WO2022226230A1 - Production d'ammoniac, de méthanol et de produits de synthèse à partir d'un ou plusieurs produits de gazéification - Google Patents

Production d'ammoniac, de méthanol et de produits de synthèse à partir d'un ou plusieurs produits de gazéification Download PDF

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Publication number
WO2022226230A1
WO2022226230A1 PCT/US2022/025825 US2022025825W WO2022226230A1 WO 2022226230 A1 WO2022226230 A1 WO 2022226230A1 US 2022025825 W US2022025825 W US 2022025825W WO 2022226230 A1 WO2022226230 A1 WO 2022226230A1
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Prior art keywords
product
produce
unit
syngas
hydrogen
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PCT/US2022/025825
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English (en)
Inventor
Ravi Ravikumar
Sunil Singhal
Soumya Jyoti CHOUDHURY
Kakul SINGH
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Fluor Technologies Corporation
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Priority claimed from US17/725,296 external-priority patent/US20220340419A1/en
Application filed by Fluor Technologies Corporation filed Critical Fluor Technologies Corporation
Priority to AU2022262626A priority Critical patent/AU2022262626A1/en
Priority to CA3215768A priority patent/CA3215768A1/fr
Priority to EP22722938.2A priority patent/EP4326839A1/fr
Publication of WO2022226230A1 publication Critical patent/WO2022226230A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/005—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0956—Air or oxygen enriched air
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0959—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
    • C10J2300/1618—Modification of synthesis gas composition, e.g. to meet some criteria
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1662—Conversion of synthesis gas to chemicals to methane (SNG)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1665—Conversion of synthesis gas to chemicals to alcohols, e.g. methanol or ethanol
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1668—Conversion of synthesis gas to chemicals to urea; to ammonia
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1684—Integration of gasification processes with another plant or parts within the plant with electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/169—Integration of gasification processes with another plant or parts within the plant with water treatments
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807—Recycle loops, e.g. gas, solids, heating medium, water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the present disclosure relates to the production of one or more of ammonia, methanol, Fischer Tropsch products, and derivatives thereof.
  • Biomass and municipal solid waste (MSW) are growing problems because disposal thereof, whether by burning, incineration, or placing in landfills, results in significant sources of carbon dioxide and methane emissions.
  • MSW Municipal solid waste
  • FIG. 1 illustrates a process and system for producing green ammonia from biomass and water.
  • FIG. 2 illustrates a process and system for producing green urea and derivatives from biomass and water.
  • FIG. 3 illustrates a process and system for producing green methanol and derivatives from biomass and water.
  • FIG. 4 illustrates a process and system for producing green hydrocarbon products from biomass and water.
  • each embodiment may represent a single combination of disclosed elements, the disclosed subject matter is considered to include all possible combinations of the disclosed elements. Thus, if one embodiment comprises elements A, B, and C, and a second embodiment comprises elements B and D, then the disclosed subject matter is also considered to include other remaining combinations of A, B, C, or D, even if not explicitly disclosed.
  • the terms “comprise,” “comprises,” “comprising,” or any other variations thereof, are intended to cover a non-exclusive inclusion, such that a process or method that comprises a list of steps does not include only those steps but may include other steps not expressly listed or inherent to such process or method.
  • one or more devices or sub-systems or elements or structures preceded by “comprises Brook a” does not, without more constraints, preclude the existence of other devices or other sub-systems or other elements or other structures or additional devices or additional sub-systems or additional elements or additional structures.
  • a “splitter” can be embodied as a joint having three flow openings: an inlet opening for receiving the flow of fluid, and two outlet openings for flowing fluid out of the splitter, where the received fluid flow is split into two separate flow portions within the splitter.
  • the diameter of the two outlet openings can be appropriately sized to facilitate the desired flow or “split percentage” disclosed herein; or in alternative aspects, within the scope of “splitter” as used herein is equipment, such as valving and instrumentation, that can control the flow of fluid through each outlet opening to achieve a “split percentage” that is disclosed herein.
  • a “combiner” refers to a joint of conduit or pipe that functions to combine the flow of two streams, lines, conduits, or pipe into one stream, line, conduit, or pipes.
  • a “combiner” can be embodied as a joint having three flow openings: two inlet openings for receiving the flow of fluid, and one outlet opening for flowing fluid out of the combiner, where the received fluid flow is combined into a single stream, line, conduit, or pipe.
  • Disclosed herein is a process for using biomass and/or a municipal solid water gasification system in combination with water electrolysis to produce various products such as green ammonia, green methanol, green derivatives of ammonia and methanol, and various green Fischer Tropsch products such as diesel, jet fuel, lubrication oils and greases, and waxes.
  • the products may be considered green by using renewable power as the electricity source in the electrolysis unit to produce oxygen and hydrogen.
  • the resulting oxygen and hydrogen can then be used in separate portions of the system to generate the products.
  • the oxygen can be used in the gasification unit to avoid the need for an air separation unit to otherwise generate oxygen.
  • Such a system and methods allow for the use of biomass to produce value added products that are green and avoid placing the biomass and waste into a landfill while also avoiding associated carbon dioxide and methane generation in various landfill applications.
  • the ability to produce products such as ammonia and/or urea may also allow the use of the products in fuel cells.
  • Each process and system described herein produces a green product because the feed to the gasification unit 110 may be biomass and/or municipal waste 1 and the electrolysis unit 120 may be powered at least partially, and optionally wholly, by renewable power 126, such as solar, wind, or geothermal.
  • each process and system can remove carbon dioxide to produce a C02 product 11 that can be sequestered, stored, used (e.g., in secondary hydrocarbon recovery or as described herein), or a combination thereof.
  • the gasification unit 110 can be embodied as one or more vessels in plasma configuration, a fixed-bed configuration, or a fluidized-bed configuration that are configured to gasify biomass in the presence of oxygen (and optionally nitrogen via air supply) to produce syngas.
  • Various configurations for gasification unit 110 are known in the art with the aid of this disclosure.
  • the electrolysis unit 120 can be embodied as one or more vessels having a cathode and anode therein that are configured to receive water and use electricity to decompose water molecules into hydrogen and oxygen gas. Configurations for electrolysis 120 are known in the art with the aid of this disclosure.
  • Each process and system described herein includes a gasification unit 110 and an electrolysis unit 120 coupled to the gasification unit 110.
  • the gasification unit 110 may be coupled to the electrolysis unit 120 to receive an oxygen product 3 from the electrolysis unit 120 so that oxygen product 3 be used in the gasification process.
  • the electrolysis unit 120 can be coupled to renewable energy source 125 and to the gasification unit 110 so that the oxygen product 3, made by electrolysis of water in the electrolysis unit 120 with electricity supply from the renewable energy source 125, can be used in the gasification process.
  • the hydrogen product 14 produced by the electrolysis unit 120 can be combined with a treated syngas stream that may be downstream of the gasification unit 110 (e.g., a treated gasification product 12 in FIGS.
  • a treated gasification product 10A in FIGS. 3 and 4 to enrich the syngas with hydrogen and to form a synthesis feed stream (stream 16 in FIGS. 1 and 2; stream 101 in FIGS. 3 and 4) that may be suitable as a feed to a synthesis unit configured to produce ammonia, methanol, or Fischer Tropsch products.
  • a portion of the hydrogen product 14 can also be fed to an upgrading unit for upgrading the Fischer Tropsch products (described in more detail for FIG. 4).
  • the process and system 100 in FIG. 1 feeds a biomass 1, air 2, and oxygen product 3 to the gasification unit 110 to produce an unshifted syngas 4.
  • the unshifted syngas 4 can include hydrogen, carbon monoxide, and optionally: carbon dioxide, methane (e.g., unreacted methane, unreformed methane), sulfur-containing compounds in case of passivated reformer catalyst (e.g., hydrogen sulfide, carbon sulfide, carbonyl sulfide, carbon disulfide, organic sulfur compounds, etc.), chlorides, steam, or a combination thereof.
  • the unshifted syngas 4 can be characterized by a molar ratio of hydrogen to carbon monoxide of from about 1.7:1 to about 2.5:1, alternatively from about 1.8:1 to about 2.3:1, or alternatively from about 1.9:1 to about 2.1:1, for example if a reformer including a sulfur passivated nickel-based catalyst may be used, such as a new reformer.
  • the unshifted syngas 4 can have a molar ratio of hydrogen to carbon monoxide of about 2:1.
  • the unshifted syngas 4 can be characterized by a molar ratio of hydrogen to carbon monoxide of from about 3:1 to about 4:1, for example if a reformer comprising a sulfur sensitive nickel-based catalyst may be used, such as an existing reformer.
  • the unshifted syngas 4 can include carbon dioxide in an amount of less than about 20 mole % (mol%), alternatively less than about 10 mol%, or alternatively less than about 5 mol%, for example if a reformer including a sulfur passivated nickel-based catalyst may be used, such as a new reformer. In other embodiments, the unshifted syngas 4 can include carbon dioxide in an amount of less than about 50 mol%, for example if a reformer including a sulfur sensitive nickel -based catalyst may be used, such as an existing reformer (e.g., conventional reformer).
  • the unshifted syngas 4 can include methane (e.g., unreacted methane, unreformed methane) in an amount of less than about 5 mol%, alternatively less than about 2.5 mol%, alternatively less than about 2 mol%, or alternatively less than about 1 mol%.
  • methane e.g., unreacted methane, unreformed methane
  • the unshifted syngas 4 can include sulfur-containing compounds in an amount of less than about 1 parts per million volume (ppmv).
  • ppmv parts per million volume
  • the unshifted syngas 4 can have a pressure of from about 5 pounds per square inch gauge (psig) to about 50 psig, for example if a reformer including a sulfur passivated nickel-based catalyst may be used, such as a new reformer. In other embodiments, the unshifted syngas 4 can have a pressure of from about 300 psig to about 500 psig, for example if a reformer including a sulfur sensitive nickel-based catalyst may be used, such as an existing reformer.
  • psig pounds per square inch gauge
  • the process can further include introducing the unshifted syngas (e.g., via the stream 4) to a water gas shift unit 140 to produce a shifted syngas (e.g., in the stream 5).
  • the shifted syngas 5 comprises hydrogen, carbon monoxide, and carbon dioxide.
  • the molar ratio of hydrogen to carbon monoxide in the unshifted syngas 4 can be increased (e.g., adjusted) by introducing the unshifted syngas 4 to a water gas shift unit 140 comprising a sour shift catalyst to convert carbon monoxide and water into additional hydrogen and carbon dioxide according to the general reaction CO + H20 ⁇ H2 + C02, also known as the water-gas shift (WGS) reaction.
  • WGS water-gas shift
  • the WGS reaction can be conducted in the presence of a variety of sour shift catalysts at a WGS reaction temperature of from about 204.4 °C to about 482.2 °C, alternatively from about 232.2 °C to about 454.5 °C, or alternatively from about 260 °C to about 426.7 °C.
  • the WGS reaction does not change the total number of moles (e.g., two moles of products are produced from two moles of reactants), and as such an effect of pressure on the WGS reaction may be minimal.
  • the equilibrium of the WGS reaction can be shifted towards hydrogen production in the presence of high moisture content.
  • the unshifted syngas 4 can be heated to a temperature that may be greater than a syngas moisture saturation temperature by from about 11.1 °C to about 41.7 °C, alternatively from about 13.8 °C to about 33.3 °C, or alternatively from about 16.6 °C to about 27.8 °C, prior to introducing the unshifted syngas 4 to the water gas shift unit 140.
  • the syngas moisture saturation temperature can be from about 176.6 °C to about 260 °C, depending on the unshifted syngas 4 composition and process conditions for producing the unshifted syngas 4.
  • the water gas shift unit 140 can comprise any suitable reactor, such as for example a fixed bed reactor, an adiabatic reactor, a radial reactor, and the like, or combinations thereof.
  • a water gas shift reactor can comprise a catalyst bed comprising a sour shift catalyst in sulfur that may be present in the feed syngas.
  • the water gas shift unit 140 can be a multi-stage unit, for example the water gas shift unit 140 can comprise multiple reactors and/or multiple fixed beds.
  • the WGS reaction can be catalyzed by both metals and metal oxides.
  • sour shift catalysts suitable for use include cobalt, molybdenum, copper, iron, a cobalt-molybdenum catalyst, a chromium promoted iron-based catalyst, a copper promoted iron- based catalyst, a copper-zinc-aluminum catalyst, copper oxide (CuO), iron oxide (Fe203), oxides thereof, and the like, or combinations thereof.
  • Sweet shift catalysts are generally iron based.
  • a molar ratio of hydrogen to carbon monoxide in the shifted syngas can be greater than a molar ratio of hydrogen to carbon monoxide in the unshifted syngas.
  • the shifted syngas can be characterized by a molar ratio of hydrogen to carbon monoxide of equal to or greater than about 100:1, alternatively from about 5:1 to about 100:1, alternatively from about 10:1 to about 75:1, or alternatively from about 15:1 to about 40:1.
  • the molar ratio of hydrogen to carbon monoxide depends on shifting (e.g., CO conversion via the WGS reaction) conditions (e.g., type of WGS unit, type of catalyst used in the WGS unit, etc.).
  • full shifting e.g., almost all CO undergoes the WGS reaction
  • single stage, mild shifting can lead to hydrogen to carbon monoxide molar ratios of from about 5:1 to about 10:1
  • a more moderate level of full shift can lead to hydrogen to carbon monoxide molar ratios of about 7:1
  • the hydrogen to carbon monoxide molar ratio decreases with catalyst age.
  • an amount of carbon dioxide in the shifted syngas can be greater than an amount of carbon dioxide in the unshifted syngas.
  • carbon dioxide may be produced in equimolar amounts with hydrogen via the WGS reaction.
  • the shifted syngas in the stream 5 also contains unreacted steam.
  • the compressing steps disclosed herein can be performed with one or more gas compressors that are locating in the unit 140.
  • the compressors can be connected in series, in parallel, or in series and in parallel.
  • the compressor(s) can be any compressor known in the art for compressing streams containing syngas.
  • the unshifted syngas 4 can then be cooled in a heat exchanger 130 to form a cooled syngas 5, followed by compressing, shifting, and cleaning (e.g., to remove sulfur-containing compounds) the syngas in unit 140 to form a shifted syngas 8 and a sulfur product 9.
  • the gasification unit 110 may be configured to receive air 2 (containing oxygen and nitrogen)
  • the shifted syngas 8 contains nitrogen in addition to hydrogen, carbon monoxide, and carbon dioxide.
  • Carbon dioxide can be separated from the shifted syngas 8 in an absorption unit 150 to produce a C02 product 11 and a C02 depleted syngas 10 containing nitrogen, carbon monoxide, and hydrogen.
  • the C02 product 11 can be sequestered, stored, or used (e.g., in secondary hydrocarbon recovery).
  • the C02 depleted syngas 10 can be subjected to methanation in a methanation unit 160 so as to convert carbon monoxide and carbon dioxide (COx) molecules to methane and water, thereby producing steam and a methanation product stream containing methane, hydrogen, and nitrogen.
  • the steam can be removed from the methanation unit in stream 13.
  • the methane may be passed in a treated gasification product 12 to the ammonia synthesis unit 180 where a purge stream 19 prevents accumulation of methane and inert gases such as argon.
  • the methanation unit 160 can include a separator that may be configured to separate the methane from the hydrogen and nitrogen to produce the treated gasification product 12 containing hydrogen and nitrogen and to produce a methane product 26 that can be used as fuel for plant needs.
  • the process and system 100 in FIG. 1 uses renewable power 126 to operate an electrolysis unit 120 that separates water 15 into hydrogen (in hydrogen product 14) and oxygen (in oxygen product 3).
  • the electrolysis unit 120 may be coupled to a renewable energy source 125 so as to receive the renewable power 126.
  • the oxygen can be fed to the gasification unit 110 via the oxygen product 3, and the hydrogen can flow in a hydrogen product 14 that combines with the treated gasification product 12 via a combiner 170 to form an ammonia synthesis feed stream 16.
  • the mole ratio of hydrogen to nitrogen in the ammonia synthesis feed stream 16 can be between about 2: 1 to about 4:1, or about 3:1.
  • the mole ratio of hydrogen to nitrogen in the ammonia synthesis feed stream 16 may be controlled to be between about 2:1 to about 4:1, or about 3:1.
  • the flow of hydrogen in the hydrogen product 14, relative to the flow of the treated gasification product 12, can be controlled such that the mole ratio of hydrogen to nitrogen in the ammonia synthesis feed stream 16 can be between about 2:1 to about 4:1, or about 3:1.
  • the treated gasification product 12, the hydrogen product 14, and the ammonia synthesis feed stream 16 can have sensors, control valves, and associated instrumentation configured to measure the amount of hydrogen and nitrogen in one or more of the treated gasification product 12, the hydrogen product 14, and the ammonia synthesis feed stream 16 and to control the flow of hydrogen in the hydrogen product 14 to the combiner 170 such that the process and system 100 control the mole ratio of hydrogen to nitrogen in the ammonia synthesis feed stream 16 to be between about 2: 1 to about 4: 1, or about 3:1.
  • the ammonia synthesis feed stream 16 can be fed to an ammonia synthesis unit 180 where an ammonia product 17 may be produced.
  • the ammonia product 17 may be considered green ammonia because the feed to the gasification unit 110 may be biomass 1, air 2, and oxygen product 3 that may be made utilizing renewable power 126.
  • the ammonia synthesis unit 180 can produce steam 18 and the purge gas 19.
  • the steam 18 can be used as steam 7, in some aspects.
  • the purge gas 19 can be used in an auxiliary boiler.
  • the steam 13 that may be removed from the methanation unit 160 can be used in unit 140 for shifting the unshifted syngas 4.
  • the unit 140 can recover a process condensate 6 (aqueous condensate) that can be used as coolant in the heat exchanger 130, the heating of the condensate in the heat exchanger 130 thereby producing steam 15.
  • a process condensate 6 aqueous condensate
  • the heat exchanger 130 can be configured as a cross-exchanger, where one side of the heat exchanger 130 may be the syngas side, and the other side of the heat exchanger 130 contains the coolant that cools the syngas 4 and may be the coolant side.
  • the syngas side of the heat exchanger 130 may be configured to receive the syngas 4 and cool the syngas.
  • the cooled syngas 5 exits the syngas side of the heat exchanger 130 in stream 5.
  • the coolant side of the heat exchanger 130 receives the aqueous condensate 6 that may be heated by contact with the syngas side inside the heat exchanger 130. Heating the coolant produces steam which flows from the heat exchanger 130 via stream 15.
  • the process and system 200 in FIG. 2 feeds a biomass 1, air 2, and oxygen product 3 to the gasification unit 110 to produce an unshifted syngas 4.
  • the unshifted syngas 4 can then be cooled in a heat exchanger 130 to form a cooled syngas 5, followed by compressing, shifting, and cleaning (e.g., to remove sulfur-containing compounds) the syngas in unit 140 to form a shifted syngas 8 and a sulfur product 9.
  • the gasification unit 110 may be configured to receive air 2 (containing oxygen and nitrogen), the shifted syngas 8 contains nitrogen in addition to hydrogen, carbon monoxide, and carbon dioxide. Carbon dioxide can be separated from the shifted syngas 8 in an absorption unit 150 to produce a C02 product 11 and a C02 depleted syngas 10 containing nitrogen, carbon monoxide, and hydrogen.
  • the absorption unit 150 as illustrated in the figures may be generally configured to receive the cooled shifted syngas in stream 8 (FIGS. 1-2) or the cooled syngas 8A (FIGS. 3-4), to remove C02 from the respective syngas to produce the C02 product in stream 11 and the C02 depleted syngas in stream 10 (FIGS. 1-2) or the treated gasification product 10A (FIGS. 3-4).
  • Removing C02 from the shifted syngas can include absorbing C02 with a lean solvent to produce the C02 depleted syngas 10 or treated gasification product 10A and a C02 enriched solvent, and flashing the C02 enriched solvent to produce the C02 product and the lean solvent. Flashing does not require a stripper, so there may be no steam needed to remove C02 when using certain solvents.
  • the solvent may be a physical solvent. Moreover, using a physical solvent allows for the equipment in the absorption unit 150 to be made of carbon steel (not made of any stainless steel). In some aspects, the solvent may comprise both a physical solvent and a chemical solvent.
  • removing C02 can include absorbing C02 with a chemical solvent such as a lean amine solvent to produce the C02 depleted syngas 10 or treated gasification product 10A and a C02 enriched amine solvent, and stripping the C02 enriched amine solvent to produce the C02 product and the lean amine solvent to produce the C02 product and the lean amine solvent or other C02 removal technologies.
  • a chemical solvent such as a lean amine solvent
  • the absorption unit 150 can include an absorber and regenerator, where at least a portion of the carbon dioxide can be removed (e.g., recovered, separated, etc.) from at least a portion of the cooled shifted syngas by a physical solvent and/or a chemical solvent in the absorber.
  • the absorption unit 150 can include the absorber having a lean physical solvent configured to absorb carbon dioxide from the shifted syngas to produce a C02 enriched solvent and the C02 depleted syngas in the stream 10.
  • the absorption unit 150 can also include a flash tank coupled to the absorber, wherein the flash tank may be configured to receive the C02 enriched solvent from the absorber and to flash carbon dioxide from the C02 enriched solvent to produce the lean physical solvent and the C02 product in the stream 11.
  • the absorption unit 150 can include an absorber having a lean chemical solvent configured to absorb carbon dioxide from the shifted syngas to produce a C02 enriched solvent and the C02 depleted syngas in the stream 10, and a stripper coupled to the absorber, wherein the stripper may be configured to receive the C02 enriched solvent from the absorber and to strip carbon dioxide from the C02 enriched solvent to produce the lean chemical solvent and the C02 product in the stream 5.
  • the regenerator can be embodied as a stripper configured to use a stripping gas to remove the carbon dioxide from the chemical solvent.
  • the stripper can include a reboiler that provides heat to the stripper for removing carbon dioxide from the chemical solvent to produce the lean chemical solvent.
  • the stripper can comprise any suitable stripping column, wherein a gas phase (e.g., the carbon dioxide) may be removed from the liquid phase (e.g., the C02 enriched solvent).
  • a gas phase e.g., the carbon dioxide
  • the stripper can be similar in configuration to the absorber, while operating at different parameters (e.g., pressure, temperature, etc.).
  • a pressure in the stripper can be lower than a pressure in the absorber and a temperature in the stripper can be higher than a temperature in the absorber, to enable the C02 enriched solvent to release carbon dioxide.
  • the stripper can be one or more vertical and cylindrical columns or towers.
  • the C02 enriched solvent can be introduced as a downflow at the top of the stripper, and a portion of the lean solvent can be re introduced at the bottom (e.g., bubbled) of the stripper as vapor (e.g., using a reboiler).
  • carbon dioxide can be recovered at the top of the stripper, and the lean solvent can be recovered at the bottom of the stripper.
  • a reboiler for the stripper can be heated with steam (e.g., low pressure steam at a pressure of from about 400 kPa to about 1,500 kPa), wherein the steam can be recovered from the reboiler as an aqueous condensate, and wherein the recovered aqueous condensate can be further converted into the steam used for heating the reboiler.
  • the stripper can comprise a packed bed column, a tray column, a spray column, a falling film column, a bubble column, a sparged tank column, and the like, or combinations thereof.
  • the stripper can operate at a pressure of from about 5 psig to about 50 psig, alternatively from about 10 psig to about 45 psig, alternatively from about 20 psig to about 40 psig, alternatively from about 25 psig to about 35 psig, or alternatively from about 25 psig to about 30 psig.
  • Examples of chemical solvent useful in the absorption unit 150 include primary amines, secondary amines, tertiary amines, sterically hindered amines, methylethylamine (MEA), methyl diethanolamine (MDEA), diglycolamine (DGA), 2-amino-2 -methyl- 1 -propanol (AMP), or a combination thereof.
  • the regenerator can be embodied as a flash tank or flash column configured to remove the carbon dioxide from the C02 rich physical solvent by pressure reduction, i.e., flashing (e.g., via pressure reduction) the carbon dioxide out of the physical solvent.
  • the flash tank can comprise any suitable vessel, wherein a gas phase (e.g., the carbon dioxide) may be flashed by differential pressure from the liquid phase (e.g., the C02 enriched solvent).
  • the flash tank can be any vessel configured to subject the C02 enriched solvent to a drop in pressure such that the carbon dioxide may be liberated from the liquid solvent to form the lean physical solvent.
  • a pressure in the flash tank may be generally lower than a pressure in the absorber to enable the carbon dioxide to flash from C02 enriched solvent to produce the lean physical solvent and the C02 product in stream 11.
  • the flash tank can operate at a pressure in a range of from a vacuum pressure to about 200 psig (1.38 MPag).
  • the flash tank may be one or more vessels (e.g., more than one flash tank) connected in series such that the reduction in pressure may be accomplished in stages.
  • Examples of physical solvents useful in the absorption unit 150 include methanol, propylene carbonate, N-methylpyrrolidone, a glycol ether, ethers of polyglycols (e.g., dimethoxytetraethylene glycol or N-substituted morpholine), or a combination thereof.
  • the absorption solvent can comprise a propylene carbonate having favorable treating properties such as high solubility for carbon dioxide, low heat solution of carbon dioxide, low solvent vapor pressure, low solvent freezing temperature, non-hazardous, non-reactive to natural gas components, non-degradable or non-foamable, water absorbent, and low solubility for light hydrocarbons and low viscosity.
  • water absorbability such a property allows the use of cheaper materials, such as carbon steel, in e.g., the absorption unit 150.
  • Some embodiments may use a process sold under the trade designation Fluor SolventSM system comprising or consisting of a propylene carbonate solvent available from Fluor Corporation of Irving, Texas.
  • the chemical solvent and/or physical solvent can absorb the carbon dioxide while the remaining components of the received syngas pass through the absorber to form the C02 depleted syngas in stream 10 or the treated gasification product in stream I0A.
  • the carbon dioxide in the C02 enriched solvent leaves the absorber and may be fed to a regenerator, where the carbon dioxide may be separated from the solvent (the solvent may be regenerated) to produce a lean solvent (e.g., a lean physical solvent or a lean chemical solvent) and a C02 product.
  • the lean solvent can be recycled to the absorber, and the C02 product may be recovered in stream 11.
  • the absorber can comprise any suitable absorber column, wherein a gas phase (e.g., the cooled shifted syngas) interacts with a liquid phase (e.g., absorption solvent) via co-current flow, counter-current flow, or cross-flow.
  • a gas phase e.g., the cooled shifted syngas
  • a liquid phase e.g., absorption solvent
  • absorption columns can be vertical and cylindrical columns or towers.
  • the absorber can comprise a countercurrent absorber column, wherein the shifted syngas can be introduced to the column countercurrent (e.g., opposing flow directions) with respect to the flow of absorption solvent.
  • the absorption solvent can be introduced as a downflow at the top of the absorber, and the received syngas can be introduced (e.g., bubbled) at the bottom of the absorber.
  • the C02 depleted syngas or treated gasification product can be recovered at the top of the absorber, and the C02 enriched solvent can be recovered at the bottom of the absorber.
  • the absorber can have one or more trays and/or packing as a contacting device. However, any other suitable contacting devices can be employed, such as for example static or dynamic mixers, spargers, impellers, etc.
  • the absorption unit 150 can comprise a packed bed column, a tray column, a spray column, a falling film column, a bubble column, a sparged tank column, and the like, or combinations thereof.
  • the absorber can operate at a pressure of from about 375 psig to about 575 psig, alternatively from about 400 psig to about 550 psig, or alternatively from about 450 psig to about 500 psig.
  • the C02 depleted syngas in stream 10 or the treated gasification product in stream 10A can comprise substantially all of the hydrogen present in the syngas in stream 8 or 8A.
  • the C02 depleted syngas 10 or the treated gasification product 10A can contain equal to or greater than about 50 mol%, alternatively equal to or greater than about 60 mol%, alternatively equal to or greater than about 70 mol%, alternatively equal to or greater than about 80 mol%, alternatively equal to or greater than about 90 mol%, alternatively equal to or greater than about 95 mol%, or alternatively equal to or greater than about 99 mol% of the hydrogen of the syngas 8 or 8A.
  • the C02 enriched solvent can comprise carbon dioxide in an amount of equal to or greater than about 30 mol%, alternatively equal to or greater than about 40 mol%, or alternatively equal to or greater than about 50 mol% of the carbon dioxide of the cooled syngas.
  • the process can include sequestering the carbon dioxide product in the C02 product stream 11.
  • the carbon dioxide product in the stream 11 can comprise substantially all of the carbon dioxide of the shifted syngas in the stream 8.
  • the carbon dioxide product can include equal to or greater than about 99 mol%, alternatively equal to or greater than about 99.5 mol%, alternatively equal to or greater than about 99.9 mol%, or alternatively equal to or greater than about 99.99 mol% of the carbon dioxide of the cooled shifted syngas in the stream 5.
  • the process can include sending the carbon dioxide product in the C02 product stream 11 to storage or a pipeline for transport, for example, for use in enhanced oil recovery.
  • the PSA unit 150 comprises an adsorbent material.
  • adsorbent materials suitable for use in the present disclosure include molecular sieves, zeolites, such as 5 A zeolite and 13X zeolite, and the like, or combinations thereof.
  • Pressure swing adsorption (PSA) may be generally based on physical binding of gas molecules (e.g., hydrogen, methane, carbon dioxide, etc.) to an adsorbent material (e.g., a solid). Binding strength between the gas molecules and the adsorbent material depends on the gas components, type of adsorbent material, partial pressures of the gas components and operating temperature.
  • Purifying a gas by the PSA separation may be based on differences in binding strength of the gas components to the adsorbent material. Highly volatile components with low polarity, such as hydrogen, are practically non-adsorbable, as opposed to molecules like methane and carbon dioxide.
  • the PSA generally has an adsorption step, and a desorption step. During the adsorption step, high purity hydrogen can be recovered from the PSA unit 150, as hydrogen will not be adsorbed. Methane and carbon dioxide will be adsorbed by the adsorbent material, and can be recovered during the desorption step.
  • the PSA works at basically constant temperature and uses the effect of alternating pressure and partial pressure to perform the adsorption step and the desorption step. Because heating or cooling may be not required, short cycles within the range of minutes can be achieved. A cycle can be defined as the time between the start of two consecutive adsorption steps.
  • the adsorption may be carried out at high pressure, until an equilibrium loading may be reached, wherein no further adsorption capacity is available and the adsorbent material is generally regenerated.
  • the desorption step can be done by lowering the pressure to slightly above atmospheric pressure resulting in a respective decrease in equilibrium loading.
  • the gases e.g., methane, carbon dioxide
  • the gases e.g., methane, carbon dioxide
  • the pressure may be increased back to adsorption pressure level and another adsorption step begins.
  • the PSA also involves a purge step between the desorption step and the adsorption step, to ensure that the adsorber material may be ready to undergo the next adsorption step.
  • the C02 depleted syngas can be introduced to the PSA unit at the bottom, and can travel upwards through the adsorbent material, wherein hydrogen can be recovered at a top of the PSA unit during the adsorption step.
  • the PSA off gas including methane and carbon dioxide can be recovered at the bottom of the PSA unit during the desorption step.
  • the PSA unit 150 comprises from about 2 to about 10 PSA units, alternatively from about 3 to about 8 PSA units, alternatively from about 3 to about 6 PSA units operating in parallel, to provide a continuous supply of hydrogen, and to provide for a continuous uptake of C02 depleted syngas.
  • an adsorption step may be completed in the PSA unit 150, and such unit starts a desorption step, another PSA unit can take over the adsorption step to ensure a continuous process.
  • more than the one PSA unit can undergo the adsorption step at the same time, and similarly, more than the one PSA unit can undergo the desorption step at the same time.
  • hydrogen production can be continuous.
  • the C02 product 11 can be split via a splitter 175 into a first portion 11a and a second portion 1 lb.
  • the first portion 11a can be used for urea synthesis (described in more detail below), and the second portion 1 lb can be sequestered, stored, or used (e.g., in secondary hydrocarbon recovery).
  • the C02 depleted syngas 10 can be subjected to methanation in a methanation unit 160 so as to convert COx molecules to methane and water, thereby producing steam 18 and a methanation product stream 26 containing methane, hydrogen, and nitrogen.
  • the steam can be removed from the methanation unit in stream 13.
  • the methanation unit 160 can include a separator that may be configured to separate the methane from the hydrogen and nitrogen to produce a treated gasification product 12 containing hydrogen and nitrogen and to produce a methane product stream 26 that can be used as fuel for plant needs.
  • methane and one or more inert gases may be purged at the ammonia synthesis unit 180, as discussed above.
  • the process and system 200 in FIG. 2 uses renewable power 126 to operate an electrolysis unit 120 that separates water into hydrogen and oxygen.
  • the electrolysis unit 120 may be coupled to a renewable energy source 125 so as to receive the renewable power 126.
  • the oxygen produced by the electrolysis unit 120 can be fed to the gasification unit 110 via the oxygen product 3, and the hydrogen produced by the electrolysis unit 120 can flow in a hydrogen product 14 that combines with the treated gasification product 12 via a combiner 170 to form an ammonia synthesis feed stream 16.
  • the mole ratio of hydrogen to nitrogen in the ammonia synthesis feed stream 16 can be between about 2: 1 to about 4:1, or about 3:1. In further aspects, the mole ratio of hydrogen to nitrogen in the ammonia synthesis feed stream 16 can be between about 2:1 to about 4:1, or about 3:1.
  • the flow of hydrogen in the hydrogen product 14, relative to the flow of the treated gasification product 12, can be controlled such that the mole ratio of hydrogen to nitrogen in the ammonia synthesis feed stream 16 can be between about 2: 1 to about 4: 1, or about 3:1.
  • the treated gasification product 12, the hydrogen product 14, and the ammonia synthesis feed stream 16 can have sensors, control valves, and associated instrumentation configured to measure the amount of hydrogen and nitrogen in one or more of the treated gasification product 12, the hydrogen product 14, and the ammonia synthesis feed stream 16 and to control the flow of hydrogen in the hydrogen product 14 to the combiner 170 such that the process and system 200 control the mole ratio of hydrogen to nitrogen in the ammonia synthesis feed stream 16 to be between about 2: 1 to about 4: 1, or about 3:1.
  • the ammonia synthesis feed stream 16 can be fed to an ammonia synthesis unit 180 where an ammonia product 17 may be produced.
  • the ammonia product 17 may be considered green ammonia because the feed to the gasification unit 110 can be biomass 1, air 2, and oxygen product 3 that may be made utilizing renewable power 126.
  • the ammonia synthesis unit 180 can produce steam 18 and a purge gas 19.
  • the steam 18 can be used as steam 7, in some aspects.
  • the purge gas 19 can be used in an auxiliary boiler.
  • the steam 13 that may be removed from the methanation unit 160 can be used in unit 140 for shifting the unshifted syngas.
  • the unit 140 can recover a process condensate 6 (aqueous condensate) that can be used as coolant in the heat exchanger 130, the heating of the condensate in the heat exchanger 130 thereby producing steam 15.
  • a process condensate 6 aqueous condensate
  • the green ammonia can be fed to a urea synthesis unit 190, along with cleaned carbon dioxide 20.
  • the cleaned carbon dioxide 20 can be obtained by compressing, purifying, or both compressing and purifying the first portion 11a of the C02 product 11 in a C02 treatment unit 195.
  • the first portion 11a of the C02 product 11 can be compressed, purified, or both compressed and purified before being fed to the urea synthesis unit 190.
  • Green urea 21a and 21b can be produced by the urea synthesis unit 190, along with reaction product water 22.
  • the reaction product water 22 can have a purity (e.g., ⁇ 1 ppmw of NH3, C02, and urea) such that the reaction product water 22 may be passed to a water treatment unit 210 and then can be provided as treated water 23 used in place of fresh water (water 15 in FIG. 1) for feed to the electrolysis unit 120.
  • a fresh water makeup stream (e.g., water 15 in FIG. 1) to the electrolysis unit 120 can be utilized for any water lost in the process and system 200.
  • a portion 21b of the green urea can be fed to a urea formaldehyde synthesis unit 197, along with a green formaldehyde stream 25 (e.g., produced as a derivative of methanol from the process and system 300 in FIG. 3), to produce green urea formaldehyde 24.
  • the process and system 300 in FIG. 3 can produce methanol and derivatives thereof.
  • the process and system 300 in FIG. 3 can feed a biomass 1 and an oxygen product 3 to a gasification unit 110 to produce an unshifted syngas 4.
  • the unshifted syngas 4 can then be cooled in a heat exchanger 130 to form a cooled syngas 5 and the heating of the condensate in the heat exchanger 130 thereby producing steam 7A, similar to the steam 15 described above.
  • compressing and cleaning the syngas e.g., to remove sulfur-containing compounds
  • a water gas shift unit 145 similar to the water gas shift unit 140 described above, forms a cleaned syngas 8A and a sulfur product 9.
  • the gasification unit 110 may be configured not to receive air and to only receive oxygen from the oxygen product 3 of the electrolysis unit 120; thus, there may be no nitrogen in the cleaned syngas 8 A due to the introduction of air to the gasification unit 110, and the cleaned syngas 8A contains hydrogen, carbon monoxide, and carbon dioxide.
  • Carbon dioxide can be separated from the cleaned syngas 8A to produce a C02 product 11 and a treated gasification product 10A containing carbon monoxide, hydrogen, and residual amounts of carbon dioxide.
  • the C02 product 11 can be sequestered, stored, or used (e.g., in secondary hydrocarbon recovery).
  • the process and system 300 in FIG. 3 can use renewable power 126 to operate an electrolysis unit 120 that separates water into hydrogen and oxygen.
  • the electrolysis unit 120 may be coupled to a renewable energy source 125 so as to receive the renewable power 126.
  • the oxygen produced by the electrolysis unit 120 can be fed to the gasification unit 110 via the oxygen product 3, and the hydrogen produced by the electrolysis unit 120 can flow in a hydrogen product 14 that can be combine with the treated gasification product 10A via a combiner 220 to form a synthesis feed stream 101 enriched in hydrogen and containing carbon monoxide, hydrogen, and carbon dioxide.
  • the mole ratio of (H2-C02)/(C0+C02) can be between about 1:1 to about 3:1, or about 2:1 in the synthesis feed stream 101. In an embodiment, the mole ratio can be about 2.05:1 in the synthesis feed stream 101. In further aspects, the mole ratio of (H2-C02)/(C0+C02) in the synthesis feed stream 101 may be controlled.
  • the flow of hydrogen in the hydrogen product 14, relative to the flow of the treated gasification product 10 A, can be controlled such that the mole ratio of (H2-C02)/(C0+C02) in the synthesis feed stream 101 can be between about 1:1 to about 3:1, about 2:1, or about 2:05:1.
  • the treated gasification product 10A, the hydrogen product 14, and the synthesis feed stream 101 can have sensors, control valves, and associated instrumentation configured to measure the amount of hydrogen, carbon monoxide, carbon dioxide, or a combination thereof in one or more of the treated gasification product 10 A, the hydrogen product 14, and the synthesis feed stream 101 and to control the flow of hydrogen in the hydrogen product 14 to the combiner 220 such that the process and system 300 control the mole ratio of (H2- C02)/(C0+C02) in the synthesis feed stream 101 to be between about 1:1: to about 3:1, about 2:1, or 2.05:1.
  • the synthesis feed stream 101 can be fed to a methanol synthesis unit 230 where a methanol product 102 and 104 can be produced.
  • the methanol product 102 and 104 can be considered green methanol because the feed to the gasification unit 110 may be biomass 1 and oxygen product 3 made utilizing renewable power 126.
  • the methanol synthesis unit 230 can produce a purge gas 105 and a reaction water product 103.
  • the purge gas 105 can be used in an auxiliary boiler.
  • Green methanol 102 and 104 produced in the methanol synthesis unit 230 can have a purity of at least about 95 mol% methanol with the balance being water.
  • Another product of the methanol synthesis can be reaction product water 103 that can optionally be treated in a water treatment unit 210 and then treated water 106, similarly as the treated water 23 as described above, fed to the electrolysis unit 120.
  • the reaction product water 103 can have a purity (e.g., ⁇ 1 part per million weight (ppmw) of methanol, C02, and carbon monoxide) such that the reaction product water 103 can be used in place of fresh water (e.g., water 15 in FIG. 1) for feed to the electrolysis unit 120.
  • ppmw part per million weight
  • a fresh water makeup stream (e.g., water 15 in FIG. 1) to the electrolysis unit 120 can be utilized for any water lost in the process and system 300.
  • a portion 102 of the green methanol can be used in a methanol derivatives synthesis unit 240 to produce methanol derivatives 107, such as green formaldehyde, green DME, green gasoline, green acetic acid, green formic acid, green ethanol, green ethylene, green propylene, or combinations thereof.
  • the process and system 400 produces Fischer Tropsch products and upgraded products thereof.
  • the process and system 400 in FIG. 4 feeds a biomass 1 and an oxygen product 3 to a gasification unit 110 to produce an unshifted syngas 4.
  • the unshifted syngas 4 can then be cooled in a heat exchanger 130 to form a cooled syngas 5 and the heating of the condensate in the heat exchanger 130 thereby producing steam 7A, similar to the steam 15 described above.
  • compressing and cleaning the syngas e.g., to remove sulfur-containing compounds
  • a water gas shift unit 145 similar to the water gas shift unit 140 described above, forms a cleaned syngas 8 A and a sulfur product 9.
  • the gasification unit 110 may be configured not to receive air and to only receive oxygen from the oxygen product 3 of the electrolysis unit 120; thus, there may be no nitrogen in the cleaned syngas 8 A due to the introduction of air to the gasification unit 110, and the cleaned syngas 8A can include hydrogen, carbon monoxide, and carbon dioxide. Carbon dioxide can be separated from the cleaned syngas 8A to produce a C02 product 11 and a treated gasification product 10A containing carbon monoxide, hydrogen, and residual amounts of carbon dioxide. The C02 product 11 can be sequestered, stored, or used (e.g., in secondary hydrocarbon recovery).
  • the process and system 400 in FIG. 4 uses renewable power 126 to operate an electrolysis unit 120 that can separate water into hydrogen and oxygen.
  • the electrolysis unit 120 can be coupled to a renewable energy source 125 so as to receive the renewable power 126.
  • the oxygen produced by the electrolysis unit 120 can be fed to the gasification unit 110 via the oxygen product 3, and the hydrogen produced by the electrolysis unit 120 can flow in a hydrogen product 14.
  • the hydrogen product 14 may be split into a first portion 14a and a second portion 14b via a splitter 270.
  • a first portion 14a of the hydrogen product 14 can be combined with the treated gasification product 10A via a combiner 220 to form a synthesis feed stream 101 that may be enriched in hydrogen and may contain carbon monoxide, hydrogen, and carbon dioxide.
  • a second portion 14b of the hydrogen product 14 can be used for upgrading Fischer Tropsch product (described in more detail below).
  • the mole ratio of (H2-C02)/(C0+C02) is about 2:1 in the synthesis feed stream 101. In an embodiment, the mole ratio is about 2.05:1 in the synthesis feed stream 101. In further aspects, the mole ratio of (H2-C02)/(C0+C02) in the synthesis feed stream 101 may be controlled.
  • the flow of hydrogen in first portion 14a of the hydrogen product 14, relative to the flow of the treated gasification product 10A, can be controlled such that the mole ratio of (H2- C02)/(C0+C02) in the synthesis feed stream 101 may be about 2:1, or about 2:05:1.
  • the treated gasification product 10A, the hydrogen product 14, and the synthesis feed stream 101 can have sensors, control valves, and associated instrumentation configured to measure the amount of hydrogen, carbon monoxide, carbon dioxide, or a combination thereof in one or more of the treated gasification product 10A, the hydrogen product 14, and the synthesis feed stream 101 and to control the flow of hydrogen in the hydrogen product 14 to the combiner 220 such that the process and system 400 control the mole ratio of (H2-C02)/(C0+C02) in the synthesis feed stream 101 to be about 2:l, or about 2.05:1.
  • the synthesis feed stream 101 can be fed to a Fischer Tropsch (FT) synthesis unit 250 where a Fischer Tropsch (FT) product 112 containing long chain hydrocarbons may be produced.
  • the FT product 112 can be considered a green FT product because the feed to the gasification unit 110 can be biomass 1 and oxygen product 3 that may be made utilizing renewable power 126.
  • the FT synthesis unit 250 can produce a tail gas 111, a wax 116, and a reaction water product 113.
  • the reaction water product 113 can be fed to a water treatment unit 210, which may provide a treated water 114 to the electrolyzer 120, similarly as described above.
  • the tail gas 111 can be used in an auxiliary boiler.
  • Long chain hydrocarbons in the FT product 112 along with wax 116 formed in the FT synthesis unit 250 and the second portion 14b of the hydrogen product 14 can be used to made green FT derivative products 115 in a FT product upgrading unit 260.
  • the derivative products 115 can include green LPG, green naphtha, green jet fuel, green diesel, green wax, green lubricants, or a combination thereof. In some aspects, some of the derivatives 115 can be used as fuel for the gasification unit 110.
  • a process comprises: producing an unshifted syngas from biomass and oxygen in a gasification unit; introducing water into an electrolyzer to produce an oxygen product and a hydrogen product, wherein the electrolyzer may be powered by renewable energy; and introducing the oxygen product to the gasification unit, wherein the oxygen product supplies at least a portion of the oxygen to the gasification unit.
  • a second aspect can include the process of the first aspect, further comprises: introducing air to the gasification unit, wherein the air supplies at least a portion of the oxygen to the gasification unit; cooling the unshifted syngas to form a cooled syngas; introducing the cooled syngas to a water gas shift unit to produce a shifted syngas; removing sulfur from the shifted syngas to produce sulfur depleted syngas and sulfur product; removing C02 from the sulfur depleted syngas to produce a C02 depleted syngas and a C02 product; introducing the C02 depleted syngas to a methanation unit to produce a methanation product to produce a treated gasification product comprising nitrogen and hydrogen; and combining the treated gasification product and the hydrogen product to form an ammonia synthesis feed stream having a mole ratio of hydrogen to nitrogen of 3 : 1.
  • a third aspect can include the process of the first or second aspect, further comprises: introducing the ammonia synthesis feed stream to an ammonia synthesis unit to produce an ammonia product.
  • a fourth aspect can include the process of any of the first to third aspects, further comprises: introducing the ammonia product and a C02 feed stream to a urea synthesis unit to produce a urea product and a water product.
  • a fifth aspect can include the process of any of the first to fourth aspects, further comprises: compressing and purifying the C02 product to produce the C02 feed stream.
  • a sixth aspect can include the process of any of the first to fifth aspects, further comprises: introducing the water product to the electrolyzer, wherein the water product may be the water that may be introduced to the electrolyzer, wherein the water product may be optionally treated before introducing the water product to the electrolyzer.
  • a seventh aspect can include the process of any of the first to sixth aspects, further comprises: introducing a portion of the urea product and a formaldehyde feed to a urea formaldehyde synthesis unit to produce a urea formaldehyde product.
  • a ninth aspect can include the process of any of the first to eighth aspects, wherein a mole ratio of hydrogen to carbon monoxide in the treated gasification product is about 1:1.
  • a tenth aspect can include the process of any of the first to ninth aspects, wherein the treated gasification product is combined with all of the hydrogen product, the process further comprising: introducing the synthesis feed stream to a methanol synthesis unit to produce a methanol product and a water product.
  • An eleventh aspect can include the process of any of the first to tenth aspects, further comprises: introducing the water product to the electrolyzer, wherein the water product is the water that is introduced to the electrolyzer.
  • a twelfth aspect can include the process of any of the first to eleventh aspects, further comprises: introducing a portion of the methanol product to a derivatives synthesis unit to produce formaldehyde, dimethyl ether (DME), gasoline, acetic acid, formic acid, ethanol, ethylene, propylene, or a combination thereof.
  • a derivatives synthesis unit to produce formaldehyde, dimethyl ether (DME), gasoline, acetic acid, formic acid, ethanol, ethylene, propylene, or a combination thereof.
  • a thirteenth aspect can include the process of any of the first to twelfth aspects, further comprises: splitting the hydrogen product into a first portion and a second portion, wherein the treated gasification product is combined with the first portion of the hydrogen product to form the synthesis feed stream; and introducing the synthesis feed stream to a Fischer Tropsch (FT) synthesis unit to produce a FT product, a wax product, and a water product.
  • FT Fischer Tropsch
  • a fourteenth aspect can include the process of any of the first to thirteenth aspects, further comprises: introducing the water product to the electrolyzer, wherein the water product is the water that is introduced to the electrolyzer, wherein the water product is optionally treated before introducing the water product to the electrolyzer.
  • a fifteenth aspect can include the process of any of the first to fourteenth aspects, further comprises: introducing the second portion of the hydrogen product, the wax product, and the FT product to a derivative synthesis unit to produce naphtha, jet fuel, diesel, wax, lubricant, or a combination thereof.
  • a system comprises: a gasification unit configured to produce an unshifted syngas from biomass and oxygen; and an electrolyzer coupled to the gasification unit and configured to receive water and to produce an oxygen product and a hydrogen product, wherein the oxygen product supplies at least a portion of the oxygen to the gasification unit, and wherein the electrolyzer is coupled to a renewable energy source.
  • a seventeenth aspect can include a system of the sixteenth aspect, further comprises: an air stream connected to the gasification unit and configured to supply air to the gasification unit, wherein the air supplies at least a portion of the oxygen to the gasification unit; a heat exchanger coupled to the gasification unit and configured to cool the unshifted syngas to produce a cooled syngas; a water gas shift unit coupled to the heat exchanger and configured to receive the cooled syngas and to produce a shifted syngas; a sulfur removal unit coupled to the water gas shift unit and configured to receive the shifted syngas and to produce a sulfur depleted syngas and a sulfur product; an absorption unit coupled to the sulfur removal unit and configured to receive the sulfur depleted syngas, remove carbon dioxide from the sulfur depleted syngas, and produce a C02 depleted syngas and a C02 product; a methanation unit coupled to the absorption unit and configured to receive the C02 depleted syngas to produce a treated gasification product comprising hydrogen and nitrogen; and a combiner configured
  • An eighteenth aspect can include a system of the sixteenth or seventeenth aspect, further comprises: an ammonia synthesis unit coupled to the combiner and configured to receive the ammonia synthesis feed stream from the combiner and to produce an ammonia product.
  • a nineteenth aspect can include a system of any of the sixteenth to eighteenth aspects, further comprises: a urea synthesis unit coupled to the ammonia synthesis unit and configured to receive the ammonia product and a C02 feed stream and to produce a urea product and a water product.
  • a twentieth aspect can include a system of any of the sixteenth to nineteenth aspects, further comprises: a C02 treatment unit coupled to the absorption unit and to the urea synthesis unit and configured to receive the C02 product from the absorption unit and to produce the C02 feed stream.
  • a twenty first aspect can include a system of any of the sixteenth to twentieth aspects, wherein the urea synthesis unit is coupled to the electrolyzer, and wherein the electrolyzer is configured to receive the water product.
  • a twenty second aspect can include a system of any of the sixteenth to twenty first aspects, further comprises: a urea formaldehyde synthesis unit coupled to the urea synthesis unit and configured to receive at portion of the urea product from the urea synthesis unit and to produce a urea formaldehyde produce.
  • a twenty third aspect can include a system of any of the sixteenth to twenty second aspects, wherein the gasification unit is configured to receive the oxygen product as the only source of oxygen that is fed to the gasification unit.
  • a twenty fifth aspect can include a system of any of the sixteenth to twenty fourth aspects, wherein the combiner is configured to receive all of the hydrogen product to produce the synthesis feed stream, the system further comprises: a methanol synthesis unit coupled to the combiner and configured to receive the synthesis feed stream and to produce a methanol product and a water product.
  • a twenty sixth aspect can include a system of any of the sixteenth to twenty fifth aspects, further comprises: a derivatives synthesis unit coupled to the methanol synthesis unit and configured to receive the methanol product and to produce formaldehyde, dimethyl ether (DME), gasoline, acetic acid, formic acid, ethanol, ethylene, propylene, or a combination thereof.
  • a derivatives synthesis unit coupled to the methanol synthesis unit and configured to receive the methanol product and to produce formaldehyde, dimethyl ether (DME), gasoline, acetic acid, formic acid, ethanol, ethylene, propylene, or a combination thereof.
  • DME dimethyl ether
  • a twenty seventh aspect can include a system of any of the sixteenth to twenty sixth aspects, wherein the methanol synthesis unit is coupled to the electrolyzer, optionally via a water treatment unit, and the electrolyzer is configured to receive the water product.
  • a twenty eighth aspect can include a system of any of the sixteenth to twenty seventh aspects, further comprises: a splitter coupled to the electrolyzer and configured to split the hydrogen product into a first portion and a second portion, wherein the combiner is coupled to the splitter and configured to receive the first portion of the hydrogen product to form the synthesis feed stream; and a Fischer Tropsch (FT) synthesis unit coupled to the combiner and configured to receive the synthesis feed stream and to produce a FT product, a wax product, and a water product.
  • FT Fischer Tropsch
  • a twenty ninth aspect can include a system of any of the sixteenth to twenty eighth aspects, further comprises: a FT product unit coupled to the FT synthesis unit and to the splitter and configured to receive the second portion of the hydrogen product, the wax product, and the FT product and to produce naphtha, jet fuel, diesel, wax, lubricant, or a combination thereof.
  • a thirtieth aspect can include a system of any of the sixteenth to twenty ninth aspects, wherein the FT synthesis unit is coupled to the electrolyzer, optionally via a water treatment unit, and the electrolyzer is configured to receive the water product.
  • any number falling within the range is specifically disclosed.
  • any numerical range defined by two R numbers as defined in the above is also specifically disclosed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

De l'ammoniac, du méthanol, des produits de Fischer Tropsch, et des dérivés de ceux-ci sont fabriqués à l'aide d'hydrogène et d'oxygène fournis par un électrolyseur qui est au moins partiellement alimenté par une énergie renouvelable, ce qui permet d'obtenir un procédé et des systèmes écologiques qui produisent les produits écologiques divulgués ici. Un procédé utilisant de la biomasse et de l'énergie renouvelable consiste à produire un gaz de synthèse non converti à partir de biomasse et d'oxygène dans une unité de gazéification, à introduire de l'eau dans un électrolyseur pour produire un produit à base d'oxygène et un produit à base d'hydrogène, et à introduire le produit à base d'oxygène dans l'unité de gazéification. L'électrolyseur est alimenté par une énergie renouvelable, et le produit à base d'oxygène fournit au moins une partie de l'oxygène à l'unité de gazéification.
PCT/US2022/025825 2021-04-23 2022-04-21 Production d'ammoniac, de méthanol et de produits de synthèse à partir d'un ou plusieurs produits de gazéification WO2022226230A1 (fr)

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AU2022262626A AU2022262626A1 (en) 2021-04-23 2022-04-21 Production of ammonia, methanol, and synthesis products from one or more gasification products
CA3215768A CA3215768A1 (fr) 2021-04-23 2022-04-21 Production d'ammoniac, de methanol et de produits de synthese a partir d'un ou plusieurs produits de gazeification
EP22722938.2A EP4326839A1 (fr) 2021-04-23 2022-04-21 Production d'ammoniac, de méthanol et de produits de synthèse à partir d'un ou plusieurs produits de gazéification

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US202163179023P 2021-04-23 2021-04-23
US63/179,023 2021-04-23
US17/725,296 2022-04-20
US17/725,296 US20220340419A1 (en) 2021-04-23 2022-04-20 Production of ammonia, methanol, and synthesis products from one or more gasification products

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023217703A1 (fr) * 2022-05-11 2023-11-16 Topsoe A/S Procédé et installation de production de combustibles renouvelables

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080041284A1 (en) * 2006-08-21 2008-02-21 Albert Calderon Method for co-producing electric power and urea from carbonaceous material
US20100175320A1 (en) * 2006-12-29 2010-07-15 Pacific Renewable Fuels Llc Energy efficient system and process for the continuous production of fuels and energy from syngas
US9163180B2 (en) * 2011-12-07 2015-10-20 IFP Energies Nouvelles Process for the conversion of carbon-based material by a hybrid route combining direct liquefaction and indirect liquefaction in the presence of hydrogen resulting from non-fossil resources
US10882800B2 (en) * 2018-07-13 2021-01-05 Gas Technology Institute Integrated gasification and electrolysis process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080041284A1 (en) * 2006-08-21 2008-02-21 Albert Calderon Method for co-producing electric power and urea from carbonaceous material
US20100175320A1 (en) * 2006-12-29 2010-07-15 Pacific Renewable Fuels Llc Energy efficient system and process for the continuous production of fuels and energy from syngas
US9163180B2 (en) * 2011-12-07 2015-10-20 IFP Energies Nouvelles Process for the conversion of carbon-based material by a hybrid route combining direct liquefaction and indirect liquefaction in the presence of hydrogen resulting from non-fossil resources
US10882800B2 (en) * 2018-07-13 2021-01-05 Gas Technology Institute Integrated gasification and electrolysis process

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023217703A1 (fr) * 2022-05-11 2023-11-16 Topsoe A/S Procédé et installation de production de combustibles renouvelables

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