WO2021150285A1 - Procédés et systèmes de production d'éthanol qui intègrent la cokéfaction et la fermentation - Google Patents

Procédés et systèmes de production d'éthanol qui intègrent la cokéfaction et la fermentation Download PDF

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WO2021150285A1
WO2021150285A1 PCT/US2020/057604 US2020057604W WO2021150285A1 WO 2021150285 A1 WO2021150285 A1 WO 2021150285A1 US 2020057604 W US2020057604 W US 2020057604W WO 2021150285 A1 WO2021150285 A1 WO 2021150285A1
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vol
flexicoking
stream
gasifier
syngas
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PCT/US2020/057604
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English (en)
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Hyung R. KIM
Arun K. Sharma
William J. Novak
James R. Bielenberg
Zarath M. SUMMERS
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Exxonmobil Research And Engineering Company
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Publication of WO2021150285A1 publication Critical patent/WO2021150285A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/06—Ethanol, i.e. non-beverage
    • C12P7/065—Ethanol, i.e. non-beverage with microorganisms other than yeasts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
    • C10B55/02—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials
    • C10B55/04—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials
    • C10B55/08—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials in dispersed form
    • C10B55/10—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials in dispersed form according to the "fluidised bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/005—Coking (in order to produce liquid products mainly)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/28—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material
    • C10G9/32—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material according to the "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/463—Gasification of granular or pulverulent flues in suspension in stationary fluidised beds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0943—Coke
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0956—Air or oxygen enriched air
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0959—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C10J2300/0976—Water as steam
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C10J2300/0989—Hydrocarbons as additives to gasifying agents to improve caloric properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1665—Conversion of synthesis gas to chemicals to alcohols, e.g. methanol or ethanol
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1681—Integration of gasification processes with another plant or parts within the plant with biological plants, e.g. involving bacteria, algae, fungi
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin

Definitions

  • the present disclosure relates to methods and systems for the production of ethanol from syngas produced in a flexicoking process.
  • Syngas is a mixture of gases comprising hydrogen, carbon monoxide, and carbon dioxide.
  • the relative concentration of each gas and other gases therein depends on the process by which the syngas is produced.
  • Syngas is an intermediate in several industrial-scale chemical processes including the production of hydrogen, ammonia, methanol, or synthetic hydrocarbon fuels. Syngas can also be used in fermentation processes to produce ethanol and other products.
  • syngas fermentation microorganisms, also known as fermenting organisms, are exposed to the syngas under fermentation conditions to produce a product stream that typically comprises ethanol, butanol, acetic acid, butyric acid, and methane.
  • a product stream typically comprises ethanol, butanol, acetic acid, butyric acid, and methane.
  • syngas fermentation benefits from milder conditions as compared to chemical processes for forming such products, syngas fermentation has significant limitations including gas-liquid mass transfer and low volumetric productivity.
  • the volumetric productivity and fermentation efficacy is further reduced when the carbon to hydrogen ratio in the syngas feed is different from the carbon to hydrogen ratio of the products, especially ethanol.
  • the present disclosure relates to methods and systems for the production of ethanol from syngas produced in a flexicoking process.
  • a method of the present disclosure may comprise: flexicoking a hydrocarbon feed stream to produce a flexicoking syngas stream; introducing a steam stream and an oxygen-rich stream into a gasifier of the flexicoking process, wherein the oxygen-rich stream has greater than 22 vol% oxygen and less than 50 vol% nitrogen; and fermenting the flexicoking syngas with fermenting organisms to produce a fermentation liquid product comprising ethanol.
  • Another method of the present disclosure may comprise: flexicoking a hydrocarbon feed to produce a flexicoking syngas; fermenting the flexicoking syngas with fermenting organisms and additional hydrogen to produce fermentation liquid products.
  • Y et another method of the present disclosure may comprise: flexicoking a hydrocarbon feed to produce a flexicoking syngas; reforming (a) methane, (b) waste, and/or (c) refused fermenting organisms in a gasifier of the flexicoking process to produce hydrogen and carbon monoxide, wherein the waste comprises biomass waste, plastic waste, municipal solid waste, paper waste, plastic pyrolysis oil, agricultural waste, wood waste, energy crops, and any combination thereof; and fermenting the flexicoking syngas with fermenting organisms to produce fermentation liquid products.
  • Additional methods of the present disclosure may be a hybrid of two or three of the foregoing methods.
  • FIG. 1 illustrates a diagram of a nonlimiting example method that integrates FLEXICOKINGTM and fermentation for the production of ethanol.
  • FIG. 2 illustrates a diagram of another nonlimiting example method that integrates FLEXICOKINGTM and fermentation for the production of ethanol.
  • FIG. 3 illustrates a diagram of yet another nonlimiting example method that integrates FLEXICOKINGTM and fermentation for the production of ethanol.
  • FIG. 4 illustrates a diagram of yet another nonlimiting example method that integrates FLEXICOKINGTM and fermentation for the production of ethanol.
  • FIG. 5 illustrates a diagram of yet another nonlimiting example method that integrates FLEXICOKINGTM and fermentation for the production of ethanol.
  • FIG. 6 illustrates a diagram of yet another nonlimiting example method that integrates FLEXICOKINGTM and fermentation for the production of ethanol.
  • the present disclosure relates to methods and systems for the production of ethanol from syngas produced in a flexicoking process.
  • the flexicoking process converts hydrocarbons in the presence of steam and air into lighter hydrocarbons and syngas.
  • the composition of the syngas produced from flexicoking can vary but typically has a composition of about 0.5 vol% to about 2 vol% C 1 -C4 hydrocarbons, about 13 vol% to about 18 vol% hydrogen, about 20 vol% to about 26 vol% C1-C4 carbon monoxide, about 4 vol% to about 10 vol% carbon dioxide, about 45 vol% to about 55 vol% nitrogen, and about 1 vol% to about 5 vol% water.
  • flexicoking syngas is (a) high in nitrogen, which inhibits the gas-liquid mass transfer that allows the fermenting organisms access to the hydrogen and carbon monoxide used to produce ethanol, and (b) hydrogen- deficient, which further reduces the volumetric productivity of the fermentation.
  • flexicoking syngas taking into account only the hydrogen and carbon monoxide, has a H:C atomic ratio of about 5:4 whereas ethanol has a H:C atomic ratio of 6:2 (or 12:4). That is, if all of the hydrogen in the flexicoking syngas is consumed in the fermentation, only about half of the carbon monoxide is consumed. Therefore, flexicoking syngas is hydrogen- deficient.
  • the present disclosure provides several systems and methods that reduce the nitrogen concentration in the flexicoking syngas and/or increase the hydrogen concentration in the flexicoking syngas. Implementation of one or more of these systems/methods could improve the gas-liquid mass transfer, which provides greater concentrations of hydrogen and carbon monoxide to the fermenting organisms, and improves the percent conversion of carbon monoxide to ethanol.
  • the FLEXICOKINGTM process developed by Exxon Research and Engineering Company, is a non-catalytic thermal conversion process where fluid coke produced in the reactor is gasified with process steam and air to produce a higher value fuel gas (FLEXIGASTM, also referred to herein as flexicoking syngas).
  • the process is, in fact, a variant of the fluid coking process that is operated in a unit including a cracking reactor and a gasifier for gasifying the coke product by reaction with an air/steam mixture to form a fuel gas.
  • a stream of coke passes to the gasifier, where almost all of the coke is gasified by the addition of steam and air in a fluidized bed in an oxygen-deficient environment at very high temperatures to form a low-Btu fuel gas ( ' 4800 kJ/kg, ⁇ 128 BTU/SCF) comprising carbon monoxide and hydrogen.
  • the fuel gas product from the gasifier containing entrained coke particles at high temperature, is conventionally returned to an intermediate heater vessel to provide most of the heat required for thermal cracking in the reactor with the balance of the reactor heat requirement supplied by combustion of coke in the heater.
  • a small amount of net coke (about 1% percent of feed) is withdrawn from the heater to purge the system of metals and ash.
  • the liquid yield and properties are comparable to those from fluid coking.
  • the flexicoking syngas is withdrawn from the heater following separation in internal cyclones, which return coke particles to the bed of hot coke particles in the heater through their diplegs.
  • the flexicoker may be a conventional three-vessel unit of cracking reactor, heater, and gasifier or, alternatively, a two-vessel unit of reactor and gasifier in which the coke from the reactor passes directly to the gasifier and hot, partly gasified coke particles from the gasifier are cycled back to the reactor to provide the heat for the endothermic cracking reactions.
  • a unit of this type is described in U.S. Patent Application Ser. No. 14/729,101, which is incorporated herein by reference.
  • FIG. 1 illustrates a diagram of a nonlimiting example method 100 that integrates FLEXICOKINGTM A and fermentation B for the production of ethanol.
  • the concentration of nitrogen in the flexicoking syngas is reduced.
  • a hydrocarbon feed 102 and a steam 104 are thermally converted in a reactor 106 to lighter hydrocarbons 108 (having a lower average carbon number than the hydrocarbon feed 102) and coke 110.
  • the coke 110 is transported to a heater 114 where the coke 110 in the presence of additional air 112 is heated and combusted to produce flexicoking syngas 118 and heat the coke 110.
  • the coke is then conveyed as hot coke 116 back to the reactor 106 or as coke 120 to a gasifier 124.
  • steam and an oxygen-rich feed 122 are also added.
  • the steam and an oxygen-rich gas 122 are illustrated as a single stream but could alternatively be added to the gasifier 124 as separate streams.
  • all but a small fraction of the coke 120 is gasified by the addition of the steam and an oxygen-rich feed 122, which produces flexicoking syngas 118.
  • a mixture 126 of the flexicoking syngas 118 and remaining coke particles are recycled back to the heater 114 from where the flexicoking syngas 118 is collected.
  • the flexicoking process A uses an oxygen-rich gas having a higher oxygen content and a lower nitrogen content than air.
  • the oxygen-rich gas comprises about 25 vol% or greater (or about 25 vol% to about 100 vol%, or about 50 vol% to about 100 vol%, or about 50 vol% to about 99 vol%, or about 75 vol% to about 100 vol%, or about 75 vol% to about 99 vol%, or about 90 vol% to about 100 vol%, or about 90 vol% to about 99 vol%) oxygen and 0 vol% to about 70 vol% (or 0 vol% to about 50 vol%, or 0 vol% to about 25 vol%, or 0 vol% to about 10 vol%, or 0 vol% to about 5 vol%, or 0.1 vol% to about 5 vol%) nitrogen.
  • the fl exi coking syngas 118, 130 produced has a lower nitrogen-content, which improves the gas
  • the flexicoking syngas 118 is then conveyed to a clean-up system 128 to remove any remaining fine coke particles 132 and produce flexicoking syngas 130.
  • the flexicoking syngas 130 is conveyed to a fermentation vessel 136 that contains fermenting organisms. Medium 134 is also added to the fermentation vessel 136 as needed to support the fermenting organisms.
  • the fermenting organisms produce liquid products like ethanol and gas products 138 like methane.
  • the liquid products and fermenting organisms 140 are filtered in filtration unit 142 to separate the fermentation liquid products 148 and the fermenting organisms, which are further separated into refused (dead) fermenting organisms 146, which are waste, and live fermenting organisms 144, which are recycled back to the fermentation vessel 136.
  • the fermentation liquid products 148 may comprise one or more selected form the group consisting of: ethanol, acetate, propanol, butanol, 2,3-butanediol, butyrate, propionate, caproate, propylene, butadiene, isobutylene, and ethylene.
  • the fermentation liquid products 148 comprise ethanol and one or more selected form the group consisting of: acetate, ethanol, propanol, butanol, 2,3-butanediol, butyrate, propionate, caproate, propylene, butadiene, isobutylene, and ethylene.
  • the fermentation liquid products 148 may be used as is or optionally purified.
  • the fermentation liquid products 148 may be conveyed to a distillation unit 150 that separates ethanol (illustrated as an ethanol stream 152) from other liquid byproducts 154.
  • the ethanol stream 152 may comprise at least 90 wt% (or about 90 wt% to 100 wt%, or 95 wt% to 99.9 wt%, or 98 wt% to 99.9 wt%) ethanol.
  • Examples of fermenting organisms that are suitable for use in syngas fermentation include those of the genus Acetobacterium, such as strains of Acetobacterium woodii ((Dernier, M., Weuster-Botz, “Reaction Engineering Analysis of Hydrogenotrophic Production of Acetic Acid by Acetobacterum Woodii Biotechnology and Bioengineering, Vol. 108, No. 2, February 2011).
  • Acetobacterium woodii has been shown to produce acetate by fermentation of gaseous substrates comprising CCh and Eh.
  • Buschhom et al. demonstrated the ability of A woodii to produce ethanol in a glucose fermentation with a phosphate limitation.
  • Suitable bacteria include those of the genus Moorella , including Moorella sp HUC22-1, (Sakai et al, Biotechnology Letters 29: pp 1607-1612), and those of the genus Carboxydothermus (Svetlichny, V. A., Sokolova, T. G. et al. (1991), Systematic and Applied Microbiology 14: 254-260).
  • Examples of additional bacterial fermenting organism genera include, but are not limited to, Clostridium, Sporomusa, Oxobacter, and Acetitomaculum.
  • Examples of Clostridium include, but are not limited to, Clostridium Ljungdahlii and Clostridium Autoethanogenum. It will also be appreciated that the syngas fermentation may be applied to a mixed culture of two or more bacteria.
  • a method of the present disclosure can comprise: flexicoking A a hydrocarbon feed 102 to produce a flexicoking syngas 130, where a gasifier 124 used in the flexicoking A is supplied with coke 120, and steam and an oxygen-rich gas 122 having a higher oxygen content and a lower nitrogen content than air to produce flexicoked gas; fermenting B fermenting the syngas 130 with fermenting organisms to produce fermentation liquid products 148, and optionally separating the fermentation liquid products 148 into an ethanol stream 152 and liquid byproducts 154.
  • the ethanol stream 152 may comprise at least 90 wt% (or about 90 wt% to 100 wt%, or 95 wt% to 99.9 wt%, or 98 wt% to 99.9 wt%) ethanol.
  • a system of the present disclosure can comprises: a flexicoking unit (e.g ., corresponding to A of FIG. 1 or a variation thereol) comprising a gasifier that receives an oxygen- rich gas having a higher oxygen content and a lower nitrogen content than air; a fermentation unit (e.g., corresponding to B of FIG. 1 or a variation thereol) fluidly coupled to the flexicoking unit and configured to receive a flexicoking syngas from the flexicoking unit; and a distillation column fluidly coupled to the fermentation unit and configured to receive a liquid product from the fermentation unit and produce an ethanol stream.
  • a flexicoking unit e.g ., corresponding to A of FIG. 1 or a variation thereol
  • a gasifier that receives an oxygen- rich gas having a higher oxygen content and a lower nitrogen content than air
  • a fermentation unit e.g., corresponding to B of FIG. 1 or a variation thereol
  • a distillation column fluidly coupled to the
  • FIG. 2 illustrates a diagram of a nonlimiting example method 200 that integrates FLEXICOKINGTM A and fermentation B for the production of ethanol.
  • the hydrogen concentration in the flexicoking syngas is increased (as compared to typical flexicoking syngas) and, optionally, the concentration of nitrogen in the flexicoking syngas is reduced.
  • a hydrocarbon feed 202 and a steam 204 are thermally converted in a reactor 206 to lighter hydrocarbons 208 (having a lower average carbon number than the hydrocarbon feed 202) and coke 210.
  • the coke 210 is transported to a heater 214 where the coke 210 in the presence of additional air 212 is heated and combusted to produce flexicoking syngas 218 and heat the coke 210.
  • the coke is then conveyed as hot coke 216 back to the reactor 206 or as coke 220 to a gasifier 224.
  • steam and air (or an oxygen- rich feed) 222 are also added.
  • the steam and air (or an oxygen-rich feed) 222 are illustrated as a single stream but could alternatively be added to the gasifier 224 as separate streams.
  • the gasifier 224 all but a small fraction of the coke 220 is gasified by the addition of the steam and air (or an oxygen-rich feed) 222, which produces flexicoking syngas 218.
  • a mixture 226 of the flexicoking syngas 218 and remaining coke particles are recycled back to the heater 214 from where the flexicoking syngas 218 is collected.
  • the gasifier 224 can be fed with air or the oxygen-rich feed if a reduced nitrogen concentration in the flexicoking syngas 218, 230 is preferred.
  • the oxygen-rich gas having a higher oxygen content and a lower nitrogen content than air can be used instead of air.
  • the oxygen-rich gas comprises about 25 vol% or greater (or about 25 vol% to about 100 vol%, or about 50 vol% to about 100 vol%, or about 50 vol% to about 99 vol%, or about 75 vol% to about 100 vol%, or about 75 vol% to about 99 vol%, or about 90 vol% to about 100 vol%, or about 90 vol% to about 99 vol%) oxygen and 0 vol% to about 70 vol% (or 0 vol% to about 50 vol%, or 0 vol% to about 25 vol%, or 0 vol% to about 10 vol%, or 0 vol% to about 5 vol%, or 0.1 vol% to about 5 vol%) nitrogen.
  • the flexicoking syngas 218, 230 produced has a lower nitrogen-content, which improves the gas- liquid mass transfer in the downstream fermentation process B.
  • the flexicoking syngas 218 is then conveyed to a clean-up system 228 to remove any remaining fine coke particles 232 and produce flexicoking syngas 230.
  • the flexicoking syngas 230 is mixed with hydrogen before being conveyed to a fermentation vessel 238 that contains fermenting organisms. While the method 200 illustrates hydrogen 234 addition to the flexicoking syngas 230 after filtration to remove fine coke 232, the hydrogen could be added at different locations. For example, not illustrated, hydrogen may be added to the flexicoking syngas 218 before filtration to remove fine coke 232. In another example, not illustrated, hydrogen may be added directly to the fermentation vessel 238.
  • the hydrogen 234 may be sourced from any suitable location.
  • hydrogen sources can include, but are not limited to, steam methane reforming, autothermal reforming, partial oxidation processes, and any combination thereof.
  • flexicoking units are often located at plants where one or more of these processes are also occurring with hydrogen produced as a byproduct. Therefore, the hydrogen source may be readily available at or near flexicoking units.
  • Medium 236 is also added to the fermentation vessel 238 as needed to support the fermenting organisms.
  • the fermenting organisms produce liquid products like ethanol and gas products 240 like methane.
  • the liquid products and fermenting organisms 242 are filtered in filtration unit 244 to separate the fermentation liquid products 250 and the fermenting organisms, which are further separated into refused (dead) fermenting organisms 248, which are waste, and live fermenting organisms 246, which are recycled back to the fermentation vessel 238.
  • the fermentation liquid products 250 may comprise one or more selected form the group consisting of: ethanol, acetate, propanol, butanol, 2,3-butanediol, butyrate, propionate, caproate, propylene, butadiene, isobutylene, and ethylene.
  • the fermentation liquid products 250 comprise ethanol and one or more selected form the group consisting of: acetate, ethanol, propanol, butanol, 2,3-butanediol, butyrate, propionate, caproate, propylene, butadiene, isobutylene, and ethylene.
  • the fermentation liquid products 250 may be used as is or optionally purified.
  • the fermentation liquid products 250 are conveyed to a distillation unit 252 that separates ethanol (illustrated as an ethanol stream 254) from other liquid byproducts 256.
  • the ethanol stream 254 may comprise at least 90 wt% (or about 90 wt% to 100 wt%, or 95 wt% to 99.9 wt%, or 98 wt% to 99.9 wt%) ethanol.
  • a method of the present disclosure can comprise: flexicoking A a hydrocarbon feed 202 to produce a flexicoking syngas 230; optionally supplying a gasifier 224 used in the flexicoking A with stream 222 (comprising steam and an oxygen-rich gas having a higher oxygen content and a lower nitrogen content than air); fermenting the syngas 230 with fermenting organisms in the presence of additional hydrogen 234 to produce fermentation liquid products 250, and separating the fermentation liquid products 250 into an ethanol stream 254 and liquid byproducts.
  • the ethanol stream 254 may comprise at least 90 wt% (or about 90 wt% to 100 wt%, or 95 wt% to 99.9 wt%, or 98 wt% to 99.9 wt%) ethanol.
  • a system of the present disclosure can comprise: a flexicoking unit (e.g . , corresponding to A of FIG. 2 or a variation thereof) comprising a gasifier that optionally receives an oxygen-rich gas having a higher oxygen content and a lower nitrogen content than air; a fermentation unit (e.g. , corresponding to B of FIG. 2 or a variation thereof) fluidly coupled to the flexicoking unit and configured to receive a flexicoking syngas from the flexicoking unit and receive additional hydrogen (previously mixed with the flexicoking syngas or received separately); and a distillation column fluidly coupled to the fermentation unit and configured to receive a liquid product from the fermentation unit and produce an ethanol stream.
  • a flexicoking unit e.g . , corresponding to A of FIG. 2 or a variation thereof
  • a gasifier that optionally receives an oxygen-rich gas having a higher oxygen content and a lower nitrogen content than air
  • a fermentation unit e.g. , corresponding to B of
  • the methods 200 illustrated in this nonlimiting example and related systems may include additional components like compressors, membranes, valves, flow meters, heat exchangers, traps, and the like for proper and safe operation of said methods and systems.
  • FIG. 3 illustrates a diagram of a nonlimiting example method 300 that integrates FLEXICOKINGTM A and fermentation B for the production of ethanol.
  • the hydrogen concentration in the flexicoking syngas is increased (as compared to typical flexicoking syngas) and, optionally, the concentration of nitrogen in the flexicoking syngas is reduced.
  • a hydrocarbon feed 302 and a steam 304 are thermally converted in a reactor 306 to lighter hydrocarbons 308 (having a lower average carbon number than the hydrocarbon feed 302) and coke 310.
  • the coke 310 is transported to a heater 314 where the coke 310 in the presence of additional air 312 is heated and combusted to produce flexicoking syngas 318 and heat the coke 310.
  • the coke is then conveyed as hot coke 316 back to the reactor 306 or as coke 320 to a gasifier 326.
  • steam and air (or an oxygen- rich feed) 322 and methane 324 are also added.
  • the steam and air (or an oxygen-rich feed) 322 are illustrated as a single stream but could alternatively be added to the gasifier 326 as separate streams.
  • the gasifier 326 all but a small fraction of the coke 320 is gasified by the addition of the steam and air (or an oxygen-rich feed) 322, which produces flexicoking syngas 318. Further, the methane 324 undergoes a reforming reaction with the water and oxygen to produce hydrogen and carbon monoxide. Methane 324 is preferably used because it has a higher H:C atomic ratio than coke and, therefore, will increase the H:C atomic ratio in the resultant syngas. A mixture 328 of the flexicoking syngas and remaining coke particles are recycled back to the heater 314 from where the flexicoking syngas 318 is collected.
  • reforming the methane 324 in the gasifier 326 increases the hydrogen concentration in the flexicoking syngas 318, 332, which can be used to achieve aH:C atomic ratio in the flexicoking syngas 318, 332 that is close to ethanol and thereby increase the ethanol yield in the downstream fermentation process B.
  • the flexicoking syngas 318 is then conveyed to a clean up system 330 to remove any remaining fine coke particles 334 and produce flexicoking syngas 332.
  • the gasifier can be fed with air or the oxygen-rich feed if a reduced nitrogen concentration in the flexicoking syngas 318, 332 is preferred.
  • the oxygen-rich gas having a higher oxygen content and a lower nitrogen content than air can be used instead of air.
  • the oxygen-rich gas comprises about 25 vol% or greater (or about 25 vol% to about 100 vol%, or about 50 vol% to about 100 vol%, or about 50 vol% to about 99 vol%, or about 75 vol% to about 100 vol%, or about 75 vol% to about 99 vol%, or about 90 vol% to about 100 vol%, or about 90 vol% to about 99 vol%) oxygen and 0 vol% to about 70 vol% (or 0 vol% to about 50 vol%, or 0 vol% to about 25 vol%, or 0 vol% to about 10 vol%, or 0 vol% to about 5 vol%, or 0.1 vol% to about 5 vol%) nitrogen.
  • the flexicoking syngas 318, 332 produced has a lower nitrogen-content, which improves the gas- liquid mass transfer in the downstream fermentation process B.
  • the method 300 and related system preferably uses the oxygen-rich gas for greater conversion of methane 324 to hydrogen and carbon monoxide.
  • the flexicoking syngas 332 is conveyed to a fermentation vessel 338.
  • Medium 336 is also added to the fermentation vessel 338 as needed to support the fermenting organisms.
  • the fermenting organisms produce liquid products like ethanol and gas products 340 like methane.
  • the liquid products and fermenting organisms 342 are filtered in filtration unit 344 to separate the fermentation liquid products 350 and the fermenting organisms, which are further separated into refused (dead) fermenting organisms 348, which are waste, and live fermenting organisms 346, which are recycled back to the fermentation vessel 338.
  • the fermentation liquid products 350 may comprise one or more selected form the group consisting of: acetate, ethanol, propanol, butanol, 2,3-butanediol, butyrate, propionate, caproate, propylene, butadiene, isobutylene, and ethylene.
  • the fermentation liquid products 350 comprise ethanol and one or more selected form the group consisting of: acetate, ethanol, propanol, butanol, 2,3-butanediol, butyrate, propionate, caproate, propylene, butadiene, isobutylene, and ethylene.
  • the fermentation liquid products 350 may be used as is or optionally purified.
  • the fermentation liquid products 350 are conveyed to a distillation unit 352 that separates ethanol (illustrated as an ethanol stream 354) from other liquid byproducts 356.
  • the ethanol stream 354 may comprise at least 90 wt% (or about 90 wt% to 100 wt%, or 95 wt% to 99.9 wt%, or 98 wt% to 99.9 wt%) ethanol.
  • a method of the present disclosure can comprise: flexicoking A a hydrocarbon feed 302 to produce a flexicoking syngas 332; optionally supplying a gasifier 224 used in the flexicoking A with stream 222 (comprising steam and an oxygen-rich gas having a higher oxygen content and a lower nitrogen content than air);; reforming methane 324 in the gasifier 326 to produce hydrogen and carbon monoxide; fermenting B the syngas 332 with fermenting organisms to produce fermentation liquid products 350; and separating the fermentation liquid products 350 into an ethanol stream 354 and liquid byproducts 356.
  • the ethanol stream 354 may comprise at least 90 wt% (or about 90 wt% to 100 wt%, or 95 wt% to 99.9 wt%, or 98 wt% to 99.9 wt%) ethanol.
  • a system of the present disclosure can comprise: a flexicoking unit (e.g . , corresponding to A of FIG. 3 or a variation thereof) comprising a gasifier that (a) receives methane and (b) optionally receives an oxygen-rich gas having a higher oxygen content and a lower nitrogen content than air; a fermentation unit (e.g., corresponding to B of FIG. 3 or a variation thereof) fluidly coupled to the flexicoking unit and configured to receive a flexicoking syngas from the flexicoking unit ; and a distillation column fluidly coupled to the fermentation unit and configured to receive a liquid product from the fermentation unit and produce an ethanol stream.
  • a flexicoking unit e.g . , corresponding to A of FIG. 3 or a variation thereof
  • a gasifier that (a) receives methane and (b) optionally receives an oxygen-rich gas having a higher oxygen content and a lower nitrogen content than air
  • a fermentation unit e.g., corresponding
  • the methods 300 illustrated in this nonlimiting example and related systems may include additional components like compressors, membranes, valves, flow meters, heat exchangers, traps, and the like for proper and safe operation of said methods and systems.
  • FIG. 4 illustrates a diagram of a nonlimiting example method 400 that integrates FLEXICOKINGTM A and fermentation B for the production of ethanol.
  • the hydrogen concentration in the flexicoking syngas is increased (as compared to typical flexicoking syngas) and, optionally, the concentration of nitrogen in the flexicoking syngas is reduced.
  • a hydrocarbon feed 402 and a steam 404 are thermally converted in a reactor 406 to lighter hydrocarbons 408 (having a lower average carbon number than the hydrocarbon feed 402) and coke 410.
  • the coke 410 is transported to a heater 414 where the coke 410 in the presence of additional air 412 is heated and combusted to produce flexicoking syngas 418 and heat the coke 410.
  • the coke is then conveyed as hot coke 416 back to the reactor 406 or as coke 420 to a gasifier 426.
  • steam and air (or an oxygen- rich feed) 422 and waste 424 e.g., biomass waste, plastic waste, and/or municipal waste
  • waste 424 e.g., biomass waste, plastic waste, and/or municipal waste
  • the steam and air (or an oxygen-rich feed) 422 are illustrated as a single stream but could alternatively be added to the gasifier 426 as separate streams.
  • the gasifier 426 all but a small fraction of the coke 420 is gasified by the addition of the steam and air (or an oxygen-rich feed) 422, which produces flexicoking syngas 418. Further, the waste 424 undergoes a reforming reaction with the water and oxygen to produce hydrogen and carbon monoxide.
  • the waste 424 used preferably have a higher H:C atomic ratio than coke and, therefore, will increase the H:C atomic ratio in the resultant syngas.
  • a mixture 428 of the flexicoking syngas and remaining coke particles are recycled back to the heater 414 from where the flexicoking syngas 418 is collected.
  • waste 424 examples include, but are not limited to, biomass waste, plastic waste, municipal solid waste, paper waste, plastic pyrolysis oil, agricultural waste (e.g. , com stover, wheat straw, sugar cane bagasse, and the like), wood waste, energy crops, and the like, and any combination thereof.
  • reforming the biomass and/or plastic waste 424 in the gasifier 426 increases the hydrogen concentration in the flexicoking syngas 418, 432, which can be used to achieve a H:C atomic ratio in the flexicoking syngas 418, 432 that is close to ethanol and thereby increase the ethanol yield in the downstream fermentation process B.
  • the flexicoking syngas 418 is then conveyed to a clean-up system 430 to remove any remaining fine coke particles 434 and produce flexicoking syngas 432.
  • the gasifier can be fed with air or the oxygen-rich feed if a reduced nitrogen concentration in the flexicoking syngas 418, 432 is preferred.
  • the oxygen-rich gas having a higher oxygen content and a lower nitrogen content than air can be used instead of air.
  • the oxygen-rich gas comprises has about 25 vol% or greater (or about 25 vol% to about 100 vol%, or about 50 vol% to about 100 vol%, or about 50 vol% to about 99 vol%, or about 75 vol% to about 100 vol%, or about 75 vol% to about 99 vol%, or about 90 vol% to about 100 vol%, or about 90 vol% to about 99 vol%) oxygen and 0 vol% to about 70 vol% (or 0 vol% to about 50 vol%, or 0 vol% to about 25 vol%, or 0 vol% to about 10 vol%, or 0 vol% to about 5 vol%, or 0.1 vol% to about 5 vol%) nitrogen.
  • the flexicoking syngas 418, 432 produced has a lower nitrogen-content, which improves the gas- liquid mass transfer in the downstream fermentation process B.
  • the method 400 and related system preferably uses the oxygen-rich gas for greater conversion of waste 424 to hydrogen and carbon monoxide.
  • the flexicoking syngas 432 is conveyed to a fermentation vessel 438.
  • Medium 436 is also added to the fermentation vessel 438 as needed to support the fermenting organisms.
  • the fermenting organisms produce liquid products like ethanol and gas products 440 like methane.
  • the liquid products and fermenting organisms442 are filtered in filtration unit 444 to separate the fermentation liquid products 450 and the fermenting organisms, which are further separated into refused (dead) fermenting organisms448, which are waste, and live fermenting organisms 446, which are recycled back to the fermentation vessel 438.
  • the fermentation liquid products 480 may comprise one or more selected form the group consisting of: ethanol, acetate, propanol, butanol, 2,3-butanediol, butyrate, propionate, caproate, propylene, butadiene, isobutylene, and ethylene.
  • the fermentation liquid products 450 comprise ethanol and one or more selected form the group consisting of: ethanol, acetate, propanol, butanol, 2,3-butanediol, butyrate, propionate, caproate, propylene, butadiene, isobutylene, and ethylene.
  • the fermentation liquid products 450 may be used as is or optionally purified.
  • the fermentation liquid products 450 are conveyed to a distillation unit 452 that separates ethanol (illustrated as ethanol stream 454) from other liquid byproducts 456.
  • the ethanol stream 454 may comprise at least 90 wt% (or about 90 wt% to 100 wt%, or 95 wt% to 99.9 wt%, or 98 wt% to 99.9 wt%) ethanol.
  • Fermentation of syngas has been described in U.S. Pat. No. 8,809,015 (Schultz), which is incorporated herein by reference.
  • the concentration of hydrogen present in the fermentation vessel 438 is increased because of the biomass and/or plastic waste reforming in the gasifier 426 and, optionally, the nitrogen concentration in the fermentation syngas 418, 432 is reduced because an oxygen-rich gas having a higher oxygen content and a lower nitrogen content than air is used instead of air in the gasifier 426. Therefore, the H:C atomic ratio of the feed present in the fermentation vessel 438 is closer to the H:C atomic ratio of ethanol, thereby improving the ethanol yield. Further, optionally, the gas-liquid mass transfer in the fermentation vessel 438 is advantageously improved.
  • a method of the present disclosure can comprise: flexicoking A a hydrocarbon feed 402 to produce a flexicoking syngas 432; optionally supplying a gasifier 224 used in the flexicoking A with stream 222 (comprising steam and an oxygen-rich gas having a higher oxygen content and a lower nitrogen content than air); reforming waste 424 in the gasifier 426 to produce hydrogen and carbon monoxide; fermenting B the syngas 432 with fermenting organisms to produce fermentation liquid products 450; and separating the fermentation liquid products 450 into ethanol stream 454 and liquid byproducts 456.
  • the ethanol stream 454 may comprise at least 90 wt% (or about 90 wt% to 100 wt%, or 95 wt% to 99.9 wt%, or 98 wt% to 99.9 wt%) ethanol.
  • a system of the present disclosure can comprises: a flexicoking unit ( e.g ., corresponding to A of FIG. 4 or a variation thereol) comprising a gasifier that (a) receives waste and (b) optionally receives an oxygen-rich gas having a higher oxygen content and a lower nitrogen content than air; a fermentation unit (e.g., corresponding to B of FIG.
  • the methods 400 illustrated in this nonlimiting example and related systems may include additional components like compressors, membranes, valves, flow meters, heat exchangers, traps, and the like for proper and safe operation of said methods and systems.
  • FIG. 5 illustrates a diagram of a nonlimiting example method 500 that integrates FLEXICOKINGTM A and fermentation B for the production of ethanol.
  • the hydrogen concentration in the flexicoking syngas is increased (as compared to typical flexicoking syngas) and, optionally, the concentration of nitrogen in the flexicoking syngas is reduced.
  • a hydrocarbon feed 502 and a steam 504 are thermally converted in a reactor 506 to lighter hydrocarbons 508 (having a lower average carbon number than the hydrocarbon feed 502) and coke 510.
  • the coke 510 is transported to a heater 514 where the coke 510 in the presence of additional air 512 is heated and combusted to produce flexicoking syngas 518 and heat the coke 510.
  • the coke is then conveyed as hot coke 516 back to the reactor 506 or as coke 520 to a gasifier 524.
  • steam and air (or an oxygen- rich feed) 522 and refused (dead) fermenting organisms 546 are also added.
  • the steam and air (or an oxygen-rich feed) 522 are illustrated as a single stream but could alternatively be added to the gasifier 524 as separate streams.
  • the gasifier 524 all but a small fraction of the coke 520 is gasified by the addition of the steam and air (or an oxygen-rich feed) 522, which produces flexicoking syngas 518. Further, the refused fermenting organisms 546 undergoes a reforming reaction with the water and oxygen to produce hydrogen and carbon monoxide. The refused fermenting organisms 546 used preferably have a higher H:C atomic ratio than coke and, therefore, will increase the H:C atomic ratio in the resultant syngas. A mixture 526 of the flexicoking syngas and remaining coke particles are recycled back to the heater 514 from where the flexicoking syngas 518 is collected.
  • reforming the refused fermenting organisms 546 in the gasifier 524 increases the hydrogen concentration in the flexicoking syngas 518, 530, which can be used to achieve a H:C atomic ratio in the flexicoking syngas 418518530 that is close to ethanol and thereby increase the ethanol yield in the downstream fermentation process B.
  • the flexicoking syngas 518 is then conveyed to a clean-up system 528 to remove any remaining fine coke particles 532 and produce flexicoking syngas 530.
  • the gasifier can be fed with air or the oxygen-rich feed if a reduced nitrogen concentration in the flexicoking syngas 518, 530 is preferred.
  • the oxygen-rich gas having a higher oxygen content and a lower nitrogen content than air can be used instead of air.
  • the oxygen-rich gas comprises about 25 vol% or greater (or about 25 vol% to about 100 vol%, or about 50 vol% to about 100 vol%, or about 50 vol% to about 99 vol%, or about 75 vol% to about 100 vol%, or about 75 vol% to about 99 vol%, or about 90 vol% to about 100 vol%, or about 90 vol% to about 99 vol%) oxygen and 0 vol% to about 70 vol% (or 0 vol% to about 50 vol%, or 0 vol% to about 25 vol%, or 0 vol% to about 10 vol%, or 0 vol% to about 5 vol%, or 0.1 vol% to about 5 vol%) nitrogen.
  • the flexicoking syngas 518, 530 produced has a lower nitrogen-content, which improves the gas- liquid mass transfer in the downstream fermentation process B.
  • the method 500 and related system preferably uses the oxygen-rich gas for greater conversion of refused fermenting organisms 546 to hydrogen and carbon monoxide.
  • the flexicoking syngas 530 is conveyed to a fermentation vessel 536.
  • Medium 534 is also added to the fermentation vessel 536 as needed to support the fermenting organisms.
  • the fermenting organisms produce liquid products like ethanol and gas products 538 like methane.
  • the liquid products and fermenting organisms 540 are filtered in filtration unit 542 to separate the fermentation liquid products 548 and the fermenting organisms, which are further separated into the refused fermenting organisms 546, which are recycled back to the gasifier 524, and live fermenting organisms 544, which are recycled back to the fermentation vessel 536.
  • the fermentation liquid products 548 may comprise one or more selected form the group consisting of: ethanol, acetate, propanol, butanol, 2,3-butanediol, butyrate, propionate, caproate, propylene, butadiene, isobutylene, and ethylene.
  • the fermentation liquid products 548 comprise ethanol and one or more selected form the group consisting of: ethanol, acetate, propanol, butanol, 2,3-butanediol, butyrate, propionate, caproate, propylene, butadiene, isobutylene, and ethylene.
  • the fermentation liquid products 548 may be used as is or optionally purified.
  • the fermentation liquid products 548 are conveyed to a distillation unit 550 that separates ethanol (illustrated as ethanol stream 552) from other liquid byproducts 554.
  • the ethanol stream 552 may comprise at least 90 wt% (or about 90 wt% to 100 wt%, or 95 wt% to 99.9 wt%, or 98 wt% to 99.9 wt%) ethanol.
  • a method of the present disclosure can comprise: flexicoking A a hydrocarbon feed 502 to produce a flexicoking syngas 530, where a gasifier 524 used in the flexicoking A is optionally supplied with steam and an oxygen-rich gas 522 having a higher oxygen content and a lower nitrogen content than air; reforming refused fermenting organisms 546 in the gasifier 524 to produce hydrogen and carbon monoxide; fermenting B the syngas 530 with fermenting organisms to produce fermentation liquid products 548; and separating the fermentation liquid products 548 into ethanol stream 552 and liquid byproducts 554.
  • the ethanol stream 552 may comprise at least 90 wt% (or about 90 wt% to 100 wt%, or 95 wt% to 99.9 wt%, or 98 wt% to 99.9 wt%) ethanol.
  • a system of the present disclosure can comprise: a flexicoking unit (e.g. , corresponding to A of FIG. 5 or a variation thereof) comprising a gasifier that (a) receives refused fermenting organisms and (b) optionally receives an oxygen-rich gas having a higher oxygen content and a lower nitrogen content than air; a fermentation unit (e.g., corresponding to B of FIG.
  • the methods 500 illustrated in this nonlimiting example and related systems may include additional components like compressors, membranes, valves, flow meters, heat exchangers, traps, and the like for proper and safe operation of said methods and systems.
  • FIG. 6 illustrates a diagram of a nonlimiting example method 600 that integrates FLEXICOKINGTM A and fermentation B for the production of ethanol.
  • the concentration of nitrogen in the flexicoking syngas is reduced and carbon dioxide is captured.
  • a hydrocarbon feed 602 and a steam 604 are thermally converted in a reactor 606 to lighter hydrocarbons 608 (having a lower average carbon number than the hydrocarbon feed 602) and coke 610.
  • the coke 610 is transported to a heater 614 where the coke 610 in the presence of additional air 612 is heated and combusted to produce flexicoking syngas 618 and heat the coke 610.
  • the coke is then conveyed as hot coke 616 back to the reactor 606 or as coke 620 to a gasifier 624.
  • a gasifier 624 steam and an oxygen-rich feed 622 are also added.
  • the steam and an oxygen-rich gas 622 are illustrated as a single stream but could alternatively be added to the gasifier 624 as separate streams.
  • all but a small fraction of the coke 620 is gasified by the addition of the steam and an oxygen- rich feed 622, which produces flexicoking syngas 618.
  • a mixture 626 of the flexicoking syngas 618 and remaining coke particles are recycled back to the heater 614 from where the flexicoking syngas 618 is collected.
  • the flexicoking process A uses an oxygen-rich gas having a higher oxygen content and a lower nitrogen content than air is used instead of air.
  • the oxygen-rich gas comprises has about 25 vol% or greater (or about 25 vol% to about 100 vol%, or about 50 vol% to about 100 vol%, or about 50 vol% to about 99 vol%, or about 75 vol% to about 100 vol%, or about 75 vol% to about 99 vol%, or about 90 vol% to about 100 vol%, or about 90 vol% to about 99 vol%) oxygen and 0 vol% to about 70 vol% (or 0 vol% to about 50 vol%, or 0 vol% to about 25 vol%, or 0 vol% to about 10 vol%, or 0 vol% to about 5 vol%, or 0.1 vol% to about 5 vol%) nitrogen.
  • the flexicoking syngas 618, 630 produced has a lower nitrogen-content, which
  • the flexicoking syngas 618 is then conveyed to a clean-up system 628 to remove any remaining fine coke particles 632 and produce flexicoking syngas 630.
  • the flexicoking syngas 630 is conveyed to a fermentation vessel 636 that contains fermenting organisms. Medium 634 is also added to the fermentation vessel 636 as needed to support the fermenting organisms.
  • the fermenting organisms produce liquid products like ethanol and gas products 638 like methane.
  • the liquid products and fermenting organisms 640 are filtered in filtration unit 642 to separate the fermentation liquid products 648 and the fermenting organisms, which are further separated into refused (dead) fermenting organisms 646, which are waste, and live fermenting organisms 644, which are recycled back to the fermentation vessel 636.
  • the fermentation liquid products 648 may comprise one or more selected form the group consisting of: ethanol, acetate propanol, butanol, 2,3-butanediol, butyrate, propionate, caproate, propylene, butadiene, isobutylene, and ethylene.
  • the fermentation liquid products 648 comprise ethanol and one or more selected form the group consisting of: ethanol, acetate, propanol, butanol, 2,3-butanediol, butyrate, propionate, caproate, propylene, butadiene, isobutylene, and ethylene.
  • the fermentation liquid products 648 may be used as is or optionally purified.
  • the fermentation liquid products 648 may be conveyed to a distillation unit 650 that separates ethanol (illustrated as an ethanol stream 652) from other liquid byproducts 654.
  • the ethanol stream 652 may comprise at least 90 wt% (or about 90 wt% to 100 wt%, or 95 wt% to 99.9 wt%, or 98 wt% to 99.9 wt%) ethanol.
  • the fermentation process B produces gas products 638 that may comprise combustible gases like methane and/or carbon monoxide and/or hydrogen.
  • the gas products 638 are combusted in combustion vessel 658 where additional air 656 may be added to improve the combustion yield to a combustion product 660 comprising nitrogen and carbon dioxide.
  • the combustion product 660 may then be separated in a separation process 662 into a carbon dioxide stream 664 and a nitrogen stream 666.
  • separation processes 662 include, but are not limited to, solvent-based separation process, sorbent-based processes, membrane-based processes, and the like, and any combination thereof.
  • the carbon dioxide stream 664 may comprise at least 90 wt% (or about 90 wt% to 100 wt%, or 95 wt% to 99.9 wt%, or 98 wt% to 99.9 wt%) carbon dioxide. Accordingly, the carbon dioxide stream 664 may be sequestration-ready and transported to another site for sequestration by known methods.
  • a method of the present disclosure can comprise: flexicoking A a hydrocarbon feed 602 to produce a flexicoking syngas 630, where a gasifier 624 used in the flexicoking A is supplied with steam and an oxygen-rich gas 622 having a higher oxygen content and a lower nitrogen content than air; fermenting B the syngas 630 with fermenting organisms to produce fermentation liquid products 148 and gas products 638; combusting the gas products 638 to produce a combustion products stream 660; separating a carbon dioxide stream 664 from the combustion products stream 666; and optionally separating the fermentation liquid products 648 into an ethanol stream 152 and liquid byproducts 654.
  • the ethanol stream 652 may comprise at least 90 wt% (or about 90 wt% to 100 wt%, or 95 wt% to 99.9 wt%, or 98 wt% to 99.9 wt%) ethanol.
  • the carbon dioxide stream 664 may comprise at least 90 wt% (or about 90 wt% to 100 wt%, or 95 wt% to 99.9 wt%, or 98 wt% to 99.9 wt%) carbon dioxide.
  • a system of the present disclosure can comprises: a flexicoking unit (e.g ., corresponding to A of FIG. 6 or a variation thereof); a fermentation unit (e.g., corresponding to B of FIG. 6 or a variation thereof) fluidly coupled to the flexicoking unit and configured to receive a flexicoking syngas from the flexicoking unit; a distillation column fluidly coupled to the fermentation unit and configured to receive a liquid product from the fermentation unit and produce an ethanol stream; a combustion vessel fluidly coupled to the fermentation unit and configured to receive gas products from the fermentation unit; and a separation unit fluidly coupled to the combustion vessel and configured to receive a combustion products stream from the combustion vesse..
  • a flexicoking unit e.g ., corresponding to A of FIG. 6 or a variation thereof
  • a fermentation unit e.g., corresponding to B of FIG. 6 or a variation thereof
  • a distillation column fluidly coupled to the fermentation unit and configured to receive a liquid product from the fermentation unit and
  • the methods 100 illustrated in this nonlimiting example and related systems may include additional components like compressors, membranes, valves, flow meters, heat exchangers, traps, and the like for proper and safe operation of said methods and systems.
  • Additional methods and systems of the present disclosure may include hybrids of the foregoing. That is, a method or system of the present disclosure may have one or more of the following: (a) introducing, into a gasifier, an oxygen-rich gas having a higher oxygen content and a lower nitrogen content than air; (b) introducing, into a gasifier, a methane; and reforming the methane in the gasifier; (c) introducing, into a gasifier, biomass and/or plastic waste; and reforming the biomass and/or plastic waste in the gasifier; (d) recycling, into a gasifier, refused fermenting organisms from the fermentation unit; and reforming the refused fermenting organisms in the gasifier; and (e) fermenting the flexicoking syngas with fermenting organisms in the presence of additional hydrogen.
  • method or system of the present disclosure may further include: (f) combusting the gas products from the fermentation process to produce a combustion products stream; and separating a carbon dioxide stream from the combustion products stream.
  • a first nonlimiting example embodiment of the present disclosure is a method comprising: flexicoking a hydrocarbon feed stream to produce a syngas stream; introducing a steam stream and an oxygen-rich stream into a gasifier of the flexicoking process, wherein the oxygen-rich stream has greater than 22 vol% oxygen and less than 50 vol% nitrogen; and fermenting the syngas with fermenting organisms to produce a fermentation liquid product comprising ethanol.
  • Said method may further include one or more of: Element 1: wherein the fermentation liquid product further comprises at least one selected from the group consisting of: acetate, propanol, butanol, 2,3-butanediol, butyrate, propionate, caproate, propylene, butadiene, isobutylene, and ethylene, and wherein the method further comprises: distilling the fermentation liquid product to yield an ethanol stream comprising at least 90 wt% ethanol; Element 2: wherein the oxygen-rich stream comprises 90 vol% to 100 vol% oxygen and 0 vol% to 10 vol% nitrogen; Element 3: the method further comprising: introducing, into the gasifier, a methane; and reforming the methane in the gasifier; Element 4: the method further comprising: introducing, into the gasifier, waste comprising biomass waste, plastic waste, municipal solid waste, paper waste, plastic pyrolysis oil, agricultural waste, wood waste, energy crops, and any combination thereof; and reforming the waste in the gasifier;
  • combinations include, but are not limited to, Element 1 and Element 2 in combination; two or more of Elements 3, 4, 5, and 6 in combination; Element 1 in combination with one or more of Elements 3, 4, 5, and 6 and optionally in further combination with Element 2; Element 2 in combination with one or more of Elements 3, 4, 5, and 6; and Element 7 in combination with one or more of Elements 1, 2, 3, 4, 5, and 6.
  • a second nonlimiting example embodiment of the present disclosure is a method comprising: flexicoking a hydrocarbon feed to produce a flexicoking syngas; fermenting the syngas with fermenting organisms in the presence of additional hydrogen to produce fermentation liquid products.
  • Said method may further include one or more of: Element 8: wherein the fermentation liquid product further comprise at least one selected from the group consisting of: acetate, propanol, butanol, 2,3-butanediol, butyrate, propionate, caproate, propylene, butadiene, isobutylene, and ethylene, and wherein the method further comprises: distilling the fermentation liquid product to yield an ethanol stream comprising at least 90 wt% ethanol; Element 9: the method further comprising: introducing a steam stream and an oxygen-rich stream into a gasifier of the flexicoking process, wherein the oxygen-rich stream has greater than 22 vol% oxygen and less than 50 vol% nitrogen; Element 10: Element 9 and wherein the oxygen-
  • combinations include, but are not limited to, Element 9 and optionally Element 10 in combination with one or more of Elements 11, 12, and 13; two or more of Elements 11, 12, and 13 in combination; Element 8 in combination with one or more of Elements 9-14; and Element 14 in combination with one or more of Elements 8-13.
  • a third nonlimiting example embodiment of the present disclosure is a method comprising: flexicoking a hydrocarbon feed to produce a flexicoking syngas; reforming (a) methane, (b) waste, and/or (c) refused fermenting organisms in a gasifier of the flexicoking process to produce hydrogen and carbon monoxide, wherein the waste comprises biomass waste, plastic waste, municipal solid waste, paper waste, plastic pyrolysis oil, agricultural waste, wood waste, energy crops, and any combination thereof; and fermenting the flexicoking syngas with fermenting organisms to produce fermentation liquid products.
  • Said method may further include one or more of: Element 15: wherein the fermentation liquid product further comprise at least one selected from the group consisting of: acetate, propanol, butanol, 2,3-butanediol, butyrate, propionate, caproate, propylene, butadiene, isobutylene, and ethylene, and wherein the method further comprises: distilling the fermentation liquid product to yield an ethanol stream comprising at least 90 wt% ethanol; Element 16: the method further comprising: introducing a steam stream and an oxygen- rich stream into a gasifier of the flexicoking process, wherein the oxygen-rich stream has greater than 22 vol% oxygen and less than 50 vol% nitrogen; Element 17: Element 16 and wherein the oxygen-rich stream comprises 90 vol% to 100 vol% oxygen and 0 vol% to 10 vol% nitrogen; and Element 18: wherein the fermenting also produces a gas products stream, and wherein the method further comprises: combusting the gas products from the fermentation process to produce
  • compositions and methods are described herein in terms of “comprising” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps.
  • compositions and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps. All numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed. In particular, every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values.

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Abstract

Procédés de production d'éthanol à partir de gaz de synthèse de cokéfaction pouvant comprendre : la cokéfaction d'un courant d'alimentation d'hydrocarbure pour produire un courant de gaz de synthèse de cokéfaction; l'introduction d'un courant de vapeur et d'un courant riche en oxygène dans un gazéifieur du processus de cokéfaction, le courant riche en oxygène ayant plus de 22 % en volume d'oxygène et moins de 50 % en volume d'azote; et la fermentation du gaz de synthèse de cokéfaction avec des organismes de fermentation pour produire un produit liquide de fermentation comprenant de l'éthanol. En plus ou en variante du flux riche en oxygène, les procédés peuvent comprendre le reformage de (a) méthane, (b) de déchets et/ou (c) des acétogènes refusionnés dans un gazéifieur du procédé de cokéfaction. En plus ou en variante de chacun des éléments précédents, de l'hydrogène supplémentaire peut être présent dans l'étape de fermentation.
PCT/US2020/057604 2020-01-20 2020-10-28 Procédés et systèmes de production d'éthanol qui intègrent la cokéfaction et la fermentation WO2021150285A1 (fr)

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