon fuels or olefins.
  • Any existing FCC unit 400 or dual FCC reactor system 500 within an existing hydrocarbon production facility may be leveraged within the various embodiments of the processes and systems for generating low-carbon fuels and chemicals.
  • example FCC unit 400 is illustrated in FIG. 5
  • example dual FCC reactor system 500 is illustrated in FIG. 6. It will be appreciated that other styles of existing FCC units and configurations of the existing FCC units within a hydrocarbon production facility may be leveraged within the various embodiments by providing co-feeds in a substantially similar manner as described in relation to FIGS. 5 and 6.
  • a fifth aspect of the present disclosure may include any one of the first through fourth aspects, wherein a weight ratio of the natural gas stream to the captured CO2 feed stream introduced to the methanol production unit is from 0.1 to 40.
  • a fourteenth aspect of the present disclosure may include any one of the ninth through thirteenth aspects, comprising introducing the captured CO2 feed stream, the low-carbon hydrogen feed stream, or both to the methanol production unit downstream of the secondary reformer.
  • a nineteenth aspect of the present disclosure may include the eighteenth aspect, wherein a first portion of the low-carbon H2 feed stream is combined with the primary reformer outlet stream upstream of the secondary reformer, and a second portion of the low-carbon H2 feed stream is combined with the syngas stream downstream of the secondary reformer and upstream of the methanol reactor.
  • a twenty-first aspect of the present disclosure may include any one of the first through twentieth aspects, further comprising purifying the methanol reactor effluent in a methanol purification unit downstream of the methanol reactor to produce a methanol stream comprising the low-carbon methanol and the conventional methanol.
  • a twenty-second aspect of the present disclosure may include any one of the first through twenty-first aspects, wherein a proportion of the low-carbon methanol in the methanol stream may be from 0.01 wt% to 40 wt% based on total mass of methanol in the methanol stream.
  • a thirtieth aspect of the present disclosure may include either one of the twenty-eighth or twenty-ninth aspects, where the FCC catalyst may comprise a primary FCC catalyst and an FCC additive.
  • the low-carbon methanol comprises the portion of the total methanol that is attributed to the introducing the low-carbon hydrogen feed stream to the methanol production unit based on a mass balance certification basis, an energy balance certification basis, or a trace-the-atom certification basis.
  • the process may further include passing the low-carbon methanol to an FCC unit; catalytically cracking a conventional FCC feed stream with an FCC catalyst in an FCC reactor to produce an FCC effluent comprising fuel and chemical components; injecting the low-carbon methanol into the FCC reactor; recovering the FCC effluent; and certifying at least a portion of the FCC effluent as low-carbon fuel and chemical components, wherein the low-carbon fuel and chemical components are the fuel and chemical components attributed to injection of the low- carbon methanol to the FCC reactor based on a mass balance certification basis, an energy balance certification basis, or a trace-the-atom certification basis.
  • a forty-second aspect of the present disclosure may be directed to a process for producing sustainable fuel and chemical components through fluidized catalytic cracking (FCC), the process comprising: catalytically cracking a conventional FCC feed with an FCC catalyst in an FCC reactor to produce an FCC effluent comprising fuel and chemical components; injecting a low-carbon oxygenate stream into the FCC reactor, wherein the low-carbon oxygenate stream comprises oxygenate compounds produced from sustainable sources using captured CO2, low- carbon hydrogen sources, biologic sources, or combinations thereof; recovering the FCC effluent; and certifying at least a portion of the FCC effluent as low-carbon fuel and chemical components, wherein the low-carbon fuel and chemical components are the fuel and chemical components attributed to injection of the low-carbon oxygenate stream to the FCC reactor based on a mass balance certification basis, an energy balance certification basis, or a trace-the-atom certification basis.
  • FCC fluidized catalytic cracking

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Abstract

L'invention concerne un procédé de production de méthanol à faible teneur en carbone qui comprend la valorisation d'un flux de gaz naturel dans une unité de production de méthanol pour produire un effluent de réacteur de méthanol et l'introduction d'un flux d'alimentation de CO2 capturé, d'un flux d'alimentation d'hydrogène à faible teneur en carbone, ou à la fois d'une section de synthèse de gaz de synthèse ou d'un flux de gaz de synthèse en aval de la section de synthèse de gaz de synthèse et en amont d'un réacteur de méthanol d'une section de synthèse de méthanol. Au moins une partie de l'effluent de réacteur de méthanol comprend du méthanol à faible teneur en carbone. Le méthanol à faible teneur en carbone est une partie du méthanol total dans l'effluent de réacteur de méthanol qui est attribué à l'introduction du flux d'alimentation de CO2 capturé, du flux d'alimentation d'hydrogène à faible teneur en carbone, ou des deux à l'unité de production de méthanol sur la base d'une certification fondée sur un bilan massique, un bilan énergétique ou une traçabilité atomique. Le méthanol à faible teneur en carbone peut être utilisé dans un système FCC pour produire des carburants et des produits chimiques à faible teneur en carbone.
PCT/US2024/054060 2024-02-09 2024-11-01 Co-production de carburants à faible teneur en carbone durables à partir de co2 et h2 Pending WO2025170652A1 (fr)

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US18/882,444 US20250257018A1 (en) 2024-02-09 2024-09-11 Co-production of sustainable low-carbon fuels from co2 and h2
US18/882,444 2024-09-11

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1277721A2 (fr) * 2001-07-19 2003-01-22 Mitsubishi Heavy Industries, Ltd. Procédé de préparation du méthanol
US20070299144A1 (en) * 2004-03-22 2007-12-27 William Davey Coproduction Of Methanol And Ammonia From Natural Gas
WO2010118127A1 (fr) * 2009-04-10 2010-10-14 University Of Southern California Transformation du charbon en carburant neutre vis-à-vis de l'environnement en ce qui concerne le dioxyde de carbone et source régénérative de carbone
US9315452B2 (en) * 2011-09-08 2016-04-19 Expander Energy Inc. Process for co-producing commercially valuable products from byproducts of fischer-tropsch process for hydrocarbon fuel formulation in a GTL environment
US11130718B2 (en) * 2019-06-24 2021-09-28 Exxonmobil Research And Engineering Company Oxygenate conversion for distillate fuel production
US20210363007A1 (en) * 2018-09-04 2021-11-25 Basf Se Method for producing methanol from synthesis gas without the emission of carbon dioxide
WO2022232896A1 (fr) * 2021-05-04 2022-11-10 Karen Sue Kelly Déplacement de carbone dans des combustibles fossiles avec du carbone du dioxyde de carbone
WO2022248434A1 (fr) * 2021-05-28 2022-12-01 Topsoe A/S Méthanol bleu
US20230061332A1 (en) * 2021-08-27 2023-03-02 L'Air Liquide, Société Anonyme pour Etude et Exploitation des Procaédés Georges Claude Method for co-production of decarbonized methanol and ammonia
EP3658493B1 (fr) * 2017-07-25 2023-08-30 Topsoe A/S Procédé pour la coproduction de méthanol et d'ammoniac

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1277721A2 (fr) * 2001-07-19 2003-01-22 Mitsubishi Heavy Industries, Ltd. Procédé de préparation du méthanol
US20070299144A1 (en) * 2004-03-22 2007-12-27 William Davey Coproduction Of Methanol And Ammonia From Natural Gas
WO2010118127A1 (fr) * 2009-04-10 2010-10-14 University Of Southern California Transformation du charbon en carburant neutre vis-à-vis de l'environnement en ce qui concerne le dioxyde de carbone et source régénérative de carbone
US9315452B2 (en) * 2011-09-08 2016-04-19 Expander Energy Inc. Process for co-producing commercially valuable products from byproducts of fischer-tropsch process for hydrocarbon fuel formulation in a GTL environment
EP3658493B1 (fr) * 2017-07-25 2023-08-30 Topsoe A/S Procédé pour la coproduction de méthanol et d'ammoniac
US20210363007A1 (en) * 2018-09-04 2021-11-25 Basf Se Method for producing methanol from synthesis gas without the emission of carbon dioxide
US11130718B2 (en) * 2019-06-24 2021-09-28 Exxonmobil Research And Engineering Company Oxygenate conversion for distillate fuel production
WO2022232896A1 (fr) * 2021-05-04 2022-11-10 Karen Sue Kelly Déplacement de carbone dans des combustibles fossiles avec du carbone du dioxyde de carbone
WO2022248434A1 (fr) * 2021-05-28 2022-12-01 Topsoe A/S Méthanol bleu
US20230061332A1 (en) * 2021-08-27 2023-03-02 L'Air Liquide, Société Anonyme pour Etude et Exploitation des Procaédés Georges Claude Method for co-production of decarbonized methanol and ammonia

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