WO2024089472A1 - Système et méthode de gazéification améliorée - Google Patents

Système et méthode de gazéification améliorée Download PDF

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WO2024089472A1
WO2024089472A1 PCT/IB2023/052006 IB2023052006W WO2024089472A1 WO 2024089472 A1 WO2024089472 A1 WO 2024089472A1 IB 2023052006 W IB2023052006 W IB 2023052006W WO 2024089472 A1 WO2024089472 A1 WO 2024089472A1
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stream
solid
case
carbon material
sustainable
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PCT/IB2023/052006
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Conor F. Madigan
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Aether Fuels Pte. Ltd.
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Priority claimed from US18/151,046 external-priority patent/US20240141242A1/en
Priority claimed from US18/170,044 external-priority patent/US20240139788A1/en
Application filed by Aether Fuels Pte. Ltd. filed Critical Aether Fuels Pte. Ltd.
Publication of WO2024089472A1 publication Critical patent/WO2024089472A1/fr

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    • 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]
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
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    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
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    • 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
    • C10K3/001—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 thermal treatment
    • C10K3/003—Reducing the tar content
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    • 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
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    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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    • C01B2203/068—Ammonia synthesis
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    • 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
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    • 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
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    • C10J2300/00—Details of gasification processes
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    • C10J2300/00—Details of gasification processes
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    • 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
    • C10J2300/1612—CO2-separation and sequestration, i.e. long time storage
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    • 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
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    • 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
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    • 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
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Definitions

  • Solid biogenic carbon materials refers to biologically grown materials, such as wood, grass, leaves, seaweed, animal waste, food scraps, algae, the biogenic portion of municipal solid waste and the like (collectively, “biomass”).
  • biomass may be purpose grown, such as com for use in the production of bio-ethanol via fermentation, or it may be a waste byproduct of other activities, such as sawdust from a sawmill.
  • Solid non-biogenic wastes here, refers to non-biogenic municipal solid waste, including plastics, and other non-biogenic solid wastes resulting from industrial or consumer activities.
  • solid sustainable carbon materials shall be used to refer collectively to solid biogenic carbon materials and solid non-biogenic carbon materials, reflecting the potential to make chemical products with a reduced environmental burden when utilizing such “solid sustainable carbon materials” instead of conventional fossil carbon materials such as coal, natural gas, petroleum, and the like.
  • gasification which converts such materials into synthesis gas (“syngas”), a mixture of hydrogen gas (H2) and carbon monoxide (CO), which can then be used to make many useful products via known chemical conversion processes.
  • Fig. 1 is a process diagram of a conventional solid sustainable carbon gasification to chemicals conversion process 100.
  • Solid sustainable carbon material is first sized and dried, e.g. into chips or pellets with between 20% and 5% moisture by weight.
  • the sized and dried solid sustainable carbon material is then conveyed as feed 102 into a gasifier 106 within gasification stage 104, including gasifier 106 and tar converter 110.
  • oxygen 108 and steam 109 are provided to the gasification stage, including to gasifier 106 and often also tar converter 110.
  • the oxygen raw material 108 may be provided by an air separation unit (not shown) or a water electrolysis system (not shown).
  • the steam raw material 109 may be provided by downstream processing units that generate excess steam via a steam recycle loop (not shown) or from dedicated steam generation units (not shown).
  • the sized and dried solid sustainable carbon material feed 102 conveyed into gasifier 106 is therein heated, usually in the presence of oxygen and steam, and usually at elevated pressure, to make CO and H2 according to known “gasification” processes.
  • the gasification process is typically performed at conditions of temperature, pressure, oxygen partial pressure, and steam partial pressure to optimize yield of CO and H2.
  • By-product carbon dioxide (CO2), water (H2O), and tar are generally also obtained.
  • tar includes, for example, medium and heavy organic hydrocarbons and other non-hydrocarbon organic compounds.
  • the gasification stage 104 often has a tar converter 110 that processes the tar, also according to known processes, to obtain additional CO and H2, along with additional by-product CO2.
  • tar conversion is “partial oxidation” (“POX”), in which the tars are subjected to high temperatures in the presence of oxygen and steam (which may be supplied at 108 and 109, if sufficient oxygen and steam are not already in the process) to convert such tars into additional syngas, along with additional byproduct CO2 and water.
  • Such tar conversion processes usually also convert any light hydrocarbons, such as methane (CH4), that may be present in the gasifier, such that the resulting effluent of the gasification stage 104 consists of substantially all syngas, CO2, and water.
  • CH4 methane
  • other tar conversion processes such as catalytic conversion, are used instead of POX.
  • Such other tar conversion processes may yield an output stream that is substantially free of tars but which contains methane and other light hydrocarbons.
  • Gases produced by the gasifier 106 can be routed to the tar converter 110, or some or all can be separated and routed to bypass the tar converter 110.
  • the syngas preferably has a volumetric ratio of H2 to CO of between 2 and 2.5, as, for example, in the production of methanol or Fischer-Tropsch (“FT”) hydrocarbons from syngas.
  • a downstream process may convert syngas as well as CO2 into useful chemicals, and in some such instances additional H2 may be used to convert such CO2; for example, whereas an H2:CO ratio of 2 to 2.5 may be suitable for methanol or FT hydrocarbon production from syngas, an additional H2 molecule is required to convert CO2 such that a H2:CO2 ratio of 3 to 3.5 may be suitable for methanol or FT hydrocarbon production from H2 and CO2.
  • the downstream process requires not syngas but rather pure H2.
  • a representative gasification stage 104 described above, with tar processing may produce an effluent 111 with H2:CO:CO2 relative composition (by volume) of 0.3:0.4:0.3.
  • the refining stage 112 typically includes at least a CO2 removal unit 114 to separate, or “capture”, CO2 from the process.
  • the typical CO2 removal unit is an “acid gas removal” (“AGR”) unit that separates CO2, sulfur compounds, such as H2S, and other “acid gases” from a gas stream using any suitable process, such as cryogenic distillation. Such processes are known.
  • the refining stage 112 may also have an additional further downstream purification unit 117 to remove any residual impurities.
  • purification unit 117 may include a sulfur removal unit, such as a fixed bed catalytic, chemisorption, or physisorption purification unit, to remove sulfur species from the process.
  • a precursor 132 which is a mixture of a CO2 free, or CO2 depleted, effluent of the CO2 removal unit 114 may be routed to the purification unit 117, if desired, or the purification unit can be omitted if further purification is not needed. Where the purification unit 117 is used, the purification unit 117 yields a refining stage effluent 120. Where the purification unit 117 is omitted, the precursor 132 becomes the refining stage effluent 120 directly.
  • Purification unit 117 may include a pressure swing absorber (PSA) suitable for producing high purity H2 streams, useful for ammonia production (or for producing high purity H2 itself as an end product); in such cases the precursor 132 that follows the CO2 removal unit would contain substantially all H2, and the PSA would serve to further increase the purity of such H2 by removing, for example, residual CO, CO2, and CH4.
  • PSA pressure swing absorber
  • solid sustainable carbon material gasification plants increase the amount of H2 in the output of the refining stage 112 by reacting the CO in the refining stage with H2O in a CO converter 113 to yield CO2 and H2 using the well-known “water- gas shift” reaction (“WGS”), thus lowering the concentration of CO and raising the concentration of H2 to yield a stream with a more suitable composition for downstream processing.
  • WGS water- gas shift reaction
  • Such CO converter 113 is provided upstream of CO2 removal unit 114, so that CO2 produced by the CO converter 113 may be removed by the CO2 removal unit 114 if desired.
  • the CO converter 113 converts at least a portion of the gasification stage effluent 111 to produce a converted stream 130, which can be the product of converting the entire gasification stage effluent 111 or only a portion thereof. At least a portion of the converted stream 130 is routed to the CO2 removal unit 114.
  • a WGS unit and an AGR unit can be used in combination, each configured with controllable bypass lines, so that by controlling the flows through each unit and its bypass a final refining stage effluent 120 has a ratio of H2, CO, and CO2 (potentially including substantially zero CO2) suitable for downstream processing.
  • CO2 captured and removed from a process as described above can be permanently sequestered, for example in subterranean geologic formations. Permanently sequestering CO2 in this manner can reduce the environmental burden of an industrial activity like chemical production.
  • This concept is referred to broadly as carbon “capture and sequestration” (CCS).
  • CCS carbon capture and sequestration
  • a portion 118 of the captured CO2 may be recycled back to the gasification stage 104 (instead of being directed to CO2 by-product 116 for sequestration), for use inside such gasification block (e.g. in cases where gasification block 104 requires CO2 input).
  • the refining stage 112 yields a refining stage effluent 120 that is suitable for use as a feedstock for a downstream chemical production process, e.g. the FT hydrocarbon process, methanol process, or ammonia process. It is possible to have a monitoring system 122 that monitors the flow rates of the different species in the refining stage effluent 120, including separating the streams to enable such monitoring if needed, and then recombining them into a conversion feed 124.
  • a monitoring system 122 that monitors the flow rates of the different species in the refining stage effluent 120, including separating the streams to enable such monitoring if needed, and then recombining them into a conversion feed 124.
  • the refining stage effluent 120 becomes the conversion feed 124 directly (so if the purification unit 117 is also omitted, the precursor 132 can become the conversion feed 124 directly), and the composition and mass flow rates of the refining stage effluent 120 and the conversion feed 124 are the same.
  • the conversion feed 124 is routed to a conversion stage 126, which makes chemical products such as methanol, hydrocarbons, or ammonia from the conversion feed 124.
  • the conversion stage 126 makes a fuel gas by-product 129 that can be used in up-stream processes as an energy source, such as in gasification stage 104.
  • excess hydrocarbons and syngas from an FT hydrocarbon plant may be recycled and supplied to gasification stage 104 as an energy source.
  • conversion stage 126 may produce one or more additional by-product materials, such as steam, that can be useful in upstream processes, such as in gasification stage 104.
  • excess steam from a methanol or FT hydrocarbon plant may be recycled to gasification stage 104.
  • a nitrogen feed 142 is further provided to the conversion stage 126.
  • waste solid sustainable carbon materials As opposed to purpose grown (or produced) solid sustainable carbon materials, into useful chemicals as a pathway to produce chemicals with a very low (or even zero) environmental burden associated with their production and use.
  • This burden is commonly metricized through a “greenhouse gas life-cycle assessment” (“GHG LCA”) that computes the total amount of GHGs emitted into the environment over the entire lifecycle of a product.
  • GHG LCA greenhouse gas life-cycle assessment
  • waste solid sustainable carbon materials contribute GHGs to a product lifecycle only starting from their collection.
  • the GHG LCA contribution from cultivation, growth, and harvesting of purpose grown (or produced) solid sustainable carbon material is normally much larger than the GHG LCA contribution from solid sustainable carbon waste material collection, so products made from waste solid sustainable carbon material often have much lower GHG LCA values.
  • a key challenge in converting waste solid sustainable carbon material into low (or even zero) GHG LCA chemicals is the traditionally low production efficiency of chemical output compared with solid sustainable carbon material input, along with the very high plant capital cost. For example, in a typical biomass gasification to methanol process, less than 1/3 of the input carbon goes to produce methanol, while the remaining input carbon is “wasted” in byproducts like CO2 emissions. On a carbon basis, this means that the process is only producing about 1/3 of the theoretical maximum product yield. Due to the inherently distributed nature of waste solid sustainable carbon material generation, and the relatively high cost of waste solid sustainable carbon material transport, it is found that the most economical production facilities utilize waste solid sustainable carbon material that is generated in the immediate vicinity (e.g.
  • Embodiments described herein provide a process for making chemical products from solid sustainable carbon materials, the process comprising converting a first solid sustainable carbon to energy and an exhaust comprising CO2 in connection with drying a second solid sustainable carbon material to produce a dried solid sustainable carbon material; sequestering at least a portion of CO2 from the exhaust in a sequestration facility; gasifying the dried solid sustainable carbon material to produce a first stream comprising CO, H2, CO2, and a mixture of organic compounds; providing a second stream comprising hydrocarbon derived from a fossil source; converting the organic compounds in the first stream and the hydrocarbon in the second stream into CO, H2, and CO2, to form one or more gas streams comprising CO, H2, and CO2; converting at least a portion of CO in the one or more gas streams to CO2 to increase H2 in the one or more gas streams and to form one or more converted streams; separating CO2 from the one or more converted streams to form a conversion feed; sequestering at least a portion of the separated CO2 in the sequestration
  • FIG. 1 Other embodiments described herein provide an apparatus for making organic chemical products, the apparatus comprising a solid sustainable carbon material processing unit configured to reduce moisture in a second solid sustainable carbon material and comprisingg an energy conversion unit and a drying unit, wherein the energy conversion is configured to convert a first solid sustainable carbon material into energy and an exhaust containing CO2; and the drying unit is configured to apply the energy produced by the energy conversion unit to form a dried solid sustainable carbon material from the second solid sustainable carbon material; a gasification stage comprising a gasifier coupled to the solid sustainable carbon material processing unit to receive the dried solid sustainable carbon material to form CO, H2, CO2, and organic molecules from the dried solid sustainable carbon material, and a converter to convert the organic molecules to CO, H2, and CO2; a source of fossil-derived hydrocarbon coupled to the converter; a CO converter to convert CO to H2 and CO2; a first CO2 removal unit to remove CO2 and form a conversion feed; a second CO2 removal unit to remove CO2 from the exhaust of the energy conversion unit; a conduit to route removed CO2
  • FIG. 1 Another embodiments described herein provide a process for making chemical products containing carbon from solid sustainable carbon materials, the process comprising converting a first solid sustainable carbon to energy and an exhaust comprising CO2 in connection with drying a second solid sustainable carbon material to produce a dried solid sustainable carbon material; sequestering at least a portion of CO2 from the exhaust in a sequestration facility; gasifying the dried solid sustainable carbon material to produce a first stream comprising CO, H2, CO2, and a mixture of organic compounds; providing a second stream comprising hydrocarbon derived from a fossil source; converting the organic compounds in the first stream and the hydrocarbon in the second stream into CO, H2, and CO2, to form one or more gas streams comprising CO, H2, and CO2; converting at least a portion of CO in the one or more gas streams to CO2 to increase H2 in the one or more gas streams and to form one or more converted streams; separating CO2 from the one or more converted streams to form a conversion feed; controlling an amount of fossil-derived carbon in the conversion feed; sequestering
  • Fig. 1 is a process diagram of a conventional solid sustainable carbon material conversion process.
  • Fig. 2 is a process diagram of a solid sustainable carbon material conversion process according to one embodiment.
  • Fig 3 is a flow sheet comparing aspects of a conventional solid sustainable carbon material to Methanol process with two embodiments of the process of Fig. 2.
  • Fig 4 is a flow sheet comparing aspects of a conventional solid sustainable carbon material to FT hydrocarbon process with two embodiments of the process of Fig. 2.
  • Fig 5 is a flow sheet comparing aspects of a conventional solid sustainable carbon material to ammonia process with two embodiments of the process of Fig. 2.
  • Fig. 6 is a process diagram of a solid sustainable carbon material conversion process according to another embodiment.
  • Fig. 7 is a process diagram of a solid sustainable carbon material conversion process according to another embodiment.
  • Fig 8 is a flow sheet comparing aspects of a conventional solid sustainable carbon material to Methanol process with three embodiments of the process of Fig. 6.
  • Fig 9 is a flow sheet comparing aspects of a conventional solid sustainable carbon material to FT hydrocarbon process with three embodiments of the process of Fig. 6.
  • Fig 10 is a flow sheet comparing aspects of a conventional solid sustainable carbon material to ammonia process with two embodiments of the process of Fig. 6.
  • Fig. 11 is a flow sheet comparing aspects of a solid sustainable carbon material to methanol process for embodiments of the processes of Figs. 6 and 7.
  • Fig. 12 is a flow sheet comparing aspects of a solid sustainable carbon material to FT hydrocarbon process for embodiments of the processes of Figs. 6 and 7.
  • Fig. 13 is a process diagram of a solid sustainable carbon material conversion process according to another embodiment.
  • Fig. 14A is a process diagram of a solid sustainable carbon material conversion process according to another embodiment.
  • Fig. 14B is a process diagram of a biomass processing unit according to one embodiment.
  • Fig. 15 is a flow sheet comparing aspects of a solid sustainable carbon material to ammonia process according to embodiments herein.
  • Fig. 16 is a flow sheet comparing aspects of a solid sustainable carbon material to methanol process according to embodiments herein.
  • Fig. 17 is a flow sheet comparing aspects of a solid sustainable carbon material to FT hydrocarbon process according to embodiments herein. DETAILED DESCRIPTION
  • fossil-derived hydrocarbons from a suitable source such as a natural gas source, a light hydrocarbon stream from an LPG plant, which may process natural gas or refinery gas into LPG and by-product light hydrocarbons, or another gaseous hydrocarbon stream can be integrated with a solid sustainable carbon material gasification process using CCS to boost syngas and/or H2 output, and thus boost production of chemical products derived from such solid sustainable carbon material, while still maintaining a low environmental burden when measured via the GHG LCA of the produced product.
  • a suitable source such as a natural gas source, a light hydrocarbon stream from an LPG plant, which may process natural gas or refinery gas into LPG and by-product light hydrocarbons, or another gaseous hydrocarbon stream
  • CCS solid sustainable carbon material gasification process
  • Such integration takes advantage of: (a) the sharing of equipment between the combined processes of solid sustainable carbon material gasification, hydrocarbon conversion, and chemical product synthesis; and (b) sequestration of biogenic CO2 to remove GHGs from the surface environment, and thus to provide a negative GHG LCA contribution that can be used to offset positive GHG LCA contributions in other parts of the process. It is believed that, currently, ways to create net zero chemical products in a process that utilizes a significant amount of fossil-derived hydrocarbon are unknown. It has now been discovered that this challenge can be addressed by offsetting, in a single integrated process and facility, the positive GHG LCA contribution from the use of such fossil- derived hydrocarbon with the sequestration of the biogenic CO2 produced in biogenic material gasification.
  • biomass conversion facilities having nominal biomass throughput of 1000 short tons (st) /day (corresponding to 771 dry mt/day) to 3000 st/day (corresponding to 2313 dry mt/day) at the gasifier can be used to make fuels with attractive costs that can return economic benefits.
  • Economically advantageous versions of the processes described herein can have nominal biomass gasifier throughput rates of up to 1000 st/day (corresponding to 771 dry mt/day), 1500 st/day (corresponding to 1157 dry mt/day), 2000 st/day (corresponding to 1542 dry mt/day), 2500 st/day (corresponding to 1928 dry mt/day), or 3000 st/day (corresponding to 2313 dry mt/day).
  • the ability to incorporate large amounts of natural gas while maintaining GHGLCA below that of conventionally-produced fuels derived from fossil fuels drives positive economic outcomes for facilities having relatively low throughput of biomass.
  • Fig. 2 is a process diagram of a solid sustainable carbon material conversion process 200A, according to one embodiment.
  • the solid sustainable carbon material conversion process 200A incorporates a source of fossil-derived hydrocarbon to yield higher quantities of syngas that in turn yield higher quantities of end product for the same amount of solid sustainable carbon input.
  • the hydrocarbon source can be a natural gas stream or a hydrocarbon stream from another process, such as an LPG manufacturing process, which can use natural gas and/or refinery gas as feedstock, or another gaseous hydrocarbon stream.
  • the solid sustainable carbon material conversion process 200A uses a gasification stage 204, refining stage 212 and conversion stage 226, similar to the corresponding stages 104, 112, and 126 in the process 100 of Fig. 1.
  • the gasification stage 204 has the gasifier 106, but has a converter 210 configured to incorporate an added fossil-derived hydrocarbon material 206.
  • the converter 210 comprises a reactor configured to convert tars and hydrocarbon molecules 206 into syngas. Such reactors are known, and include POX reactors.
  • the fossil-derived hydrocarbon material 206 can be derived from fossil sources such as natural gas or oil, and can include light hydrocarbon molecules having one to three carbon atoms each (/.e.
  • the hydrocarbon material 206 can include hydrocarbon molecules of moderate size, as well, for example hydrocarbon molecules having 4-6 carbon atoms.
  • the moderately sized hydrocarbons molecules can be linear, branched, cyclic, aliphatic, or aromatic, and mixtures of C1-C6 molecules can be used.
  • any hydrocarbon molecules in the hydrocarbon material 206 may be liquid prior to reaching a processing unit, the hydrocarbon material 206 can be heated to prevent any liquid condensation.
  • Streams having hydrocarbon and non-hydrocarbon molecules can be used as, or added to, the hydrocarbon material 206 after removing the non-hydrocarbon molecules by any suitable means.
  • hydrocarbon streams examples include natural gas, refinery gas, steam cracking feedstocks (ethane, naphtha, and other mixed hydrocarbon streams), steam cracked naphtha, and various C4-C6 streams typically encountered in processing of hydrocarbon materials.
  • Heavier hydrocarbon molecules can also be used, but the heavier hydrocarbons must be converted for use in the processes described herein, with resulting increased energy budget. Heavier hydrocarbons are generally thought to be less efficient in yielding H2 and CO in conversion processes than lighter hydrocarbons or natural gas.
  • the hydrocarbons described herein for use with a solid sustainable carbon material conversion facility may be purified prior to use. For example, where nitrogen may be included in natural gas, the nitrogen can be removed, for example by cryogenic distillation, prior to using the natural gas in the processes herein.
  • the converter 210 has expanded capacity relative to the tar converter 110, which would be used solely to convert the tars in the stream produced by gasifier 106.
  • the converter 210 is a POX reactor.
  • the process resulting from converting the stream produced by the gasifier 106 and the fossil-derived hydrocarbon material 206 in the converter 210 is a gasification stage effluent 211 .
  • Operation of the POX process of the converter 210, in the embodiment described above, can be controlled such that processing of the added hydrocarbon material 206 yields primarily CO and H2, with some CO2 and H2O produced as by-products.
  • the gasification stage effluent 211 is routed to a refining stage 212 that uses a CO converter 213, a CO2 removal unit 214, and an optional purification unit 217 that are similar to those of the process 100 of Fig. 1 , but scaled to the increased volume resulting from use of the hydrocarbon material 206.
  • the CO converter 213 converts at least a portion of CO in the gasification stage effluent 211 to CO2 and H2 to form a converted stream 230, which can be the product of converting the entire gasification stage effluent 211 or a portion thereof.
  • the CO2 removal unit 214 can be used to remove at least a portion of CO2 from the converted stream 230 to form a precursor 232.
  • a refining stage effluent 220 is routed to a conversion stage 226 as a conversion feed 224, and a fuel gas, optionally including excess syngas, can be routed from the conversion stage 226 to the gasification stage 204 where the conversion stage 226 produces a by-product that can be used as a fuel gas.
  • a nitrogen feed 242 is provided to the conversion stage 226.
  • Such nitrogen feed may be supplied by an air separation unit (“ASU”), and in such case, the same ASU may provide nitrogen feed 242 and oxygen feed 108.
  • ASU air separation unit
  • the precursor 232 can become the conversion feed 224 directly.
  • the solid sustainable carbon material is softwood (e.g. pine) forestry residues collected in the southeastern United States, which is assumed to be suitably sized and dried (to 15% by weight moisture) before feeding to the gasifier;
  • the gasification stages 104 and 204 are provided with an input of 1000 short tons per day (st/d) of such softwood (e.g. pine) forestry residues and 135 metric tonnes per day (mt/d) of CO2; i.
  • 1000 stpd solid sustainable carbon material feed represents a feed of 771 dry-mt/d, after converting from short tons (st) to metric tonnes (mt) and accounting for the 15% moisture; ii.
  • 771 dry-mt/d feed represents an atomic carbon feed rate of 369 mt/d using a typical value of 50% by mass for the carbon content in softwood;
  • a first portion of the gasification stage effluent 211 derived from the solid sustainable carbon material input to the gasification stage 204 is equal in rate and composition to the effluent 111 of the gasification stage 104, which is to say that the first portion of the gasification stage effluent 211 derived from the solid sustainable carbon material input has a composition by volume that is 40% CO, 30% CO2, and 30% H2, yielding approximately 505 mt/d CO, 595 mt/d CO2, and 27 mt/d H2, and only trace amounts of other species; and v. a second portion of the gasification stage effluent 211 derived from the fossil-derived natural gas converted in the converter 210 has flow rate and composition computed assuming:
  • the second portion consists of CO, CO2, and H2, and only trace amounts of other species;
  • the CO converters 113 and 213 are both WGS units that convert 100% of input CO into H2 and CO2 via reaction with water;
  • the CO2 removal units 114 and 214 are both AGR units that remove 100% of input CO2 but also leak 5% of that removed CO2 into the atmosphere;
  • each of the conversion feeds 124 and 224 contains 2.05 moles of H2 for each mole of CO, and 3.05 moles of H2 for each mole of CO2; ii. there is no nitrogen source 142 or 242; iii. each of the conversion units 126 and 226 converts 96% of the carbon in the respective conversion feeds 124 and 224 into methanol product, with the remaining 4% of the carbon converted into CO2 and emitted into the atmosphere; and iv.
  • each of the purification units 117 and 217 includes sulfur removal via a catalytic, chemisorption, and/or physisorption process that does not otherwise change the mass flow rates, so that with respect to CO, CO2, and H2, refining stage effluent 120 is the same as precursor 132 and refining stage effluent 220 is the same as precursor 232;
  • each of the conversion feeds 124 and 224 contains 2.20 moles of H2 for each mole of CO, and 3.20 moles of H2 for each mole of CO2; ii. there is no nitrogen source 142 or 242; iii. each of the conversion units 126 and 226 converts 96% of the carbon in the respective conversion feeds 124 and 224 into FT hydrocarbon product, with the remaining 4% of the carbon converted into CO2 and emitted into the atmosphere; iv.
  • each of the purification units 117 and 217 includes sulfur removal via a catalytic, chemisorption, and/or physisorption process that does not otherwise change the mass flow rates, so that with respect to CO, CO2, and H2, refining stage effluent 120 is the same as precursor 132 and refining stage effluent 220 is the same as precursor 232; and v. the fuel gas 229 consists of hydrocarbon and syngas; while it is not shown in the Examples, such fuel gas 229 may be routed to the gasification stage 204 as an additional energy source, for example, as an additional contribution to the hydrocarbon material 206 or as a separate stream.
  • each of the conversion feeds 124 and 224 contains high purity H2; ii. the nitrogen source 142 or 242 contains approximately 3 moles of high purity N2 for each mole of high purity H2 supplied in the respective conversion feeds 124 and 224, and the N2 may be supplied, for example, by an ASU, which may further supply oxygen for the gasification stages 104 and 204 as oxygen source 108; iii. each of the conversion stages 126 and 226 converts 96% of the hydrogen in the respective conversion feeds 124 and 224 into an ammonia product, with the remaining 4% converted into H2O and emitted into the atmosphere; and iv.
  • each of the purification units 117 and 217 includes a PSA that produces a high purity H2 stream, in which process 20% of H2 in the stream is removed as tail gas; while it is not shown in the Examples, such tail gas may be recycled for power/energy elsewhere in the facility;
  • the monitoring unit 122 is either not present or does not change the mass flow rates in the input and output streams, such that refining stage effluent 120 is the same as conversion feed 124 and refining stage effluent 220 is the same as conversion feed 224; and
  • the LCA is assumed to be a “well-to-wake” type that includes the upstream contributions for any feedstock or utility inputs to the production facility, the production process itself, and any downstream end-product transportation, distribution, and use, and reference values and calculation methodologies consistent with the 2022 version of the GREET model provided by the Argonne National Laboratory (accessible at https://greet.es.anl.gov/greet.models as of December 23, 2022) are used, yielding the following GHG LCA contribution metrics in terms of equivalent CO2 emissions (C02e): i. for collection/transport of the 1000 st/d of such softwood (e.g.
  • the process 200A includes optional use of CO2 in the gasification stage 104 for the gasifier 106, the converter 210, or both.
  • the CO2 recycle line from the CO2 removal unit to the gasification stage 106 can optionally be used, or an external source of CO2 260 can provide CO2 to the gasification stage 104 (gasifier 106 and/or converter 210) through an external CO2 conduit 218.
  • Each source of CO2 can be used in any suitable ratio or mixture, or only one of the CO2 sources can be used, or none can be used, depending on the embodiment.
  • Fig 3 is a flow sheet comparing aspects of a conventional solid sustainable carbon material to methanol process with two embodiments of the process of Fig. 2, each parameterized as set forth above.
  • Fig. 3 additionally shows the GHG LCA of the produced product, and a number of embodiment metrics.
  • CASE 3A referring to conventional process 100
  • no natural gas is supplied to the tar converter 110 and the total product output is 318 mt/d.
  • 43% of the gasification stage effluent 111 is routed to the CO converter 113 (to increase the proportion of H2 in the stream relative to CO), and 100% of the stream 130 is routed to the CO2 removal unit 114.
  • the CO2 removal unit 114 As shown in Fig.
  • the GHG LCA of the final product is highly negative, because 100% of the carbon in the methanol product is biogenic (so its downstream combustion does not produce any net emissions) and a large amount of biogenic CO2 is permanently sequestered, leading to a large net removal of CO2 from the surface environment.
  • CASE 3B referring to an embodiment of the process 200A, 246 mt/d of natural gas is supplied to the converter 210 via hydrocarbon material 206, and the total methanol output increases to 667 mt/d (about 2.10 times the output of the conventional process 100).
  • CASE 3B In the process defined by CASE 3B, 27% of the gasification stage effluent 211 is routed to the CO converter 213 (to increase the proportion of H2 in the stream relative to CO), a proportion less than in CASE 3A by about 16%, and 100% of the stream 230 is routed to CO2 removal unit 214.
  • the GHG LCA of the final product In CASE 3B, the GHG LCA of the final product is approximately zero.
  • the process 200A is capable of combining solid sustainable carbon gasification, natural gas reforming via POX, and CCS to produce a maximum amount of net zero methanol product.
  • Methanol products with a negative GHG LCA may also be produced via an embodiment of the process 200A. Some embodiments produce methanol products with a GHG LCA that is between -100% and 0% of the equivalent fossil baseline, by supplying a lower amount of natural gas than in CASE 3B at the cost of reduced plant productivity. Alternately, Methanol products with a slightly positive GHG LCA may be produced.
  • Some embodiments of the process 200A produce methanol products with a GHG LCA that is 20% of the fossil baseline, as in the embodiment labeled “CASE 3C” referring to an embodiment of the process 200A in which 350 mt/d of natural gas is supplied to the converter 210 via hydrocarbon material 206, and the total methanol output increases to 814 mt/d (about 2.56 times the output of the conventional process 100).
  • Methanol products can also be produced with GHG LCA between 0 and 20% of the fossil baseline by supplying a natural gas feed that is between the amount supplied in CASE 3B and CASE 3C, with resulting productivities that are between these two cases, respectively.
  • Some embodiments of the process 200A produce methanol products with a GHG LCA that is -50% of the fossil baseline, as in the embodiment labeled “CASE 3D” referring to an embodiment of the process 200A in which 101 mt/d of natural gas is supplied to the converter 210 via hydrocarbon material 206, and the total methanol output is 461 mt/d (about 1 .45 times the output of the conventional process 100).
  • CASE 3D 34% of the gasification stage effluent 211 is routed to the CO converter 213 (to increase the proportion of H2 in the stream relative to CO), and 100% of the stream 230 is routed to the CO2 removal unit 214.
  • Methanol products can also be produced with GHG LCA between 0% and -50% of the fossil baseline by supplying a natural gas feed that is between the amount supplied in CASE 3A and CASE 3D, with resulting productivities that are between these two cases, respectively. Additionally, methanol products can be produced with GHG LCA greater than 20% of the fossil baseline by supplying a natural gas feed that is greater than what is supplied in CASE 3C, resulting, for example, in GHG LCA up to 30%, 40% or 50% of the fossil baseline.
  • one impact of introducing natural gas to the converter 210 is that the carbon atoms in the produced methanol are no longer 100% biogenic (in the sense of being derived from biogenic sources), but rather include 39% fossil carbon atoms in CASE 3B, 48% fossil carbon atoms in CASE 3C, and 21 % fossil carbon atoms in CASE 3D.
  • the GHG LCA of each of these cases reflects the production process, including the contribution of fossil-derived natural gas offset by the sequestered biogenic CO2, as well as downstream combustion.
  • many regulatory regimes penalize fuels containing fossil-derived carbon atoms, regardless of the GHG LCA, and thus in certain marketplaces there may be a need for an alternative approach that does not produce an end product containing fossil-derived carbon atoms.
  • “External inputs into the process” herein refers to net material inputs into the process, and accordingly excludes materials that are used solely outside of the process as well as internal recycle streams. For example, if the gasifier 106 or tar converter 110 or 210 utilizes a stream of externally supplied natural gas to fire a combustor to externally heat a reactor chamber, such natural gas feed would not be an “external input into the process” (because such natural gas remains physically outside the process).
  • CO2 recycle 118 is not an “external input into the process” (because it is an internal recycle stream), whereas the externally supplied CO2 through CO2 conduit 218 discussed below is an “external input into the process”. It is useful to then introduce the following three metrics:
  • Embodiments of Fig 3 share the characteristic that a % of net atomic carbon input into the process from fossil sources (here associated with the hydrocarbon material 206) is significant- 32%, 41 %, and 16% in CASE 3B CASE 3C, and CASE 3D respectively - whereas none of the atomic carbon feed into the process used in the conventional process 100 is from fossil sources.
  • the percentage of net atomic carbon input into the process from hydrocarbons is computed by dividing the atomic carbon flow in the hydrocarbon material 206 by the combined atomic carbon flows of streams 102, 206, and 218 (which will be introduced later). For purposes of computing the percentage of net atomic carbon, streams that are not present in an embodiment would be allocated a value of zero.
  • the embodiments of Fig 3 share the characteristic that a significant portion of the CO2 directed into by-product 116 and sequestered has a fossil origin (here derived from the hydrocarbon material 206) - 31 %, 38%, 16% in CASE 3B, CASE 3C, and CASE 3D respectively - whereas none of the CO2 sequestered in the conventional process 100 has a fossil origin.
  • the volumetric flow rates of the gasification stage effluent 211 emerging from the converter 210 are substantially increased relative to the corresponding flow rate of the gasification stage effluent 111 emerging from the tar converter 110 of the conventional process 100 (i.e.
  • Fig 4 is a flow sheet comparing aspects of a conventional solid sustainable carbon material to FT hydrocarbon process with two embodiments of the process 200A of Fig. 2, each configured to produce FT hydrocarbons and parameterized as set forth above.
  • Fig. 4 additionally shows the GHG LCA of the produced product, and a number of embodiment metrics. It is noted that in the embodiment labeled “CASE 4A” referring to conventional process 100, no natural gas is supplied to the tar converter 110 and the total FT hydrocarbon output is 134 mt/d.
  • the gasification stage effluent 111 is routed to the CO converter 113 (to increase the proportion of H2 in the stream relative to CO), and 100% of the stream 130 is routed to the CO2 removal unit 114.
  • the GHG LCA of the FT hydrocarbon product is highly negative, as 100% of the carbon in the FT hydrocarbon product is biogenic (so its downstream combustion does not produce any net emissions) and a large amount of biogenic CO2 is permanently sequestered, leading to a large net removal of CO2 from the surface environment.
  • CASE 4B In contrast, in the embodiment labeled “CASE 4B,” referring to an embodiment of the process 200A, 268 mt/d of natural gas is supplied to the converter 210 via the hydrocarbon material 206, and the total FT hydrocarbon product output increases to 293 mt/d (about 2.19 times the output of the conventional process 100).
  • CASE 4B 29% of the gasification stage effluent 211 is routed to the CO converter 213 (to increase the proportion of H2 in the stream relative to CO), a proportion less than in CASE 4A by about 16%, and 100% of the stream 230 is routed to the CO2 removal unit 214.
  • the GHG LCA of the FT hydrocarbon product is approximately zero.
  • the process 200A effectively combines solid sustainable carbon gasification, natural gas reforming via POX, and CCS to produce a maximum amount of net zero FT hydrocarbon product.
  • FT hydrocarbon products with a slightly negative GHG LCA may also be produced via an embodiment of the process 200A.
  • Some embodiments produce hydrocarbon products with a GHG LCA that is between -100% and 0% of the fossil baseline, by supplying a lower amount of natural gas than in CASE 4B at the cost of reduced plant productivity.
  • FT hydrocarbon products with a slightly positive GHG LCA may be produced.
  • Some embodiments of the process 200A produce hydrocarbon products with a GHG LCA that is 20% of the fossil baseline, as in the embodiment labeled “CASE 4C” referring to an embodiment of the process 200A.
  • CASE 4C 376 mt/d of natural gas is supplied to the converter 210 via the hydrocarbon material 206, and the total hydrocarbon product output increases to 357 mt/d (about 2.67 times the output of the conventional process 100).
  • 26% of the gasification stage effluent 211 is routed to the CO converter 213 (to increase the proportion of H2 in the stream relative to CO) a proportion less than in CASE 4A by about 19% and less than in CASE 4B by about 3%, and 100% of the stream 230 is routed to the CO2 removal unit 214.
  • Hydrocarbon products can also be produced with between 0 and 20% of the fossil baseline GHG LCA by supplying a natural gas feed that is between the amount supplied in CASE 4B and CASE 4C, with resulting productivities that are between these two cases, respectively.
  • hydrocarbon products can be produced with GHG LCA greater than 20% of the fossil baseline by supplying a natural gas feed that is greater than that supplied in CASE 4C, resulting, for example, in GHG LCA up to 30%, 40% or 50% of the fossil baseline.
  • Some embodiments of the process 200A produce hydrocarbon products with a GHG LCA that is -50% of the fossil baseline, as in the embodiment labeled “CASE 4D” referring to an embodiment of the process 200A in which 117 mt/d of natural gas is supplied to the converter 210 via hydrocarbon material 206, and the total hydrocarbon output is 203 mt/d (about 1 .52 times the output of the conventional process 100).
  • CASE 3D 36% of the gasification stage effluent 211 is routed to the CO converter 213 (to increase the proportion of H2 in the stream relative to CO), and 100% of the stream 230 is routed to the CO2 removal unit 214.
  • Hydrocarbon products can also be produced with GHG LCA between 0% and -50% of the fossil baseline by supplying a natural gas feed that is between the amount supplied in CASE 4A and CASE 4D, with resulting productivities that are between these two cases, respectively.
  • Embodiments of Fig 4 share the characteristic that a significant percentage of the total atomic carbon feed into the process has a fossil origin (here associated with hydrocarbon material 206) - 34%, 42%, and 19% in CASE 4B, CASE 4C, and CASE 4D, respectively - whereas none of the carbon used in the conventional process has a fossil origin.
  • the embodiments of Fig 4 share the characteristic that a significant portion of the CO2 directed into by-product 116 for sequestration has a fossil origin (here again derived from the hydrocarbon material 206) - 33%, 40%, and 18% for CASE 4B, CASE 4C, and CASE 4D respectively - whereas none of the CO2 sequestered in the conventional process 100 has a fossil origin.
  • the volumetric flow rates of the gasification stage effluent 211 emerging from the converter 210 are substantially increased relative to the corresponding flow rate of gasification stage effluent 111 emerging from the tar converter 110 of the conventional process 100 (i.e.
  • Fig. 5 is a flow sheet comparing aspects of a conventional solid sustainable carbon material to ammonia process with two embodiments of the process 200A of Fig. 2, each configured for ammonia production and parameterized as set forth above.
  • Fig. 5 additionally shows the GHG LCA of the produced product, and a number of embodiment metrics. It is noted that in the embodiment labeled “CASE 5A” referring to conventional process 100, no natural gas is supplied to the tar converter 110 and the total product output is 275 mt/d.
  • 100% of the gasification stage effluent 111 is routed to the CO converter 113 to convert substantially all of the CO into CO2 to maximize the production of H2, and 100% of the stream 130 is routed to the CO2 removal unit 114, to remove substantially all of the CO2, resulting in a stream that is substantially all H2, which is useful for the ammonia production process.
  • the GHG LCA of the ammonia product is highly negative, because ammonia contains no carbon and subsequent combustion thereof releases no CO2, while at the same time sequestration of the biogenic CO2 produced by gasification (excepting the portion that leaks from the overall system), representing substantially all carbon input to the process, provides a very large net removal of CO2 from the surface environment.
  • CASE 5B 1400 mt/d of natural gas is supplied to the converter 210 via the hydrocarbon material 206, and the total ammonia output increases to 1988 mt/d (about 7.24 times the output of the conventional process 100).
  • 100% of the gasification stage effluent 211 is routed to the CO converter 213 to convert substantially all of the CO into CO2 to maximize the production of H2, and 100% of the stream 230 is routed to the CO2 removal unit 214, to remove substantially all of the CO2.
  • the GHG LCA of the ammonia product in CASE 5B is approximately zero.
  • ammonia products with a slightly negative GHG LCA may also be produced via an embodiment of the process 200A. Some embodiments produce ammonia products with a GHG LCA that is between -100% and 0% of the fossil baseline by supplying a lower amount of natural gas than in CASE 5B at the cost of reduced plant productivity. Alternately, ammonia products with a slightly positive GHG LCA may be produced.
  • Some embodiments of the process 200A produce ammonia products with a GHG LCA that is 10% of the fossil baseline, as in the embodiment labeled “CASE 5C” referring to an embodiment of the process 200A in which 2600 mt/d of natural gas is supplied to the converter 210 via the hydrocarbon material 206, and the total ammonia product output increases to 3457 mt/d (about 12.58 times the output of the conventional process 100).
  • Ammonia products can also be produced with a GHG LCA that is between 0 and 10% of the fossil baseline by supplying an amount of natural gas to the converter 210 that is in between the amount supplied in CASE 5B and CASE 5C, with resulting productivities that are between these two cases respectively.
  • ammonia products can be produced with GHG LCA greater than 10% of the fossil baseline by supplying an amount of natural gas to the converter 210 that is greater than what is supplied in CASE 5C.
  • Some embodiments of the process 200A produce ammonia products with a GHG LCA that is -50% of the fossil baseline, as in the embodiment labeled “CASE 5D” referring to an embodiment of the process 200A in which 315 mt/d of natural gas is supplied to the converter 210 via hydrocarbon material 206, and the total ammonia output is 660 mt/d (about 2.40 times the output of the conventional process 100).
  • Ammonia products can also be produced with GHG LCA between 0% and -50% of the fossil baseline by supplying a natural gas feed that is between the amount supplied in CASE 5A and CASE 5D, with resulting productivities that are between these two cases, respectively.
  • One noteworthy simplification in the production of ammonia relative to methanol and FT hydrocarbons is that the end product does not contain carbon, avoiding any need (as encountered above in the context of methanol and FT hydrocarbons) to modify the process so the end product contains no fossil-derived carbon as a way to maximize product value in certain markets.
  • the inventive embodiments in Fig 5 share the characteristic that a significant percentage of the total atomic carbon feed into the process has a fossil origin (here again associated the hydrocarbon material 206) - 73%, 83%, and 38% in CASE 5B, CASE 5C, and CASE 5D respectively - whereas none of the carbon used the conventional process 100 has a fossil origin.
  • the embodiments of Fig 5 share the characteristic that a significant portion of the CO2 sequestered has a fossil origin (here again derived from the hydrocarbon material 206) - 75%, 87%, and 41 % in CASE 5B, CASE 5C, and CASE 5D respectively - whereas none of the CO2 sequestered in the conventional process 100 has a fossil origin.
  • the volumetric flow rates gasification stage effluent 211 emerging from the converter 210 are substantially increased relative to the corresponding flow rates of the gasification stage effluent 111 emerging from the tar converter 110 of the conventional process 100 - approximately 5.85, 10.01 , 2.09 times in CASE 5B, CASE 5C, and CASE 5D respectively.
  • the processes 100 and 200A may be operated to produce hydrogen as an end product through appropriate plant configuration where no conversion stage 126 or 226 is included.
  • the ammonia unit can be omitted and the rest of the process 200A operated as shown in Fig. 5.
  • the conversion feeds 124 and 224 in the ammonia process of Fig. 5 consist of high purity H2, and as noted in the description of the process 200A, the purification units 117 and 217 can include a PSA that removes impurities from the intermediate precursors 132 and 232.
  • the resulting hydrogen could be delivered, for example, to hydrogen trucks or pipelines for transport, distribution, and/or for use in road transportation, industrial processing, chemical production, or power generation. It is readily observed that for such a hydrogen end product application, for each of the simulated ammonia cases in Figure 5 one would expect similar embodiment metrics but using the H2 flow in conversion feeds 124 and 224 as the end product output; namely: A.
  • GHG LCA for a hydrogen end product application is calculated “well-to-gate” instead of “well-to-wake” as here with methanol, hydrocarbons, and ammonia.
  • the difference is that in the “well-to-gate” case, emission contributions from transportation, distribution, and use are not included. Since the downstream contributions from ammonia are small, it is readily observed that the net zero GHG LCA CASE 5B should produce approximately net zero hydrogen when adapted to produce hydrogen as an end product. And similarly one would expect that the 10% of fossil GHG LCA CASE 5C should produce modestly positive GHG LCA hydrogen and the -50% fossil GHG LCA CASE 5D should produce moderately negative GHG LCA hydrogen
  • 20% of the H2 stream is removed as tail gas in connection with purification by a PSA in 217, due to the high purity requirements for ammonia synthesis.
  • a PSA purification unit
  • the purification units 117 and 217 may be altered or controlled to provide higher yield by using, for example, a PSA with a lower output H2 purity rating or a methanation unit.
  • the PSA unit can be omitted entirely where a certain amount of CO and/or CO2 contamination is acceptable.
  • Fig. 6 is a process diagram of a solid sustainable carbon material conversion process 200B, according to another embodiment.
  • the process 200B uses a source of fossil- derived hydrocarbon to yield higher quantities of syngas that in turn yield higher quantities of end product for the same amount of solid sustainable carbon input.
  • a key difference in 200B vs 200A is that in cases where the end product is a carbon containing material, such as methanol or hydrocarbons, the process 200B produces an end product that contains little to substantially no fossil-derived carbon, while otherwise maintaining approximately the same GHG LCA and end product output.
  • the gasification stage 104 that uses sized and dried solid sustainable carbon material 102 contains a gasification unit 106 and tar converter 110, and produces a gasification stage effluent 111 containing CO, H2, and CO2, and may use oxygen source 108 and steam source 109, just as in the conventional process 100. Additionally, just as in process 100, there is a refining stage, here 212B, that contains a CO converter 113 (and bypass) for selectively routing a portion of the gasification stage effluent 111 for CO conversion to increase the H2 content of the gasification stage effluent 111 relative to CO.
  • the process 200B also has the CO2 removal unit 114 (and bypass) for removing CO2 from intermediate stream 230, wherein the CO2 removal unit 114 yields a stream of removed CO2 which may be directed, in part or wholly, into CO2 recycle 118 for recycling back into gasification stage 104 and into by-product 116, in part or wholly, for sequestration.
  • a hydrocarbon processing stage effluent 256, product of the hydrocarbon processing stage 250 is combined with precursor 132 downstream of the CO2 removal unit 114.
  • This combined stream may then be directed through purification unit 217, if further purification is required, similar to the process 200A of Fig. 2.
  • the resulting refining stage effluent 220 may be directed through the monitoring unit 122, if present, resulting in conversion feed 224 which is then directed into conversion stage 226.
  • the process 200B has a fossil hydrocarbon processing stage 250 to produce the hydrocarbon processing stage effluent 256.
  • the hydrocarbon processing stage 250 includes the hydrocarbon converter 210B which uses a reactor or reaction facility configured to convert the hydrocarbon material 206 into syngas. Such facilities are known, and include steam methane reforming (SMR) facilities, auto-thermal reforming (ATR) facilities, and POX facilities.
  • SMR steam methane reforming
  • ATR auto-thermal reforming
  • POX POX facilities.
  • the hydrocarbon material 206 derived from fossil sources, is introduced into the process 200B as an input to the hydrocarbon converter 210B within the hydrocarbon processing stage 250.
  • the hydrocarbon material 206 used with the process 200B can have the same source and composition as any of the hydrocarbon streams described above in connection with the process 200A.
  • the hydrocarbon converter 210B is sized to convert a hydrocarbon stream with a mass flow rate of atomic carbon that is at least 15% of the net mass flow rate of atomic carbon input to the overall process. That is to say, in some embodiments, the hydrocarbon converter 210B handles at least 15% of atomic carbon input to the process.
  • the hydrocarbon converter 210B produces an effluent 252 containing substantially syngas and CO2, which is then routed to a second CO converter 213B, which may be a WGS unit, to produce an intermediate 254 that is substantially H2 and CO2.
  • Intermediate 254 which is a second converted stream, is then routed to a second CO2 removal unit 214B, which may be an AGR unit, to produce the hydrocarbon processing stage effluent 256.
  • the second CO2 removal unit 214B produces a stream of CO2 that can be entirely routed for sequestration, either combined with by-product 116 or separately.
  • a second purification unit may be used immediately after the second CO2 removal unit 214B, which may be a PSA or methanation unit, if further purification of the hydrocarbon processing stage effluent 256 is desired.
  • the hydrocarbon processing stage effluent 256 can be a second conversion feed, that is mixed with the precursor 132 (under such circumstances a first conversion feed) to produce the conversion feed 224 that is provided to the conversion stage 226.
  • a flow controller 260 can be used to control flow of the fossil- derived CO2 258 to the hydrocarbon processing stage effluent 256 to withdraw a desired amount of fossil-derived CO2 from sequestration and route a controlled amount of fossil-derived carbon into the conversion feed 224 and thus into the final conversion stage 226 products.
  • an arbitrary amount of fossil-derived carbon up to the entire amount of carbon available from the hydrocarbon stream 206, modulated by CO2 conversion to final products in the conversion stage 226, can be included in the final products.
  • process 200B substantially all the fossil-derived carbon from the hydrocarbon material 206 is converted to CO2 and sequestered. Whereas embodiments of process 200A and 200B may be engineered to have similar inputs, outputs, and GHG LCA product values, the process 200B inherently has a lower degree of system integration, since the process 200A has a single conversion unit 210, whereas in 200B the tar converter 110 and the hydrocarbon converter 210B are separate.
  • Fig. 7 is a process diagram of a solid sustainable carbon material conversion process 200C according to another embodiment.
  • the process 200C includes a hydrocarbon processing stage 250C that has no CO2 removal unit (the CO2 removal unit 214B of the process 200B is omitted from the hydrocarbon processing stage 250C).
  • the intermediate 254 can be a hydrocarbon processing effluent that contains H2 as well as CO2 derived from fossil sources.
  • the hydrocarbon processing effluent, 254 in this case, is routed to the CO2 removal unit 214, included in the refining stage 212C of the process 200C instead of the CO2 removal unit 114, to remove substantially all (e.g. >90%, >95%, or > 95%) of the CO2, fossil-derived and biogenic, from the intermediate 254 and the portion of the intermediate 130 routed for CO2 removal.
  • substantially all e.g. >90%, >95%, or > 95%) of the CO2, fossil-derived and biogenic
  • the process 200C produces a carbon containing product that has little to substantially no fossil carbon, but with fewer processing units.
  • the CO2 recycle 118 has been removed, the two CO removal units 114 and 214B have been replaced by the single unit 214 (similar to the unit in the process 200A), and the intermediate 254 of the process 200B is instead routed directly to the CO2 removal unit 214 along with the portion of stream 130 diverted for CO2 removal, so as to produce a precursor 232 that is substantially free of fossil carbon (provided, as noted below, the added CO2 stream 218 is itself substantially free of fossil-derived carbon).
  • intermediate 254 contains substantially H2 and fossil-derived CO2, and substantially all of the CO2 in intermediate 254 is removed by the CO2 removal unit 214 without recycling any of the removed CO2 back into the process through recycle 118, then the precursor 232 is substantially free of fossil-derived carbon, and products resulting from the precursor 232 are also substantially free of fossil-derived carbon.
  • a source of CO2 260 can be provided to supply CO2 to the gasification stage 104 using a CO2 conduit 218, if needed. If not needed, the CO2 source 260 and CO2 conduit 218 may be omitted, ensuring that no fossil-derived CO2 enters the gasification stage 104.
  • the CO2 source 260 may be, or may include, any or all of a CO2 pipeline, a CO2 capture system that captures CO2 from another industrial process, or a direct air capture (DAC) facility that removes CO2 directly from the atmosphere.
  • DAC direct air capture
  • the CO2 conduit 218 will add fossil-derived CO2 to the precursor 232 and downstream products.
  • a CO2 source that is biogenic such as a DAC process or CO2 captured an industrial process that produced biogenic CO2, in the process 200C, may be superior to the process 200B in cases where such biogenic CO2 source 260 can be secured economically.
  • Example embodiments of the processes 200B and 200C are simulated below.
  • the parameters and assumptions introduced above apply to the simulated processes 200B and 200C, below, with the following additions:
  • the hydrocarbon conversion unit 21 OB is a POX reactor in which:
  • the output stream 252 is mostly CO, CO2, and H2, and only trace amounts of other species;
  • the hydrocarbon material 206 is a natural gas stream, and 75% of the carbon in the hydrocarbon material 206 is converted into CO, and the remaining 25% is converted into CO2; and,
  • a volumetric ratio of H2:CO in the output stream 252 is equal to 2;
  • the CO converter 213B is a WGS unit that converts 100% of the input CO into H2 and CO2 via reaction with water;
  • the CO2 removal unit 214B is an AGR unit that removes 100% of the input CO2 from the process and in so doing leaks 5% of that removed CO2 into the atmosphere.
  • Fig. 8 is a flow sheet comparing the conventional solid sustainable carbon material conversion process 100, simulated as CASE 3A described above, with three embodiments of the solid sustainable carbon material conversion process 200B, parameterized as set forth above and configured for the production of methanol.
  • Fig. 8 additionally shows the GHG LCA of the produced product, and a number of embodiment metrics.
  • CASE 8B referring to an embodiment of the process 200B, 246 mt/d of natural gas is supplied to the hydrocarbon converter 21 OB via hydrocarbon material 206, and the total methanol product output increases to 666 mt/d.
  • CASE 8B the natural gas input, methanol product, and GHG LCA in CASE 8B are approximately the same as in corresponding CASE 3B, indicating that process 200B (simulated in CASE 8B) and process 200A (simulated in CASE 3B) have approximately the same overall process performance.
  • the % of net atomic carbon input into process from natural gas is 29%, and total sequestered CO2 is approximately 920 mt/d.
  • 0% of the carbon in the methanol product is fossil-drived carbon
  • CASE 3B 40% of the carbon in the methanol product is fossil-derived carbon.
  • CASE 8B results in more fossil- derived carbon being routed to by-product 116 for sequestration and more biogenic carbon retained in the main process (by reducing, as noted above, the portion of gasification stage effluent 111 that flows into CO converter 113 and the portion of stream 130 that flows into CO2 removal unit 114 compared to the corresponding values in CASE 3B).
  • the increase in fossil-derived CO2 directed to sequestration in CASE 8B, relative to CASE 3B, is observed in the proportion of CO2 by-product 116 that is fossil-derived CO2, which is 31 % in CASE 3B and 70% CASE 8B.
  • CASE 8C reflects a similar relationship to CASE 3C as described above for CASE 8B and CASE 3B. In both cases the input natural gas (and share of fossil- derived carbon in the input carbon streams), output methanol product, and GHG LCA are all approximately the same, while the proportion of fossil-derived carbon in the methanol product is 0% for CASE 8C and 48% for CASE 3C.
  • Methanol free of fossil- derived carbon is achieved in CASE 8C by increasing the amount of fossil-derived CO2 routed to sequestration and retaining an equal amount of biogenic carbon in the main process by reducing the portion of gasification stage effluent 111 that flows into CO converter 113 and the portion of stream 130 that flows into CO2 removal unit 114 compared to the corresponding values in CASE 3C.
  • CASE 8D is a modified version of CASE 8C in which additional natural gas is supplied (here 390 mt/d vs 350 mt/d in CASE 8C) so that there is sufficient hydrogen available to fully consume all of the available biogenic carbon and maximize the production of 100% biogenic methanol, with a yield of 870 mt/d (approximately 2.74 times the conventional CASE 3A, process 100, value.)
  • no biogenic CO2 is sequestered, as reflected by the fact that 100% of the CO2 by-product 116 is fossil- derived CO2.
  • the process 200B can be used to direct an arbitrary amount of fossil-derived CO2 to the final products available from the conversion stage 226.
  • the percentage of fossil-derived carbon in the final products could be up to around 50% if all carbon provided to the process 200B in all forms is maximally converted to final products.
  • the percent of fossil-derived carbon in the final products can be selected to be any value between 0% and about 50%.
  • the processes described herein generally make products having less than 50% fossil-derived carbon content, and using certain embodiments herein the percentage can be selected to be any value below about 50% down to 0%.
  • CO2 removal unit 214B may remove only a portion of the fossil CO2 from effluent 254, for example >50%, >80%, >90%, or >95%, and in such case effluent 256 will retain some of the fossil-derived CO2, which would also ultimately contribute to the fossil-derived carbon content in the finished fuel.
  • Fig. 9 is a flow sheet comparing the previously introduced conventional solid sustainable carbon material conversion process 100, simulated in CASE 4A as producing FT hydrocarbons, and three embodiments of the solid sustainable carbon material conversion process 200B, parameterized as set forth above and configured for the production of FT hydrocarbons.
  • Fig. 9 additionally shows the GHG LCA of the produced hydrocarbons, and a number of embodiment metrics.
  • CASE 9B referring to an embodiment of the process 200B, 266 mt/d of natural gas is supplied to the hydrocarbon converter 210B via the hydrocarbon material 206, and the total hydrocarbon product output increases to 292 mt/d.
  • none of the gasification stage effluent 111 is routed to the first CO converter 113 since there is no need to increase the proportion of H2 share in the stream, and 70% of the intermediate stream 130 is diverted into the first CO2 removal unit 114. Additional hydrogen is supplied in the hydrocarbon conversion stage effluent 256.
  • the GHG LCA of the hydrocarbon product is approximately zero in CASE 9B. It is notable that the natural gas input, hydrocarbon product, and GHG LCA in CASE 9B are approximately the same as in corresponding CASE 4B, indicating that process 200B (simulated in CASE 9B) and process 200A (simulated in CASE 4B) have approximately the same overall process performance. Similarly, in both CASE 9B and CASE 4B the % of net atomic carbon input into process from natural gas is 31 %, and total sequestered CO2 is approximately 978 mt/d. In CASE 9B, however, 0% of the carbon in the hydrocarbon product is fossil-derived carbon, whereas in CASE 9B 41 % of the carbon in the hydrocarbon product is fossil-derived carbon.
  • CASE 9B results in more fossil-derived carbon being routed to the CO2 by-product 116 while retaining an equal amount of additional biogenic carbon in the main process (by reducing, as noted above, the portion of the gasification stage effluent 111 that flows into the CO converter 113 and the portion of stream 130 that flows into the first CO2 removal unit 114 compared to CASE 4B.
  • the increase in fossil-derived CO2 directed to sequestration is observed in the proportion of the CO2 by-product 116 that is fossil-derived CO2, which is 25% in CASE 9B and 70% in CASE 9B.
  • CASE 9C reflects a similar relationship to CASE 4C as described above for CASE 9B and CASE 4B.
  • CASE 9C In both cases (CASE 9C and CASE 4C) the input natural gas (and proportion of fossil-derived carbon in the input carbon streams), output hydrocarbon product, and GHG LCA are all approximately the same, while the proportion of fossil-derived carbon the methanol product is 0% for CASE 9C and 49% for CASE 4C.
  • CASE 9C also results in more fossil-derived carbon directed to sequestration while retaining an equal amount of additional solid sustainable carbon in the main process by reducing the portion of the gasification stage effluent 111 that flows into the CO converter 113 and the portion of stream 130 that flows into the first CO2 conversion unit 114 compared to CASE 4C.
  • CASE 9D is a modified version of CASE 9C in which additional natural gas is supplied (here 420 mt/d vs 375 mt/d in CASE 9C) so that there is sufficient hydrogen available to fully consume all of the available biogenic carbon and maximize the production of 100% biogenic hydrocarbons, with a yield of 384 mt/d (approximately 2.87 times the conventional CASE 4A, process 100, value.) In this case, no biogenic CO2 is sequestered, as reflected by the fact that 100% of the CO2 by-product 116 is fossil-derived CO2.
  • Fig. 10 is a flow sheet comparing the previously introduced conventional solid sustainable carbon material conversion process 100, simulated in CASE 5A, and two embodiments of the solid sustainable carbon material conversion process 200B, parameterized as set forth above and configured for the production of ammonia.
  • Fig. 10 additionally shows the GHG LCA of the produced ammonia, and a number of embodiment metrics.
  • CASE 10B referring to an embodiment of process 200B, 1400 mt/d of natural gas is supplied to the hydrocarbon converter 21 OB via the hydrocarbon material 206, and the total ammonia product output increases to 1988 mt/d.
  • the process performance and process metrics of CASE 10B are approximately the same as in CASE 5B, corresponding to process 200A.
  • CASE 10C In the embodiment labeled CASE 10C referring to an embodiment of process 200B, 3000 mt/d of natural gas is supplied to the hydrocarbon converter 210B via the hydrocarbon material 206, and the total ammonia product output increases to 3457 mt/d.
  • the process performance and process metrics of CASE 10C are approximately the same as in CASE 5C, corresponding to process 200A. This finding that process 200B and 200A have approximately the same performance and metrics is consistent with the understanding that process 200B is functionally equivalent to process 200A but without routing any fossil-derived carbon into the conversion feeds 124 and 224.
  • each of the conversion feeds 124 and 224 entering the respective conversion stages 126 and 226 is pure hydrogen in the case of ammonia production, there is no practical difference between the two processes, except, as discussed above, in the degree of module integration. Accordingly, other things being equal, it would be normally expected that process 200A would be less costly to operate than process 200B (or 200C).
  • biogenic CO2 source 260 may be a direct air capture system or a carbon capture system configured to remove biogenic CO2 from an industrial process.
  • process 200C over 200B (via the use of a single CO2 removal unit 214 in process 200C rather than two CO2 removal units 114 and 214B in process 200B) would be expected to reduce total plant capital cost and operating cost. In most cases it would be expected that providing biogenic CO2 source 260 and CO2 conduit 218 would be more expensive than providing CO2 recycle 118, but the higher integration of process 200C may offset the higher cost of employing process 200B so as to ensure fossil/biogenic carbon segregation.
  • the net total amount of sustainable atomic carbon input can be increased for the same size gasifier and the same solid sustainable carbon material input due to the additional biogenic CO2 input, offering an opportunity (when producing carbon containing products like methanol and hydrocarbons) to increase the total amount of 100% biogenic carbon product output.
  • Fig. 11 is a flow sheet comparing three embodiments, CASE 11 B, CASE 11 C, and CASE 11 D, of solid sustainable carbon material conversion process 200C, each parameterized as set forth above and configured for the production of methanol, and each corresponding to adaptations of CASE 8B, CASE 8C, and CASE 8D respectively.
  • Fig. 11 additionally shows the GHG LCA of the produced methanol, and a number of embodiment metrics.
  • CASE 11 B, CASE 11 C, and CASE 11 D processes 200C and CASE 11 D relative to CASE 8B, CASE 8C, and CASE 8D, respectively, (process 200B) is the removal of the CO2 recycle, so that the 135 mt/d of CO2 input to the gasifier 106 is provided as a net input to the process 200C, and is here assumed to be biogenic for simulation purposes.
  • This increased inflow of sustainable carbon allows for increasing the productivity of each of CASE 11 B, CASE 11 C, and CASE 11 D relative to the corresponding cases while otherwise maintaining the same GHG LCA for the end product.
  • These increases in productivity are associated with increased natural gas supply to provide the additional hydrogen to react with this additional biogenic carbon.
  • the % of net atomic carbon input into the process from natural gas is between 38% and 49%
  • the product atomic carbon yield per sustainable atomic carbon input into the process is between 0.66 and 0.86
  • the product yield per dry solid sustainable carbon material input into the process is between 0.96 and 1 .26.
  • Fig. 12 is a flow sheet comparing three embodiments, CASE 12B, CASE 12C, and CASE 12D, of solid sustainable carbon material conversion process 200C, each parameterized as set forth above and configured for the production of FT hydrocarbons, and each corresponding to adaptations of CASE 9B, CASE 9C, and CASE 9D respectively.
  • Fig. 12 additionally shows the GHG LCA of the produced hydrocarbon, and a number of embodiment metrics.
  • CASE 12 is the removal of the CO2 recycle in CASE 12B, CASE 12C, and CASE 12D, so that the 135 mt/d CO2 input to gasifier 106 is provided as a net input, and is here assumed to be biogenic.
  • This increased inflow of biogenic carbon allows for increasing the productivity of each of CASE 12B, CASE 12C, and CASE 12D relative to the corresponding cases, while otherwise maintaining the same GHG LCA for the end product.
  • These increases in productivity are associated with increased natural gas supply to provide the additional hydrogen to react with this additional biogenic carbon.
  • the % of net atomic carbon input into the process from natural gas is between 37% and 47%
  • the product atomic carbon yield per sustainable atomic carbon input into the process is between 0.65 and 0.86
  • the product yield per dry solid sustainable carbon material input into the process is between 0.42 and 0.55.
  • Fig. 13 is a process diagram of a solid sustainable carbon material conversion process 200D according to another embodiment.
  • the process 200D is similar in many respects to the process 200A of Fig. 2, but with a different gasification stage 270 instead of the gasification stage 204.
  • the gasification stage 270 includes the gasifier 106 and tar converter 110 to produce a first effluent from processing waste solid sustainable carbon material 102 and the hydrocarbon converter 210B to product a second effluent from processing the fossil-derived hydrocarbon material 206.
  • the first and second effluents are combined to yield the gasification stage effluent 211 , which is further processed in a manner similar to the rest of the process 200A of Fig. 2.
  • the solid sustainable carbon material conversion processes described herein use hydrocarbons derived from conventional sources to supplement carbon and hydrogen in the syngas produced by solid sustainable carbon material gasification. Such supplementation can boost yield of products from solid sustainable carbon material conversion processes, and where biogenic CO2 formed from solid sustainable carbon material gasification is sequestered, still yield low, or even zero or negative GHG LCA products.
  • the solid sustainable carbon material conversion processes described herein may be operated with a % of net atomic carbon input into the process from fossil-derived hydrocarbons of between 15% and 50% so as to produce carbon containing chemicals, for example methanol and hydrocarbons, with GHG LCA that ranges from modestly negative to modestly positive, including zero.
  • Some processes described herein can use fossil-derived hydrocarbon to make hydrogen for an ammonia plant that uses solid sustainable carbon material as a feedstock.
  • the solid sustainable carbon material conversion processes described herein may be operated with a % of net atomic carbon input into the process from fossil-derived hydrocarbons of between 35% and 90% so as to produce carbon free chemicals, for example hydrogen or ammonia, with GHG LCA that ranges from modestly negative to modestly positive, including zero.
  • each of the biomass conversion processes described herein may be operated as a single integrated facility that produces carbon-containing products with “well-to-wake” GHG LCA less than 20%, less than 10%, or less than 5% of the corresponding fossil baseline GHG LCA (based on reference values and a GHG LCA methodology consistent with the 2022 GREET model).
  • These processes can be operated to produce a product atomic carbon yield per sustainable atomic carbon input into the process that is at least 0.45, at least 0.50, at least 0.60, at least 0.70, or at least 0.80.
  • the biogenic input carbon mass flow rate is 369 mt/d
  • the output carbon mass flow rate for methanol is equal to the methanol production rate multiplied by 12/32
  • the output carbon mass flow rate for FT hydrocarbons is equal to the hydrocarbon production rate multiplied by 0.85 (utilizing the approximation that such hydrocarbons comprise about 85% carbon by weight.)
  • the product atomic carbon yield per sustainable atomic carbon input into the process of CASE 3A is just 0.31 , reflecting the conventional solid sustainable carbon material conversion to methanol process.
  • the CASE 4A value is just 0.29.
  • each of the biomass conversion processes described herein may be operated as a single integrated facility that produces ammonia with GHG LCA less than 10%, less than 5%, or less than 2% of the corresponding fossil baseline GHG LCA (based on reference values and a GHG LCA methodology consistent with the 2022 GREET model).
  • These processes can be operated to have a product yield per dry solid sustainable carbon material input into the process of 1 .0, at least 2.0, at least 3.0, or at least 4.0.
  • the product yield per dry solid sustainable carbon material input into the process for CASE 5A is just 0.36, reflecting the conventional solid sustainable carbon material conversion to ammonia process.
  • the embodiments shown herein demonstrate that contrary to conventional wisdom, it is possible to substantially boost ammonia product yield through integration of fossil- derived natural gas conversion and solid sustainable carbon material gasification while also producing a very low, zero, or even negative GHG LCA product.
  • the processes disclosed herein for converting waste solid sustainable carbon materials into chemical products generally use an amount of additional hydrocarbon, such as natural gas, sourced from fossil sources to boost output of the chemical products for little additional capital cost.
  • additional hydrocarbon such as natural gas
  • CO2 produced by the conversion of raw materials into useable chemical precursors is sequestered or otherwise consumed to make the final products, so the GHG LCA of the produced final products can be much lower than similar products made in conventional ways, and the increased output of final products provides economy of scale to make such processes more attractive.
  • these processes use hydrocarbon at a mass flow rate that is at least about 15% of the dry weight mass flow rate of waste solid sustainable carbon material used.
  • hydrocarbon conversion to CO and hydrogen is balanced with conversion of CO from biomass gasification into hydrogen and CO2 to yield a syngas material, as a precursor to chemical production, that has a volumetric ratio of hydrogen to CO that is at least 2.0, and may be higher, for example 2.2, 2.5, or 3.0.
  • CO2 produced by hydrocarbon and biomass conversion is mostly sequestered, for example in a subterranean facility (or any suitable facility), but some can be recycled and used to enhance gasification of the solid sustainable carbon material.
  • the hydrocarbon can be converted entirely to hydrogen and CO2 and the waste solid sustainable carbon material can be converted entirely to hydrogen and CO2, and the hydrogen can be used to make ammonia.
  • carbon from the hydrocarbon can be segregated from biogenic carbon so that the final chemical products contain only biogenic carbon.
  • biogenic CO2 can be used to enhance gasification, rather than recycling CO2 that might contain fossil-derived carbon, so the final chemical products can remain free of fossil-derived carbon.
  • sequestering more CO2 decreases environmental burden of all the processes described herein.
  • sequestering CO2 from the fossil-derived hydrocarbon added to the processes is beneficial.
  • the processes described herein can be operated to sequester at least 90%, or at least 95%, or at least 99% of the carbon from the fossil-derived hydrocarbon material 206 as captured and sequestered CO2.
  • at least 5%, but not more than 40%, of sustainable atomic carbon input from waste carbon containing material is sequestered in a sequestration facility.
  • sequestered CO2 has a first component from sustainable carbon input and a second component from fossil-derived hydrocarbon.
  • the first component has a mass flow rate of CO2 that is 44/12 times 90% of the mass flow rate of atomic carbon from the input fossil-derived hydrocarbon and the second component has a mass flow rate of CO2 that is 44/12 times 5% of the mass flow rate of atomic carbon from the input solid sustainable carbon material.
  • These components may flow separately to sequestration, or may be combined at any suitable point in a particular embodiment.
  • biomass has a high moisture content in its initial (or “green”) state that is much higher than the optimal moisture level for feeding into a gasifier reactor as described herein.
  • biomass residues often have a moisture content of 40% to 50% by weight, whereas it is typical for the biomass fed into a gasifier to have a moisture content of between 5% and 25% by weight.
  • the same biomass mass flow rate into a gasifier yields a higher carbon flow rate when the moisture level is lower, which boosts plant output for the same size gasifier. It is also easier to control the amount of steam in the gasifier reactor when using a biomass with a low moisture level by selectively adding steam into the process, whereas using biomass with higher moisture content can add unpredictable amounts of steam to the process.
  • Fig. 14A is a process diagram of a solid sustainable carbon material conversion process 300A, according to another embodiment.
  • a biomass processing unit 1410 is configured to receive biomass 1430 and biomass fuel 1480, and deliver a dried and sized biomass stream 102 suitable for loading into a gasifier such as the gasifiers 104, 204, and 270.
  • the biomass processing unit 1410 is configured to combust or gasify biomass fuel 1480 to produce at least a portion of the energy to dry, size, or both dry and size the biomass 1430 using the biomass processing unit 1410.
  • the biomass fuel 1480 may be combusted to heat a boiler that provides steam that is then used to provide heat used in biomass processing unit 1410 to remove moisture from the biomass 1430 so that the biomass stream 102 has a lower moisture content than the biomass 1430.
  • the biomass fuel 1480 may, for example, be combusted to heat a boiler that provides steam that is used to directly drive machinery that performs a sizing operation on biomass 1430, such as shredding, grinding, chipping, or pelletizing.
  • Fig. 14B is a process diagram of a biomass processing unit 1410, according to one embodiment.
  • the biomass fuel 1480 may, for example, be combusted to heat a boiler 1403 that provides high temperature and pressure steam (e.g. at 60 atm and >420C) that is used to drive a turbine 1406 to generate electricity 1492 to power a biomass sizing unit 1401 , and a portion of the residual low temperature and pressure steam (e.g. at 12 atm and 191 C) may be used to provide heat to a biomass dryer 1402 to remove moisture from the biomass stream 1430.
  • high temperature and pressure steam e.g. at 60 atm and >420C
  • a portion of the residual low temperature and pressure steam e.g. at 12 atm and 191 C
  • Condensed steam from the biomass dryer 1402 and unused residual low pressure and temperature steam 1494 may be recovered in a residual heat and water integration unit 1405 and used to provide a pre-heated water stream to the boiler 1403. Water may be supplied to the integration unit 1405 to supply make-up water. Dryer gas, for example air or flue gas from another process unit, is provided to the dryer 1402. Similarly boiler gas, for example air or flue gas from another process unit, is provided to the boiler 1403. In this example, stream 1420 includes the flue exhaust from boiler 1403. Alternatively, unit 1403 may instead be a biomass gasification to steam and heat system, in which biomass fuel 1480 is gasified to produce heat and fuel gas, and such fuel gas is used to fire a boiler to produce steam and more heat.
  • stream 1420 includes the boiler flue exhaust resulting from the combustion of the gasifier fuel gas.
  • biomass fuel 1480 can be any biomass suitable for combustion (in the case a combustion process is used in 1410) or gasification (in the case a gasification process is used in 1410), for example forestry residues, saw mill waste, and bark wood.
  • biomass fuel 1480 can be any biomass suitable for combustion (in the case a combustion process is used in 1410) or gasification (in the case a gasification process is used in 1410), for example forestry residues, saw mill waste, and bark wood.
  • the specification in terms of chemical and mechanical properties for the biomass 1430 may be relatively narrow to ensure suitability for a gasification to chemicals synthesis plant
  • the corresponding specification for the biomass in 1480 may be relatively wide due to the relative simplicity and robustness of a combustion or gasification to heat and power plant, and thus it may be possible use lower cost biomass in 1480 compared to 1430.
  • bark wood and saw dust may be generated in producing 1430 from pre-commercial forest thinnings, and such bark
  • the conversion of biomass 1480 into the energy using the biomass processing unit 1410 produces flue exhaust stream 1420 that contains biogenic CO2.
  • the CO2 produced by the conversion of biomass 1480 would be exhausted into the atmosphere, since that is the lowest cost way to handle such CO2.
  • Such CO2 is also biogenic, and therefore does not contribute any net GHG LCA (since there is no net addition of CO2 into the environment compared to allowing the biomass to simply aerobically decompose into CO2).
  • the biogenic CO2 in exhaust stream 1420 is captured by CO2 removal unit 1460 to produce captured biogenic CO2 stream 1450 and residual exhaust stream 1440.
  • Biogenic CO2 stream 1450 is then directed to one or more of: (a) the gasification and tar conversion units to satisfy the CO2 demand of such units, if any; (b) sequestration so as to further reduce the GHG LCA of the end product; and (c) downstream processing units so as to provide additional biogenic CO2 for conversion in chemicals, such as methanol and FT hydrocarbons.
  • Prior art process 100 may be upgraded in this manner to use biogenic CO2 1450 (a) in gasification stage 104 to satisfy the CO2 demand, if any, of gasifier 106 and converter 110, eliminating the need for CO2 recycle stream 118; (b) in sequestration stream 116; and/or (c) in process stream 132, 120 or 124.
  • Process 200A can also utilize the biogenic CO2 stream 1450 (a) in gasification stage 204 to satisfy the CO2 demand, if any, of gasifier 106 and converter 210, eliminating the need for CO2 recycle stream 118 and/or separate CO2 stream 218 (and CO2 source 260); (b) in sequestration stream 116; and (c) in process stream 232, 220 or 224.
  • Process 200B can also utilize the biogenic CO2 stream 1450 (a) in gasification stage 104 to satisfy the CO2 demand, if any, of gasifier 106 and converter 110, eliminating the need for CO2 recycle stream 118; (b) in sequestration stream 116; and (c) in process stream 132, 220 or 224.
  • Process 200C can also utilize the biogenic CO2 stream 1450 (a) in gasification stage 104 to satisfy the CO2 demand, if any, of gasifier 106 and converter 110, eliminating the need for separate CO2 stream 218 (and CO2 source 260); (b) in sequestration stream 116; and (c) in process stream 232, 220 or 224.
  • Process 200D can also utilize the biogenic CO2 stream 1450 (a) in gasification stage 270 to satisfy the CO2 demand, if any, of gasifier 106, converter 110, and converter 210B, eliminating the need for CO2 recycle stream 118 and/or separate CO2 stream 218 (and CO2 source 260); (b) in sequestration stream 116; and (c) in process stream 232, 220 or 224.
  • flue exhaust stream 1450 is mostly air and a relatively low amount of CO2, e.g. ⁇ 5%, ⁇ 10%, or ⁇ 20% by volume CO2.
  • the removal by unit 1460 of CO2 from such a stream is conventionally viewed as uneconomical because CO2 removal from streams with relatively low CO2 concentration demands relatively larger equipment and the processing of relatively larger gas volumes to remove a given amount of CO2, when compared to CO2 removal from streams with relatively high CO2 concentrations (e.g. >20%, >30%, >50% by volume).
  • the capture rate may be selected during design engineering to optimize the project economics to provide a capture rate of >50%, >80%, >90%, and >95%. Since the leakage of biogenic CO2 into the atmosphere does not contribute any net GHG LCA, and so does not negatively impact the project’s sustainability, the analysis can be optimized primarily in terms of these economics.
  • Biomass fuel stream 1480 comprises 318 dry-mt/d (ash free basis) of bark wood having a 50% (dry ash free weight) carbon content;
  • CO2 removal unit 1460 removes and directs to stream 1450 90% of the CO2 contained in stream 1420;
  • biomass fuel stream amount of 318 dry-mt/d of bark wood was selected to provide sufficient energy to a biomass boiler to support drying 771 dry-mt/d of softwood forestry residues from a typical green moisture level of 50% by weight down to the 15% moisture by weight level in stream 102 in our illustrative embodiments. It is readily understood that different amounts of biomass fuel would be required for different biomass types and different processing conditions, including different starting and ending moisture levels.
  • Fig. 15 is a flow sheet comparing aspects of a solid sustainable carbon material to ammonia process for embodiments of the process 300 of Fig. 14A, as applied to process 200A of Fig. 2 (or equivalently, to process 200D of Fig. 13).
  • new embodiments 15B, 15C, and 15D are described, which respectively are versions of previous embodiments 5B, 5C, and 5D, but utilizing the process 300A.
  • 135 mt/d of biogenic CO2 from capture unit 1460 is directed to meet the demand from the gasifier and converter(s) and 390 mt/d of biogenic CO2 from capture unit 1460 is sequestered (helping to offset other contributions to the end product GHG LCA).
  • Case 15B produces 523 mt/d compared to 366 mt/d in Case 5B (a 43% increase)
  • Case 15C produces 861 mt/d compared to 636 mt/d in Case 5C (a 35% increase)
  • Case 15D produces 168 mt/d compared to 121 mt/d in Case 5D (a 39% increase).
  • Case 15B produces 2845 mt/d compared to 1988 mt/d in Case 5B (a 43% increase and representing 1035% of the conventional case output)
  • Case 15C produces 4681 mt/d compared to 3457 mt/d in Case 5C (a 35% increase and representing 1704% of the conventional case output)
  • Case 15D produces 911 mt/d compared to 660 mt/d in Case 5D (a 39% increase and representing 332% of the conventional case output).
  • ammonia yield per dry solid sustainable carbon material input into the process similarly rises in Cases 15B, 15C, and 15D to 3.69, 6.07, and 1.18 respectively (in each case a respective 43%, 35%, and 39% increase compared to Cases 5B, 5C, and 5D.)
  • One key impact of the increased natural gas import is an increase in the % of net atomic carbon input into the process from fossil sources from 73% in Case 5B to 79% in Case 15B, from 83% in Case 5C to 86% in Case 15C, and from 38% in Case 5D to 48% in Case 15D.
  • Fig. 16 is a flow sheet comparing aspects of a solid sustainable carbon material to methanol process for embodiments of the process 300 of Fig. 14A, implemented in the configuration of process 200C of Fig. 7.
  • new embodiments 16B, 16C, and 16D are described, which respectively are versions of previous embodiments 11 B, 11 C, and 11 D, but now utilizing process 300 to increase methanol output.
  • 135 mt/d of biogenic CO2 from capture unit 1460 is directed to meet the demand from the gasifier and converter(s) and varying amounts of biogenic CO2 are routed from capture unit 1460 to sequestration (helping to offset other contributions to the end product GHG LCA).
  • Fig. 16 is a flow sheet comparing aspects of a solid sustainable carbon material to methanol process for embodiments of the process 300 of Fig. 14A, implemented in the configuration of process 200C of Fig. 7.
  • new embodiments 16B, 16C, and 16D are described, which respectively are versions of previous embodiments 11 B, 11 C,
  • cases 16B, 16C, and 16D provide output of 923 mt/day, 1123 mt/day, and 1242 mt/day, respectively, which compares with 738 mt/day, 899 mt/day, and 970 mt/day for the respective comparison cases 11 B, 11 C, and 11 D, for an increase of 25%, 25%, and 28%, respectively.
  • Product yield per dry solid sustainable carbon material input into the process for these cases is 1.20, 1.46, and 1.61 , respectively, compared with 0.96, 1.17, and 1.26, for cases 11 B, 11 C, and 11 D, respectively, for an increase of 25%, 25%, and 28%, respectively.
  • Fig. 17 is a flow sheet comparing aspects of a solid sustainable carbon material to FT hydrocarbon process for embodiments of the process 300 of Fig. 14Aas applied to process 200C of Fig. 7.
  • new embodiments 17B, 17C, and 17D are described, which respectively are versions of previous embodiments 12B, 12C, and 12D, but utilizing process 300 to increase FT hydrocarbon output.
  • 135 mt/d of biogenic CO2 from capture unit 1460 is directed to meet the demand from the gasifier and converter(s) and varying amounts of biogenic CO2 are routed from capture unit 1460 to sequestration (helping to offset other contributions to the end product GHG LCA).
  • cases 17B, 17C, and 17D provide output of 406 mt/day, 492 mt/day, and 548 mt/day, respectively, which compares with 324 mt/day, 393 mt/day, and 428 mt/day for the respective comparison cases 12B, 12C, and 12D, for an increase of 25%, 25%, and 28%, respectively.
  • Product yield per dry solid sustainable carbon material input into the process for these cases is 0.53, 0.64, and 0.71 , respectively, compared with 0.42, 0.51 , and 0.55, for cases 12B, 12C, and 12D, respectively, for an increase of 26%, 25%, and 29%, respectively.

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Abstract

L'invention concerne une méthode et un appareil de conversion de matériau carboné durable solide de déchets en produits chimiques. Les méthodes ajoutent des hydrocarbures dérivés de sources fossiles au gaz dérivé de la gazéification de matériau carboné durable solide de déchets pour améliorer la disponibilité de l'hydrogène, et dans certains cas la disponibilité du carbone, pour la production des produits chimiques. De la biomasse est utilisée pour fournir de l'énergie à un matériau carboné solide durable pour former un matériau carboné durable sec à gazéifier. Le dioxyde de carbone obtenu par le procédé est au moins partiellement séquestré pour produire un procédé de fabrication chimique avec une charge environnementale sensiblement inférieure à celle des procédés classiques. L'utilisation des hydrocarbures augmente le rendement des produits finaux.
PCT/IB2023/052006 2022-10-26 2023-03-03 Système et méthode de gazéification améliorée WO2024089472A1 (fr)

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