WO2025240146A1 - Method and apparatus for combined carbon capture, utilization, and storage - Google Patents
Method and apparatus for combined carbon capture, utilization, and storageInfo
- Publication number
- WO2025240146A1 WO2025240146A1 PCT/US2025/027618 US2025027618W WO2025240146A1 WO 2025240146 A1 WO2025240146 A1 WO 2025240146A1 US 2025027618 W US2025027618 W US 2025027618W WO 2025240146 A1 WO2025240146 A1 WO 2025240146A1
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- Prior art keywords
- gas
- stream
- fermentation
- carbon
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Classifications
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/20—Bacteria; Culture media therefor
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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
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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
- C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
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- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- 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
Definitions
- gas fermentation is emerging as a powerful biotechnological advancement as an alternative platform for the biological fixation of such gases such as CH4, CO, CO 2 , and/or H 2 into sustainable fuels and chemicals.
- gas fermentation technology can utilize a wide range of feedstocks including gasified carbon-containing matter such as municipal solid waste or agricultural waste, or industrial waste gases such as off- gases from steel manufacturing, petroleum refineries, and petrochemical processes to produce ethanol, aviation fuel, chemicals, and a variety of other products.
- Gas fermentation processes can be used to generate target materials from gas substrates or other input materials, particularly carbon-based materials.
- Greenhouse gases are an example of gas substrates.
- particular biological systems can be used to perform gas fermentation.
- Industrial processes can output gases that have significant amounts of carbon-based materials.
- Chemical processors and oil refiners generally view flaring and venting carbon rich sources to the atmosphere or otherwise discarding them as traditional standard operations.
- CCS carbon capture and sequestration
- CCS and carbon capture and utilization results in both sequestering carbon and recycling carbon.
- SUMMARY Described herein are systems and methods for incorporating gas fermentation into oil and gas production and refining or chemical, such as petrochemical, complexes to convert various feedstocks, waste gas, and other gas by-products into useful products, such as ethylene, ethanol, and the like.
- One embodiment is directed to a method of processing greenhouse gas carbon for both utilization and sequestration comprising: a) passing an input gas stream comprising at least 50 vol-%, on a dry basis, CO and 10 vol-%, on a dry basis, CO2 to a fermentation process; b) fermenting under suitable conditions at least a portion of the CO using a C1- fixing microorganism for: 1) generating at least one fermentation product, and 2) generating a tail gas stream comprising at least 60 vol-%, on a dry basis, CO2, wherein the CO2 was present in the input gas stream; c) conditioning the tail gas stream by liquefaction to generate a liquified CO2 stream comprising at least 90 vol-%, on a dry basis, CO2; and d) sequestering the liquified CO 2 stream.
- the input gas stream further comprises a gas selected from hydrogen, nitrogen, oxygen, other inert gases, or any combination thereof.
- the hydrogen in the stream comprises hydrogen selected from green hydrogen, blue hydrogen, grey hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen, white hydrogen, or any combination thereof.
- the method of an embodiment, wherein the input gas stream is industrial off-gas.
- the method of an embodiment, wherein the industrial off-gas is from a production process comprising steel or alloy.
- the C1-fixing microorganism is Clostridium autoethanogenum.
- the at least one fermentation product is selected from ethanol, single-cell protein, or any combination thereof.
- One embodiment is directed to a method for purifying CO2 comprising: a) passing an input gaseous stream comprising from about 50 vol-%, on a dry basis, to 75 vol-%, on a dry basis, CO and from about 10 vol-%, on a dry basis, to 35 vol-%, on a dry basis, CO2 to a gas fermentation process; b) removing the CO by generating at least one fermentation product; c) recovering the CO2 in a concentrated CO2 tail gas stream; d) purifying the CO2 tail gas stream by liquefaction to generate a purified CO 2 ; and e) providing the purified CO 2 stream for sequestration.
- One embodiment is directed to a method of capturing carbon for combined utilization and sequestration comprising: a) passing a gas stream comprising CO and CO2 to a gas fermentation process under suitable conditions; b) fermenting at least a portion of the CO using a C1-fixing microorganism to: 1) generate at least one fermentation product, and 2) generate an enriched residual CO 2 stream comprising about 20-95 vol-%, on a dry basis, CO 2 ; c) conditioning the enriched residual CO2 stream using cryogenic liquefaction to generate a purified CO 2 stream comprising greater than 99 vol-%, on a dry basis, CO 2 ; and d) providing the purified CO2 stream for sequestration.
- gas stream comprising CO and CO2 comprises about 17.5 vol-%, on a dry basis, CO 2.
- enriched residual CO2 stream comprises about 86 vol-%, on a dry basis, CO 2 .
- purified CO2 stream comprises about 99.9 vol-%, on a dry basis, CO 2 .
- One embodiment is directed to an apparatus for both carbon capture and utilization and carbon capture and sequestration comprising: a) a CO/CO 2 gas source; b) a gas fermentation process unit in fluid communication with the gas source; c) a gas fermentation product conduit in fluid communication with the gas fermentation process unit; d) a tail gas conduit in fluid communication with the gas fermentation process unit and a liquefaction unit; and e) a purified CO 2 conduit in fluid communication with the liquefaction unit and a sequestration facility.
- FIG.1 is a flow diagram according to one embodiment of the disclosure.
- FIG.2 is a process flow scheme according to one embodiment of the disclosure.
- FIG.3 is an overview of the piping and associated components of an embodiment of the gas fermentation process portion of the disclosure.
- FIG.4 is a schematic flow scheme of an embodiment of the disclosure.
- CCS carbon capture and sequestration
- CCU carbon capture and utilization
- the present disclosure relates to systems and methods for combining both CCU and CCS into carbon capture utilization and sequestration (CCUS) by using gas fermentation to convert various feedstock, waste gas, and other gas by-products into useful products, such as ethylene, ethanol, single-cell protein and the like while at the same time also sequestering a portion of the waste carbon.
- CCUS carbon capture utilization and sequestration
- the term “acid” as used herein includes both carboxylic acids and the associated carboxylate anion, such as the mixture of free acetic acid and acetate present in a fermentation broth as described herein.
- the ratio of molecular acid to carboxylate in the fermentation broth is dependent upon the pH of the system.
- acetate includes both acetate salt alone and a mixture of molecular or free acetic acid and acetate salt, such as the mixture of acetate salt and free acetic acid present in a fermentation broth as described herein.
- carbon capture refers to the fixation and utilization of carbon including carbon from CO2, CO, and/or CH4 from a stream comprising CO2, CO, and/or CH 4 and converting the CO 2 , CO, and/or CH 4 into useful products.
- substrate comprising carbon monoxide and like terms should be understood to include any substrate in which carbon monoxide is available to one or more strains of bacteria for growth and/or fermentation, for example.
- gaseous substrates comprising carbon monoxide includes any gas which contains carbon monoxide. The gaseous substrate will typically contain a significant proportion of CO, preferably at least about 5% to about 100% CO by volume.
- C1 carbon and like terms should be understood to refer to carbon sources that are suitable for use by a microorganism, particularly those of the gas fermentation process disclosed herein.
- C1 carbon may include, but should not be limited to, carbon monoxide (CO), carbon dioxide (CO2), and methane (CH4), methanol (CH3OH), and formate (HCOOH).
- substrate comprising carbon dioxide and like terms should be understood to include any substrate in which carbon dioxide is available to one or more strains of bacteria for growth and/or fermentation, for example.
- gaseous substrates comprising carbon dioxide includes any gas which contains carbon dioxide. The gaseous substrate will typically contain a significant proportion of CO 2 , preferably at least about 5% to about 100% CO 2 by volume.
- green hydrogen refers to hydrogen generated from clean electricity or surplus renewable energy sources.
- blue hydrogen refers to hydrogen primarily generated from steam reforming of natural gas thereby producing hydrogen and carbon dioxide.
- grey hydrogen refers to hydrogen primarily generated from steam reforming of natural gas thereby producing hydrogen and carbon dioxide, but the carbon dioxide is not obtained through carbon capture and storage.
- pink hydrogen refers to hydrogen generated through electrolysis from nuclear energy.
- Turquoise hydrogen refers to hydrogen generated by methane pyrolysis producing solid carbon and hydrogen.
- yellow hydrogen refers to hydrogen generated by electrolysis using solar power.
- white hydrogen refers to hydrogen that is naturally occurring hydrogen.
- biomass includes a fermentation device consisting of one or more vessels and/or towers or piping arrangements, which includes the continuous stirred tank reactor (CSTR), immobilized cell reactor (ICR), trickle bed reactor (TBR), bubble column, gas lift fermenter, membrane reactor such as hollow fiber membrane bioreactor (HFMBR), static mixer, or other vessel or other device suitable for gas-liquid contact.
- CSTR continuous stirred tank reactor
- ICR immobilized cell reactor
- TBR trickle bed reactor
- HMBR hollow fiber membrane bioreactor
- static mixer or other vessel or other device suitable for gas-liquid contact.
- co-substrate refers to a substance that, while not necessarily being the primary energy and material source for product synthesis, can be utilized for product synthesis when added to another substrate, such as the primary substrate.
- the term “directly”, as used in relation to the passing of industrial off or gases to a bioreactor, is used to mean that no or minimal processing or treatment steps, such as cooling and particulate removal are performed on the gases prior to them entering the bioreactor (note: an oxygen removal step may be required for anaerobic fermentation).
- the terms “fermenting,” “fermentation process,” “fermentation reaction,” and like terms as used herein, are intended to encompass both the growth phase and product biosynthesis phase of the process.
- the bioreactor may comprise a primary bioreactor and a secondary bioreactor.
- the term “nutrient medium” as used herein should be understood as the solution added to the fermentation broth containing nutrients and other components appropriate for the growth of the microorganism culture.
- primary bioreactor or “first reactor” as used herein this term is intended to encompass one or more reactors that may be connected in series or parallel with a secondary bioreactor.
- the primary bioreactors generally use anaerobic or aerobic fermentation to produce a product (e.g., ethylene, ethanol, acetate, etc.) from a gaseous substrate.
- secondary bioreactor or “second reactor” as used herein are intended to encompass any number of further bioreactors that may be connected in series or in parallel with the primary bioreactors. Any one or more of these further bioreactors may also be connected to a further separator.
- the term “stream” is used to refer to a flow of material into, through and away from one or more stages of a process, for example, the material that is fed to a bioreactor.
- the composition of the stream may vary as it passes through particular stages. For example, as a stream passes through the bioreactor.
- the term “enriched” can mean that the outlet stream has a greater concentration of the indicated component than in the inlet stream to a vessel.
- the term “depleted stream” means that the depleted stream coming out of a vessel has a smaller concentration of the component than the feed to the vessel.
- feedstock when used in the context of the stream flowing into a gas fermentation bioreactor (i.e., gas fermenter) or “gas fermentation feedstock” should be understood to encompass any material (solid, liquid, or gas) or stream that can provide a substrate and/or C1-carbon source to a gas fermenter or bioreactor either directly or after processing of the feedstock.
- waste gas or “waste gas stream” may be used to refer to any gas stream that is either emitted directly, flared with no additional value capture, or combusted for energy recovery purposes.
- synthesis gas or “syngas” refers to a gaseous mixture that contains at least one carbon source, such as carbon monoxide (CO), carbon dioxide (CO2), or any combination thereof, and, optionally, hydrogen (H2) that can used as a feedstock for the disclosed gas fermentation processes and can be produced from a wide range of carbonaceous material, both solid and liquid.
- carbon source such as carbon monoxide (CO), carbon dioxide (CO2), or any combination thereof
- H2 hydrogen
- intermediate and “precursor” can be used interchangeably to refer to a substance, such as a molecule, compound, or protein, that is produced upstream of a particular product.
- the intermediate may be directly upstream of the product.
- the intermediate may be indirectly upstream of the product.
- electrolysis process may include any substrate leaving the electrolysis process.
- the electrolysis process is comprised of CO, H2, or combinations thereof.
- the electrolysis process may contain portions of unconverted CO2.
- the electrolysis process is fed from the electrolysis process to the fermentation process.
- electrolysis process may include any substrate leaving the electrolysis process.
- the electrolysis process is comprised of CO, H 2 , or combinations thereof.
- the electrolysis process may contain portions of unconverted CO2.
- the electrolysis process is fed from the electrolysis process to the fermentation process.
- the terms “improving the economics”, “optimizing the economics” and the like, when used in relationship to a fermentation process include, but are not limited to, the increase of the amount of one or more of the products produced by the fermentation process during periods of time in which the value of the products produced is high relative to the cost of producing such products.
- the economics of the fermentation process may be improved by way of increasing the supply of feedstock to the bioreactor, which may be achieved for instance by supplementing the C1 feedstock from the industrial process with electrolysis process from the electrolysis process.
- the additional supply of feedstock may result in the increased efficiency of the fermentation process.
- Another means of improving the economics of the fermentation process is to select feedstock based upon the relative cost of the feedstock available. For example, when the cost of the C1 feedstock from the industrial process is higher than the cost of the electrolysis process from the electrolysis process, the electrolysis process may be utilized to displace at least a portion of the C1 feedstock. By selecting feedstock based upon the cost of such feedstock the cost of producing the resulting fermentation product is reduced.
- the electrolysis process is capable of supplying feedstock comprising one or both of H 2 and CO.
- the “cost per unit of electrolysis process” may be expressed in terms of any given product produced by the fermentation process and any electrolysis process, for example for the production of ethanol with the electrolysis process defined as H 2 , the cost per unit of electrolysis process is defined by the following equation: $ ⁇ ⁇ ⁇ ⁇ x ⁇ x ⁇ ⁇ ⁇ x ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ process efficiency, and y represents the yield of ethanol.
- the cost per unit of electrolysis process is defined by the following equation: ⁇ $ ⁇ ⁇ x ⁇ ⁇ ⁇ x ⁇ ⁇ ⁇ ⁇ x ⁇ ⁇ ⁇ ⁇ process efficiency, and y represents the yield of ethanol.
- the fermentation process includes “production costs.”
- the “production costs” exclude the cost of the feedstock.
- “Production costs”, “marginal cost of production”, and the like, include the variable operating costs associated with running the fermentation process. This value may be dependent on the product being produced.
- the marginal cost of production may be represented by a fixed cost per unit of product, which may be represented in terms of the heating value of combustion of the product.
- the calculation of the marginal cost of production for ethanol is defined by the following equation: ⁇ $ ⁇ ⁇ x ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ . ⁇ ⁇ ⁇ ⁇ operating costs associated with running the bioreactor value of combustion of ethanol.
- the variable operating costs associated with running the bioreactor, c is $200 for ethanol excluding the price of H2/CO/CO2.
- the fermentation process is capable of producing a number of products. Each product defining a different value. The “value of the product” may be determined based upon the current market price of the product and the heating value of combustion of the product.
- the calculation for the value of ethanol is defined by the following equation: ⁇ $ ⁇ ⁇ ⁇ ⁇ x ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ . ⁇ ⁇ ⁇ ⁇ of ethanol per metric ton and 26.8 GJ represents the lower heating value of combustion of ethanol.
- the value of the product produced must exceed the “cost of producing” such product.
- the cost of producing a product is defined as the sum of the “cost of feedstock” and the “marginal cost of production.”
- the economics of the fermentation process may be expressed in terms of a ratio defined by the value of product produced compared to the cost of producing such product.
- the economics of the fermentation process is improved as the ratio of the value of the product compared to the cost of producing such product increases.
- the economics of the fermentation process may be dependent on the value of the product produced, which may change dependent, at least in part, on the fermentation process implemented, including but not limited to the bacterial culture and/or the composition of the gas used in the fermentation process.
- the economics may be determined by the following ratio: ⁇ $ ⁇ ⁇ ⁇ ⁇ $ ⁇ ⁇ ⁇ $ ⁇ ⁇ ⁇ $ ⁇ ⁇ ⁇ ⁇ where z represents the value of ethanol, x represents the cost of feedstock, and y represents the marginal cost of production (excluding feedstock).
- factors may be dependent on the cost or price of product, cost or price of hydrogen, cost of sequestration, and/or incentive credits, all of which may be determined and balanced with a suitable algorithm.
- the terms “increasing the efficiency”, “increased efficiency” and the like, when used in relation to a fermentation process, include, but are not limited to, increasing one or more of the rate of growth of microorganisms catalysing the fermentation, the growth and/or product production rate at elevated product concentrations, the volume of desired product produced per volume of substrate consumed, the rate of production or level of production of the desired product, and the relative proportion of the desired product produced compared with other by- products of the fermentation.
- electrolysis process increases the efficiency of the fermentation process.
- electrolysis module and “electrolyzer” can be used interchangeably to refer to a unit that uses electricity to drive a non-spontaneous reaction.
- Electrolysis technologies are known in the art. Exemplary processes include alkaline water electrolysis, proton or anion exchange membrane (PEM, AEM) electrolysis, and solid oxide electrolysis (SOE) (Ursua et al., Proceedings of the IEEE 100(2):410-426, 2012; Jhong et al., Current Opinion in Chemical Engineering 2:191-199, 2013).
- the term “faradaic efficiency” is a value that references the number of electrons flowing through an electrolyzer and being transferred to a reduced product rather than to an unrelated process.
- SOE modules operate at elevated temperatures. Below the thermoneutral voltage of an electrolysis module, an electrolysis reaction is endothermic. Above the thermoneutral voltage of an electrolysis module, an electrolysis reaction is exothermic. In some embodiments, an electrolysis module is operated without added pressure. In some embodiments, an electrolysis module is operated at a pressure of 5-10 bar.
- a “CO2 electrolysis module” refers to a unit capable of splitting CO2 into CO and O2 and is defined by the following stoichiometric reaction: 2CO2 + electricity ⁇ 2CO + O2.
- H2 electrolysis module refers to a unit capable of splitting H2O, in the form of steam, into H2 and O2 and is defined by the following stoichiometric reaction: 2H2O + electricity ⁇ 2H2 + O2.
- An H2O electrolysis module reduces protons to H2 and oxidizes O2- to O2.
- H2 produced by electrolysis can be blended with a C1-comprising gaseous substrate as a means to supply additional feedstock and to improve substrate composition.
- H2 and CO2 electrolysis modules have 2 gas outlets.
- One side of the electrolysis module, the anode comprises H2 or CO (and other gases such as unreacted water vapor or unreacted CO2).
- the second side, the cathode comprises O2 (and potentially other gases).
- the composition of a feedstock being passed to an electrolysis process may determine the presence of various components in a CO stream. For instance, the presence of inert components, such as CH4 and/or N2, in a feedstock may result in one or more of those components being present in the CO-enriched stream.
- an “O2 separation module” is used to refer to a technology capable of dividing a substance into two or more components.
- an “O2 separation module” may be used to separate an O2-comprising gaseous substrate into a stream comprising primarily O2 (also referred to as an “O2-enriched stream” or “O2-rich gas”) and a stream that does not primarily comprise O2, comprises no O2, or comprises only trace amounts of O2 (also referred to as an “O2-lean stream” or “O2-depleted stream”).
- enriched stream As used herein, the terms “enriched stream,” “rich gas,” “high purity gas,” and the like refer to a gas stream having a greater proportion of a particular component following passage through a module, such as an electrolysis module, as compared to the proportion of the component in the input stream into the module.
- a “CO-enriched stream” may be produced upon passage of a CO2-comprising gaseous substrate through a CO2 electrolysis module.
- An “H2-enriched stream” may be produced upon passage of a water gaseous substrate through an H2 electrolysis module.
- An “O2-enriched stream” emerges automatically from the anode of a CO2 or H2 electrolysis module; an “O2-enriched stream” may also be produced upon passage of an O2-comprising gaseous substrate through an O2 separation module.
- a “CO2-enriched stream” may be produced upon passage of a CO2- comprising gaseous substrate through a CO2 concentration module.
- the terms “lean stream,” “depleted gas,” and the like refer to a gas stream having a lesser proportion of a particular component following passage through a module, such as a concentration module or a separation module, as compared to the proportion of the component in the input stream into the module.
- an O2-lean stream may be produced upon passage of an O2-comprising gaseous substrate through an O2 separation module.
- the O2-lean stream may comprise unreacted CO2 from a CO2 electrolysis module.
- the O2-lean stream may comprise trace amounts of O2 or no O2.
- a “CO2-lean stream” may be produced upon passage of a CO2-comprising gaseous substrate through a CO2 concentration module.
- the CO2-lean stream may comprise CO, H2, and/or a constituent such as a microbe inhibitor or a catalyst inhibitor.
- the CO2-lean stream may comprise trace amounts of CO2 or no CO2.
- the disclosure provides an integrated process wherein the pressure of the gas stream is capable of being increased and/or decreased.
- pressure module refers to a technology capable of producing (i.e., increasing) or decreasing the pressure of a gas stream.
- the pressure of the gas may be increased and/or decreased through any suitable means, for example one or more compressor and/or valve.
- a gas stream may have a lower than optimum pressure, or the pressure of the gas stream may be higher than optimal, and thus, a valve may be included to reduce the pressure.
- a pressure module may be located before or after any module described herein. For example, a pressure module may be utilized prior to a removal module, prior to a concentration module, prior to an electrolysis module, and/or prior to a CO-consuming process.
- a “pressurized gas stream” refers to a gaseous substrate that has passed through a pressure module.
- a “pressurized gas stream” may also be used to refer to a gas stream that meets the operating pressure requirements of a particular module.
- the terms “post-CO-consuming process gaseous substrate,” “post-CO-consuming process tail gas,” “tail gas,” and the like may be used interchangeably to refer to a gas that has passed through a CO-consuming process.
- the post-CO-consuming process gaseous substrate may comprise unreacted CO, unreacted H2, and/or CO2 produced (or not taken up in parallel) by the CO-consuming process.
- the post-CO-consuming process gaseous substrate may further be passed to one or more of a pressure module, a removal module, a CO2 concentration module, and/or an electrolysis module.
- a “post-CO- consuming process gaseous substrate” is a post-fermentation gaseous substrate.
- the term “desired composition” is used to refer to the desired level and types of components in a substance, such as, for example, of a gas stream. More particularly, a gas is considered to have a “desired composition” if it contains a particular component (i.e., CO, H2, and/or CO2) and/or contains a particular component at a particular proportion and/or does not comprise a particular component (i.e., a contaminant harmful to the microorganisms) and/or does not comprise a particular component at a particular proportion. More than one component may be considered when determining whether a gas stream has a desired composition.
- a particular component i.e., CO, H2, and/or CO2
- More than one component may be considered when determining whether a gas stream has a desired composition.
- “Selectivity” refers to the ratio of the production of a target product to the production of all fermentation products produced by a microorganism.
- the microorganism of the disclosure may be engineered to produce products at a certain selectivity or at a minimum selectivity.
- a target product such as ethylene glycol
- ethylene accounts for at least about 5%, 10%, 15%, 20%, 30%, 50%, or 75% of all fermentation products produced by the microorganism of the disclosure.
- ethylene accounts for at least 10% of all fermentation products produced by the microorganism of the disclosure, such that the microorganism of the disclosure has a selectivity for ethylene glycol of at least 10%.
- ethylene accounts for at least 30% of all fermentation products produced by the microorganism of the disclosure, such that the microorganism of the disclosure has a selectivity for ethylene of at least 30%.
- At least one of the one or more fermentation products may be biomass produced by the culture.
- At least a portion of the microbial biomass may be converted to a single cell protein (SCP).
- SCP single cell protein
- At least a portion of the single cell protein may be utilized as a component of animal feed.
- the disclosure provides an animal feed comprising microbial biomass and at least one excipient, wherein the microbial biomass comprises a microorganism grown on a gaseous substrate comprising one or more of CO, CO2, and H2.
- a “single cell protein” refers to a microbial biomass that may be used in protein-rich human and/or animal feeds, often replacing conventional sources of protein supplementation such as soymeal or fishmeal.
- the process may comprise additional separation, processing, or treatments steps.
- the method may comprise sterilizing the microbial biomass, centrifuging the microbial biomass, and/or drying the microbial biomass.
- the microbial biomass is dried using spray drying or paddle drying.
- the method may also comprise reducing the nucleic acid content of the microbial biomass using any method known in the art, since intake of a diet high in nucleic acid content may result in the accumulation of nucleic acid degradation products and/or gastrointestinal distress.
- the single cell protein may be suitable for feeding to animals, such as livestock or pets.
- the animal feed may be suitable for feeding to one or more beef cattle, dairy cattle, pigs, sheep, goats, horses, mules, donkeys, deer, buffalo/bison, llamas, alpacas, reindeer, camels, bantengs, gayals, yaks, chickens, turkeys, ducks, geese, quail, guinea fowl, squabs/pigeons, fish, shrimp, crustaceans, cats, dogs, and rodents.
- the composition of the animal feed may be tailored to the nutritional requirements of different animals.
- the process may comprise blending or combining the microbial biomass with one or more excipients.
- Microbial biomass refers biological material comprising microorganism cells.
- microbial biomass may comprise or consist of a pure or substantially pure culture of a bacterium, archaea, virus, or fungus.
- microbial biomass When initially separated from a fermentation broth, microbial biomass generally contains a large amount of water. This water may be removed or reduced by drying or processing the microbial biomass.
- the microbial biomass may comprise any of the components listed in this application but is not limited to the disclosures herein.
- the microbial biomass of an embodiment comprises 15% moisture (water) by weight. Accordingly, the values may refer to amounts of each component per amount of wet (i.e., non-dried) microbial biomass.
- the composition of the microbial biomass is described in terms of weight of a component per weight of wet (i.e., non-dried) microbial biomass.
- the microbial biomass generally contains a large fraction of protein, such as more than 50% (50 g protein/100 g biomass), more than 60% (60 g protein/100 g biomass), more than 70% (70 g protein/100 g biomass), or more than 80% (80 g protein/100 g biomass) protein by weight.
- the microbial biomass comprises at least 72% (72 g protein/100 g biomass) protein by weight.
- the protein fraction comprises amino acids, including aspartic acid, alanine, arginine, cysteine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tyrosine, and/or valine.
- the microbial biomass may comprise more than 10 mg methionine/g biomass, more than 15 mg methionine/g biomass, more than 20 mg methionine/g biomass, or more than 25 mg methionine/g biomass.
- the microbial biomass comprises at least 17.6 mg methionine/g biomass.
- the microbial biomass may contain a number of vitamins, including vitamins A (retinol), C, B1 (thiamine), B2 (riboflavin), B3 (niacin), B5 (pantothenic acid), and/or B6 (pyridoxine).
- the microbial biomass may contain relatively small amounts of carbohydrates and fats.
- the microbial biomass may comprise less than 15% (15 g carbohydrate/100 g biomass), less than 10% (10 g carbohydrate/100 g biomass), or less than 5% (5 g carbohydrate/100 g biomass) of carbohydrate by weight.
- the microbial biomass may comprise less than 10% (10 g fat/100 g biomass), or less than 5% (5 g fat/100 g biomass), less than 2% (2 g fat/100 g biomass), or less than 1% (1 g fat/100 g biomass) of fat by weight.
- the microorganism may classified based on functional characteristics.
- the microorganism may be or may be derived from a C1-fixing microorganism, an aerobe, a hydrogen-oxidizing bacteria, a hydrogenotroph, an anaerobe, an acetogen, an ethanologen, and/or a carboxydotroph.
- excipient may refer to any substance that may be added to the microbial biomass to enhance or alter the form, properties, or nutritional content of the animal feed.
- the excipient may comprise one or more of a carbohydrate, fiber, fat, protein, vitamin, mineral, water, flavour, sweetener, antioxidant, enzyme, preservative, probiotic, or antibiotic.
- the excipient may be hay, straw, silage, grains, oils or fats, or other plant material.
- the excipient may be any feed ingredient identified in Chiba, Section 18: Diet Formulation and Common Feed Ingredients, Animal Nutrition Handbook, 3rd revision, pages 575-633, 2014.
- a “biopolymer” refers to natural polymers produced by the cells of living organisms.
- the biopolymer is PHA. In certain embodiments, the biopolymer is PHB.
- a “bioplastic” refers to plastic materials produced from renewable biomass sources. A bioplastic may be produced from renewable sources, such as vegetable fats and oils, corn starch, straw, woodchips, sawdust, or recycled food waste. As used herein, the terms “protein-based bioplastic,” “protein bio-based plastic” and “protein biocomposite” can be used interchangeably. “Protein-based bioplastics” and “protein-based protein-based biofilms” refer to naturally-derived biodegradable polymers. Protein-based bioplastics and protein-based biofilms are largely composed of proteins.
- a “protein-based material” refers to a three-dimensional macromolecular network comprising hydrogen bonds, hydrophobic interactions, and disulphide bonds. See, e.g., Martinez, Journal of Food Engineering, 17: 247-254, 2013 and Pommet, Polymer, 44: 115-122, 2003.
- the protein component of a protein-based bioplastic or protein-based biofilm is microbial biomass. Production of protein-based bioplastics and protein-based biofilms may require a step of protein denaturation by chemical, thermal, or pressure-induced methods. See, e.g., Mekonnen, Biocomposites: Design and Mechanical Performance, 2015.
- Production of protein-based bioplastics and protein-based biofilms may further require a step of isolating or fractionating the microbial biomass to produce a purified protein material.
- Disclosed Systems and Methods in accordance with the present disclosure can be used to integrate gas fermentation systems with processes capable of generating an input gas comprising at least CO2, and more commonly, both CO and CO2, such as existing oil and gas processing infrastructure, refining infrastructure, petrochemical infrastructure, and infrastructure in complexes that combine any of the foregoing as well as plants, mills, refineries, or other infrastructure that generates carbon-based materials as outputs, including as waste.
- Integrating a gas fermentation unit with existing infrastructure allows users and operators to reduce their overall carbon emissions by converting their waste carbon into marketable products without additional capital investment and operating costs for equipment and processes that can be leveraged from infrastructure an operator may already have or is building for another primary purpose. At the same time, operators will be able to also sequester CO 2 and potentially receive benefits from sequestration. For some operators, integration can also increase their overall production yield if the product produced by the gas fermentation process is a product that the operator is capable of producing or is a feed component to a process an operator is already performing. For many industrial processes, emission of gases that are rich in carbon are commonplace. Chemical processors and oil refiners generally view flaring and venting carbon rich sources to the atmosphere or otherwise discarding them as traditional standard techniques.
- CCS carbon capture and sequestration
- CCU can be combined with CCS operations.
- CCS processes are improved since the gas fermentation process may produce a tail gas stream of concentrated CO 2 which is readily purified and sequestered. Common steps such as a separate concentration step typically employed with for example, emissions from flue gas, can be eliminated.
- Gas fermentation already provides a concentrated CO2 tails gas stream.
- the substrate and/or C1 carbon source is obtained from the refining or chemical operations in which the gas fermentation process is being integrated.
- the substrate and/or C1 carbon source is obtained from outside the refining or petrochemical operations in which the gas fermentation process is being integrated and it is the product of the gas fermentation process that is being integrated with infrastructure of the refining or chemical operations. In yet other embodiments it is both the substrate and/or C1 carbon source.
- the substrate and or C1 carbon source may be already in the form of a gas (e.g., a waste gas or underutilized gas), or a solid or liquid material may be first processed in a preliminary step of the overall gas fermentation process to generate synthesis gas known as syngas which in turn is provided to the bioreactor of the gas fermentation system.
- the preliminary step to generate syngas may involve, reforming, partial oxidation, plasma, or gasification processes.
- gasification processes include gasification of coal, gasification of refinery residues, gasification of petroleum coke, gasification of biomass, gasification of lignocellulosic material, gasification of waste wood, gasification of black liquor, gasification of municipal solid waste, gasification of municipal liquid waste, gasification of industrial solid waste, gasification of industrial liquid waste, gasification of refuse derived fuel, gasification of sewerage, gasification of sewerage sludge, gasification of sludge from wastewater treatment, gasification of landfill gas, gasification of biogas such as when biogas is added to enhance gasification of another material, gasification of tires, pieces of tires, and or components of tires, and gasification of tires, pieces of tires, and or components of tires combined with an organic material.
- Examples of reforming processes include, steam methane reforming, steam naphtha reforming, reforming of natural gas, reforming of biogas, reforming of landfill gas, reforming of coke oven gas, reforming of pyrolysis off-gas, reforming of ethylene production off-gas, naphtha reforming, and dry methane reforming.
- Examples of partial oxidation processes include thermal and catalytic partial oxidation processes, catalytic partial oxidation of natural gas, partial oxidation of hydrocarbons, partial oxidation of biogas, partial oxidation of landfill gas, or partial oxidation of pyrolysis off-gas.
- Examples of municipal solid waste include tires, plastics, refuse derived fuel, and fibers such as in shoes, apparel, and textiles.
- Municipal solid waste may be simply landfill-type waste and may be sorted or unsorted.
- tires include end of life tires, defective tires, surplus tires, and tire scraps.
- biomass may include lignocellulosic material and microbial biomass.
- Lignocellulosic material may include agriculture waste and forest waste.
- the substrate and/or C1-carbon source may be a gas stream comprising methane.
- Such a methane containing gas may be obtained from fossil methane emissions such as during fracking or other hydrocarbon well stimulation processes or from coalbeds, or may be obtained from wastewater treatment, livestock, agriculture, and municipal solid waste landfills.
- the methane may be burned or employed as a feed in a fuel cell to produce electricity or heat, and the C1 by-products may be used as the substrate or carbon source.
- the method of the disclosure may be used to produce one or more products.
- the products may include ethanol, acetate, 1-butanol, 2,3-butanediol, lactate, butene, butadiene, methyl ethyl ketone (2-butanone), ethylene, acetone, isopropanol, lipids, 3- hydroxypropionate (3-HP), terpenes, including isoprene, fatty acids, 2-butanol, 1,2- propanediol, 1 propanol, 1 hexanol, 1 octanol, chorismate-derived products, 3 hydroxybutyrate, 1,3 butanediol, 2-hydroxyisobutyrate or 2-hydroxyisobutyric acid, isobutylene, adip
- microbial biomass itself may be considered a product.
- the microorganism of the disclosure may be cultured with the gaseous substrate to produce one or more carbon products.
- the microorganism of the disclosure may produce or may be engineered to produce ethanol, acetate, 1-butanol, 2,3-butanediol, lactate, butene, butadiene, methyl ethyl ketone (2- butanone), ethylene, acetone, isopropanol, lipids, 3-hydroxypropionate (3-HP), terpenes, including isoprene, fatty acids, 2-butanol, 1,2-propanediol, 1 propanol, 1 hexanol, 1 octanol, chorismate-derived products, 3 hydroxybutyrate, 1,3 butanediol, 2-hydroxyisobutyrate or 2- hydroxyisobutyric acid, isobutylene, adipic acid, 1,3
- microbial biomass itself may be considered a product.
- industrial process have feedstocks or gas (e.g., waste gas) suitable as substrate and/or C1 carbon source and are selected from ferrous metal products manufacturing, such as a steel manufacturing, non-ferrous products manufacturing, petroleum production, petroleum refining, electric power production, carbon black production, paper and pulp manufacturing, ammonia production, methanol production, coke manufacturing, coke gasification, petrochemical production, polymer production, ethylene production, olefin production, carbohydrate fermentation, cement making, aerobic digestion, anaerobic digestion, catalytic processes, natural gas extraction, cellulosic fermentation, oil extraction, industrial processing of geological reservoirs, processing fossil resources such as natural gas coal and oil, landfill operations, or any combination thereof.
- ferrous metal products manufacturing such as a steel manufacturing, non-ferrous products manufacturing, petroleum production, petroleum refining, electric power production, carbon black production, paper and pulp manufacturing, ammonia production, methanol production, coke manufacturing, coke gasification, petro
- Examples of specific processing steps within an industrial process which may generate substrate and/or C1 carbon source for gas fermentation include catalyst regeneration, fluid catalyst cracking, and steam cracking. Air separation and direct air capture are other suitable industrial processes to provide substrate and/or C1 carbon source for the gas fermentation process.
- Specific examples in steel and ferroalloy manufacturing include blast furnace gas, basic oxygen furnace gas, coke oven gas, direct reduction of iron furnace top- gas, and residual gas from smelting iron.
- C1 carbon may be produced with the oil or may be produced from a well separately.
- Other general examples include flue gas from fired boilers and fired heaters, such as natural gas, oil, or coal fired boilers or heaters, and gas turbine exhaust.
- the substrate and/or C1- carbon source may be captured from the industrial process before it is emitted into the atmosphere, using any known method.
- the product of the gas fermentation process may provide an additional point of integration.
- Products listed above as capable of being produced by gas fermentation may be reactants or components used in refining or chemical processes and integrating the product into a refining or chemical process may take advantage of equipment and operations in common with both the gas fermentation and the refining or chemical process.
- Points of integration as either providing the gas fermentation substrate and/or carbon source or as accepting the product of gas fermentation or both include the following.
- the integration may involve the gas fermentation substrate and/or carbon source from one refining or chemical process and the acceptance of the gas fermentation product into a second different refining or chemical process.
- Exemplary processes include distillation, including as examples, at atmospheric pressure, at reduced pressure, stripping, rerunning, stabilization, super fractionation, azeotropic, extractive, or any combination thereof; thermal cracking including for example, Visbreaking, coking, delayed coking, fluid coking, coke gasification, Flexicoking TM process, Aquaconversion TM process, Asphalt Coking Technology Process (ASCOT) Process, Cherry-P Process, Continuous Coking Process, Decarbonizing Process, ET-II Process, Eureka Process, FTC Process, HSC Process, Mixed-Phase Cracking Process, Shell Thermal Cracking Process, Tervahl-T Process, or any combination thereof; catalytic cracking as exemplified by fixed bed, moving bed, fluid bed, coke formation, Asphalt Residual Treating (ART) Process, Residue Fluid Catalyst Cracking Process, Heavy Oil Treating Process, R2R Process, Reduced Crude Oil Conversion Process, Shell FCC Process, and S&W Fluid Catalytic Cracking Process, or any combination thereof;
- Examples of reforming processes include thermal reforming, catalytic reforming in fixed bed mode and in moving bed mode, and fluid bed reforming.
- Examples of isomerization processes include Butamer Process, Butomerate Process, Hysomar Process, Iso-Kel Process, Isomate Process, Isomerate Process, Penex Process, and Pentafining Process.
- Examples of alkylation processes include sulfuric acid alkylation and hydrofluoric alkylation.
- Examples of polymerization processes include thermal, solidphosporic acid, and bulk acid.
- Examples of caustic treating processes include Dualayer Distillate Process, Dualayer Gasoline Process, Electrolytic Mercaptan Process, Ferrocyanide Process, Lye Treatment, Mercapsol Process, Polysulfide Process, Sodasol Process, Solutizer Process, Steam-Regenerative Caustic Treatment, and Unisol Process.
- Examples of acid treating processes include Nalfining Process, and Sulfuric Acid Treatment.
- Example of Clay treating processes include Alkylation Effluent Treatment, Arosorb Process, bauxite treatment, continuous contact filtration process, cyclic adsorption process, gray clay treatment, percolation filtration process, and Thermofor Continuous Percolation Process.
- oxidative treatment processed examples include Bender Process, Copper Sweetening Process, Doctor Process, Hypochlorine Sweetening Process, Inhibitor Sweetening Process, and Merox Process.
- Refining processes listed are known and described in Speight, James G. Handbook of Petroleum Refining. Taylor & Francis, 2017. Gas fermentation may be integrated with the following chemical manufacturing exemplary processes: alkylation, amination, condensation and addition, dehydration, dehydrogenation, esterification, ethynylation, other fermentation processes, Friedel-Crafts reactions, halogenation, hydration, hydrolysis, hydroformylation, hydrogenation, nitration, oxidation, oxo reaction, polymerization, sulfonation, and vinylation.
- Products made or resulting from any of the above chemical processes may include, but are not limited to, a commodity chemical selected from ethanol, isopropanol, monoethylene glycol, sulfuric acid, propylene, sodium hydroxide, sodium carbonate, ammonia, benzene, acetic acid, ethylene, ethylene oxide, formaldehyde, methanol, or any combination thereof.
- the commodity chemical is incorporated into one or more articles, converted into one or more second products, or any combination thereof.
- the one or more articles, the one or more second products, or any combination thereof are selected from acetate, 1-butanol, butyrate, 2,3-butanediol, lactate, butene, butadiene, methyl ethyl ketone, acetone, lipids, 3-hydroxyproprionate, terpenes, isoprene, fatty acids, 2-butanol, 1,2-propanediol, 1 propanol, 1 hexanol, 1 octanol, chorismite-derived products, 3-hydroxybutyrate, 1,3-butanediol, 2-hydroxyisobutyrate, 2- hydroxyisobutyric acid, isobutylene, adipic acid, keto-adipic acid, 1,3-hexanediol, 3-methyl- 2-butanol, 2-buten-1-ol, isovalerate, isoamyl alcohol, or any combination thereof.
- Gas fermentation may be used to produce desirable products on site or off site.
- gas fermentation may be employed to convert methane directly from a gas or oil well into valuable products with possible carbon dioxide as a by-product.
- the gas fermentation reactor may be located at the well site, or may be remote to the well site.
- the carbon dioxide itself may be converted into products by gas fermentation, or released to the atmosphere, or may be advantageously used as part of further processes at the well site, such as for enhanced oil recovery operations.
- gasification of tires, pieces of tires, and or components of tires, optionally in combination with organic material, followed by gas fermentation may be employed to convert end of life tires, defective tires, and or tire scraps into valuable products.
- the gasification and gas fermentation process may be co-located with and integrated with chemical production processes used to generate chemicals and intermediates for use in the generation of new tires. Processing units in common with the gasification and gas fermentation process and the chemical production process may be integrated with each of the processes so that fewer units in total are needed. Capital equipment costs and operating costs may be minimized.
- the gas fermentation system may be co-located with an energy production facility, such as a power plant, that generates carbon dioxide as an undesired by-product. The carbon dioxide may be provided to the gas fermentation process as feedstock/substrate along with hydrogen.
- the hydrogen may be from any source such as green hydrogen (from solar, wind or water), grey hydrogen (from natural gas or methane), blue hydrogen (from natural gas or methane with carbon capture), brown hydrogen (gasification), black hydrogen (from coal), and or turquoise hydrogen (from methane pyrolysis).
- the gas fermentation system is located at the source of the carbon-dioxide substrate eliminating need for transport of carbon dioxide. Additionally, end of life tires may be collected or transported to the site for gasification and production of additional feedstock or substrate to the gas fermentation process.
- a source first generates an input gas stream, 110.
- the input gas stream may comprise greenhouse gasses such as CO and CO2. Sources are listed in detail above, examples of industrial gas, process gas, and syngas are provided.
- the input stream is fermented in a gas fermentation operation, 120.
- the gas fermentation operation may utilize a C1-fixing microorganism to ferment the input gas and generate a fermentation product.
- the fermentation product may be separated from the fermentation broth and collected, 130.
- CO is preferentially converted by the fermentation, thereby leaving unconverted CO 2 as a tail gas from the fermentation operation.
- the tail gas is a concentrated CO2 stream containing, for example, from about 60 vol-%, on a dry basis, CO 2 to about 90 vol-%, on a dry basis, CO2.
- the concentrated CO2 tail gas may be purified to meet sequestration specifications, 140.
- Purification or CO 2 concentration techniques may involve known techniques such as amine gas treating, pressure swing adsorption, membrane separation, solvent or sorbents, enzyme-based such as carbonic anhydrase, calcium looping, chemical looping, hot potassium carbonate, and cryogenic capture.
- the purification uses the technique of cryogenic separation.
- the purification uses the technique of cryogenic separation which incorporates liquefaction. Cryogenic liquefaction is particularly suited to concentrated CO2 streams. As an added benefit, due to the liquefaction, the purified CO 2 is readily transported for storage, for example, sequestration 150.
- FIG.2 is a process flow scheme of one embodiment of the disclosure.
- Input gas source 210 produces input gas stream 202.
- Input gas sources are listed in detail above, and examples of industrial gas, process gas, and syngas are provided.
- Input gas stream 202 generated by input gas source 210 may comprise greenhouse gasses such as CO and CO 2 .
- Input gas stream 202 is passed to gas fermentation process 220 comprising a fermentor having a C1-fixing microorganism, such as for example, clostridium autoethanogenum. Multiple gas fermentation processes 220 can be employed depending upon the volume of input gas.
- Gas fermentation process 220 generates gas fermentation product stream 204 which can be collected or potentially catalytically converted by any suitable catalytic conversion process (not shown).
- the products of gas fermentation can be catalytically converted, for example, by catalytically upgrading, into molecules, or one or more second products, wherein the one or more second products are integrated into existing or newly built infrastructure or feedstock and product transportation networks.
- molecules produced via the catalysis of the products of gas fermentation processes may also be considered desirable products or further products of fermentation.
- ethanol in a gas fermentation system that produces ethanol, that ethanol can be reacted into a range of molecules, such as described below.
- the CO of input gas 202 may be preferentially converted by fermentation in the fermentor, thereby leaving residual or unconsumed CO 2 to be removed as tail gas 206 from the fermentor.
- Tail gas 206 is a concentrated CO2 tail gas.
- tail gas 206 is a concentrated CO 2 stream containing, for example, from about 60 vol-%, on a dry basis, CO 2 to about 90 vol-%, on a dry basis, CO2.
- Tail gas 206 is passed to purification process 230.
- An exemplary purification process is a cryogenic separation process, a more specific example is cryogenic liquefaction.
- Purification process 230 generates purified CO2 stream 208 containing 90 vol-%, on a dry basis, CO 2 or more.
- purified CO 2 stream 208 contains 95 vol-%, on a dry basis, CO2 or more.
- purified CO 2 stream 208 contains 98 vol-%, on a dry basis, CO 2 or more.
- purified CO2 stream 208 contains 99 vol-%, on a dry basis, CO2 or more. In another embodiment purified CO 2 stream 208 contains 99.9 vol-%, on a dry basis, CO 2 or more. While other purification techniques such as amine gas treating, pressure swing adsorption, membrane separation calcium looping, chemical looping, may be employed, cryogenic separation provides the added benefit of liquefaction so purified CO2 stream 208 is readily transported to sequestration operation 240.
- ethanol or ethyl alcohol produced according to the method of the disclosure may be used in numerous product applications, including antiseptic hand rubs (WO 2014/100851), therapeutic treatments for methylene glycol and methanol poisoning (WO 2006/088491), as a pharmaceutical solvent for applications such as pain medication (WO 2011/034887) and oral hygiene products (U.S. Patent No.6,811,769), as well as an antimicrobial preservative (U.S. Patent Application No.2013/0230609), engine fuel (US Patent No.1,128,549), rocket fuel (U.S. Patent No.3,020,708), plastics, fuel cells (U.S.
- Patent No.2,405,986) home fireplace fuels (U.S. Patent No.4,692,168), as an industrial chemical precursor (U.S. Patent No.3,102,875), cannabis solvent (WO 2015/073854), as a winterization extraction solvent (WO 2017/161387), as a paint masking product (WO 1992/008555), as a paint or tincture (U.S. Patent No.1,408,091), purification and extraction of DNA and RNA (WO 1997/010331), and as a cooling bath for various chemical reactions (U.S. Patent No.2,099,090).
- the ethanol generated by the disclosed method may be used in any other application for which ethanol might otherwise be applicable.
- a further embodiment comprises converting the ethanol generated by the method into ethylene.
- the ethylene generated in this way may be used for a variety of applications on its own or can be used as a raw material for more refined chemical products.
- ethylene alone may be used as an anesthetic, as part of a mixture with nitrogen to control ripening of fruit, as a fertilizer, as an element in the production of safety glass, as part of an oxy-fuel gas in metal cutting, welding and high velocity thermal spraying, and as a refrigerant.
- ethylene can used in the manufacture of polymers such as polyethylene (PE), polyethylene terephthalate (PET) and polyvinyl chloride (PVC) as well as fibres and other organic chemicals.
- PE polyethylene
- PET polyethylene terephthalate
- PVC polyvinyl chloride
- Ethylene can be chlorinated to ethylene dichloride (EDC) and can then be cracked to make vinyl chloride monomer (VCM). Nearly all VCM is used to make polyvinyl chloride which has its main applications in the construction industry.
- ethylene derivatives include alpha olefins which are used in Linear low-density polyethylene (LLDPE) production, detergent alcohols and plasticizer alcohols; vinyl acetate monomer (VAM) which is used in adhesives, paints, paper coatings and barrier resins; and industrial ethanol which is used as a solvent or in the manufacture of chemical intermediates such as ethyl acetate and ethyl acrylate.
- Ethylene may further be used as a monomer base for the production of various polyethylene oligomers by way of coordination polymerization using metal chloride or metal oxide catalysts.
- the most common catalysts consist of titanium (III) chloride, the so-called Ziegler–Natta catalysts.
- chromium oxide is a common catalyst.
- Phillips catalyst prepared by depositing chromium (VI) oxide on silica.
- Polyethylene oligomers so produced may be classified according to its density and branching. Further, mechanical properties depend significantly on variables such as the extent and type of branching, the crystal structure, and the molecular weight.
- Ultra-high-molecular-weight polyethylene UHMWPE
- Ultra-low-molecular-weight polyethylene ULMWPE or PE-WAX
- High-molecular-weight polyethylene HMWPE
- High-density polyethylene HDPE
- High-density cross-linked polyethylene HDXLPE
- Cross-linked polyethylene PEX or XLPE
- MDPE Medium-density polyethylene
- LLDPE Linear low-density polyethylene
- LDPE Low-density polyethylene
- VLDPE Very-low-density polyethylene
- CPE Chlorinated polyethylene
- Low density polyethylene (LDPE) and linear low-density polyethylene (LLDPE) mainly go into film applications such as food and non-food packaging, shrink and stretch film, and non-packaging uses.
- High density polyethylene (HDPE) is used primarily in blow molding and injection molding applications such as containers, drums, household goods, caps and pallets. HDPE can also be extruded into pipes for water, gas and irrigation, and film for refuse sacks, carrier bags and industrial lining.
- the ethylene formed from the ethanol described above may be converted to ethylene oxide via direct oxidation according to the following formula: C2H4 + O2 ⁇ C2H4O
- the ethylene oxide produced thereby is a key chemical intermediate in a number of commercially important processes including the manufacture of monoethylene glycol.
- Other EO derivatives include ethoxylates (for use in shampoo, kitchen cleaners, etc.), glycol ethers (solvents, fuels, etc.) and ethanolamines (surfactants, personal care products, etc.).
- the ethylene oxide produced as described above may be used to produce commercial quantities of monoethylene glycol by way of the formula: (CH 2 CH 2 )O + H 2 O ⁇ HOCH 2 CH 2 OH
- the claimed microorganism can be modified in order to directly produce monoethylene glycol.
- the microorganism further comprises one or more of an enzymes capable of converting acetyl-CoA to pyruvate; an enzyme capable of converting pyruvate to oxaloacetate; an enzyme capable of converting pyruvate to malate; an enzyme capable of converting pyruvate to phosphoenolpyruvate; an enzyme capable of converting oxaloacetate to citryl-CoA; an enzyme capable of converting citryl-CoA to citrate; an enzyme capable of converting citrate to aconitate and aconitate to iso-citrate; an enzyme capable of converting phosphoenolpyruvate to oxaloacetate; an enzyme capable of converting phosphoenolpyruvate to 2-phospho-D-glycerate; an enzyme capable of converting 2- phospho-D-glycerate to 3-phospho-D-glycerate; an enzyme capable of converting phosphoenolpyruvate to 2-phospho-D-glycerate;
- Monoethylene glycol produced according to either of the described methods may be used as a component of a variety of products including as a raw material to make polyester fibers for textile applications, including nonwovens, cover stock for diapers, building materials, construction materials, road-building fabrics, filters, fiberfill, felts, transportation upholstery, paper and tape reinforcement, tents, rope and cordage, sails, fish netting, seatbelts, laundry bags, synthetic artery replacements, carpets, rugs, apparel, sheets and pillowcases, towels, curtains, draperies, bed ticking, and blankets.
- MEG may be used on its own as a liquid coolant, antifreeze, preservative, dehydrating agent, drilling fluid or any combination thereof.
- the MEG produced may also be used to produce secondary products such as polyester resins for use in insulation materials, polyester film, de-icing fluids, heat transfer fluids, automotive antifreeze and other liquid coolants, preservatives, dehydrating agents, drilling fluids, water-based adhesives, latex paints and asphalt emulsions, electrolytic capacitors, paper, and synthetic leather.
- the monoethylene glycol produced may be converted to the polyester resin polyethylene terephthalate (“PET”) according to one of two major processes.
- the first process comprises transesterification of the monoethylene glycol utilizing dimethyl terephthalate, according to the following two-step process: First step C 6 H 4 (CO 2 CH 3 ) 2 + 2 HOCH 2 CH 2 OH ⁇ C 6 H 4 (CO 2 CH 2 CH 2 OH) 2 + 2 CH 3 OH Second step n C 6 H 4 (CO 2 CH 2 CH 2 OH) 2 ⁇ [(CO)C 6 H 4 (CO 2 CH 2 CH 2 O)] n + n HOCH 2 CH 2 OH
- the monoethylene glycol can be the subject of an esterification reaction utilizing terephthalic acid according to the following reaction: n C6H4(CO2H)2 + n HOCH2CH2OH ⁇ [(CO)C6H4(CO2CH2CH2O)]n + 2n H2O
- the polyethylene terephthalate produced according to either the transesterification or esterification of monoethylene glycol has significant applicability to numerous packaging applications such as jars
- PET can be made into a high-strength plastic that can be shaped by all the common methods employed with other thermoplastics. Magnetic recording tape and photographic film are produced by extrusion of PET film.
- isopropanol or isopropyl alcohol (IPA) produced according to the method may be used in numerous product applications, including either in isolation or as a feedstock for the production for more complex products.
- Isopropanol may also be used in solvents for cosmetics and personal care products, de-icers, paints and resins, food, inks, adhesives, and pharmaceuticals, including products such as medicinal tablets as well as disinfectants, sterilizers, and skin creams.
- the IPA produced may be used in the extraction and purification of natural products such as vegetable and animal oil and fats. Other applications include its use as a cleaning and drying agent in the manufacture of electronic parts and metals, and as an aerosol solvent in medical and veterinary products. It can also be used as a coolant in beer manufacture, a coupling agent, a polymerization modifier, a de-icing agent and a preservative. Alternatively, the IPA produced according to the method of the disclosure may be used to manufacture additional useful compounds, including plastics, derivative ketones such as methyl isobutyl ketone (MIBK), isopropylamines and isopropyl esters.
- MIBK methyl isobutyl ketone
- the propylene produced may be used as a monomer base for the production of various polypropylene oligomers by way of chain-growth polymerization via either gas-phase or bulk reactor systems.
- the most common catalysts consist of titanium (III) chloride, the so- called Ziegler–Natta catalysts and metallocene catalysts.
- Polypropylene oligomers so produced may be classified according to tacticity and can be formed into numerous products by either extrusion or molding of polypropylene pellets, including piping products, heat-resistant articles such as kettles and food containers, disposable bottles (including plastic bottles), clear bags, flooring such as rugs and mats, ropes, adhesive stickers, as well as foam polypropylene which can be used in building materials.
- Polypropylene may also be used for hydrophilic clothing and medical dressings.
- Commodity Chemicals and Articles According to one embodiment, the gas fermentation product is a commodity chemical.
- the gas fermentation product is a commodity chemical, where the commodity chemical is catalytically converted, for example, by catalytically upgrading, into molecules, or one or more second products, wherein the one or more second products are integrated into existing or newly built infrastructure or feedstock and product transportation networks.
- the commodity chemical is selected from ethanol, isopropanol, monoethylene glycol, sulfuric acid, propylene, sodium hydroxide, sodium carbonate, ammonia, benzene, acetic acid, ethylene, ethylene oxide, formaldehyde, methanol, or any combination thereof.
- the commodity chemical is aluminum sulfate, ammonia, ammonium nitrate, ammonium sulfate, carbon black, chlorine, diammonium phosphate, monoammonium phosphate, hydrochloric acid, hydrogen fluoride, hydrogen peroxide, nitric acid, oxygen, phosphoric acid, sodium silicate, titanium dioxide, or any combination thereof.
- the commodity chemical is acetic acid, acetone, acrylic acid, acrylonitrile, adipic acid, benzene, butadiene, butanol, caprolactam, cumene, cyclohexane, dioctyl phthalate, ethylene glycol, methanol, octanol, phenol, phthalic anhydride, polypropylene, polystyrene, polyvinyl chloride, polypropylene glycol, propylene oxide, styrene, terephthalic acid, toluene, toluene diisocyanate, urea, vinyl chloride, xylenes, or any combination thereof.
- the disclosed systems and methods are also suitable for providing one or more secondary products that are independent of the gas fermentation product (e.g., ethylene, ethanol, acetate, etc.).
- microbial biomass itself may be considered a secondary product.
- biomass from a bioreactor such as dead microorganisms, may be used as a carbon source for further fermentation by gasifying the biomass.
- microbial proteins or other biomass may be recovered from a bioreactor and sold/used separately from the primary product (e.g., ethylene, ethanol, acetate, 1-butanol, etc.) as a supplement, such as a nutritional supplement and/or an animal feed.
- biochar may be a secondary product.
- biochar In embodiments that involve or comprise gasification of solid or liquid carbonaceous materials to produce a feedstock, biochar can be incidentally produced.
- Biochar is carbon rich and highly structured, and therefore it can be useful as, for example, fertilizer, among other applications.
- unutilized carbon dioxide which may be in the form of an off-gas from the gas fermentation, may be a secondary product. Such unutilized carbon dioxide will be in a stoichiometrically higher proportion in the off-gas compared to the feedstock, and this relative purity can make the carbon dioxide useful.
- the unutilized carbon can be sequestered by an operator for the purposes of obtaining carbon credits, or it may be combined with hydrogen gas (H 2 ), such as “green hydrogen” resulting from electrolysis, and recycled back into the gas fermenter or bioreactor as feedstock.
- H 2 hydrogen gas
- FIG.3 shows an enlarged gas fermentation process including an optional gasification zone 302, a gas fermentation zone 328, a product recovery zone 344, and an optional wastewater treatment zone 334.
- Optional gasification process 302 receives a gasification feed 300, which may be any suitable material capable of being gasified to produce syngas stream 302.
- gasification feed 300 may be comprised at least partially of sorted and/or unsorted industrial or municipal solid waste.
- the gasification feed 300 is comprised at least partially of forest and/or agricultural waste.
- the gasification feed 300 is comprised of any combination of two or more of the following: sorted municipal or industrial solid waste, unsorted municipal or industrial solid waste, forest waste, agricultural waste, or other solid or liquid waste from the refining or chemical process integrated with the enlarged gas fermentation process.
- gasification feed 300 comprises tire, pieces of tires, and or components of tires.
- gasification feed 300 comprises tires, pieces of tires, and or components of tires, in combination with an organic-based feed material.
- Gasification zone 302 is to produce syngas as substrate for gas fermentation zone 328. If a gas feedstock is already present for use as substrate for gas fermentation zone, such as from the refining or chemical process integrated with the enlarged gas fermentation process, gasification zone 302 may not be required. In some embodiments, syngas 318 produced by the gasification process 302, or gas obtained from another source contains one or more constituent that needs to be removed and/or converted.
- Typical constituents found in the syngas stream 318 that may need to be removed and/or converted include, but are not limited to, sulfur compounds, aromatic compounds, alkynes, alkenes, alkanes, olefins, nitrogen compounds, phosphorous-containing compounds, particulate matter, solids, oxygen, halogenated compounds, silicon-containing compounds, carbonyls, metals, alcohols, esters, ketones, peroxides, aldehydes, ethers, and tars. These constituents may be removed by one or more removal zones 322 positioned between gasification zone 302 and gas fermentation zone 328.
- Removal zone 322 may comprise one or more of the following modules: hydrolysis module, acid gas removal module, deoxygenation module, catalytic hydrogenation module, particulate removal module, chloride removal module, tar removal module, and hydrogen cyanide polishing module. Two or more modules may be combined into a single module performing the same functions. For instance, the hydrolysis module, acid gas removal module, deoxygenation module, and catalytic hydrogenation module may be combined into a single module. When incorporating removal process 322, at least a portion of the syngas 318 from gasification zone 302 is passed to removal process 322 to remove and/or convert at least a portion of at least one constituent found in syngas stream 318.
- Removal zone 322 may operate to bring the constituent(s) within allowable levels to produce a treated stream 324 suitable for fermentation in gas fermentation zone 328.
- Gas fermentation process 328 employs at least one C1-fixing microorganism in a liquid nutrient media to ferment a feedstock, gas, or syngas stream 318 and produce one or more product.
- the C1-fixing microorganism in the gas fermentation process 328 may be a carboxydotrophic bacterium.
- the carboxydotrophic bacterium is selected from the group comprising Moorella, Clostridium, Ruminococcus, Acetobacterium, Eubacterium, Butyribacterium, Oxobacter, Methanosarcina, Methanosarcina, Cupriavidus and Desulfotomaculum.
- the carboxydotrophic bacterium is Clostridium.
- the carboxydotrophic bacterium is Clostridium autoethanogenum. The one or more products produced in gas fermentation zone 328 are removed and/or separated from the fermentation broth in product recovery zone 344.
- Product recovery zone 344 separates and removes one or more product(s) 332 and produces at least one effluent 342, 330, 312, which comprise reduced amounts of at least one product.
- Product depleted effluent 342 may be passed to wastewater treatment zone 334 to produce at least one wastewater treatment zone effluent 336, which may be recycled to the gasification process 302 in line 308 and/or the fermentation process 328 in line 326.
- tail-gas effluent 314 from fermentation zone 328 is tail- gas containing gas generated by the fermentation, inert gas, and or unmetabolized substrate. At least a portion 304 of tail gas 314 may be optionally passed to the gasification zone 302 to be used as part of the gasification feed 300.
- At least a portion 316 of the tail gas 314 may be passed to quench the syngas stream 318. At least a portion of the tail gas may be passed to the refinery or chemical manufacture process integrated with the enlarged gas fermentation process (not shown). At least a portion of the tail gas 315 may be passed to a purification operation such as 230 of FIG.2 followed by sequestration.
- the effluent from the fermentation zone 328 is fermentation broth 346. At least a portion of the fermentation broth 346 may be passed to product recovery zone 344. In at least one embodiment, product recovery zone 344 separates at least a portion of the microbial biomass from the fermentation broth.
- At least a portion of the microbial biomass that is separated from the fermentation broth is recycled to the fermentation zone 328 via a conduit 330.
- at least a portion 310 of microbial biomass-depleted water 312 that is separated from the fermentation broth 346 is recycled to the fermentation zone 328.
- at least a portion 306 of the microbial biomass-depleted water 312 separated from the fermentation broth 346 is passed to optional gasification zone 302 for use as part of gasification feed 300.
- fermentation zone 328 produces fusel oil (not shown) which may also be recovered in product recovery zone 344 through any suitable means such as within the rectification column of a distillation system.
- At least a portion of the fusel oil from the product recovery zone 344 is used as a heating source for one or more zones or elsewhere in the refinery or chemical process.
- at least a portion of fermentation broth 346 containing microbial biomass from fermentation zone 328 may be passed to optional gasification zone 302, without being passed to product recovery zone 344 (not shown).
- at least a portion of wastewater stream 340 may be passed to optional gasification zone 302 without being passed to wastewater treatment zone 334 (not shown).
- At least a portion of the microbial biomass depleted water, produced through the removal of microbial biomass from the fermentation broth, may be returned to fermentation zone 328 via a conduits 312 and 310 and/or sent via a conduits 312 and 306 to gasification zone 302.
- At least a portion 306 of the microbial biomass depleted water 312 may be passed to gasification zone 302 to be used as part of gasification feed 300.
- At least a portion 310 of the microbial biomass depleted water 312 may be passed to quench syngas stream 318.
- At least a portion of the effluent from product recovery zone 344 may be passed via a conduit 342 to wastewater treatment zone 334.
- Wastewater treatment zone 334 receives and treats effluent from one or more zones to produce clarified water.
- the clarified water may be passed or recycled via a conduit 336 to one or more zones.
- at least a portion 326 of the clarified water 336 may be passed to the fermentation zone 328
- at least a portion 308 of the clarified water 336 may be passed to gasification zone 302 to be used as part of the gasification feed 300
- at least a portion 320 of the clarified water 336 may be passed to quench syngas stream 318.
- the wastewater treatment process 334 generates biomass as part of the treatment process.
- Wastewater treatment zone 334 as a by- product of treating microbial biomass, may produce biogas. At least a portion of the biogas may be passed via conduit 308 to gasification zone 302 to be used as part of gasification feed 300 and or via a conduit 320 to quench syngas stream 318.
- Optional wastewater treatment effluent removal unit 338 is positioned downstream of wastewater treatment zone 334. At least a portion of biogas from wastewater treatment zone 334 is passed to removal unit 338 to remove and/or convert at least a portion of at least one constituent found in the biogas stream.
- FIG.4 depicts a flow scheme of one embodiment of the disclosure.
- Input gas stream 400 generated by an input gas source may comprise greenhouse gases including CO and CO 2 .
- Input gas stream 400 is passed to gas fermentation process 410 comprising a fermentor having a C1-fixing microorganism, such as, for example, Clostridium autoethanogenum. Multiple gas fermentation processes 410 can be employed depending upon the volume of input gas.
- Gas fermentation process 410 generates raw tail gas stream 402 and/or fermentation product stream 403.
- tail gas stream 402 is a concentrated CO 2 stream comprising, for example, from about 50 vol-%, on a dry basis, CO2 to about 90 vol-%, on a dry basis, CO 2 .
- Tail gas stream 402 is passed to tail gas scrubber 420 where impurities are removed thereby generating scrubbed tail gas stream 404.
- Scrubbed tail gas stream 404 is passed to tail gas purification process 430.
- An exemplary tail gas purification process is a cryogenic separation process, a more specific example is cryogenic liquefaction.
- Tail gas purification process 430 generates purified CO 2 stream 406 comprising 90 vol-%, on a dry basis, CO2 or more.
- purified CO2 stream 406 comprises 95 vol-%, on a dry basis, CO 2 or more.
- purified CO 2 stream 406 comprises 98 vol- %, on a dry basis, CO2 or more.
- purified CO2 stream 406 comprises 99 vol-%, on a dry basis, CO 2 or more. In another embodiment purified CO 2 stream 406 comprises 99.9 vol-%, on a dry basis, CO2 or more.
- Tail gas purification process 430 also generates residual stream 411. Residual stream 411 comprises, for example, residual CO and residual H2 that were not consumed in the fermentation. Residual stream 411 may optionally be passed to gas treatment conversion unit 440 before being recycled back to fermentation process 410.
- Optional gas treatment conversion unit 440 may be a CO2 to CO conversion unit may be at least one unit selected from a reverse water gas shift unit, a thermo-catalytic conversion unit, a partial combustion unit, a reforming unit, or a plasma conversion unit.
- Purified CO2 stream 406 may optionally be passed to separation unit 450. Separation unit 450 separates purified CO 2 stream into inert gas stream 412, hydrocarbon stream 408, and enriched CO2 stream 420. It is envisioned that alternatively or additionally, purified CO 2 stream may be divided, instead of separated, and passed to different processing units. The divided streams would have the same composition as the purified CO 2 stream. Hydrocarbon stream 408 may optionally be passed to regenerative thermal oxidizer 460 thereby generating combustion product emissions 414. Enriched CO 2 stream 420 may be divided into first portion enriched CO 2 stream 420a and second portion enriched CO2 stream 420b. First portion enriched CO2 stream 420a is passed to sequestration 470.
- Second portion enriched CO 2 stream 420b may optionally be passed to CO2 to CO conversion system 480 before being passed to gas fermentation process 410.
- CO 2 to CO conversion system 480 may be at least one unit selected from a reverse water gas shift unit, a thermo-catalytic conversion unit, a partial combustion unit, a reforming unit, or a plasma conversion unit.
- raw tail gas stream 402 may be treated to limit the amount of H2S in the tail gas before passing to sequestration 470.
- the H 2 S is less than 10 ppm.
- the H2S is less than 5 ppm.
- the H2S is less than 1 ppm.
- CO2 to CO conversion system 480 and or gas treatment conversion unit 440 is a reverse water gas shift unit.
- Reverse water gas shift (rWGS) technology is known and is used for producing carbon monoxide from carbon dioxide and hydrogen, with water as a side product. Temperature of the rWGS process is the main driver of the shift.
- Reverse water gas shift units may comprise a single stage reaction system or two or more reaction stages. The different stages may be conducted at different temperatures and may use different catalysts.
- CO 2 to CO conversion system 480 and or gas treatment conversion unit 440 involves thermo-catalytic conversion, which involves disrupting the stable atomic and molecular bonds of CO 2 and other reactants over a catalyst by using thermal energy as the driving force of the reaction to produce CO.
- CO2 molecules are thermodynamically and chemically stable, if CO2 is used as a single reactant, large amounts of energy are required. Therefore, often other substances such as hydrogen are used as a co- reactant to make the thermodynamic process easier.
- Many catalysts are known for the process such as metals and metal oxides as well as nano-sized catalyst metal-organic frameworks. Various carbon materials have been employed as carriers for the catalysts.
- CO 2 to CO conversion system 480 and or gas treatment conversion unit 440 involves partial combustion where oxygen supplies at least a portion of the oxidant requirement for the partial oxidation and the reactants carbon dioxide and water are substantially converted to carbon monoxide and hydrogen.
- CO 2 to CO conversion system 480 and or gas treatment conversion unit 440 involves plasma conversion which is the combination of plasma with catalysts, also called plasma-catalysis.
- Plasma is an ionized gas consisting of electrons, various types of ions, radicals, excited atoms, and molecules, along with neutral ground state molecules.
- the three most common plasma types for CO 2 to CO conversion include, dielectric barrier discharges (DBDs), microwave (MW) plasmas, and gliding arc (GA) plasmas.
- Advantages of selecting plasma conversion for CO 2 to CO conversion include (i) high process versatility, allowing different kinds of reactions to be carried out, such as pure CO 2 splitting, as well as CO 2 conversion in presence of a hydrogen source, such as CH 4 , H 2 or H2O; (ii) low investment and operating costs; (iii) no requirement for rare earth metals; (iv) convenient modular setting, as plasma reactors scale up linearly with the plant output; and (v) it can be very easily combined with various kinds of renewable electricity.
- the figures are described where CO2 to CO conversion system 480 and or gas treatment conversion unit 440 is selected to include at least one rWGS unit.
- the rWGS reaction is the reversible hydrogenation of CO2 to produce CO and H2O.
- rWGS catalysts selections include Fe/Al2O3, Fe- Cu/Al2O3, Fe-Cs/Al2O3, Fe-Cu-Cs/Al2O3 or combinations thereof.
- Another option is the rWGS catalyst as described in WO2022/225938, which is a porous support and an alkali carbonate dispersed on the porous support.
- Second portion enriched CO 2 stream 420b may optionally be recycled back to fermentation process 410.
- a gas fermentation process is integrated at an oil refining site, and biologically produces a gas fermentation product.
- the gas fermentation process would be co-located within the operating site of the oil refiner.
- Underutilized carbon streams e.g., waste carbon streams
- a product stream from the gas fermentation process may be integrated at an oil refining or chemical manufacturing site.
- integration of gas fermentation units with existing facilities and infrastructure provides multitude of advantageous synergies for operators. These synergies include using the gas from one portion of a chemical manufacturing unit as the feed for the gas fermentation unit.
- the gas fermentation unit being adapted to convert the gas feed into a product that the same unit is overall designed to produce.
- the gas fermentation unit’s output can then be directed to a portion of the unit that can recover the product from the gas fermentation unit’s output.
- a gas fermentation unit that is integrated within a chemical manufacturing complex or oil refining complex can have its output directly coupled to a separation, purification, or extraction unit.
- the separation, purification, or extraction unit being adapted to receive the output of the gas fermentation unit and separate or purify the output mixture.
- the recovered product can then be routed to a product storage tank located within the chemical manufacturing or oil-refining complex to be sold.
- the recovered product can be mixed with other products as an additive to increase desirable properties of the base product or to decrease the effect of undesirable properties of the base product.
- the recovered product can be stored separately and sold as a standalone product.
- a gas fermentation unit that is integrated within a chemical manufacturing complex or oil refining complex can have its output directly utilized by a process of the chemical manufacturing operation or refinery.
- the product of the gas fermentation process for example, may be a reactant needed for an existing operation, it may be a solvent needed for an existing operation, it may be an extractant for an existing operation, and the like.
- the existing process of the chemical manufacturing operation or the refinery being adapted to receive the output of the gas fermentation unit and employ the product for a needed function.
- gas fermentation unit’s integrated within chemical manufacturing complexes can be adapted to convert gases as described above into fuel for various operationally critical components such as furnaces, boilers, co-generation units, or power generation units.
- the converted gases can then be routed from the gas fermentation unit to the feed lines for the aforementioned components to supplement or replace the fuel feed that would otherwise be derived from fossil carbon sources such as natural gas.
- This synergy allows the operator to lower their overall spend on external fuel sources to continue operations. Additionally, this synergy allows operators to be more energy independent and less dependent on external fuel supply fluctuations caused by market activity or natural disasters such as hurricanes.
- the gas fermentation unit is adapted to output to an on-site storage tank.
- the on-site storage tank can then accept the gas fermentation unit’s output and store the output until the price of the product contained in the gas fermentation unit’s output mixture is sufficiently high such that it becomes desirable for the production operator to sell the product.
- the storage tank or the gas fermentation unit output can each have a metering flow meter installed therein to determine the amount of product that is exiting the output of the gas fermentation unit or the product storage tank. Metering can be done with any suitable metering device; non-limiting examples include a mass flow meter and a volumetric flow meter.
- multiple gas fermentation units can be integrated at a single chemical manufacturing or oil-refining complex wherein each gas fermentation unit is configured to accept the same or different types of gas sources. This can be done such that each gas fermentation unit can be individually adapted to output a different product in its respective output mixture. Varying the input streams to each gas fermentation unit can be done to increase the feed to gas fermentation units adapted to produce products that are contemporaneously more profitable than others. Likewise, the feed to contemporaneously less profitable products can be throttled down or halted completely.
- the various outputs from the various gas fermentation units can be configured such to be routed to individual storage tanks for short, medium, or long term storage or routed directly into a feed source for other sections of the complex.
- the gas fermentation unit can be configured to produce fuels that can be utilized on-site by the chemical manufacturing or oil-refining complex. Such synergy allows for the complex to lower the overall operating costs by decreasing the spend related to such fuels and fuel sources, thereby increasing the overall profitability of the complex.
- the gas fermentation unit can be fed from pressure relief safety valves (“PRSV”).
- PRSV pressure relief safety valves
- a PRSV is typically installed on a pressure containing vessel and is adapted to open at a set pressure value to protect the vessel it is connected to.
- the streams contained within the pressure vessel are carbon rich and are routed to a safe relief point, either a flare source or the atmosphere.
- Operators can further increase their site productivity and efficiency by harvesting these otherwise wasted streams of carbon rich material (i.e., any gas stream that is either emitted directly, flared with no additional value capture or combusted for energy recovery purposes) by routing them to the integrated gas fermentation unit to be converted into marketable products.
- these otherwise wasted streams can be used as a feedstock for the integrated gas fermentation, which can upgrade the C1 components of the underutilized carbon into desirable products or chemicals with two or more carbon-carbon bonds.
- multiple gas fermentation units can be integrated within a single chemical manufacturing or oil-refining complex. The multiple gas fermentation units can be adapted to produce a similar or identical product from various different input streams.
- the multiple gas fermentation units can then have their respective outputs configured to output to a single storage tank. This synergy can allow the production operator to capture a maximum amount of underutilized gases or streams and convert it into a marketable product.
- A. Microorganisms and Fermentation The disclosed systems and methods integrate microbial fermentation into existing or newly built infrastructure of, for example, a gas (e.g., natural gas) transportation pipeline, oil well, or the like to convert various feedstocks, gas, or other by-products into useful products such as ethylene.
- a gas e.g., natural gas
- the systems allow for feedstocks, gas, or other by- products to be directly provided to a bioreactor, and the bioreactor is directly connected to a system for facilitating transport of a desirable product of fermentation to an end point (e.g., a chemical plant or refinery).
- an end point e.g., a chemical plant or refinery
- the disclosed systems and methods are applicable for producing useful products (e.g., ethylene, ethanol, acetate, etc.) from gaseous substrates, such as gases that may optionally contain H2, that are utilized as a carbon source by microbial cultures.
- useful products e.g., ethylene, ethanol, acetate, etc.
- gases such as gases that may optionally contain H2
- Such microorganisms may include bacteria, archaea, algae, or fungi (e.g., yeast), and these classes of microorganism may be suitable for the disclosed systems and methods.
- the selection of the microorganism(s) is not particularly limited so long as the microorganism is C1-fixing, carboxydotrophic, acetogenic, methanogenic, capable of Wood- Ljungdahl synthesis, a hydrogen oxidizer, autotrophic, chemolithoautotrophic, or any combination thereof.
- bacteria are particularly well suited for integration in the disclosed systems and methods. When bacteria are utilized in the disclosed systems and methods, the bacteria may be aerobic or anaerobic, depending on the nature of the carbon source and other inputs being fed into the bioreactor or fermentation unit. Further, the bacteria utilized in the disclosed systems and methods can include one of more strains of carboxydotrophic bacteria.
- the carboxydotrophic bacterium can be selected from a genus including, but not limited to, Cupriavidus, Clostridium, Moorella, Carboxydothermus, Ruminococcus, Acetobacterium, Eubacterium, Butyribacterium, Oxobacter, Methanosarcina, Methanosarcina, and Desulfotomaculum.
- the carboxydotrophic bacterium is Clostridium.
- the carboxydotrophic bacterium is Clostridium autoethanogenum.
- the carboxydotrophic bacterium is Cupriavidus.
- the carboxydotrophic bacterium is Cupriavidus necator.
- a number of anaerobic bacteria are known to be capable of carrying out fermentation for the disclosed methods and system.
- Examples of such bacteria that are suitable for use in the disclosure include bacteria of the genus Clostridium, such as strains of Clostridium ljungdahlii (including those described in WO 00/68407, EP 117309, U.S. Pat. Nos.
- Clostridium carboxydivorans Liou et al., International Journal of Systematic and Evolutionary Microbiology 33: pp 2085-2091
- Clostridium autoethanogenum Clostridium autoethanogenum
- Other suitable bacteria include those of the genus Moorella, including Moorella sp HUC22-1 (Sakai et al., (2004) Biotechnology Letters 26: pp 1607-1612), and those of the genus Carboxydothermus (Svetlichny, V. A., et al.
- the Clostridium autoethanogenum is a Clostridium autoethanogenum having the identifying characteristics of the strain deposited at the German Resource Centre for Biological Material (DSMZ) under the identifying deposit number 19630.
- the Clostridium autoethanogenum is a Clostridium autoethanogenum having the identifying characteristics of DSMZ deposit number DSMZ 10061.
- the Clostridium autoethanogenum is a Clostridium autoethanogenum having the identifying characteristics of DSMZ deposit number DSMZ 23693.
- the anaerobic bacteria is Clostridium carboxidivorans having the identifying characteristics of deposit number DSM15243.
- the anaerobic bacteria is Clostridium drakei having the identifying characteristics of deposit number DSM12750. In some embodiments, the anaerobic bacteria is Clostridium ljungdahlii having the identifying characteristics of deposit number DSM13528. Other suitable Clostridium ljungdahlii strains may include those described in WO 00/68407, EP 117309, U.S. Pat. Nos.5,173,429, 5,593,886, and 6,368,819, WO 98/00558 and WO 02/08438, all of which are incorporated herein by reference.
- the anaerobic bacteria is Clostridium scatologenes having the identifying characteristics of deposit number DSM757. In some embodiments, the anaerobic bacteria is Clostridium ragsdalei having the identifying characteristics of deposit number ATCC BAA-622. In some embodiments, the anaerobic bacteria is Acetobacterium woodii. In some embodiments, the anaerobic bacteria is from the genus Moorella, such as Moorella sp HUC22-1, (Sakai et al, (2004) Biotechnology Letters, 26: pp 1607-1612).
- suitable anaerobic bacteria include, but are not limited to, Morella thermoacetica, Moorella thermoautotrophica, Ruminococcus productus, Acetobacterium woodii, Eubacterium limosum, Butyribacterium methylotrophicum, Oxobacter pfennigii, Methanosarcina barkeri, Methanosarcina acetivorans, Desulfotomaculum kuznetsovii (Simpa et. al. Critical Reviews in Biotechnology, 2006 Vol.26. Pp41-65).
- C1-fixing carboxydotrophic anaerobes may be suitable for the disclosed systems and methods.
- a mixed culture of two or more bacteria may be utilized as well.
- a number of aerobic bacteria are known to be capable of carrying out fermentation for the disclosed methods and system. Examples of such bacteria that are suitable for use in the disclosure include bacteria of the genus Cupriavidus and Ralstonia.
- the aerobic bacteria is Cupriavidus necator or Ralstonia eutropha.
- the aerobic bacteria is Cupriavidus alkaliphilus.
- the aerobic bacteria is Cupriavidus basilensis.
- the aerobic bacteria is Cupriavidus campinensis.
- the aerobic bacteria is Cupriavidus gilardii.
- the aerobic bacteria is Cupriavidus laharis.
- the aerobic bacteria is Cupriavidus metallidurans. In some embodiments, the aerobic bacteria is Cupriavidus nantongensis. In some embodiments, the aerobic bacteria is Cupriavidus numazuensis. In some embodiments, the aerobic bacteria is Cupriavidus oxalaticus. In some embodiments, the aerobic bacteria is Cupriavidus pampae. In some embodiments, the aerobic bacteria is Cupriavidus pauculus. In some embodiments, the aerobic bacteria is Cupriavidus pinatubonensis. In some embodiments, the aerobic bacteria is Cupriavidus plantarum. In some embodiments, the aerobic bacteria is Cupriavidus respiraculi.
- the aerobic bacteria is Cupriavidus taiwanensis. In some embodiments, the aerobic bacteria is Cupriavidus yeoncheonensis.
- the fermentation may be carried out in any suitable bioreactor.
- the bioreactor may comprise a first, growth reactor in which the microorganisms (e.g., bacteria) are cultured, and a second, fermentation reactor, to which fermentation broth from the growth reactor is fed and in which most of the fermentation product (e.g. ethylene, ethanol, acetate, etc.) is produced. It will be appreciated that for growth of the bacteria and fermentation to occur, in addition to a carbon-containing substrate gas, a suitable liquid nutrient medium will need to be fed to the bioreactor.
- a nutrient medium will contain vitamins and minerals sufficient to permit growth of the micro-organism used.
- Aerobic and anaerobic media suitable for the fermentation using carbon-containing substrate gases as the sole carbon source are known in the art.
- suitable media are described in U.S. Pat. Nos.5,173,429, 5,593,886, WO 02/08438, WO2007/115157, and WO2008/115080, referred to above and all of which are incorporated herein by reference.
- the fermentation can be carried out under appropriate conditions for the desired fermentation to occur.
- Reaction conditions that should be considered include pressure, temperature, gas flow rate, liquid flow rate, media pH, media redox potential, agitation rate (if using a continuous stirred tank reactor), inoculum level, maximum gas substrate concentrations, and maximum product concentrations to avoid product inhibition.
- the optimum reaction conditions will depend partly on the particular micro-organism used. However, in general, it may be preferable that the fermentation be performed at a pressure higher than ambient pressure. Operating at increased pressures may allow for, for example, a significant increase in the rate of CO transfer from the gas phase to the liquid phase where it can be taken up by the micro-organism as a carbon source.
- the retention time (defined as the liquid volume in the bioreactor divided by the input gas flow rate) can be reduced when bioreactors are maintained at elevated pressure rather than atmospheric pressure.
- the use of pressurized systems can greatly reduce the volume of the bioreactor required, and consequently the capital cost of the fermentation equipment.
- the temperature of the culture may vary as needed.
- the fermentation is carried out at a temperature of about 34°C to about 37° C. In some embodiments, the fermentation is carried out at a temperature of about 34°C.
- This temperature range may assist in supporting or increasing the efficiency of fermentation including, for example, maintaining or increasing the growth rate of bacteria, extending the period of growth of bacteria, maintaining or increasing production of the desired product (e.g., ethylene, ethanol, acetate, etc.), or maintaining or increasing CO or CO2 uptake or consumption.
- Culturing of the bacteria used in the disclosed systems and methods may be conducted using any number of processes known in the art for culturing and fermenting substrates.
- a culture of a bacterium can be maintained in an aqueous culture medium.
- the aqueous culture medium may be a minimal anaerobic microbial growth medium. Suitable media are known in the art and described for example in U.S. Pat.
- yeast that may be used in the disclosed systems and methods include genus Cryptococcus, such as strains of Cryptococcus curvatus (also known as Candida curvatus) (see Chi et al. (2011), Oleaginous yeast Cryptococcus curvatus culture with dark fermentation hydrogen production effluent as feedstock for microbial lipid production, International Journal of Hydrogen Energy, 36:9542-9550, which is incorporated herein by reference).
- Other suitable yeasts include those of the genera Candida, Lipomyces, Rhodosporidium, Rhodotorula, Saccharomyces, and Yarrowia.
- the disclosed systems and methods may utilize a mixed culture of two or more yeasts.
- Additional fungi that may be suitable for the disclosed systems and methods include, but are not limited to, fungi selected from Blakeslea, Cryptococcus, Cunninghamella, Mortierella, Mucor, Phycomyces, Pythium, Thraustochytrium and Trichosporon.
- Culturing of yeast or other fungi may be conducted using any number of processes known in the art for culturing and fermenting substrates using yeasts or fungi.
- fermentation is carried out in any suitable bioreactor, such as a continuous stirred tank reactor (CTSR), a bubble column reactor (BCR) or a trickle bed reactor (TBR).
- CSR continuous stirred tank reactor
- BCR bubble column reactor
- TBR trickle bed reactor
- the bioreactor may comprise a first, growth reactor in which the micro-organisms are cultured, and a second, fermentation reactor, to which fermentation broth from the growth reactor is fed and in which most of the fermentation product (e.g., ethylene, ethanol, acetate, etc.) is produced.
- the disclosed systems and method may comprise a primary bioreactor and a secondary bioreactor.
- the efficiency of the fermentation processes may be further improved by a further process of recycling a stream exiting the secondary bioreactor to at least one primary reactor.
- the stream exiting the secondary bioreactor may contain unused substrates, salts, and other nutrient components.
- the stream exiting the bioreactor can optionally be treated before being passed back to a primary reactor.
- any media recycled from a secondary bioreactor to a primary bioreactor may need to have all oxygen substantially removed, as any oxygen present in the primary bioreactor will be harmful to an anaerobic culture in the primary bioreactor. Therefore, the broth stream exiting the secondary bioreactor may be passed through an oxygen scrubber to remove substantially all of the oxygen prior to being passed to the primary reactor.
- biomass from a bioreactor e.g., a primary bioreactor, secondary bioreactor, or any combination thereof
- biomass from a bioreactor may be separated and processed to recover one or more products.
- both anaerobic and aerobic gases can be used to feed separate cultures (e.g., an anaerobic culture and an aerobic culture) in two or more different bioreactors that are both integrated into the same process stream.
- the feedstock gas stream providing a carbon source for the disclosed cultures is not particularly limited, so long as it contains a carbon source.
- C1 feedstocks comprising methane, carbon monoxide, carbon dioxide, or any combination thereof may be preferred.
- H 2 may also be present in the feedstock.
- the feedstock may comprise a gaseous substrates comprising substrate comprising carbon monoxide.
- the feedstock may comprise a gaseous substrates comprising substrate comprising carbon dioxide.
- the feedstock may comprise a gaseous substrates comprising substrate comprising both carbon monoxide and carbon dioxide. In some embodiments, the feedstock may comprise a gaseous substrates comprising carbon monoxide. In some embodiments, the feedstock may comprise a gaseous substrates comprising carbon dioxide. In some embodiments, the feedstock may comprise a gaseous substrates comprising carbon monoxide, carbon dioxide, or any combination thereof. Regardless of the source or precise content of the gas used as a feedstock, the feedstock may be metered (e.g., for carbon credit calculations or mass balancing of sustainable carbon with overall products) into a bioreactor in order to maintain control of the follow rate and amount of carbon provided to the culture.
- metered e.g., for carbon credit calculations or mass balancing of sustainable carbon with overall products
- the output of the bioreactor may be metered (e.g., for carbon credit calculations or mass balancing of sustainable carbon with overall products) or comprise a valved connection that can control the flow of the output and products (e.g., ethylene, ethanol, acetate, 1-butanol, etc.) produced via fermentation.
- a valve or metering mechanism can be useful for a variety of purposes including, but not limited to, slugging of product through a connected pipeline and measuring the amount of output from a given bioreactor such that if the product is mixed with other gases or liquids the resulting mixture can later be mass balanced to determine the percentage of the product that was produced from the bioreactor.
- the microorganisms of the disclosure may be cultured with the gaseous substrate to produce one or more products.
- products of interest for the disclosed systems and methods can include, but are not limited to, alcohols, acids, diacids, alkanes, alkenes, alkynes, and the like.
- a product of interest for the disclosed systems and method can include alcohols such as ethanol.
- the microorganisms of the present disclosure may produce or may be engineered to produce ethylene (WO 2012/026833, US 2013/0157322), ethanol (WO 2007/117157, US 7,972,824), acetate (WO 2007/117157, US 7,972,824), 1-butanol (WO 2008/115080, US 8,293,509, WO 2012/053905, US 9,359,611, and WO 2017/066498, US 9,738,875), butyrate (WO 2008/115080, US 8,293,509), 2,3- butanediol (WO 2009/151342, US 8,658,408 and WO 2016/094334, US 10,590,406), lactate (WO 2011/112103, US 8,900,836), butene (WO 2012/024522, US 2012/0045807), butadiene (WO 2012/024522, US 2012/0045807), methyl ethyl ketone (2-butanone) (WO 2012/0245)
- the microorganisms may produce or may be engineered to produce one or more of the foregoing products (e.g., ethanol, acetate, 1-butanol, etc.) in addition to ethylene.
- the substrate and/or C1-carbon source may be a gas obtained as a by-product of an industrial process or from another source, such as combustion engine exhaust fumes, biogas, landfill gas, direct air capture, flaring, or from electrolysis.
- the substrate and/or C1-carbon source may be syngas generated by pyrolysis, torrefaction, or gasification.
- carbon in solid or liquid materials may be recycled by pyrolysis, torrefaction, or gasification to generate syngas which is used as the substrate and/or C1-carbon source in gas fermentation.
- the substrate and/or C1-carbon source may be natural gas.
- the substrate and/or C1-carbon source carbon dioxide from conventional and unconventional gas production.
- the substrate and/or C1-carbon source may be a gas comprising methane. Gas fermentation processes are flexible and any of these substrate and/or C1-carbon sources may be employed.
- the industrial process source of the substrate and/or C1 carbon source is selected from ferrous metal products manufacturing, such as a steel manufacturing, non-ferrous products manufacturing, petroleum refining, electric power production, carbon black production, paper and pulp manufacturing, ammonia production, methanol production, coke manufacturing, petrochemical production, carbohydrate fermentation, cement making, aerobic digestion, anaerobic digestion, catalytic processes, natural gas extraction, cellulosic fermentation, oil extraction, industrial processing of geological reservoirs, processing fossil resources such as natural gas coal and oil, landfill operations, or any combination thereof.
- specific processing steps within an industrial process include catalyst regeneration, fluid catalyst cracking, and catalyst regeneration. Air separation and direct air capture are other suitable industrial processes.
- steel and ferroalloy manufacturing include blast furnace gas, basic oxygen furnace gas, coke oven gas, direct reduction of iron furnace top-gas, and residual gas from smelting iron.
- Other general examples include flue gas from fired boilers and fired heaters, such as natural gas, oil, or coal fired boilers or heaters, and gas turbine exhaust.
- flue gas from fired boilers and fired heaters such as natural gas, oil, or coal fired boilers or heaters
- gas turbine exhaust Another example is the flaring of compounds such as at oil and gas production sites.
- the substrate and/or C1-carbon source may be captured from the industrial process before it is emitted into the atmosphere, using any known method.
- the substrate and/or C1-carbon source may be synthesis gas known as syngas, which may be obtained from reforming, partial oxidation, plasma, or gasification processes.
- gasification processes include gasification of coal, gasification of refinery residues, gasification of petroleum coke, gasification of biomass, gasification of lignocellulosic material, gasification of wood, gasification of black liquor, gasification of municipal solid waste, gasification of municipal liquid waste, gasification of industrial solid waste, gasification of industrial liquid waste, gasification of refuse derived fuel, gasification of sewerage, gasification of sewerage sludge, gasification of sludge from wastewater treatment, gasification of landfill gas, gasification of biogas such as when biogas is added to enhance gasification of another material, and/or gasification of tires, pieces of tires, and or components of tires or tires, pieces of tires, and or components of tires in combination with an organic material.
- Examples of reforming processes include, steam methane reforming, steam naphtha reforming, reforming of natural gas, reforming of biogas, reforming of landfill gas, reforming of coke oven gas, reforming of pyrolysis off-gas, reforming of ethylene production off-gas, naphtha reforming, and dry methane reforming.
- Examples of partial oxidation processes include thermal and catalytic partial oxidation processes, catalytic partial oxidation of natural gas, partial oxidation of hydrocarbons, partial oxidation of biogas, partial oxidation of landfill gas, or partial oxidation of pyrolysis off-gas.
- Examples of municipal solid waste include tires, plastics, refuse derived fuel, and fibers such as in shoes, apparel, and textiles.
- Municipal solid waste may be simply landfill-type waste and may be sorted or unsorted.
- Examples of biomass may include lignocellulosic material and microbial biomass.
- Lignocellulosic material may include agriculture by-products, forest by-products, and some industrial by-products.
- Biomass may be created as by-products of “nature-based solutions” (NBS) and thus natured-based solutions may provide feedstock to the gas fermentation process.
- NBS nature-based solutions
- Nature-based solutions is articulated by the European Commission as solutions inspired and supported by nature, which are cost-effective, simultaneously provide environmental, social, and economic benefits and help build resilience. Such solutions bring more, and more diverse, nature and natural features and processes into cities, landscapes, and seascapes, through locally adapted, resource-efficient, and systemic interventions.
- the substrate and/or C1-carbon source may be a gas stream comprising methane.
- a methane containing gas may be obtained from: fossil methane emissions such as during fracking, wastewater treatment, livestock, agriculture, and municipal solid waste landfills. It is also envisioned that the methane may be burned to produce electricity or heat and the C1 by-products may be used as the substrate or carbon source.
- the substrate and/or C1-carbon source may be a gas stream comprising natural gas. B. Examples The following examples are given to illustrate the present disclosure. It should be understood that the disclosure is not to be limited to the specific conditions or details described in these examples.
- Example 1 – Carbon Capture, Utilization, and Storage Gas fermentation technology is operated similarly to traditional brewing. However, instead of using yeast to ferment sugars into alcohol, this gas fermentation process employed a specialized microorganism known as Clostridium autoethanogenum. This C1-fixing microorganism metabolizes carbon and energy from gases, producing alcohol as a result. This microorganism is an obligate anaerobe that lives only in oxygen-free environments.
- the process begins with an input gas comprising CO and CO2, and optionally hydrogen, being sourced directly from an industrial facility such as a steel or alloy producing facility.
- the input gas is compressed, for example to ⁇ 10 barg, to provide enough pressure to run the gas through a pretreatment unit and the bioreactor.
- the input gas is then introduced into a gas fermentation process comprising a bioreactor containing the biocatalyst, which is a C1-fixing microorganism.
- the gas fermentation yields a chemical product such as ethanol, and a single-cell protein.
- the chemical product and the single-cell protein are the CCU portion, which is continually removed from the fermentation broth and stored.
- the system is designed to ensure a steady and ongoing flow of gas into the bioreactor and the ethanol product being removed. In one embodiment, system design may be for 6,000 to 10,000 operating hours per year.
- un-metabolized CO 2 from the input gas is combined with any CO2 that may be generated during fermentation thereby generating an CO 2 – enriched stream that is removed from the bioreactor.
- the CO 2 -enriched stream is also termed the tail gas stream.
- This example demonstrates economic opportunities according to available renewable energy sources, such as green hydrogen.
- green hydrogen the carbon may be directed to utilization or sequestration. When the cost of hydrogen is low then carbon can be directed to CCU. When the cost of hydrogen is high then carbon can be directed to CCS.
- the CO2-enriched stream, or tail gas stream may be purified and converted into a liquid by cryogenic technologies, such as cryogenic liquefaction, which cools the tail gas to very low temperatures.
- the resulting purified liquid CO2 stream may be stored temporarily on site until transported for sequestration.
- the input stream is the carbon-dense industrial off-gases from steel and alloy plants, comprising from about 7 to about 80 vol-%, on a dry basis, CO, from about 4 to about 63 vol- %, on a dry basis, H2, from about 2 to about 25 vol-%, on a dry basis, CO2, from about 6 to about 50 vol.- % N 2 , and less than 2,000 ppm O 2 and other inert gases.
- the input gas with a volume of from about 12,500 to about 18000 Nm 3 /h , will be channeled into the gas fermentation system from the steel and alloy facility through hundreds of meters of piping.
- the implemented methods and systems use biotechnology to capture carbon in industrial emissions, remove carbon monoxide (CO) by metabolism in a gas fermentation process, and leave a concentrated CO 2 stream.
- the concentrated CO 2 stream may be purified and optionally stored for transportation for ultimately sequestration or used for purposes such as beverage carbonation.
- carbon is captured and utilized to provide a valuable product, such as low carbon intensity ethanol.
- any concentration range, percentage range, ratio range, integer range, size range, or thickness range is to be understood to include the value of any integer within the recited range and, when appropriate, fractions thereof (such as one tenth and one hundredth of an integer), unless otherwise indicated. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context.
- the use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the disclosure and does not pose a limitation on the scope of the disclosure unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the disclosure. Preferred embodiments of this disclosure are described herein.
- a method of processing greenhouse gas carbon for both utilization and sequestration comprising: a) passing an input gas stream comprising at least greater than 50 vol-%, on a dry basis, CO and 10 vol-%, on a dry basis, CO 2 to a fermentation process; b) fermenting under suitable conditions at least a portion of the CO using a C1- fixing microorganism for: 1) generating at least one fermentation product, and 2) generating a tail gas stream comprising at least 60 vol-%, on a dry basis, CO2, wherein the CO2 was present in the input gas stream; c) conditioning the tail gas stream by liquefaction to generate a liquified CO 2 stream comprising at least 90 vol-%, on a dry basis, CO2; and d) sequestering the liquified CO 2 stream.
- Embodiment 2 The method according to embodiment 1, wherein the input gas stream further comprises a gas selected from hydrogen, nitrogen, oxygen, other inert gases, or any combination thereof.
- Embodiment 3. The method according to any of embodiments 1 to 2, wherein the input gas stream is industrial off-gas.
- Embodiment 4. The method according to any of embodiments1 to 3, wherein the industrial off-gas is from a production process comprising steel or alloy.
- the method according to any of embodiments 1 to 4, wherein the C1- fixing microorganism is Clostridium autoethanogenum.
- Embodiment 6. The method according to any of embodiments 1 to 5, wherein the at least one fermentation product is selected from ethanol, single-cell protein, or any combination thereof.
- Embodiment 8 A method for purifying CO 2 comprising: a) passing an input gaseous stream comprising from about 50 vol-%, on a dry basis, to 75 vol-%, on a dry basis, CO and from about 10 vol-%, on a dry basis, to 45 vol-%, on a dry basis, CO 2 to a gas fermentation process; b) removing the CO by generating at least one fermentation product; c) recovering the CO 2 in a concentrated CO 2 tail gas stream; d) purifying the CO 2 tail gas stream by liquefaction to generate a purified CO2; and e) providing the purified CO2 stream for sequestration.
- the input gas stream further comprises a gas selected from hydrogen, nitrogen, oxygen, other inert gases, or any combination thereof.
- Embodiment 10. The method according to any of embodiments 8 to 9, wherein the input gas stream is industrial off-gas.
- Embodiment 11 The method according to any of embodiments 8 to 10, wherein the industrial off-gas is from a production process comprising steel or alloy.
- Embodiment 12. The method according to any of embodiments 8 to 11, wherein the C1-fixing microorganism is Clostridium autoethanogenum.
- Embodiment, 13 The method according to any of embodiments 8 to 12, wherein the at least one fermentation product is selected from ethanol, single-cell protein, or any combination thereof.
- Embodiment 15 A method of capturing carbon for combined utilization and sequestration comprising: a) passing a gas stream comprising CO and CO2 to a gas fermentation process under suitable conditions; b) fermenting at least a portion of the CO using a C1-fixing microorganism to:1) generate at least one fermentation product, and 2) generate an enriched residual CO 2 stream comprising about 20-95 vol-%, on a dry basis, CO 2 ; c) conditioning the enriched residual CO2 stream using cryogenic liquefaction to generate a purified CO 2 stream comprising greater than 99 vol-%, on a dry basis, CO 2 ; and d) providing the purified CO2 stream for sequestration.
- Embodiment 16 The method according to embodiment 15, wherein the gas stream comprising CO and CO2 comprises about 20 vol-%, on a dry basis, CO2. Embodiment 17. The method according to any of embodiments 15 to 16, wherein the enriched residual CO2 stream comprises about 86 vol-%, on a dry basis, CO2. Embodiment 18. The method according to any of embodiments 15 to 17, wherein the purified CO2 stream comprises about 99.9 vol-%, on a dry basis, CO2. Embodiment 19. The method according to any of embodiments 15 to 18, wherein the C1-fixing microorganism is Clostridium autoethanogenum. Embodiment 20.
- An apparatus for both carbon capture and utilization and carbon capture and sequestration comprising: a) a CO/CO2 gas source; b) a gas fermentation process unit in fluid communication with the gas source; c) a gas fermentation product conduit in fluid communication with the gas fermentation process unit; d) a tail gas conduit in fluid communication with the gas fermentation process unit and a liquefaction unit; and e) a purified CO 2 conduit in fluid communication with the liquefaction unit and a sequestration facility.
- a method of processing greenhouse gas carbon for both utilization and sequestration comprising: a) passing an input gas stream comprising at least greater than about 50 vol-%, on a dry basis, CO and at least lower than about 45 vol-%, on a dry basis, CO2 to a fermentation process; b) fermenting under suitable conditions at least a portion of the CO using a C1- fixing microorganism for: 1) generating at least one fermentation product, and 2) generating a tail gas stream comprising at least 60 vol-%, on a dry basis, CO2, wherein the CO2 was present in the input gas stream; c) conditioning the tail gas stream by liquefaction to generate a liquified CO 2 stream comprising at least 90 vol-%, on a dry basis, CO2; and d) sequestering the liquified CO2 stream.
- Embodiment 22 A method for controlling the processing of greenhouse gas carbon for both utilization and sequestration comprising: a) identifying an amount of carbon for utilization; b) determining a composition of an input gas stream to obtain an identified amount of carbon directed to utilization, wherein the input gas stream comprises hydrogen, at least 50 vol-%, on a dry basis, CO, and at least 10 vol- %, on a dry basis, CO 2 ; c) passing the input gas stream to a fermentation process; d) fermenting under suitable conditions at least a portion of the CO using a C1- fixing microorganism for: 1) generating at least one fermentation product, and 2) generating a tail gas stream comprising at least 60 vol-%, on a dry basis, CO 2 , wherein the CO 2 was present in the input gas stream; e) conditioning the tail gas stream by liquefaction to generate a liquified CO2 stream comprising at least 90 vol-%, on a dry basis, CO 2 ; and f) sequestering the liqu
- Embodiment 23 The method according to embodiment 22, wherein the determining the composition of the input gas stream is a ratio of CO:CO2.
- Embodiment 24 The method according to embodiment 22, wherein cost of H2 is high then the amount of carbon directed for utilization is low and the amount of carbon directed for sequestration is high.
- Embodiment 25 The method according to embodiment 22, wherein cost of H 2 is low then the amount of carbon directed for utilization is high and the amount of carbon directed for sequestration is low.
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Abstract
Combining carbon capture, utilization, and sequestration to improve product yield and gas purity. In certain aspects, the methods and systems disclose converting carbon monoxide gas that would otherwise be vented to the atmosphere or discarded as waste to one or more products, while concurrently concentrating and purifying tail gas streams comprising carbon dioxide for sequestration.
Description
METHOD AND APPARATUS FOR COMBINED CARBON CAPTURE, UTILIZATION, AND STORAGE CROSS REFERENCE TO RELATED APPLICATION This application claims the benefit of U.S. Provisional Patent Application No.63/648,168, filed on May 15, 2024, the entirety of all of which are incorporated herein by reference. FIELD The present disclosure relates to combining carbon capture, utilization, and storage. More specifically, the present disclosure relates to novel methods and systems for capturing industrial emissions to prepare the gas for sequestration while concurrently producing fermentation products, including ethanol and single-cell protein. BACKGROUND The following discussion is provided to aid the reader in understanding the disclosure and is not admitted to describe or constitute prior art thereto. Mitigation of impending climate change requires drastic changes in manufacturing and greater reliance on biotechnology. Sustainable sources of fuels and chemicals are currently insufficient to significantly displace dependence on fossil carbon. Biotechnology harnesses the power of biology to create new products in a way that improves the quality of life and the environment, Gas fermentation is emerging as a powerful biotechnological advancement as an alternative platform for the biological fixation of such gases such as CH4, CO, CO2, and/or H2 into sustainable fuels and chemicals. In particular, gas fermentation technology can utilize a wide range of feedstocks including gasified carbon-containing matter such as municipal solid waste or agricultural waste, or industrial waste gases such as off- gases from steel manufacturing, petroleum refineries, and petrochemical processes to produce ethanol, aviation fuel, chemicals, and a variety of other products. Gas fermentation alone could displace 30% of crude oil use and reduce global CO2 emissions by 10%. As with any disruptive technology, many technical challenges must be overcome before this potential is fully achieved. The science of scale-up production and the reduction of obstacles for continued commercialization of gas fermentation are advanced by this disclosure. Gas fermentation processes can be used to generate target materials from gas substrates or other input materials, particularly carbon-based materials. Greenhouse gases are an example of gas substrates. For example, particular biological systems can be used to perform gas fermentation.
Industrial processes can output gases that have significant amounts of carbon-based materials. Chemical processors and oil refiners generally view flaring and venting carbon rich sources to the atmosphere or otherwise discarding them as traditional standard operations. Currently, the primary alternative available to chemical processors and oil refiners is to engage in some form of carbon capture and sequestration (“CCS”). CCS can include finding permanent underground storage such as depleted oil wells or sealed saline aquifers to permanently store the gaseous carbon. This may be cost prohibitive for chemical processors, oil refiners, or any other operator that produces underutilized carbon, as it requires them to locate a suitable location, construct a pipeline to that location, and then monitor the location indefinitely for leaks or other signs of failure. Additionally, many domestic and international governmental entities are placing tighter restrictions on the total amount of carbon that a particular site, complex, or entity is allowed to release into the atmosphere. Such restrictions are pushing industrial, commercial, and agricultural operators alike to pursue and implement expensive efficiency upgrades to already well-developed technologies within their respective fields. Reducing the carbon intensity of all parts of the steel sector is critical for a low- carbon and carbon neutral economy. Unfortunately, the production of ferroalloys is a highly energy-consuming process. Producing ferroalloys generates process emissions from carbothermic reduction of metal oxides, and these emissions are bound by physical limitations that prevent further lowering of the emission levels. Even while the current CO2 emission levels of the European ferroalloy sector are very close to the theoretical chemical and physical limits, the industry is still responsible for an amount of emissions having a large greenhouse gas footprint. There remains a need to reduce greenhouse gas emissions beyond only CCS. Combining CCS and carbon capture and utilization (CCU) together results in both sequestering carbon and recycling carbon. SUMMARY Described herein are systems and methods for incorporating gas fermentation into oil and gas production and refining or chemical, such as petrochemical, complexes to convert various feedstocks, waste gas, and other gas by-products into useful products, such as ethylene, ethanol, and the like. One embodiment is directed to a method of processing greenhouse gas carbon for both utilization and sequestration comprising: a) passing an input gas stream comprising at least 50 vol-%, on a dry basis, CO and 10 vol-%, on a dry basis, CO2 to a fermentation
process; b) fermenting under suitable conditions at least a portion of the CO using a C1- fixing microorganism for: 1) generating at least one fermentation product, and 2) generating a tail gas stream comprising at least 60 vol-%, on a dry basis, CO2, wherein the CO2 was present in the input gas stream; c) conditioning the tail gas stream by liquefaction to generate a liquified CO2 stream comprising at least 90 vol-%, on a dry basis, CO2; and d) sequestering the liquified CO2 stream. The method of an embodiment, wherein the input gas stream further comprises a gas selected from hydrogen, nitrogen, oxygen, other inert gases, or any combination thereof. In some embodiments, the hydrogen in the stream comprises hydrogen selected from green hydrogen, blue hydrogen, grey hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen, white hydrogen, or any combination thereof. The method of an embodiment, wherein the input gas stream is industrial off-gas. The method of an embodiment, wherein the industrial off-gas is from a production process comprising steel or alloy. The method of an embodiment, wherein the C1-fixing microorganism is Clostridium autoethanogenum. The method of an embodiment, wherein the at least one fermentation product is selected from ethanol, single-cell protein, or any combination thereof. The method of an embodiment, wherein liquefaction is cryogenic liquefaction. One embodiment is directed to a method for purifying CO2 comprising: a) passing an input gaseous stream comprising from about 50 vol-%, on a dry basis, to 75 vol-%, on a dry basis, CO and from about 10 vol-%, on a dry basis, to 35 vol-%, on a dry basis, CO2 to a gas fermentation process; b) removing the CO by generating at least one fermentation product; c) recovering the CO2 in a concentrated CO2 tail gas stream; d) purifying the CO2 tail gas stream by liquefaction to generate a purified CO2; and e) providing the purified CO2 stream for sequestration. One embodiment is directed to a method of capturing carbon for combined utilization and sequestration comprising: a) passing a gas stream comprising CO and CO2 to a gas fermentation process under suitable conditions; b) fermenting at least a portion of the CO using a C1-fixing microorganism to: 1) generate at least one fermentation product, and 2) generate an enriched residual CO2 stream comprising about 20-95 vol-%, on a dry basis, CO2; c) conditioning the enriched residual CO2 stream using cryogenic liquefaction to generate a purified CO2 stream comprising greater than 99 vol-%, on a dry basis, CO2; and d) providing the purified CO2 stream for sequestration.
The method of an embodiment, wherein the gas stream comprising CO and CO2 comprises about 17.5 vol-%, on a dry basis, CO2. The method of an embodiment, wherein the enriched residual CO2 stream comprises about 86 vol-%, on a dry basis, CO2. The method of embodiments, wherein the purified CO2 stream comprises about 99.9 vol-%, on a dry basis, CO2. One embodiment is directed to an apparatus for both carbon capture and utilization and carbon capture and sequestration comprising: a) a CO/CO2 gas source; b) a gas fermentation process unit in fluid communication with the gas source; c) a gas fermentation product conduit in fluid communication with the gas fermentation process unit; d) a tail gas conduit in fluid communication with the gas fermentation process unit and a liquefaction unit; and e) a purified CO2 conduit in fluid communication with the liquefaction unit and a sequestration facility. The foregoing general description and following detailed description are exemplary and explanatory and are intended to provide further explanation of the disclosure as claimed. Other objects, advantages, and features will be apparent to those skilled in the art from the following brief description of the drawings and detailed description of the disclosure. BRIEF DESCRIPTION OF THE DRAWINGS The following detailed description is merely exemplary in nature and is not intended to limit the various embodiments or the application and uses thereof. Furthermore, there is no intention to be bound by any theory presented in the preceding background or the following detailed description. The figures have been simplified by the deletion of a large number of apparatuses customarily employed in a process of this nature which are not specifically required to illustrate the performance of the disclosure. Furthermore, the illustration of the process of this disclosure in the embodiment of a specific drawing is not intended to limit the disclosure to specific embodiments. Some embodiments may be described by reference to the process configuration shown in the figures, which relate to both apparatus and methods to carry out the disclosure. Any reference to method includes reference to an apparatus unit or equipment that is suitable to carry out the step, and vice versa. FIG.1 is a flow diagram according to one embodiment of the disclosure. FIG.2 is a process flow scheme according to one embodiment of the disclosure. FIG.3 is an overview of the piping and associated components of an embodiment of the gas fermentation process portion of the disclosure.
FIG.4 is a schematic flow scheme of an embodiment of the disclosure. DETAILED DESCRIPTION The present disclosure provides systems and methods for improving carbon capture by combining both carbon capture and sequestration (CCS) and carbon capture and utilization (CCU) into a single overall process. Carbon that might otherwise be emitted into the atmosphere is captured and stored or is captured and used to generate useful and valuable products. The combined process brings technology one step closer to a carbon recycle economy. More specifically, the present disclosure relates to systems and methods for combining both CCU and CCS into carbon capture utilization and sequestration (CCUS) by using gas fermentation to convert various feedstock, waste gas, and other gas by-products into useful products, such as ethylene, ethanol, single-cell protein and the like while at the same time also sequestering a portion of the waste carbon. Definitions It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting. Technical and scientific terms used herein have the meanings commonly understood by one of ordinary skill in the art, unless otherwise defined. Unless otherwise specified, materials and/or methodologies known to those of ordinary skill in the art can be utilized in carrying out the methods described herein, based on the guidance provided herein. As used herein, the singular terms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Reference to an object in the singular is not intended to mean “one and only one” unless explicitly so stated, but rather “one or more.” As used herein, “about” when used with a numerical value means the numerical value stated as well as plus or minus 10% of the numerical value. For example, “about 10” should be understood as both “10” and “9-11.” Also as used herein, “and/or” refers to and encompasses any and all possible combinations of one or more of the associated listed items, as well as the lack of combinations when interpreted in the alternative (“or”). The term “acid” as used herein includes both carboxylic acids and the associated carboxylate anion, such as the mixture of free acetic acid and acetate present in a fermentation broth as described herein. The ratio of molecular acid to carboxylate in the fermentation broth is dependent upon the pH of the system. In addition, the term “acetate”
includes both acetate salt alone and a mixture of molecular or free acetic acid and acetate salt, such as the mixture of acetate salt and free acetic acid present in a fermentation broth as described herein. The term “carbon capture” as used herein refers to the fixation and utilization of carbon including carbon from CO2, CO, and/or CH4 from a stream comprising CO2, CO, and/or CH4 and converting the CO2, CO, and/or CH4 into useful products. The term “substrate comprising carbon monoxide” and like terms should be understood to include any substrate in which carbon monoxide is available to one or more strains of bacteria for growth and/or fermentation, for example. The term “gaseous substrates comprising carbon monoxide” includes any gas which contains carbon monoxide. The gaseous substrate will typically contain a significant proportion of CO, preferably at least about 5% to about 100% CO by volume. The term “C1 carbon” and like terms should be understood to refer to carbon sources that are suitable for use by a microorganism, particularly those of the gas fermentation process disclosed herein. C1 carbon may include, but should not be limited to, carbon monoxide (CO), carbon dioxide (CO2), and methane (CH4), methanol (CH3OH), and formate (HCOOH). The term “substrate comprising carbon dioxide” and like terms should be understood to include any substrate in which carbon dioxide is available to one or more strains of bacteria for growth and/or fermentation, for example. The term “gaseous substrates comprising carbon dioxide” includes any gas which contains carbon dioxide. The gaseous substrate will typically contain a significant proportion of CO2, preferably at least about 5% to about 100% CO2 by volume. The term “green hydrogen” refers to hydrogen generated from clean electricity or surplus renewable energy sources. The term “blue hydrogen” refers to hydrogen primarily generated from steam reforming of natural gas thereby producing hydrogen and carbon dioxide. The term “grey hydrogen” refers to hydrogen primarily generated from steam reforming of natural gas thereby producing hydrogen and carbon dioxide, but the carbon dioxide is not obtained through carbon capture and storage. The term “pink hydrogen” refers to hydrogen generated through electrolysis from nuclear energy. The term “turquoise hydrogen” refers to hydrogen generated by methane pyrolysis producing solid carbon and hydrogen.
The term “yellow hydrogen” refers to hydrogen generated by electrolysis using solar power. The term “white hydrogen” refers to hydrogen that is naturally occurring hydrogen. The term “bioreactor” includes a fermentation device consisting of one or more vessels and/or towers or piping arrangements, which includes the continuous stirred tank reactor (CSTR), immobilized cell reactor (ICR), trickle bed reactor (TBR), bubble column, gas lift fermenter, membrane reactor such as hollow fiber membrane bioreactor (HFMBR), static mixer, or other vessel or other device suitable for gas-liquid contact. The term “co-substrate” refers to a substance that, while not necessarily being the primary energy and material source for product synthesis, can be utilized for product synthesis when added to another substrate, such as the primary substrate. The term “directly”, as used in relation to the passing of industrial off or gases to a bioreactor, is used to mean that no or minimal processing or treatment steps, such as cooling and particulate removal are performed on the gases prior to them entering the bioreactor (note: an oxygen removal step may be required for anaerobic fermentation). The terms “fermenting,” “fermentation process,” “fermentation reaction,” and like terms as used herein, are intended to encompass both the growth phase and product biosynthesis phase of the process. As is described further herein, in some embodiments the bioreactor may comprise a primary bioreactor and a secondary bioreactor. The term “nutrient medium” as used herein should be understood as the solution added to the fermentation broth containing nutrients and other components appropriate for the growth of the microorganism culture. The terms “primary bioreactor” or “first reactor” as used herein this term is intended to encompass one or more reactors that may be connected in series or parallel with a secondary bioreactor. The primary bioreactors generally use anaerobic or aerobic fermentation to produce a product (e.g., ethylene, ethanol, acetate, etc.) from a gaseous substrate. The terms “secondary bioreactor” or “second reactor” as used herein are intended to encompass any number of further bioreactors that may be connected in series or in parallel with the primary bioreactors. Any one or more of these further bioreactors may also be connected to a further separator. The term “stream” is used to refer to a flow of material into, through and away from one or more stages of a process, for example, the material that is fed to a bioreactor. The
composition of the stream may vary as it passes through particular stages. For example, as a stream passes through the bioreactor. As used herein, the term “enriched” can mean that the outlet stream has a greater concentration of the indicated component than in the inlet stream to a vessel. As used herein, the term “depleted stream” means that the depleted stream coming out of a vessel has a smaller concentration of the component than the feed to the vessel. The terms “feedstock” when used in the context of the stream flowing into a gas fermentation bioreactor (i.e., gas fermenter) or “gas fermentation feedstock” should be understood to encompass any material (solid, liquid, or gas) or stream that can provide a substrate and/or C1-carbon source to a gas fermenter or bioreactor either directly or after processing of the feedstock. The term “waste gas” or “waste gas stream” may be used to refer to any gas stream that is either emitted directly, flared with no additional value capture, or combusted for energy recovery purposes. The terms “synthesis gas” or “syngas” refers to a gaseous mixture that contains at least one carbon source, such as carbon monoxide (CO), carbon dioxide (CO2), or any combination thereof, and, optionally, hydrogen (H2) that can used as a feedstock for the disclosed gas fermentation processes and can be produced from a wide range of carbonaceous material, both solid and liquid. As used herein, the terms “intermediate” and “precursor” can be used interchangeably to refer to a substance, such as a molecule, compound, or protein, that is produced upstream of a particular product. The intermediate may be directly upstream of the product. The intermediate may be indirectly upstream of the product. For example, in the exemplary reaction “compound A” à “compound B” à “compound C” à “compound D”, “compound” C is an intermediate that is directly upstream of the product, “compound D,” and “compound B” is an intermediate that is indirectly upstream of the product, “compound D.” The term “electrolysis process”, may include any substrate leaving the electrolysis process. In various instances, the electrolysis process is comprised of CO, H2, or combinations thereof. In certain instances, the electrolysis process may contain portions of unconverted CO2. Preferably, the electrolysis process is fed from the electrolysis process to the fermentation process. The term “electrolysis process”, may include any substrate leaving the electrolysis process. In various instances, the electrolysis process is comprised of CO, H2, or combinations thereof. In certain instances, the electrolysis process may contain portions of
unconverted CO2. Preferably, the electrolysis process is fed from the electrolysis process to the fermentation process. The terms “improving the economics”, “optimizing the economics” and the like, when used in relationship to a fermentation process, include, but are not limited to, the increase of the amount of one or more of the products produced by the fermentation process during periods of time in which the value of the products produced is high relative to the cost of producing such products. The economics of the fermentation process may be improved by way of increasing the supply of feedstock to the bioreactor, which may be achieved for instance by supplementing the C1 feedstock from the industrial process with electrolysis process from the electrolysis process. The additional supply of feedstock may result in the increased efficiency of the fermentation process. Another means of improving the economics of the fermentation process is to select feedstock based upon the relative cost of the feedstock available. For example, when the cost of the C1 feedstock from the industrial process is higher than the cost of the electrolysis process from the electrolysis process, the electrolysis process may be utilized to displace at least a portion of the C1 feedstock. By selecting feedstock based upon the cost of such feedstock the cost of producing the resulting fermentation product is reduced. The electrolysis process is capable of supplying feedstock comprising one or both of H2 and CO. The “cost per unit of electrolysis process” may be expressed in terms of any given product produced by the fermentation process and any electrolysis process, for example for the production of ethanol with the electrolysis process defined as H2, the cost per unit of electrolysis process is defined by the following equation: $௭ ^ெ^^ ^ ^ x ൬ x ^^ ୋ^ ^^^^౪౨^^^౪౯ x ^^ ீ^ ಹమ ^^^^^ ^ ^ ^ ^ ^
process efficiency, and y represents the yield of ethanol. For the production of ethanol with electrolysis process defined as CO, the cost per unit of electrolysis process is defined by the following equation: ^ $௭ ^ x ൬ ^ெ^^ ^ x ^^^ ୋ^ ^^^^౪౨^^^౪౯ ^ x ^^^ ீ^ ^ೀ ^
process efficiency, and y represents the yield of ethanol. In addition to the cost of feedstock, the fermentation process includes “production costs.” The “production costs” exclude the cost of the feedstock. “Production costs”,
“marginal cost of production”, and the like, include the variable operating costs associated with running the fermentation process. This value may be dependent on the product being produced. The marginal cost of production may be represented by a fixed cost per unit of product, which may be represented in terms of the heating value of combustion of the product. For example, the calculation of the marginal cost of production for ethanol is defined by the following equation: ^ $^ ^ x ^ ^ ^^௧^^^ ௧^^ ^^௧^^^ ௧^^ ଶ^.଼ ீ^ ^^^ೌ^^^ ^ operating costs associated with running the bioreactor
value of combustion of ethanol. In certain instances, the variable operating costs associated with running the bioreactor, c, is $200 for ethanol excluding the price of H2/CO/CO2. The fermentation process is capable of producing a number of products. Each product defining a different value. The “value of the product” may be determined based upon the current market price of the product and the heating value of combustion of the product. For example, the calculation for the value of ethanol is defined by the following equation: ^ $௭ ௧^^^ ௧^^ ^ x ^ ^^௧^^^ ௧^^ ^^ ^ ଶ^.଼ ீ^ ^^^ೌ^^^ ^ of ethanol per metric ton and 26.8 GJ represents the lower
heating value of combustion of ethanol. To optimize the economics of the fermentation process, the value of the product produced must exceed the “cost of producing” such product. The cost of producing a product is defined as the sum of the “cost of feedstock” and the “marginal cost of production.” The economics of the fermentation process may be expressed in terms of a ratio defined by the value of product produced compared to the cost of producing such product. The economics of the fermentation process is improved as the ratio of the value of the product compared to the cost of producing such product increases. The economics of the fermentation process may be dependent on the value of the product produced, which may change dependent, at least in part, on the fermentation process implemented, including but not limited to the bacterial culture and/or the composition of the gas used in the fermentation process. When ethanol is the product produced by the fermentation process the economics may be determined by the following ratio: ^ $௭ ^ ∶ ^ $௫ ^ ^ ^ $௬ ^
where z represents the value of ethanol, x represents the cost of feedstock, and y represents the marginal cost of production (excluding feedstock). In the step for identifying the amount of carbon for CCU, factors may be dependent on the cost or price of product, cost or price of hydrogen, cost of sequestration, and/or incentive credits, all of which may be determined and balanced with a suitable algorithm. The terms “increasing the efficiency”, “increased efficiency” and the like, when used in relation to a fermentation process, include, but are not limited to, increasing one or more of the rate of growth of microorganisms catalysing the fermentation, the growth and/or product production rate at elevated product concentrations, the volume of desired product produced per volume of substrate consumed, the rate of production or level of production of the desired product, and the relative proportion of the desired product produced compared with other by- products of the fermentation. In certain instances, the electrolysis process increases the efficiency of the fermentation process. The terms “electrolysis module” and “electrolyzer” can be used interchangeably to refer to a unit that uses electricity to drive a non-spontaneous reaction. Electrolysis technologies are known in the art. Exemplary processes include alkaline water electrolysis, proton or anion exchange membrane (PEM, AEM) electrolysis, and solid oxide electrolysis (SOE) (Ursua et al., Proceedings of the IEEE 100(2):410-426, 2012; Jhong et al., Current Opinion in Chemical Engineering 2:191-199, 2013). The term “faradaic efficiency” is a value that references the number of electrons flowing through an electrolyzer and being transferred to a reduced product rather than to an unrelated process. SOE modules operate at elevated temperatures. Below the thermoneutral voltage of an electrolysis module, an electrolysis reaction is endothermic. Above the thermoneutral voltage of an electrolysis module, an electrolysis reaction is exothermic. In some embodiments, an electrolysis module is operated without added pressure. In some embodiments, an electrolysis module is operated at a pressure of 5-10 bar. A “CO2 electrolysis module” refers to a unit capable of splitting CO2 into CO and O2 and is defined by the following stoichiometric reaction: 2CO2 + electricity ^ 2CO + O2. The use of different catalysts for CO2 reduction impact the end product. Catalysts including, but not limited to, Au, Ag, Zn, Pd, and Ga catalysts, have been shown effective for the production of CO from CO2. In some embodiments, the pressure of a gas stream leaving a CO2 electrolysis module is approximately 5-7 bar. “H2 electrolysis module,” “water electrolysis module,” and “H2O electrolysis module” refer to a unit capable of splitting H2O, in the form of steam, into H2 and O2 and is
defined by the following stoichiometric reaction: 2H2O + electricity ^ 2H2 + O2. An H2O electrolysis module reduces protons to H2 and oxidizes O2- to O2. H2 produced by electrolysis can be blended with a C1-comprising gaseous substrate as a means to supply additional feedstock and to improve substrate composition. H2 and CO2 electrolysis modules have 2 gas outlets. One side of the electrolysis module, the anode, comprises H2 or CO (and other gases such as unreacted water vapor or unreacted CO2). The second side, the cathode, comprises O2 (and potentially other gases). The composition of a feedstock being passed to an electrolysis process may determine the presence of various components in a CO stream. For instance, the presence of inert components, such as CH4 and/or N2, in a feedstock may result in one or more of those components being present in the CO-enriched stream. Additionally, in some electrolyzers, O2 produced at the cathode crosses over to the anode side where CO is generated and/or CO crosses over to the anode side, leading to cross contamination of the desired gas products. The term “separation module” is used to refer to a technology capable of dividing a substance into two or more components. For example, an “O2 separation module” may be used to separate an O2-comprising gaseous substrate into a stream comprising primarily O2 (also referred to as an “O2-enriched stream” or “O2-rich gas”) and a stream that does not primarily comprise O2, comprises no O2, or comprises only trace amounts of O2 (also referred to as an “O2-lean stream” or “O2-depleted stream”). As used herein, the terms “enriched stream,” “rich gas,” “high purity gas,” and the like refer to a gas stream having a greater proportion of a particular component following passage through a module, such as an electrolysis module, as compared to the proportion of the component in the input stream into the module. For example, a “CO-enriched stream” may be produced upon passage of a CO2-comprising gaseous substrate through a CO2 electrolysis module. An “H2-enriched stream” may be produced upon passage of a water gaseous substrate through an H2 electrolysis module. An “O2-enriched stream” emerges automatically from the anode of a CO2 or H2 electrolysis module; an “O2-enriched stream” may also be produced upon passage of an O2-comprising gaseous substrate through an O2 separation module. A “CO2-enriched stream” may be produced upon passage of a CO2- comprising gaseous substrate through a CO2 concentration module. As used herein, the terms “lean stream,” “depleted gas,” and the like refer to a gas stream having a lesser proportion of a particular component following passage through a module, such as a concentration module or a separation module, as compared to the proportion of the component in the input stream into the module. For example, an O2-lean
stream may be produced upon passage of an O2-comprising gaseous substrate through an O2 separation module. The O2-lean stream may comprise unreacted CO2 from a CO2 electrolysis module. The O2-lean stream may comprise trace amounts of O2 or no O2. A “CO2-lean stream” may be produced upon passage of a CO2-comprising gaseous substrate through a CO2 concentration module. The CO2-lean stream may comprise CO, H2, and/or a constituent such as a microbe inhibitor or a catalyst inhibitor. The CO2-lean stream may comprise trace amounts of CO2 or no CO2. In embodiments, the disclosure provides an integrated process wherein the pressure of the gas stream is capable of being increased and/or decreased. The term “pressure module” refers to a technology capable of producing (i.e., increasing) or decreasing the pressure of a gas stream. The pressure of the gas may be increased and/or decreased through any suitable means, for example one or more compressor and/or valve. In certain instances, a gas stream may have a lower than optimum pressure, or the pressure of the gas stream may be higher than optimal, and thus, a valve may be included to reduce the pressure. A pressure module may be located before or after any module described herein. For example, a pressure module may be utilized prior to a removal module, prior to a concentration module, prior to an electrolysis module, and/or prior to a CO-consuming process. A “pressurized gas stream” refers to a gaseous substrate that has passed through a pressure module. A “pressurized gas stream” may also be used to refer to a gas stream that meets the operating pressure requirements of a particular module. The terms “post-CO-consuming process gaseous substrate,” “post-CO-consuming process tail gas,” “tail gas,” and the like may be used interchangeably to refer to a gas that has passed through a CO-consuming process. The post-CO-consuming process gaseous substrate may comprise unreacted CO, unreacted H2, and/or CO2 produced (or not taken up in parallel) by the CO-consuming process. The post-CO-consuming process gaseous substrate may further be passed to one or more of a pressure module, a removal module, a CO2 concentration module, and/or an electrolysis module. In some embodiments, a “post-CO- consuming process gaseous substrate” is a post-fermentation gaseous substrate. The term “desired composition” is used to refer to the desired level and types of components in a substance, such as, for example, of a gas stream. More particularly, a gas is considered to have a “desired composition” if it contains a particular component (i.e., CO, H2, and/or CO2) and/or contains a particular component at a particular proportion and/or does not comprise a particular component (i.e., a contaminant harmful to the microorganisms) and/or does not
comprise a particular component at a particular proportion. More than one component may be considered when determining whether a gas stream has a desired composition. “Selectivity” refers to the ratio of the production of a target product to the production of all fermentation products produced by a microorganism. The microorganism of the disclosure may be engineered to produce products at a certain selectivity or at a minimum selectivity. In one embodiment, a target product, such as ethylene glycol, accounts for at least about 5%, 10%, 15%, 20%, 30%, 50%, or 75% of all fermentation products produced by the microorganism of the disclosure. In one embodiment, ethylene accounts for at least 10% of all fermentation products produced by the microorganism of the disclosure, such that the microorganism of the disclosure has a selectivity for ethylene glycol of at least 10%. In another embodiment, ethylene accounts for at least 30% of all fermentation products produced by the microorganism of the disclosure, such that the microorganism of the disclosure has a selectivity for ethylene of at least 30%. At least one of the one or more fermentation products may be biomass produced by the culture. At least a portion of the microbial biomass may be converted to a single cell protein (SCP). At least a portion of the single cell protein may be utilized as a component of animal feed. In one embodiment, the disclosure provides an animal feed comprising microbial biomass and at least one excipient, wherein the microbial biomass comprises a microorganism grown on a gaseous substrate comprising one or more of CO, CO2, and H2. A “single cell protein” (SCP) refers to a microbial biomass that may be used in protein-rich human and/or animal feeds, often replacing conventional sources of protein supplementation such as soymeal or fishmeal. To produce a single cell protein, or other product, the process may comprise additional separation, processing, or treatments steps. For example, the method may comprise sterilizing the microbial biomass, centrifuging the microbial biomass, and/or drying the microbial biomass. In certain embodiments, the microbial biomass is dried using spray drying or paddle drying. The method may also comprise reducing the nucleic acid content of the microbial biomass using any method known in the art, since intake of a diet high in nucleic acid content may result in the accumulation of nucleic acid degradation products and/or gastrointestinal distress. The single cell protein may be suitable for feeding to animals, such as livestock or pets. In particular, the animal feed may be suitable for feeding to one or more beef cattle, dairy cattle, pigs, sheep, goats, horses, mules, donkeys, deer, buffalo/bison, llamas, alpacas, reindeer, camels, bantengs, gayals, yaks, chickens, turkeys, ducks, geese, quail, guinea fowl, squabs/pigeons,
fish, shrimp, crustaceans, cats, dogs, and rodents. The composition of the animal feed may be tailored to the nutritional requirements of different animals. Furthermore, the process may comprise blending or combining the microbial biomass with one or more excipients. “Microbial biomass” refers biological material comprising microorganism cells. For example, microbial biomass may comprise or consist of a pure or substantially pure culture of a bacterium, archaea, virus, or fungus. When initially separated from a fermentation broth, microbial biomass generally contains a large amount of water. This water may be removed or reduced by drying or processing the microbial biomass. The microbial biomass may comprise any of the components listed in this application but is not limited to the disclosures herein. Notably, the microbial biomass of an embodiment comprises 15% moisture (water) by weight. Accordingly, the values may refer to amounts of each component per amount of wet (i.e., non-dried) microbial biomass. Herein, the composition of the microbial biomass is described in terms of weight of a component per weight of wet (i.e., non-dried) microbial biomass. Of course, it is also possible to calculate the composition of the microbial biomass in terms of weight of a component per weight of dry microbial biomass. The microbial biomass generally contains a large fraction of protein, such as more than 50% (50 g protein/100 g biomass), more than 60% (60 g protein/100 g biomass), more than 70% (70 g protein/100 g biomass), or more than 80% (80 g protein/100 g biomass) protein by weight. In a preferred embodiment, the microbial biomass comprises at least 72% (72 g protein/100 g biomass) protein by weight. The protein fraction comprises amino acids, including aspartic acid, alanine, arginine, cysteine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tyrosine, and/or valine. In particular, the microbial biomass may comprise more than 10 mg methionine/g biomass, more than 15 mg methionine/g biomass, more than 20 mg methionine/g biomass, or more than 25 mg methionine/g biomass. In a preferred embodiment, the microbial biomass comprises at least 17.6 mg methionine/g biomass. The microbial biomass may contain a number of vitamins, including vitamins A (retinol), C, B1 (thiamine), B2 (riboflavin), B3 (niacin), B5 (pantothenic acid), and/or B6 (pyridoxine). The microbial biomass may contain relatively small amounts of carbohydrates and fats. For example, the microbial biomass may comprise less than 15% (15 g carbohydrate/100 g biomass), less than 10% (10 g carbohydrate/100 g biomass), or less than 5% (5 g carbohydrate/100 g biomass) of carbohydrate by weight. For example, the microbial
biomass may comprise less than 10% (10 g fat/100 g biomass), or less than 5% (5 g fat/100 g biomass), less than 2% (2 g fat/100 g biomass), or less than 1% (1 g fat/100 g biomass) of fat by weight. The microorganism may classified based on functional characteristics. For example, the microorganism may be or may be derived from a C1-fixing microorganism, an aerobe, a hydrogen-oxidizing bacteria, a hydrogenotroph, an anaerobe, an acetogen, an ethanologen, and/or a carboxydotroph. An “excipient” may refer to any substance that may be added to the microbial biomass to enhance or alter the form, properties, or nutritional content of the animal feed. For example, the excipient may comprise one or more of a carbohydrate, fiber, fat, protein, vitamin, mineral, water, flavour, sweetener, antioxidant, enzyme, preservative, probiotic, or antibiotic. In some embodiments, the excipient may be hay, straw, silage, grains, oils or fats, or other plant material. The excipient may be any feed ingredient identified in Chiba, Section 18: Diet Formulation and Common Feed Ingredients, Animal Nutrition Handbook, 3rd revision, pages 575-633, 2014. A “biopolymer” refers to natural polymers produced by the cells of living organisms. In certain embodiments, the biopolymer is PHA. In certain embodiments, the biopolymer is PHB. A “bioplastic” refers to plastic materials produced from renewable biomass sources. A bioplastic may be produced from renewable sources, such as vegetable fats and oils, corn starch, straw, woodchips, sawdust, or recycled food waste. As used herein, the terms “protein-based bioplastic,” “protein bio-based plastic” and “protein biocomposite” can be used interchangeably. “Protein-based bioplastics” and “protein-based protein-based biofilms” refer to naturally-derived biodegradable polymers. Protein-based bioplastics and protein-based biofilms are largely composed of proteins. A “protein-based material” refers to a three-dimensional macromolecular network comprising hydrogen bonds, hydrophobic interactions, and disulphide bonds. See, e.g., Martinez, Journal of Food Engineering, 17: 247-254, 2013 and Pommet, Polymer, 44: 115-122, 2003. In preferred embodiments, the protein component of a protein-based bioplastic or protein-based biofilm is microbial biomass. Production of protein-based bioplastics and protein-based biofilms may require a step of protein denaturation by chemical, thermal, or pressure-induced methods. See, e.g., Mekonnen, Biocomposites: Design and Mechanical Performance, 2015. Production of protein-based bioplastics and protein-based biofilms may further require a step of isolating or fractionating the microbial biomass to produce a purified protein material.
Disclosed Systems and Methods Systems and methods in accordance with the present disclosure can be used to integrate gas fermentation systems with processes capable of generating an input gas comprising at least CO2, and more commonly, both CO and CO2, such as existing oil and gas processing infrastructure, refining infrastructure, petrochemical infrastructure, and infrastructure in complexes that combine any of the foregoing as well as plants, mills, refineries, or other infrastructure that generates carbon-based materials as outputs, including as waste. Integrating a gas fermentation unit with existing infrastructure allows users and operators to reduce their overall carbon emissions by converting their waste carbon into marketable products without additional capital investment and operating costs for equipment and processes that can be leveraged from infrastructure an operator may already have or is building for another primary purpose. At the same time, operators will be able to also sequester CO2 and potentially receive benefits from sequestration. For some operators, integration can also increase their overall production yield if the product produced by the gas fermentation process is a product that the operator is capable of producing or is a feed component to a process an operator is already performing. For many industrial processes, emission of gases that are rich in carbon are commonplace. Chemical processors and oil refiners generally view flaring and venting carbon rich sources to the atmosphere or otherwise discarding them as traditional standard techniques. Currently, the primary alternative available to chemical processors and oil refiners is to engage in some form of carbon capture and sequestration (“CCS”). CCS involves finding permanent underground storage such as empty oil wells, gas- tight saline aquifers, or salt domes to permanently store the waste gaseous carbon. This option is generally cost prohibitive for chemical processors, oil refiners, or any other operator that produces waste carbon, as it requires them to locate a suitable location, construct a pipeline to that location, and then monitor the location indefinitely for leaks or other signs of failure. Additionally, many domestic and international governmental entities are placing tighter restrictions on the total amount of waste carbon that a particular site, complex, or entity is allowed to release into the atmosphere. Such restrictions are pushing industrial, commercial, and agricultural operators alike to pursue and implement expensive efficiency upgrades to already well-developed technologies within their respective fields.
Gas fermentation processes that are capable of converting various carbon sources into other products are rapidly becoming a desirable alternative for producers of excess carbon. Such processes allow companies to convert standard techniques that emit carbon into the atmosphere into a separate revenue stream by converting the underutilized carbon into a marketable product. Moreover, the carbon that is converted into other products lowers the operator’s total carbon output, potentially serving as a way for operators to maintain current outputs without conflicting with ever-tightening government regulations. Furthermore, tail gas from gas fermentation may be treated to form a concentrated CO2 stream depleted in CO and/or sulfur thereby reducing the cost of more traditional carbon capture and sequestration processes. The widespread adoption of gas fermentation processes could be improved by the stepwise move to carbon capture and utilization. As a first step, CCU can be combined with CCS operations. Using gas fermentation, CCS processes are improved since the gas fermentation process may produce a tail gas stream of concentrated CO2 which is readily purified and sequestered. Common steps such as a separate concentration step typically employed with for example, emissions from flue gas, can be eliminated. Gas fermentation already provides a concentrated CO2 tails gas stream. In one embodiment the substrate and/or C1 carbon source is obtained from the refining or chemical operations in which the gas fermentation process is being integrated. In other embodiments, the substrate and/or C1 carbon source is obtained from outside the refining or petrochemical operations in which the gas fermentation process is being integrated and it is the product of the gas fermentation process that is being integrated with infrastructure of the refining or chemical operations. In yet other embodiments it is both the substrate and/or C1 carbon source. The substrate and or C1 carbon source may be already in the form of a gas (e.g., a waste gas or underutilized gas), or a solid or liquid material may be first processed in a preliminary step of the overall gas fermentation process to generate synthesis gas known as syngas which in turn is provided to the bioreactor of the gas fermentation system. The preliminary step to generate syngas may involve, reforming, partial oxidation, plasma, or gasification processes. Examples of gasification processes include gasification of coal, gasification of refinery residues, gasification of petroleum coke, gasification of biomass, gasification of lignocellulosic material, gasification of waste wood, gasification of black liquor, gasification of municipal solid waste, gasification of municipal liquid waste, gasification of industrial solid waste, gasification of industrial liquid waste, gasification of refuse derived fuel, gasification of sewerage, gasification of sewerage sludge,
gasification of sludge from wastewater treatment, gasification of landfill gas, gasification of biogas such as when biogas is added to enhance gasification of another material, gasification of tires, pieces of tires, and or components of tires, and gasification of tires, pieces of tires, and or components of tires combined with an organic material. Examples of reforming processes include, steam methane reforming, steam naphtha reforming, reforming of natural gas, reforming of biogas, reforming of landfill gas, reforming of coke oven gas, reforming of pyrolysis off-gas, reforming of ethylene production off-gas, naphtha reforming, and dry methane reforming. Examples of partial oxidation processes include thermal and catalytic partial oxidation processes, catalytic partial oxidation of natural gas, partial oxidation of hydrocarbons, partial oxidation of biogas, partial oxidation of landfill gas, or partial oxidation of pyrolysis off-gas. Examples of municipal solid waste include tires, plastics, refuse derived fuel, and fibers such as in shoes, apparel, and textiles. Municipal solid waste may be simply landfill-type waste and may be sorted or unsorted. Examples of tires include end of life tires, defective tires, surplus tires, and tire scraps. Examples of biomass may include lignocellulosic material and microbial biomass. Lignocellulosic material may include agriculture waste and forest waste. The substrate and/or C1-carbon source may be a gas stream comprising methane. Such a methane containing gas may be obtained from fossil methane emissions such as during fracking or other hydrocarbon well stimulation processes or from coalbeds, or may be obtained from wastewater treatment, livestock, agriculture, and municipal solid waste landfills. It is also envisioned that the methane may be burned or employed as a feed in a fuel cell to produce electricity or heat, and the C1 by-products may be used as the substrate or carbon source. The method of the disclosure may be used to produce one or more products. For instance, the products may include ethanol, acetate, 1-butanol, 2,3-butanediol, lactate, butene, butadiene, methyl ethyl ketone (2-butanone), ethylene, acetone, isopropanol, lipids, 3- hydroxypropionate (3-HP), terpenes, including isoprene, fatty acids, 2-butanol, 1,2- propanediol, 1 propanol, 1 hexanol, 1 octanol, chorismate-derived products, 3 hydroxybutyrate, 1,3 butanediol, 2-hydroxyisobutyrate or 2-hydroxyisobutyric acid, isobutylene, adipic acid, 1,3 hexanediol, 3-methyl-2-butanol, 2-buten-1-ol, isovalerate, isoamyl alcohol, and/or monoethylene glycol. In certain embodiments, microbial biomass itself may be considered a product. The microorganism of the disclosure may be cultured with the gaseous substrate to produce one or more carbon products. For instance, the microorganism of the disclosure may produce or may be engineered to produce ethanol,
acetate, 1-butanol, 2,3-butanediol, lactate, butene, butadiene, methyl ethyl ketone (2- butanone), ethylene, acetone, isopropanol, lipids, 3-hydroxypropionate (3-HP), terpenes, including isoprene, fatty acids, 2-butanol, 1,2-propanediol, 1 propanol, 1 hexanol, 1 octanol, chorismate-derived products, 3 hydroxybutyrate, 1,3 butanediol, 2-hydroxyisobutyrate or 2- hydroxyisobutyric acid, isobutylene, adipic acid, 1,3 hexanediol, 3-methyl-2-butanol, 2- buten-1-ol, isovalerate, isoamyl alcohol, and/or monoethylene glycol. In certain embodiments, microbial biomass itself may be considered a product. Systems and Methods of a gas fermentation Unit Integrated within a Chemical Manufacturing or Oil-Refining Complex for Combined CCS and CCU In certain embodiments, industrial process have feedstocks or gas (e.g., waste gas) suitable as substrate and/or C1 carbon source and are selected from ferrous metal products manufacturing, such as a steel manufacturing, non-ferrous products manufacturing, petroleum production, petroleum refining, electric power production, carbon black production, paper and pulp manufacturing, ammonia production, methanol production, coke manufacturing, coke gasification, petrochemical production, polymer production, ethylene production, olefin production, carbohydrate fermentation, cement making, aerobic digestion, anaerobic digestion, catalytic processes, natural gas extraction, cellulosic fermentation, oil extraction, industrial processing of geological reservoirs, processing fossil resources such as natural gas coal and oil, landfill operations, or any combination thereof. Examples of specific processing steps within an industrial process which may generate substrate and/or C1 carbon source for gas fermentation include catalyst regeneration, fluid catalyst cracking, and steam cracking. Air separation and direct air capture are other suitable industrial processes to provide substrate and/or C1 carbon source for the gas fermentation process. Specific examples in steel and ferroalloy manufacturing include blast furnace gas, basic oxygen furnace gas, coke oven gas, direct reduction of iron furnace top- gas, and residual gas from smelting iron. In petroleum and oil production, C1 carbon may be produced with the oil or may be produced from a well separately. Other general examples include flue gas from fired boilers and fired heaters, such as natural gas, oil, or coal fired boilers or heaters, and gas turbine exhaust. In these embodiments, the substrate and/or C1- carbon source may be captured from the industrial process before it is emitted into the atmosphere, using any known method. It is also envisioned that the product of the gas fermentation process may provide an additional point of integration. Products listed above as capable of being produced by gas
fermentation may be reactants or components used in refining or chemical processes and integrating the product into a refining or chemical process may take advantage of equipment and operations in common with both the gas fermentation and the refining or chemical process. Points of integration, as either providing the gas fermentation substrate and/or carbon source or as accepting the product of gas fermentation or both include the following. The integration may involve the gas fermentation substrate and/or carbon source from one refining or chemical process and the acceptance of the gas fermentation product into a second different refining or chemical process. Exemplary processes include distillation, including as examples, at atmospheric pressure, at reduced pressure, stripping, rerunning, stabilization, super fractionation, azeotropic, extractive, or any combination thereof; thermal cracking including for example, Visbreaking, coking, delayed coking, fluid coking, coke gasification, Flexicoking TM process, AquaconversionTM process, Asphalt Coking Technology Process (ASCOT) Process, Cherry-P Process, Continuous Coking Process, Decarbonizing Process, ET-II Process, Eureka Process, FTC Process, HSC Process, Mixed-Phase Cracking Process, Shell Thermal Cracking Process, Tervahl-T Process, or any combination thereof; catalytic cracking as exemplified by fixed bed, moving bed, fluid bed, coke formation, Asphalt Residual Treating (ART) Process, Residue Fluid Catalyst Cracking Process, Heavy Oil Treating Process, R2R Process, Reduced Crude Oil Conversion Process, Shell FCC Process, and S&W Fluid Catalytic Cracking Process, or any combination thereof; hydrotreating as exemplified by hydrodesulfurization in downflow fixed-bed, upflow expanded-bed, distillate hydrodesulfurization, heavy feedstock hydrodesulfurization, Resid Desulfurization Process, Vacuum Resid Desulfurization Process, Residfining Process; biodesulfurization, or any combination thereof; hydrocracking as exemplified by Aquaconversion Process, Asphaltenic Bottom Cracking Process, CANMET Process, Chevron RDS Isomax Process, Chevron VRDS Process, ENI Slurry-Phase Technology, Gulf Resid Hydrodesulfurization Process, H- G Hydrocracking Process, H-Oil Process, HYCAR Process, Hyvahl-F Process, IFP Hydrocracking Process, Isocracking Process, LC-Fining Process, MAKFining Process, Microcat-RC Process, Mild Hydrocracking Process, MRH Process, RCD Unibon Process, Residfining Process, Residue Hydroconversion Process, Shell Residual Oil Process, Tervahl- H Process, Unicracking Process, Uniflex Process, Veba Combi Cracking Process, or any combination thereof; solvent processes as exemplified by deasphalting processes, Deep Solvent Deasphalting Process, Demex Process, MDS Process, Residuum Process, Solvahl Process, Lube Deasphalting, dewaxing processes, Cold Press Process, Solvent Dewaxing
Process, Urea Dewaxing Process, Centrifuge Dewaxing Process, Catalytic Dewaxing Process, dewaxing heavy feedstocks, or any combination thereof; product improvement processes including reforming, isomerization, hydroisomerization, alkylation, polymerization, treating, acid processes, clay processes, oxidative processes solvent processes, or any combination thereof; gasification processes including primary gasification, secondary gasification, water-gas shift reactions, carbon dioxide gasification, hydrogasification, methanation, Fischer-Tropsch synthesis, gasification of residua and residua, gasification of residua with biomass, gasification of residual with waste, or any combination thereof; hydrogen production and hydrogen purification; electricity, heat, or other energy production via combustion, gasification, or fuel cells; gas cleaning processes as exemplified by enrichment, water removal including, for example, adsorption and membrane, liquid removal including, for example, extraction, absorption and fractionation, nitrogen removal, acid gas removal, fractionation, and Claus Process. Examples of reforming processes include thermal reforming, catalytic reforming in fixed bed mode and in moving bed mode, and fluid bed reforming. Examples of isomerization processes include Butamer Process, Butomerate Process, Hysomar Process, Iso-Kel Process, Isomate Process, Isomerate Process, Penex Process, and Pentafining Process. Examples of alkylation processes include sulfuric acid alkylation and hydrofluoric alkylation. Examples of polymerization processes include thermal, solidphosporic acid, and bulk acid. Examples of caustic treating processes include Dualayer Distillate Process, Dualayer Gasoline Process, Electrolytic Mercaptan Process, Ferrocyanide Process, Lye Treatment, Mercapsol Process, Polysulfide Process, Sodasol Process, Solutizer Process, Steam-Regenerative Caustic Treatment, and Unisol Process. Examples of acid treating processes include Nalfining Process, and Sulfuric Acid Treatment. Example of Clay treating processes include Alkylation Effluent Treatment, Arosorb Process, bauxite treatment, continuous contact filtration process, cyclic adsorption process, gray clay treatment, percolation filtration process, and Thermofor Continuous Percolation Process. Examples of oxidative treatment processed include Bender Process, Copper Sweetening Process, Doctor Process, Hypochlorine Sweetening Process, Inhibitor Sweetening Process, and Merox Process. Refining processes listed are known and described in Speight, James G. Handbook of Petroleum Refining. Taylor & Francis, 2017. Gas fermentation may be integrated with the following chemical manufacturing exemplary processes: alkylation, amination, condensation and addition, dehydration, dehydrogenation, esterification, ethynylation, other fermentation processes, Friedel-Crafts
reactions, halogenation, hydration, hydrolysis, hydroformylation, hydrogenation, nitration, oxidation, oxo reaction, polymerization, sulfonation, and vinylation. Such chemical processes are known and described in Speight, James G. Chemical Process and Design Handbook, The McGraw-Hill Companies Inc, 2002. Products made or resulting from any of the above chemical processes may include, but are not limited to, a commodity chemical selected from ethanol, isopropanol, monoethylene glycol, sulfuric acid, propylene, sodium hydroxide, sodium carbonate, ammonia, benzene, acetic acid, ethylene, ethylene oxide, formaldehyde, methanol, or any combination thereof. In another embodiment, the commodity chemical is incorporated into one or more articles, converted into one or more second products, or any combination thereof. In one embodiment, the one or more articles, the one or more second products, or any combination thereof, are selected from acetate, 1-butanol, butyrate, 2,3-butanediol, lactate, butene, butadiene, methyl ethyl ketone, acetone, lipids, 3-hydroxyproprionate, terpenes, isoprene, fatty acids, 2-butanol, 1,2-propanediol, 1 propanol, 1 hexanol, 1 octanol, chorismite-derived products, 3-hydroxybutyrate, 1,3-butanediol, 2-hydroxyisobutyrate, 2- hydroxyisobutyric acid, isobutylene, adipic acid, keto-adipic acid, 1,3-hexanediol, 3-methyl- 2-butanol, 2-buten-1-ol, isovalerate, isoamyl alcohol, or any combination thereof. Gas fermentation may be used to produce desirable products on site or off site. As a non-limiting example, in one embodiment, gas fermentation may be employed to convert methane directly from a gas or oil well into valuable products with possible carbon dioxide as a by-product. In such an embodiment, the gas fermentation reactor may be located at the well site, or may be remote to the well site. The carbon dioxide itself may be converted into products by gas fermentation, or released to the atmosphere, or may be advantageously used as part of further processes at the well site, such as for enhanced oil recovery operations. In another example, in one embodiment, gasification of tires, pieces of tires, and or components of tires, optionally in combination with organic material, followed by gas fermentation may be employed to convert end of life tires, defective tires, and or tire scraps into valuable products. The gasification and gas fermentation process may be co-located with and integrated with chemical production processes used to generate chemicals and intermediates for use in the generation of new tires. Processing units in common with the gasification and gas fermentation process and the chemical production process may be integrated with each of the processes so that fewer units in total are needed. Capital equipment costs and operating costs may be minimized.
In yet another example, the gas fermentation system may be co-located with an energy production facility, such as a power plant, that generates carbon dioxide as an undesired by-product. The carbon dioxide may be provided to the gas fermentation process as feedstock/substrate along with hydrogen. The hydrogen may be from any source such as green hydrogen (from solar, wind or water), grey hydrogen (from natural gas or methane), blue hydrogen (from natural gas or methane with carbon capture), brown hydrogen (gasification), black hydrogen (from coal), and or turquoise hydrogen (from methane pyrolysis).The gas fermentation system is located at the source of the carbon-dioxide substrate eliminating need for transport of carbon dioxide. Additionally, end of life tires may be collected or transported to the site for gasification and production of additional feedstock or substrate to the gas fermentation process. The tire industry is in need of reducing carbon dioxide footprint, and in capturing and transforming the carbon dioxide produced in suppling the energy requirement to the tire manufacturing industry while at the same time recycling end of life tires into valuable chemicals that may be used to produce new tires, the tire industry may reduce its overall carbon emissions. Referring now to FIG.1, which depicts a process flow diagram of one embodiment of the disclosure. A source first generates an input gas stream, 110. The input gas stream may comprise greenhouse gasses such as CO and CO2. Sources are listed in detail above, examples of industrial gas, process gas, and syngas are provided. The input stream is fermented in a gas fermentation operation, 120. The gas fermentation operation may utilize a C1-fixing microorganism to ferment the input gas and generate a fermentation product. The fermentation product may be separated from the fermentation broth and collected, 130. Generation of the fermentation product or the fixing of carbon from a greenhouse gas into a chemical product such as, for example ethanol, accomplishes carbon capture and utilization. In an exemplary embodiment where the C1-fixing microorganism is of the genus Clostridium such as Clostridium autoethanogenum, CO is preferentially converted by the fermentation, thereby leaving unconverted CO2 as a tail gas from the fermentation operation. As CO has been consumed by the fermentation, the tail gas is a concentrated CO2 stream containing, for example, from about 60 vol-%, on a dry basis, CO2 to about 90 vol-%, on a dry basis, CO2. The concentrated CO2 tail gas may be purified to meet sequestration specifications, 140. Purification or CO2 concentration techniques may involve known techniques such as amine gas treating, pressure swing adsorption, membrane separation, solvent or sorbents, enzyme-based such as carbonic anhydrase, calcium looping, chemical looping, hot potassium carbonate, and cryogenic capture. In one embodiment the purification
uses the technique of cryogenic separation. In one embodiment the purification uses the technique of cryogenic separation which incorporates liquefaction. Cryogenic liquefaction is particularly suited to concentrated CO2 streams. As an added benefit, due to the liquefaction, the purified CO2 is readily transported for storage, for example, sequestration 150. FIG.2 is a process flow scheme of one embodiment of the disclosure. Input gas source 210 produces input gas stream 202. Input gas sources are listed in detail above, and examples of industrial gas, process gas, and syngas are provided. Input gas stream 202 generated by input gas source 210 may comprise greenhouse gasses such as CO and CO2. Input gas stream 202 is passed to gas fermentation process 220 comprising a fermentor having a C1-fixing microorganism, such as for example, clostridium autoethanogenum. Multiple gas fermentation processes 220 can be employed depending upon the volume of input gas. Gas fermentation process 220 generates gas fermentation product stream 204 which can be collected or potentially catalytically converted by any suitable catalytic conversion process (not shown). Additionally or alternatively, the products of gas fermentation can be catalytically converted, for example, by catalytically upgrading, into molecules, or one or more second products, wherein the one or more second products are integrated into existing or newly built infrastructure or feedstock and product transportation networks. Thus, in some embodiments, molecules produced via the catalysis of the products of gas fermentation processes may also be considered desirable products or further products of fermentation. For example, in a gas fermentation system that produces ethanol, that ethanol can be reacted into a range of molecules, such as described below. The CO of input gas 202 may be preferentially converted by fermentation in the fermentor, thereby leaving residual or unconsumed CO2 to be removed as tail gas 206 from the fermentor. Tail gas 206 is a concentrated CO2 tail gas. By way of example, tail gas 206 is a concentrated CO2 stream containing, for example, from about 60 vol-%, on a dry basis, CO2 to about 90 vol-%, on a dry basis, CO2. Tail gas 206 is passed to purification process 230. An exemplary purification process is a cryogenic separation process, a more specific example is cryogenic liquefaction. Purification process 230 generates purified CO2 stream 208 containing 90 vol-%, on a dry basis, CO2 or more. In another embodiment purified CO2 stream 208 contains 95 vol-%, on a dry basis, CO2 or more. In another embodiment purified CO2 stream 208 contains 98 vol-%, on a dry basis, CO2 or more. In another embodiment purified CO2 stream 208 contains 99 vol-%, on a dry basis, CO2 or more. In another embodiment purified CO2 stream 208 contains 99.9 vol-%, on a dry basis, CO2 or more.
While other purification techniques such as amine gas treating, pressure swing adsorption, membrane separation calcium looping, chemical looping, may be employed, cryogenic separation provides the added benefit of liquefaction so purified CO2 stream 208 is readily transported to sequestration operation 240. Ethanol and Derivatives In one embodiment, ethanol or ethyl alcohol produced according to the method of the disclosure may be used in numerous product applications, including antiseptic hand rubs (WO 2014/100851), therapeutic treatments for methylene glycol and methanol poisoning (WO 2006/088491), as a pharmaceutical solvent for applications such as pain medication (WO 2011/034887) and oral hygiene products (U.S. Patent No.6,811,769), as well as an antimicrobial preservative (U.S. Patent Application No.2013/0230609), engine fuel (US Patent No.1,128,549), rocket fuel (U.S. Patent No.3,020,708), plastics, fuel cells (U.S. Patent No.2,405,986), home fireplace fuels (U.S. Patent No.4,692,168), as an industrial chemical precursor (U.S. Patent No.3,102,875), cannabis solvent (WO 2015/073854), as a winterization extraction solvent (WO 2017/161387), as a paint masking product (WO 1992/008555), as a paint or tincture (U.S. Patent No.1,408,091), purification and extraction of DNA and RNA (WO 1997/010331), and as a cooling bath for various chemical reactions (U.S. Patent No.2,099,090). In addition to the foregoing, the ethanol generated by the disclosed method may be used in any other application for which ethanol might otherwise be applicable. A further embodiment comprises converting the ethanol generated by the method into ethylene. This can be accomplished by way of an acid catalyzed dehydration of ethanol to give ethylene according to the following formula: CH3CH2OH → CH2=CH2 + H2O The ethylene generated in this way may be used for a variety of applications on its own or can be used as a raw material for more refined chemical products. Specifically, ethylene alone may be used as an anesthetic, as part of a mixture with nitrogen to control ripening of fruit, as a fertilizer, as an element in the production of safety glass, as part of an oxy-fuel gas in metal cutting, welding and high velocity thermal spraying, and as a refrigerant. As a raw material, ethylene can used in the manufacture of polymers such as polyethylene (PE), polyethylene terephthalate (PET) and polyvinyl chloride (PVC) as well as fibres and other organic chemicals. These products are used in a wide variety of industrial
and consumer markets such as the packaging, transportation, electrical/electronic, textile and construction industries as well as consumer chemicals, coatings and adhesives. Ethylene can be chlorinated to ethylene dichloride (EDC) and can then be cracked to make vinyl chloride monomer (VCM). Nearly all VCM is used to make polyvinyl chloride which has its main applications in the construction industry. Other ethylene derivatives include alpha olefins which are used in Linear low-density polyethylene (LLDPE) production, detergent alcohols and plasticizer alcohols; vinyl acetate monomer (VAM) which is used in adhesives, paints, paper coatings and barrier resins; and industrial ethanol which is used as a solvent or in the manufacture of chemical intermediates such as ethyl acetate and ethyl acrylate. Ethylene may further be used as a monomer base for the production of various polyethylene oligomers by way of coordination polymerization using metal chloride or metal oxide catalysts. The most common catalysts consist of titanium (III) chloride, the so-called Ziegler–Natta catalysts. Another common catalyst is the Phillips catalyst, prepared by depositing chromium (VI) oxide on silica. Polyethylene oligomers so produced may be classified according to its density and branching. Further, mechanical properties depend significantly on variables such as the extent and type of branching, the crystal structure, and the molecular weight. There are several types of polyethylene which may be generated from ethylene, including, but not limited to: Ultra-high-molecular-weight polyethylene (UHMWPE); Ultra-low-molecular-weight polyethylene (ULMWPE or PE-WAX); High-molecular-weight polyethylene (HMWPE); High-density polyethylene (HDPE); High-density cross-linked polyethylene (HDXLPE); Cross-linked polyethylene (PEX or XLPE); Medium-density polyethylene (MDPE); Linear low-density polyethylene (LLDPE); Low-density polyethylene (LDPE); Very-low-density polyethylene (VLDPE); and Chlorinated polyethylene (CPE). Low density polyethylene (LDPE) and linear low-density polyethylene (LLDPE) mainly go into film applications such as food and non-food packaging, shrink and stretch film, and non-packaging uses. High density polyethylene (HDPE) is used primarily in blow molding and injection molding applications such as containers, drums, household goods, caps
and pallets. HDPE can also be extruded into pipes for water, gas and irrigation, and film for refuse sacks, carrier bags and industrial lining. According to one embodiment, the ethylene formed from the ethanol described above may be converted to ethylene oxide via direct oxidation according to the following formula: C2H4 + O2 → C2H4O The ethylene oxide produced thereby is a key chemical intermediate in a number of commercially important processes including the manufacture of monoethylene glycol. Other EO derivatives include ethoxylates (for use in shampoo, kitchen cleaners, etc.), glycol ethers (solvents, fuels, etc.) and ethanolamines (surfactants, personal care products, etc.). Monoethylene Glycol and Derivatives According to one embodiment of the disclosure, the ethylene oxide produced as described above may be used to produce commercial quantities of monoethylene glycol by way of the formula: (CH2CH2)O + H2O → HOCH2CH2OH According to another embodiment, the claimed microorganism can be modified in order to directly produce monoethylene glycol. As described in WO 2019/126400, the disclosure of which is incorporated by reference herein, the microorganism further comprises one or more of an enzymes capable of converting acetyl-CoA to pyruvate; an enzyme capable of converting pyruvate to oxaloacetate; an enzyme capable of converting pyruvate to malate; an enzyme capable of converting pyruvate to phosphoenolpyruvate; an enzyme capable of converting oxaloacetate to citryl-CoA; an enzyme capable of converting citryl-CoA to citrate; an enzyme capable of converting citrate to aconitate and aconitate to iso-citrate; an enzyme capable of converting phosphoenolpyruvate to oxaloacetate; an enzyme capable of converting phosphoenolpyruvate to 2-phospho-D-glycerate; an enzyme capable of converting 2- phospho-D-glycerate to 3-phospho-D-glycerate; an enzyme capable of converting 3-phospho- D-glycerate to 3-phosphonooxypyruvate; an enzyme capable of converting 3- phosphonooxypyruvate to 3-phospho-L-serine; an enzyme capable of converting 3-phospho- L-serine to serine; an enzyme capable of converting serine to glycine; an enzyme capable of converting 5,10-methylenetetrahydrofolate to glycine; an enzyme capable of converting serine to hydroxypyruvate; an enzyme capable of converting D-glycerate to hydroxypyruvate; an enzyme capable of converting malate to glyoxylate; an enzyme capable of converting glyoxylate to glycolate; an enzyme capable of converting hydroxypyruvate to glycolaldehyde; and/or an enzyme capable of converting glycolaldehyde to ethylene glycol.
Monoethylene glycol produced according to either of the described methods may be used as a component of a variety of products including as a raw material to make polyester fibers for textile applications, including nonwovens, cover stock for diapers, building materials, construction materials, road-building fabrics, filters, fiberfill, felts, transportation upholstery, paper and tape reinforcement, tents, rope and cordage, sails, fish netting, seatbelts, laundry bags, synthetic artery replacements, carpets, rugs, apparel, sheets and pillowcases, towels, curtains, draperies, bed ticking, and blankets. MEG may be used on its own as a liquid coolant, antifreeze, preservative, dehydrating agent, drilling fluid or any combination thereof. The MEG produced may also be used to produce secondary products such as polyester resins for use in insulation materials, polyester film, de-icing fluids, heat transfer fluids, automotive antifreeze and other liquid coolants, preservatives, dehydrating agents, drilling fluids, water-based adhesives, latex paints and asphalt emulsions, electrolytic capacitors, paper, and synthetic leather. Importantly, the monoethylene glycol produced may be converted to the polyester resin polyethylene terephthalate (“PET”) according to one of two major processes. The first process comprises transesterification of the monoethylene glycol utilizing dimethyl terephthalate, according to the following two-step process: First step C6H4(CO2CH3)2 + 2 HOCH2CH2OH → C6H4(CO2CH2CH2OH)2 + 2 CH3OH Second step n C6H4(CO2CH2CH2OH)2 → [(CO)C6H4(CO2CH2CH2O)]n + n HOCH2CH2OH Alternatively, the monoethylene glycol can be the subject of an esterification reaction utilizing terephthalic acid according to the following reaction: n C6H4(CO2H)2 + n HOCH2CH2OH → [(CO)C6H4(CO2CH2CH2O)]n + 2n H2O The polyethylene terephthalate produced according to either the transesterification or esterification of monoethylene glycol has significant applicability to numerous packaging applications such as jars and, in particular, in the production of bottles, including plastic bottles. It can also be used in the production of high-strength textile fibers such as Dacron, as part of durable-press blends with other fibers such as rayon, wool, and cotton, for fiber fillings used in insulated clothing, furniture, and pillows, in artificial silk, as carpet fiber, automobile tire yarns, conveyor belts and drive belts, reinforcement for fire and garden hoses, seat belts, nonwoven fabrics for stabilizing drainage ditches, culverts, and railroad beds, and nonwovens for use as diaper topsheets, and disposable medical garments.
At a higher molecular weight, PET can be made into a high-strength plastic that can be shaped by all the common methods employed with other thermoplastics. Magnetic recording tape and photographic film are produced by extrusion of PET film. Molten PET can be blow-molded into transparent containers of high strength and rigidity that are also virtually impermeable to gas and liquid. In this form, PET has become widely used in bottles, especially plastic bottles, and in jars. Isopropanol and Derivatives In an additional embodiment, isopropanol or isopropyl alcohol (IPA) produced according to the method may be used in numerous product applications, including either in isolation or as a feedstock for the production for more complex products. Isopropanol may also be used in solvents for cosmetics and personal care products, de-icers, paints and resins, food, inks, adhesives, and pharmaceuticals, including products such as medicinal tablets as well as disinfectants, sterilizers, and skin creams. The IPA produced may be used in the extraction and purification of natural products such as vegetable and animal oil and fats. Other applications include its use as a cleaning and drying agent in the manufacture of electronic parts and metals, and as an aerosol solvent in medical and veterinary products. It can also be used as a coolant in beer manufacture, a coupling agent, a polymerization modifier, a de-icing agent and a preservative. Alternatively, the IPA produced according to the method of the disclosure may be used to manufacture additional useful compounds, including plastics, derivative ketones such as methyl isobutyl ketone (MIBK), isopropylamines and isopropyl esters. Still further, the IPA may be converted to propylene according to the following formula: CH3CH2CH2OH → CH3-CH=CH2 The propylene produced may be used as a monomer base for the production of various polypropylene oligomers by way of chain-growth polymerization via either gas-phase or bulk reactor systems. The most common catalysts consist of titanium (III) chloride, the so- called Ziegler–Natta catalysts and metallocene catalysts. Polypropylene oligomers so produced may be classified according to tacticity and can be formed into numerous products by either extrusion or molding of polypropylene pellets, including piping products, heat-resistant articles such as kettles and food containers, disposable bottles (including plastic bottles), clear bags, flooring such as rugs and mats, ropes, adhesive stickers, as well as foam polypropylene which can be used in building materials. Polypropylene may also be used for hydrophilic clothing and medical dressings.
Commodity Chemicals and Articles According to one embodiment, the gas fermentation product is a commodity chemical. In another embodiment, the gas fermentation product is a commodity chemical, where the commodity chemical is catalytically converted, for example, by catalytically upgrading, into molecules, or one or more second products, wherein the one or more second products are integrated into existing or newly built infrastructure or feedstock and product transportation networks. In one embodiment, wherein the commodity chemical is selected from ethanol, isopropanol, monoethylene glycol, sulfuric acid, propylene, sodium hydroxide, sodium carbonate, ammonia, benzene, acetic acid, ethylene, ethylene oxide, formaldehyde, methanol, or any combination thereof. In one embodiment, the commodity chemical is aluminum sulfate, ammonia, ammonium nitrate, ammonium sulfate, carbon black, chlorine, diammonium phosphate, monoammonium phosphate, hydrochloric acid, hydrogen fluoride, hydrogen peroxide, nitric acid, oxygen, phosphoric acid, sodium silicate, titanium dioxide, or any combination thereof. In another embodiment, the commodity chemical is acetic acid, acetone, acrylic acid, acrylonitrile, adipic acid, benzene, butadiene, butanol, caprolactam, cumene, cyclohexane, dioctyl phthalate, ethylene glycol, methanol, octanol, phenol, phthalic anhydride, polypropylene, polystyrene, polyvinyl chloride, polypropylene glycol, propylene oxide, styrene, terephthalic acid, toluene, toluene diisocyanate, urea, vinyl chloride, xylenes, or any combination thereof. Secondary Products The disclosed systems and methods are also suitable for providing one or more secondary products that are independent of the gas fermentation product (e.g., ethylene, ethanol, acetate, etc.). For example, in certain embodiments, microbial biomass itself may be considered a secondary product. In such embodiments, biomass from a bioreactor, such as dead microorganisms, may be used as a carbon source for further fermentation by gasifying the biomass. Additionally or alternatively, microbial proteins or other biomass may be recovered from a bioreactor and sold/used separately from the primary product (e.g., ethylene, ethanol, acetate, 1-butanol, etc.) as a supplement, such as a nutritional supplement and/or an animal feed. Known methods for using such biomass as a nutritional supplement or animal feed are disclosed in U.S. Patent No.10,856,560, which is herein incorporated by reference.
Additionally or alternatively, biochar may be a secondary product. In embodiments that involve or comprise gasification of solid or liquid carbonaceous materials to produce a feedstock, biochar can be incidentally produced. Biochar is carbon rich and highly structured, and therefore it can be useful as, for example, fertilizer, among other applications. Additionally or alternatively, unutilized carbon dioxide, which may be in the form of an off-gas from the gas fermentation, may be a secondary product. Such unutilized carbon dioxide will be in a stoichiometrically higher proportion in the off-gas compared to the feedstock, and this relative purity can make the carbon dioxide useful. For example, the unutilized carbon can be sequestered by an operator for the purposes of obtaining carbon credits, or it may be combined with hydrogen gas (H2), such as “green hydrogen” resulting from electrolysis, and recycled back into the gas fermenter or bioreactor as feedstock. FIG.3 shows an enlarged gas fermentation process including an optional gasification zone 302, a gas fermentation zone 328, a product recovery zone 344, and an optional wastewater treatment zone 334. Optional gasification process 302 receives a gasification feed 300, which may be any suitable material capable of being gasified to produce syngas stream 302. In various instances, gasification feed 300 may be comprised at least partially of sorted and/or unsorted industrial or municipal solid waste. In other instances, the gasification feed 300 is comprised at least partially of forest and/or agricultural waste. In particular embodiments, the gasification feed 300 is comprised of any combination of two or more of the following: sorted municipal or industrial solid waste, unsorted municipal or industrial solid waste, forest waste, agricultural waste, or other solid or liquid waste from the refining or chemical process integrated with the enlarged gas fermentation process. In another embodiment, gasification feed 300 comprises tire, pieces of tires, and or components of tires. In another embodiment gasification feed 300 comprises tires, pieces of tires, and or components of tires, in combination with an organic-based feed material. Integration internal to the enlarged fermentation process would also provide for at least one effluent from the fermentation process 328, at least one effluent from the product recovery process 344, and or at least one effluent from the wastewater treatment process 334 being used as gasification feed. Gasification zone 302 is to produce syngas as substrate for gas fermentation zone 328. If a gas feedstock is already present for use as substrate for gas fermentation zone, such as from the refining or chemical process integrated with the enlarged gas fermentation process, gasification zone 302 may not be required. In some embodiments, syngas 318 produced by the gasification process 302, or gas obtained from another source contains one or more
constituent that needs to be removed and/or converted. Typical constituents found in the syngas stream 318 that may need to be removed and/or converted include, but are not limited to, sulfur compounds, aromatic compounds, alkynes, alkenes, alkanes, olefins, nitrogen compounds, phosphorous-containing compounds, particulate matter, solids, oxygen, halogenated compounds, silicon-containing compounds, carbonyls, metals, alcohols, esters, ketones, peroxides, aldehydes, ethers, and tars. These constituents may be removed by one or more removal zones 322 positioned between gasification zone 302 and gas fermentation zone 328. Removal zone 322 may comprise one or more of the following modules: hydrolysis module, acid gas removal module, deoxygenation module, catalytic hydrogenation module, particulate removal module, chloride removal module, tar removal module, and hydrogen cyanide polishing module. Two or more modules may be combined into a single module performing the same functions. For instance, the hydrolysis module, acid gas removal module, deoxygenation module, and catalytic hydrogenation module may be combined into a single module. When incorporating removal process 322, at least a portion of the syngas 318 from gasification zone 302 is passed to removal process 322 to remove and/or convert at least a portion of at least one constituent found in syngas stream 318. Removal zone 322 may operate to bring the constituent(s) within allowable levels to produce a treated stream 324 suitable for fermentation in gas fermentation zone 328. Gas fermentation process 328 employs at least one C1-fixing microorganism in a liquid nutrient media to ferment a feedstock, gas, or syngas stream 318 and produce one or more product. The C1-fixing microorganism in the gas fermentation process 328 may be a carboxydotrophic bacterium. In particular embodiments, the carboxydotrophic bacterium is selected from the group comprising Moorella, Clostridium, Ruminococcus, Acetobacterium, Eubacterium, Butyribacterium, Oxobacter, Methanosarcina, Methanosarcina, Cupriavidus and Desulfotomaculum. In various embodiments, the carboxydotrophic bacterium is Clostridium. In various embodiments, the carboxydotrophic bacterium is Clostridium autoethanogenum. The one or more products produced in gas fermentation zone 328 are removed and/or separated from the fermentation broth in product recovery zone 344. Product recovery zone 344 separates and removes one or more product(s) 332 and produces at least one effluent 342, 330, 312, which comprise reduced amounts of at least one product. Product depleted effluent 342 may be passed to wastewater treatment zone 334 to produce at least one wastewater treatment zone effluent 336, which may be recycled to the gasification process 302 in line 308 and/or the fermentation process 328 in line 326.
In at least one embodiment, tail-gas effluent 314 from fermentation zone 328 is tail- gas containing gas generated by the fermentation, inert gas, and or unmetabolized substrate. At least a portion 304 of tail gas 314 may be optionally passed to the gasification zone 302 to be used as part of the gasification feed 300. At least a portion 316 of the tail gas 314 may be passed to quench the syngas stream 318. At least a portion of the tail gas may be passed to the refinery or chemical manufacture process integrated with the enlarged gas fermentation process (not shown). At least a portion of the tail gas 315 may be passed to a purification operation such as 230 of FIG.2 followed by sequestration. In at least one embodiment, the effluent from the fermentation zone 328 is fermentation broth 346. At least a portion of the fermentation broth 346 may be passed to product recovery zone 344. In at least one embodiment, product recovery zone 344 separates at least a portion of the microbial biomass from the fermentation broth. In various instances, at least a portion of the microbial biomass that is separated from the fermentation broth is recycled to the fermentation zone 328 via a conduit 330. In various instances, at least a portion 310 of microbial biomass-depleted water 312 that is separated from the fermentation broth 346 is recycled to the fermentation zone 328. In various instances, at least a portion 306 of the microbial biomass-depleted water 312 separated from the fermentation broth 346 is passed to optional gasification zone 302 for use as part of gasification feed 300. In certain instances, fermentation zone 328 produces fusel oil (not shown) which may also be recovered in product recovery zone 344 through any suitable means such as within the rectification column of a distillation system. In at least one embodiment, at least a portion of the fusel oil from the product recovery zone 344 is used as a heating source for one or more zones or elsewhere in the refinery or chemical process. In various instances, at least a portion of fermentation broth 346 containing microbial biomass from fermentation zone 328 may be passed to optional gasification zone 302, without being passed to product recovery zone 344 (not shown). In various instances, at least a portion of wastewater stream 340 may be passed to optional gasification zone 302 without being passed to wastewater treatment zone 334 (not shown). In instances where the fermentation broth is processed by the product recovery process 344, at least a portion of the microbial biomass depleted water, produced through the removal of microbial biomass from the fermentation broth, may be returned to fermentation zone 328 via a conduits 312 and 310 and/or sent via a conduits 312 and 306 to gasification zone 302. At least a portion 306 of the microbial biomass depleted water 312 may be passed to gasification zone 302 to be used as part of gasification feed 300. At least a portion 310 of
the microbial biomass depleted water 312 may be passed to quench syngas stream 318. At least a portion of the effluent from product recovery zone 344 may be passed via a conduit 342 to wastewater treatment zone 334. The effluents from product recovery zone 344 may comprise reduced amounts of product and/or microbial biomass. Wastewater treatment zone 334 receives and treats effluent from one or more zones to produce clarified water. The clarified water may be passed or recycled via a conduit 336 to one or more zones. For example, at least a portion 326 of the clarified water 336 may be passed to the fermentation zone 328, at least a portion 308 of the clarified water 336 may be passed to gasification zone 302 to be used as part of the gasification feed 300 and at least a portion 320 of the clarified water 336 may be passed to quench syngas stream 318. In certain instances, the wastewater treatment process 334 generates biomass as part of the treatment process. At least a portion of this biomass may be passed via conduit 308 to the gasification zone 302 for use as part of gasification feed 300. Wastewater treatment zone 334, as a by- product of treating microbial biomass, may produce biogas. At least a portion of the biogas may be passed via conduit 308 to gasification zone 302 to be used as part of gasification feed 300 and or via a conduit 320 to quench syngas stream 318. Optional wastewater treatment effluent removal unit 338 is positioned downstream of wastewater treatment zone 334. At least a portion of biogas from wastewater treatment zone 334 is passed to removal unit 338 to remove and/or convert at least a portion of at least one constituent found in the biogas stream. Removal unit 338 operates to lower the concentration of constituents to within preterminal allowable levels and produce a treated stream 342, 326, 320, and/or 308 suitable to be used by the subsequent one or more zones 344, 328, 322, and/or 302, respectively. FIG.4 depicts a flow scheme of one embodiment of the disclosure. Input gas stream 400 generated by an input gas source may comprise greenhouse gases including CO and CO2. Input gas stream 400 is passed to gas fermentation process 410 comprising a fermentor having a C1-fixing microorganism, such as, for example, Clostridium autoethanogenum. Multiple gas fermentation processes 410 can be employed depending upon the volume of input gas. Gas fermentation process 410 generates raw tail gas stream 402 and/or fermentation product stream 403. Multiple fermentation products may be produced, and multiple fermentation product streams 403 may be employed (not shown). The CO of input gas stream 400 may be preferentially converted to products by fermentation in the fermentor, thereby leaving residual or unconsumed CO2 to be removed in raw tail gas stream 402 from the fermentor. Because CO has been depleted as compared to the input gas
stream because of being consumed in fermentation, raw tail gas stream 402 is concentrated, or enriched, in CO2. By way of example, tail gas stream 402 is a concentrated CO2 stream comprising, for example, from about 50 vol-%, on a dry basis, CO2 to about 90 vol-%, on a dry basis, CO2. Tail gas stream 402 is passed to tail gas scrubber 420 where impurities are removed thereby generating scrubbed tail gas stream 404. Scrubbed tail gas stream 404 is passed to tail gas purification process 430. An exemplary tail gas purification process is a cryogenic separation process, a more specific example is cryogenic liquefaction. Tail gas purification process 430 generates purified CO2 stream 406 comprising 90 vol-%, on a dry basis, CO2 or more. In another embodiment purified CO2 stream 406 comprises 95 vol-%, on a dry basis, CO2 or more. In another embodiment purified CO2 stream 406 comprises 98 vol- %, on a dry basis, CO2 or more. In another embodiment purified CO2 stream 406 comprises 99 vol-%, on a dry basis, CO2 or more. In another embodiment purified CO2 stream 406 comprises 99.9 vol-%, on a dry basis, CO2 or more. Tail gas purification process 430 also generates residual stream 411. Residual stream 411 comprises, for example, residual CO and residual H2 that were not consumed in the fermentation. Residual stream 411 may optionally be passed to gas treatment conversion unit 440 before being recycled back to fermentation process 410. Optional gas treatment conversion unit 440 may be a CO2 to CO conversion unit may be at least one unit selected from a reverse water gas shift unit, a thermo-catalytic conversion unit, a partial combustion unit, a reforming unit, or a plasma conversion unit. Purified CO2 stream 406 may optionally be passed to separation unit 450. Separation unit 450 separates purified CO2 stream into inert gas stream 412, hydrocarbon stream 408, and enriched CO2 stream 420. It is envisioned that alternatively or additionally, purified CO2 stream may be divided, instead of separated, and passed to different processing units. The divided streams would have the same composition as the purified CO2 stream. Hydrocarbon stream 408 may optionally be passed to regenerative thermal oxidizer 460 thereby generating combustion product emissions 414. Enriched CO2 stream 420 may be divided into first portion enriched CO2 stream 420a and second portion enriched CO2 stream 420b. First portion enriched CO2 stream 420a is passed to sequestration 470. Second portion enriched CO2 stream 420b may optionally be passed to CO2 to CO conversion system 480 before being passed to gas fermentation process 410. CO2 to CO conversion system 480 may be at least one unit selected from a reverse water gas shift unit, a thermo-catalytic conversion unit, a partial combustion unit, a reforming unit, or a plasma conversion unit.
In one embodiment, raw tail gas stream 402 may be treated to limit the amount of H2S in the tail gas before passing to sequestration 470. In some embodiments, the H2S is less than 10 ppm. In another embodiment, the H2S is less than 5 ppm. In one embodiment, the H2S is less than 1 ppm. In a particular embodiment, CO2 to CO conversion system 480 and or gas treatment conversion unit 440 is a reverse water gas shift unit. Reverse water gas shift (rWGS) technology is known and is used for producing carbon monoxide from carbon dioxide and hydrogen, with water as a side product. Temperature of the rWGS process is the main driver of the shift. Reverse water gas shift units may comprise a single stage reaction system or two or more reaction stages. The different stages may be conducted at different temperatures and may use different catalysts. In another embodiment, CO2 to CO conversion system 480 and or gas treatment conversion unit 440 involves thermo-catalytic conversion, which involves disrupting the stable atomic and molecular bonds of CO2 and other reactants over a catalyst by using thermal energy as the driving force of the reaction to produce CO. Since CO2 molecules are thermodynamically and chemically stable, if CO2 is used as a single reactant, large amounts of energy are required. Therefore, often other substances such as hydrogen are used as a co- reactant to make the thermodynamic process easier. Many catalysts are known for the process such as metals and metal oxides as well as nano-sized catalyst metal-organic frameworks. Various carbon materials have been employed as carriers for the catalysts. In another embodiment, CO2 to CO conversion system 480 and or gas treatment conversion unit 440 involves partial combustion where oxygen supplies at least a portion of the oxidant requirement for the partial oxidation and the reactants carbon dioxide and water are substantially converted to carbon monoxide and hydrogen. In still another embodiment, CO2 to CO conversion system 480 and or gas treatment conversion unit 440 involves plasma conversion which is the combination of plasma with catalysts, also called plasma-catalysis. Plasma is an ionized gas consisting of electrons, various types of ions, radicals, excited atoms, and molecules, along with neutral ground state molecules. The three most common plasma types for CO2 to CO conversion include, dielectric barrier discharges (DBDs), microwave (MW) plasmas, and gliding arc (GA) plasmas. Advantages of selecting plasma conversion for CO2 to CO conversion include (i) high process versatility, allowing different kinds of reactions to be carried out, such as pure CO2 splitting, as well as CO2 conversion in presence of a hydrogen source, such as CH4, H2 or H2O; (ii) low investment and operating costs; (iii) no requirement for rare earth metals;
(iv) convenient modular setting, as plasma reactors scale up linearly with the plant output; and (v) it can be very easily combined with various kinds of renewable electricity. The figures are described where CO2 to CO conversion system 480 and or gas treatment conversion unit 440 is selected to include at least one rWGS unit. The rWGS reaction is the reversible hydrogenation of CO2 to produce CO and H2O. Due to its chemical stability, CO2 it is a relatively unreactive molecule and therefore the reaction to convert it to more reactive CO is energy intensive. CO2 + H2 ↔ CO + H2O ΔH°298k = + 41 kJ mol−1 (at standard conditions) Since the rWGS reaction is endothermic, it is thermodynamically favored by higher temperatures. Typically, temperature of about 500° C is desirable to generate significant amount of CO. In embodiments employing higher temperatures, iron based catalysts are often considered as one of the most successful active metals for higher temperatures, due to its thermal stability and high oxygen mobility. In embodiments employing lower temperatures, copper is often regarded to be successful due to its enhanced adsorption of reaction intermediates. In some other embodiments, rWGS catalysts selections include Fe/Al2O3, Fe- Cu/Al2O3, Fe-Cs/Al2O3, Fe-Cu-Cs/Al2O3 or combinations thereof. Another option is the rWGS catalyst as described in WO2022/225938, which is a porous support and an alkali carbonate dispersed on the porous support. The alkali carbonate may be in a form of M2CO3, where M+ = Li+, Na+, K+, Rb+, and/or Cs+ and the porous support may comprise at least one of titania (T1O2), alumina (AI2O3), zirconia (ZrCL), or a carbon material. Second portion enriched CO2 stream 420b may optionally be recycled back to fermentation process 410. According to an embodiment, a gas fermentation process is integrated at an oil refining site, and biologically produces a gas fermentation product. The gas fermentation process would be co-located within the operating site of the oil refiner. Underutilized carbon streams (e.g., waste carbon streams) from various points within the operating site could be redirected to feed the gas fermentation process to produce various gas fermentation products. Similarly, a product stream from the gas fermentation process may be integrated at an oil refining or chemical manufacturing site. According to the embodiment, integration of gas fermentation units with existing facilities and infrastructure provides multitude of advantageous synergies for operators. These synergies include using the gas from one portion of a chemical manufacturing unit as the feed for the gas fermentation unit. The gas fermentation unit being adapted to convert the gas feed into a product that the same unit is overall designed to produce. The gas
fermentation unit’s output can then be directed to a portion of the unit that can recover the product from the gas fermentation unit’s output. Thereby increasing the overall production yield and efficiency of the complex by converting previously designated waste or underutilized carbon into marketable product. In another embodiment, a gas fermentation unit that is integrated within a chemical manufacturing complex or oil refining complex can have its output directly coupled to a separation, purification, or extraction unit. The separation, purification, or extraction unit being adapted to receive the output of the gas fermentation unit and separate or purify the output mixture. The recovered product can then be routed to a product storage tank located within the chemical manufacturing or oil-refining complex to be sold. In other embodiments, the recovered product can be mixed with other products as an additive to increase desirable properties of the base product or to decrease the effect of undesirable properties of the base product. In other embodiments, the recovered product can be stored separately and sold as a standalone product. In another embodiment, a gas fermentation unit that is integrated within a chemical manufacturing complex or oil refining complex can have its output directly utilized by a process of the chemical manufacturing operation or refinery. The product of the gas fermentation process, for example, may be a reactant needed for an existing operation, it may be a solvent needed for an existing operation, it may be an extractant for an existing operation, and the like. The existing process of the chemical manufacturing operation or the refinery being adapted to receive the output of the gas fermentation unit and employ the product for a needed function. The resulting overall product may have a greater portion attributable to sustainable sources as compared to the same product without the integration of gas fermentation. According to another embodiment, gas fermentation unit’s integrated within chemical manufacturing complexes can be adapted to convert gases as described above into fuel for various operationally critical components such as furnaces, boilers, co-generation units, or power generation units. The converted gases can then be routed from the gas fermentation unit to the feed lines for the aforementioned components to supplement or replace the fuel feed that would otherwise be derived from fossil carbon sources such as natural gas. This synergy allows the operator to lower their overall spend on external fuel sources to continue operations. Additionally, this synergy allows operators to be more energy independent and less dependent on external fuel supply fluctuations caused by market activity or natural disasters such as hurricanes.
In other embodiments, the gas fermentation unit is adapted to output to an on-site storage tank. The on-site storage tank can then accept the gas fermentation unit’s output and store the output until the price of the product contained in the gas fermentation unit’s output mixture is sufficiently high such that it becomes desirable for the production operator to sell the product. In yet another embodiment, the storage tank or the gas fermentation unit output can each have a metering flow meter installed therein to determine the amount of product that is exiting the output of the gas fermentation unit or the product storage tank. Metering can be done with any suitable metering device; non-limiting examples include a mass flow meter and a volumetric flow meter. In yet another embodiment, multiple gas fermentation units can be integrated at a single chemical manufacturing or oil-refining complex wherein each gas fermentation unit is configured to accept the same or different types of gas sources. This can be done such that each gas fermentation unit can be individually adapted to output a different product in its respective output mixture. Varying the input streams to each gas fermentation unit can be done to increase the feed to gas fermentation units adapted to produce products that are contemporaneously more profitable than others. Likewise, the feed to contemporaneously less profitable products can be throttled down or halted completely. The various outputs from the various gas fermentation units can be configured such to be routed to individual storage tanks for short, medium, or long term storage or routed directly into a feed source for other sections of the complex. In another embodiment, the gas fermentation unit can be configured to produce fuels that can be utilized on-site by the chemical manufacturing or oil-refining complex. Such synergy allows for the complex to lower the overall operating costs by decreasing the spend related to such fuels and fuel sources, thereby increasing the overall profitability of the complex. In yet another embodiment, the gas fermentation unit can be fed from pressure relief safety valves (“PRSV”). A PRSV is typically installed on a pressure containing vessel and is adapted to open at a set pressure value to protect the vessel it is connected to. Typically, the streams contained within the pressure vessel are carbon rich and are routed to a safe relief point, either a flare source or the atmosphere. Operators can further increase their site productivity and efficiency by harvesting these otherwise wasted streams of carbon rich material (i.e., any gas stream that is either emitted directly, flared with no additional value capture or combusted for energy recovery purposes) by routing them to the integrated gas fermentation unit to be converted into marketable products. In other words, these otherwise
wasted streams can be used as a feedstock for the integrated gas fermentation, which can upgrade the C1 components of the underutilized carbon into desirable products or chemicals with two or more carbon-carbon bonds. In other embodiments, multiple gas fermentation units can be integrated within a single chemical manufacturing or oil-refining complex. The multiple gas fermentation units can be adapted to produce a similar or identical product from various different input streams. The multiple gas fermentation units can then have their respective outputs configured to output to a single storage tank. This synergy can allow the production operator to capture a maximum amount of underutilized gases or streams and convert it into a marketable product. A. Microorganisms and Fermentation The disclosed systems and methods integrate microbial fermentation into existing or newly built infrastructure of, for example, a gas (e.g., natural gas) transportation pipeline, oil well, or the like to convert various feedstocks, gas, or other by-products into useful products such as ethylene. As disclosed herein, the systems allow for feedstocks, gas, or other by- products to be directly provided to a bioreactor, and the bioreactor is directly connected to a system for facilitating transport of a desirable product of fermentation to an end point (e.g., a chemical plant or refinery). In particular, the disclosed systems and methods are applicable for producing useful products (e.g., ethylene, ethanol, acetate, etc.) from gaseous substrates, such as gases that may optionally contain H2, that are utilized as a carbon source by microbial cultures. Such microorganisms may include bacteria, archaea, algae, or fungi (e.g., yeast), and these classes of microorganism may be suitable for the disclosed systems and methods. In general, the selection of the microorganism(s) is not particularly limited so long as the microorganism is C1-fixing, carboxydotrophic, acetogenic, methanogenic, capable of Wood- Ljungdahl synthesis, a hydrogen oxidizer, autotrophic, chemolithoautotrophic, or any combination thereof. Among the various suitable classes of microorganisms, bacteria are particularly well suited for integration in the disclosed systems and methods. When bacteria are utilized in the disclosed systems and methods, the bacteria may be aerobic or anaerobic, depending on the nature of the carbon source and other inputs being fed into the bioreactor or fermentation unit. Further, the bacteria utilized in the disclosed systems and methods can include one of more strains of carboxydotrophic bacteria. In particular embodiments, the carboxydotrophic bacterium can be selected from a genus including, but not limited to, Cupriavidus, Clostridium, Moorella, Carboxydothermus, Ruminococcus, Acetobacterium, Eubacterium, Butyribacterium, Oxobacter, Methanosarcina,
Methanosarcina, and Desulfotomaculum. In particular embodiments, the carboxydotrophic bacterium is Clostridium. In particular embodiments, the carboxydotrophic bacterium is Clostridium autoethanogenum. In particular embodiments, the carboxydotrophic bacterium is Cupriavidus. In other particular embodiments, the carboxydotrophic bacterium is Cupriavidus necator. A number of anaerobic bacteria are known to be capable of carrying out fermentation for the disclosed methods and system. Examples of such bacteria that are suitable for use in the disclosure include bacteria of the genus Clostridium, such as strains of Clostridium ljungdahlii (including those described in WO 00/68407, EP 117309, U.S. Pat. Nos. 5,173,429, 5,593,886, and 6,368,819, WO 98/00558 and WO 02/08438), Clostridium carboxydivorans (Liou et al., International Journal of Systematic and Evolutionary Microbiology 33: pp 2085-2091) and Clostridium autoethanogenum (Abrini et al., Archives of Microbiology 161: pp 345-351). Other suitable bacteria include those of the genus Moorella, including Moorella sp HUC22-1 (Sakai et al., (2004) Biotechnology Letters 26: pp 1607-1612), and those of the genus Carboxydothermus (Svetlichny, V. A., et al. (1991), Systematic and Applied Microbiology 14: 254-260). The disclosures of each of these publications are incorporated herein by reference. In addition, other carboxydotrophic anaerobic bacteria can be used in the disclosed systems and methods by a person of skill in the art. It will also be appreciated upon consideration of the instant disclosure that a mixed culture of two or more bacteria may be used in the disclosed systems and methods. All of the foregoing patents, patent applications, and non-patent literature are incorporated herein by reference in their entirety. One exemplary anaerobic bacteria that is suitable for use in the disclosed systems and methods is Clostridium. One exemplary anaerobic bacteria that is suitable for use in the disclosed systems and methods is Clostridium autoethanogenum. In some embodiments, the Clostridium autoethanogenum is a Clostridium autoethanogenum having the identifying characteristics of the strain deposited at the German Resource Centre for Biological Material (DSMZ) under the identifying deposit number 19630. In some embodiments, the Clostridium autoethanogenum is a Clostridium autoethanogenum having the identifying characteristics of DSMZ deposit number DSMZ 10061. In some embodiments, the Clostridium autoethanogenum is a Clostridium autoethanogenum having the identifying characteristics of DSMZ deposit number DSMZ 23693. In some embodiments, the anaerobic bacteria is Clostridium carboxidivorans having the identifying characteristics of deposit number DSM15243. In some embodiments, the
anaerobic bacteria is Clostridium drakei having the identifying characteristics of deposit number DSM12750. In some embodiments, the anaerobic bacteria is Clostridium ljungdahlii having the identifying characteristics of deposit number DSM13528. Other suitable Clostridium ljungdahlii strains may include those described in WO 00/68407, EP 117309, U.S. Pat. Nos.5,173,429, 5,593,886, and 6,368,819, WO 98/00558 and WO 02/08438, all of which are incorporated herein by reference. In some embodiments, the anaerobic bacteria is Clostridium scatologenes having the identifying characteristics of deposit number DSM757. In some embodiments, the anaerobic bacteria is Clostridium ragsdalei having the identifying characteristics of deposit number ATCC BAA-622. In some embodiments, the anaerobic bacteria is Acetobacterium woodii. In some embodiments, the anaerobic bacteria is from the genus Moorella, such as Moorella sp HUC22-1, (Sakai et al, (2004) Biotechnology Letters, 26: pp 1607-1612). Further examples of suitable anaerobic bacteria include, but are not limited to, Morella thermoacetica, Moorella thermoautotrophica, Ruminococcus productus, Acetobacterium woodii, Eubacterium limosum, Butyribacterium methylotrophicum, Oxobacter pfennigii, Methanosarcina barkeri, Methanosarcina acetivorans, Desulfotomaculum kuznetsovii (Simpa et. al. Critical Reviews in Biotechnology, 2006 Vol.26. Pp41-65). In addition, it should be understood that other C1-fixing, carboxydotrophic anaerobes may be suitable for the disclosed systems and methods. It will also be appreciated that a mixed culture of two or more bacteria may be utilized as well. A number of aerobic bacteria are known to be capable of carrying out fermentation for the disclosed methods and system. Examples of such bacteria that are suitable for use in the disclosure include bacteria of the genus Cupriavidus and Ralstonia. In some embodiments, the aerobic bacteria is Cupriavidus necator or Ralstonia eutropha. In some embodiments, the aerobic bacteria is Cupriavidus alkaliphilus. In some embodiments, the aerobic bacteria is Cupriavidus basilensis. In some embodiments, the aerobic bacteria is Cupriavidus campinensis. In some embodiments, the aerobic bacteria is Cupriavidus gilardii. In some embodiments, the aerobic bacteria is Cupriavidus laharis. In some embodiments, the aerobic bacteria is Cupriavidus metallidurans. In some embodiments, the aerobic bacteria is Cupriavidus nantongensis. In some embodiments, the aerobic bacteria is Cupriavidus numazuensis. In some embodiments, the aerobic bacteria is Cupriavidus oxalaticus. In some embodiments, the aerobic bacteria is Cupriavidus pampae. In some embodiments, the aerobic bacteria is Cupriavidus pauculus. In some embodiments, the aerobic bacteria is Cupriavidus pinatubonensis. In some embodiments, the aerobic bacteria is Cupriavidus plantarum. In
some embodiments, the aerobic bacteria is Cupriavidus respiraculi. In some embodiments, the aerobic bacteria is Cupriavidus taiwanensis. In some embodiments, the aerobic bacteria is Cupriavidus yeoncheonensis. The fermentation may be carried out in any suitable bioreactor. In some embodiments, the bioreactor may comprise a first, growth reactor in which the microorganisms (e.g., bacteria) are cultured, and a second, fermentation reactor, to which fermentation broth from the growth reactor is fed and in which most of the fermentation product (e.g. ethylene, ethanol, acetate, etc.) is produced. It will be appreciated that for growth of the bacteria and fermentation to occur, in addition to a carbon-containing substrate gas, a suitable liquid nutrient medium will need to be fed to the bioreactor. A nutrient medium will contain vitamins and minerals sufficient to permit growth of the micro-organism used. Aerobic and anaerobic media suitable for the fermentation using carbon-containing substrate gases as the sole carbon source are known in the art. For example, suitable media are described in U.S. Pat. Nos.5,173,429, 5,593,886, WO 02/08438, WO2007/115157, and WO2008/115080, referred to above and all of which are incorporated herein by reference. Further, the fermentation can be carried out under appropriate conditions for the desired fermentation to occur. Reaction conditions that should be considered include pressure, temperature, gas flow rate, liquid flow rate, media pH, media redox potential, agitation rate (if using a continuous stirred tank reactor), inoculum level, maximum gas substrate concentrations, and maximum product concentrations to avoid product inhibition. The optimum reaction conditions will depend partly on the particular micro-organism used. However, in general, it may be preferable that the fermentation be performed at a pressure higher than ambient pressure. Operating at increased pressures may allow for, for example, a significant increase in the rate of CO transfer from the gas phase to the liquid phase where it can be taken up by the micro-organism as a carbon source. This, in turn, means that the retention time (defined as the liquid volume in the bioreactor divided by the input gas flow rate) can be reduced when bioreactors are maintained at elevated pressure rather than atmospheric pressure. Also, since a given CO, or CO2 and H2 conversion rate is in part a function of the substrate retention time, and achieving a desired retention time in turn dictates the required volume of a bioreactor, the use of pressurized systems can greatly reduce the volume of the bioreactor required, and consequently the capital cost of the fermentation equipment.
Similarly, the temperature of the culture may vary as needed. For example, in some embodiments, the fermentation is carried out at a temperature of about 34°C to about 37° C. In some embodiments, the fermentation is carried out at a temperature of about 34°C. This temperature range may assist in supporting or increasing the efficiency of fermentation including, for example, maintaining or increasing the growth rate of bacteria, extending the period of growth of bacteria, maintaining or increasing production of the desired product (e.g., ethylene, ethanol, acetate, etc.), or maintaining or increasing CO or CO2 uptake or consumption. Culturing of the bacteria used in the disclosed systems and methods may be conducted using any number of processes known in the art for culturing and fermenting substrates. In some embodiments a culture of a bacterium can be maintained in an aqueous culture medium. For example, the aqueous culture medium may be a minimal anaerobic microbial growth medium. Suitable media are known in the art and described for example in U.S. Pat. Nos.5,173,429 and 5,593,886; WO 02/08438, and in Klasson et al (1992), Bioconversion of Synthesis Gas into Liquid or Gaseous Fuels, Enz. Microb. Technol.14:602- 608; Najafpour and Younesi (2006) Ethanol and acetate synthesis from waste gas using batch culture of Clostridium ljungdahlii. Enzyme and Microbial Technology, 38(1-2):223-228; and Lewis et al., (2002), Making the connection: conversion of biomass-generated producer gas to ethanol, Proceedings Bioenergy 2002 Conference, p.1-8. Further general processes for using gaseous substrates for fermentation that may be utilized for the disclosed systems and methods are described in the following disclosures: WO98/00558, M. Demler and D. Weuster-Botz (2010), Reaction Engineering Analysis of Hydrogenotrophic Production of Acetic Acid by Acetobacterium woodii, Biotechnology and Bioengineering; D. R. Martin, A. Misra and H. L. Drake (1985), Dissimilation of Carbon Monoxide to Acetic Acid by Glucose-Limited Cultures of Clostridium thermoaceticum, Applied and Environmental Microbiology, 49(6):1412-1417. Further processes generally described in the following articles using gaseous substrates for fermentation may also be utilized: (i) K. T. Klasson, et al. (1991), Bioreactors for synthesis gas fermentations resources, Conservation and Recycling, 5:145-165; (ii) K. T. Klasson, et al. (1991), Bioreactor design for synthesis gas fermentations, Fuel, 70:605-614; (iii) K. T. Klasson, et al. (1992), Bioconversion of synthesis gas into liquid or gaseous fuels, Enzyme and Microbial Technology, 14:602-608; (iv) J. L. Vega, et al. (1989), Study of Gaseous Substrate Fermentation: Carbon Monoxide Conversion to Acetate.2. Continuous Culture, Biotech. Bioeng., 34(6):785-793; (vi) J. L. Vega, et al. (1989), Study of gaseous substrate
fermentations: Carbon monoxide conversion to acetate.1. Batch culture, Biotech. Bioeng., 34(6):774-784; (vii) J. L. Vega, et al. (1990), Design of Bioreactors for Coal Synthesis Gas Fermentations, Resources, Conservation and Recycling, 3:149-160; all of which are incorporated herein by reference. As noted above, while bacteria may be preferred microorganisms for the disclosed systems and methods, other microorganisms like yeast may also be suitable. For example, yeast that may be used in the disclosed systems and methods include genus Cryptococcus, such as strains of Cryptococcus curvatus (also known as Candida curvatus) (see Chi et al. (2011), Oleaginous yeast Cryptococcus curvatus culture with dark fermentation hydrogen production effluent as feedstock for microbial lipid production, International Journal of Hydrogen Energy, 36:9542-9550, which is incorporated herein by reference). Other suitable yeasts include those of the genera Candida, Lipomyces, Rhodosporidium, Rhodotorula, Saccharomyces, and Yarrowia. In addition, it should be understood that the disclosed systems and methods may utilize a mixed culture of two or more yeasts. Additional fungi that may be suitable for the disclosed systems and methods include, but are not limited to, fungi selected from Blakeslea, Cryptococcus, Cunninghamella, Mortierella, Mucor, Phycomyces, Pythium, Thraustochytrium and Trichosporon. Culturing of yeast or other fungi may be conducted using any number of processes known in the art for culturing and fermenting substrates using yeasts or fungi. Typically, fermentation is carried out in any suitable bioreactor, such as a continuous stirred tank reactor (CTSR), a bubble column reactor (BCR) or a trickle bed reactor (TBR). Also, in some embodiments, the bioreactor may comprise a first, growth reactor in which the micro-organisms are cultured, and a second, fermentation reactor, to which fermentation broth from the growth reactor is fed and in which most of the fermentation product (e.g., ethylene, ethanol, acetate, etc.) is produced. The disclosed systems and method may comprise a primary bioreactor and a secondary bioreactor. The efficiency of the fermentation processes may be further improved by a further process of recycling a stream exiting the secondary bioreactor to at least one primary reactor. The stream exiting the secondary bioreactor may contain unused substrates, salts, and other nutrient components. By recycling the exit stream to a primary reactor, the cost of providing a continuous nutrient media to the primary reactor can be reduced. This recycling step has the further benefit of potentially reducing the water requirements of the continuous fermentation process. The stream exiting the bioreactor can optionally be treated before being passed back to a primary reactor. For example, because yeasts generally require
oxygen for growth, any media recycled from a secondary bioreactor to a primary bioreactor may need to have all oxygen substantially removed, as any oxygen present in the primary bioreactor will be harmful to an anaerobic culture in the primary bioreactor. Therefore, the broth stream exiting the secondary bioreactor may be passed through an oxygen scrubber to remove substantially all of the oxygen prior to being passed to the primary reactor. In some embodiments, biomass from a bioreactor (e.g., a primary bioreactor, secondary bioreactor, or any combination thereof) may be separated and processed to recover one or more products. In some embodiments, both anaerobic and aerobic gases can be used to feed separate cultures (e.g., an anaerobic culture and an aerobic culture) in two or more different bioreactors that are both integrated into the same process stream. As disclosed herein, the feedstock gas stream providing a carbon source for the disclosed cultures is not particularly limited, so long as it contains a carbon source. C1 feedstocks comprising methane, carbon monoxide, carbon dioxide, or any combination thereof may be preferred. Optionally, H2 may also be present in the feedstock. In some embodiments, the feedstock may comprise a gaseous substrates comprising substrate comprising carbon monoxide. In some embodiments, the feedstock may comprise a gaseous substrates comprising substrate comprising carbon dioxide. In some embodiments, the feedstock may comprise a gaseous substrates comprising substrate comprising both carbon monoxide and carbon dioxide. In some embodiments, the feedstock may comprise a gaseous substrates comprising carbon monoxide. In some embodiments, the feedstock may comprise a gaseous substrates comprising carbon dioxide. In some embodiments, the feedstock may comprise a gaseous substrates comprising carbon monoxide, carbon dioxide, or any combination thereof. Regardless of the source or precise content of the gas used as a feedstock, the feedstock may be metered (e.g., for carbon credit calculations or mass balancing of sustainable carbon with overall products) into a bioreactor in order to maintain control of the follow rate and amount of carbon provided to the culture. Similarly, the output of the bioreactor may be metered (e.g., for carbon credit calculations or mass balancing of sustainable carbon with overall products) or comprise a valved connection that can control the flow of the output and products (e.g., ethylene, ethanol, acetate, 1-butanol, etc.) produced via fermentation. Such a valve or metering mechanism can be useful for a variety of purposes including, but not limited to, slugging of product through a connected pipeline and measuring the amount of output from a given bioreactor such that if the product is mixed with other
gases or liquids the resulting mixture can later be mass balanced to determine the percentage of the product that was produced from the bioreactor. The microorganisms of the disclosure may be cultured with the gaseous substrate to produce one or more products. For instance, products of interest for the disclosed systems and methods can include, but are not limited to, alcohols, acids, diacids, alkanes, alkenes, alkynes, and the like. For instance, a product of interest for the disclosed systems and method can include alcohols such as ethanol. More specifically, the microorganisms of the present disclosure may produce or may be engineered to produce ethylene (WO 2012/026833, US 2013/0157322), ethanol (WO 2007/117157, US 7,972,824), acetate (WO 2007/117157, US 7,972,824), 1-butanol (WO 2008/115080, US 8,293,509, WO 2012/053905, US 9,359,611, and WO 2017/066498, US 9,738,875), butyrate (WO 2008/115080, US 8,293,509), 2,3- butanediol (WO 2009/151342, US 8,658,408 and WO 2016/094334, US 10,590,406), lactate (WO 2011/112103, US 8,900,836), butene (WO 2012/024522, US 2012/0045807), butadiene (WO 2012/024522, US 2012/0045807), methyl ethyl ketone (2-butanone) (WO 2012/024522, US 2012/0045807 and WO 2013/185123, US 9,890,384), acetone (WO 2012/115527, US 9,410,130), isopropanol (WO 2012/115527, US 9,410,130), lipids (WO 2013/036147, US 9,068,202), 3-hydroxypropionate (3-HP) (WO 2013/180581, US 9,994,878), terpenes, including isoprene (WO 2013/180584, US 10,913,958), fatty acids (WO 2013/191567, US 9,347,076), 2-butanol (WO 2013/185123, US 9,890,384), 1,2-propanediol (WO 2014/036152, US 9,284,564), 1propanol (WO 2017/066498, US 9,738,875), 1hexanol (WO 2017/066498, US 9,738,875), 1octanol (WO 2017/066498, US 9,738,875), chorismate- derived products (WO 2016/191625, US10,174,303), 3hydroxybutyrate (WO 2017/066498, US 9,738,875), 1,3butanediol (WO 2017/066498, US 9,738,875), 2-hydroxyisobutyrate or 2- hydroxyisobutyric acid (WO 2017/066498, US 9,738,875), isobutylene (WO 2017/066498, US 9,738,875), adipic acid (WO 2017/066498, US 9,738,875), 1,3hexanediol (WO 2017/066498, US 9,738,875), 3-methyl-2-butanol (WO 2017/066498, US 9,738,875), 2- buten-1-ol (WO 2017/066498, US 9,738,875), isovalerate (WO 2017/066498, US 9,738,875), isoamyl alcohol (WO 2017/066498, US 9,738,875), and monoethylene glycol (WO 2019/126400, US 11,555,209), or any combination thereof. For example, in some embodiments, the microorganisms may produce or may be engineered to produce one or more of the foregoing products (e.g., ethanol, acetate, 1-butanol, etc.) in addition to ethylene. Substrates and C1-Carbon Sources The substrate and/or C1-carbon source may be a gas obtained as a by-product of an industrial process or from another source, such as combustion engine exhaust fumes, biogas,
landfill gas, direct air capture, flaring, or from electrolysis. The substrate and/or C1-carbon source may be syngas generated by pyrolysis, torrefaction, or gasification. In other words, carbon in solid or liquid materials may be recycled by pyrolysis, torrefaction, or gasification to generate syngas which is used as the substrate and/or C1-carbon source in gas fermentation. The substrate and/or C1-carbon source may be natural gas. The substrate and/or C1-carbon source carbon dioxide from conventional and unconventional gas production. The substrate and/or C1-carbon source may be a gas comprising methane. Gas fermentation processes are flexible and any of these substrate and/or C1-carbon sources may be employed. In certain embodiments, the industrial process source of the substrate and/or C1 carbon source is selected from ferrous metal products manufacturing, such as a steel manufacturing, non-ferrous products manufacturing, petroleum refining, electric power production, carbon black production, paper and pulp manufacturing, ammonia production, methanol production, coke manufacturing, petrochemical production, carbohydrate fermentation, cement making, aerobic digestion, anaerobic digestion, catalytic processes, natural gas extraction, cellulosic fermentation, oil extraction, industrial processing of geological reservoirs, processing fossil resources such as natural gas coal and oil, landfill operations, or any combination thereof. Examples of specific processing steps within an industrial process include catalyst regeneration, fluid catalyst cracking, and catalyst regeneration. Air separation and direct air capture are other suitable industrial processes. Specific examples in steel and ferroalloy manufacturing include blast furnace gas, basic oxygen furnace gas, coke oven gas, direct reduction of iron furnace top-gas, and residual gas from smelting iron. Other general examples include flue gas from fired boilers and fired heaters, such as natural gas, oil, or coal fired boilers or heaters, and gas turbine exhaust. Another example is the flaring of compounds such as at oil and gas production sites. In these embodiments, the substrate and/or C1-carbon source may be captured from the industrial process before it is emitted into the atmosphere, using any known method. The substrate and/or C1-carbon source may be synthesis gas known as syngas, which may be obtained from reforming, partial oxidation, plasma, or gasification processes. Examples of gasification processes include gasification of coal, gasification of refinery residues, gasification of petroleum coke, gasification of biomass, gasification of lignocellulosic material, gasification of wood, gasification of black liquor, gasification of municipal solid waste, gasification of municipal liquid waste, gasification of industrial solid waste, gasification of industrial liquid waste, gasification of refuse derived fuel, gasification of sewerage, gasification of sewerage sludge, gasification of sludge from wastewater
treatment, gasification of landfill gas, gasification of biogas such as when biogas is added to enhance gasification of another material, and/or gasification of tires, pieces of tires, and or components of tires or tires, pieces of tires, and or components of tires in combination with an organic material. Examples of reforming processes include, steam methane reforming, steam naphtha reforming, reforming of natural gas, reforming of biogas, reforming of landfill gas, reforming of coke oven gas, reforming of pyrolysis off-gas, reforming of ethylene production off-gas, naphtha reforming, and dry methane reforming. Examples of partial oxidation processes include thermal and catalytic partial oxidation processes, catalytic partial oxidation of natural gas, partial oxidation of hydrocarbons, partial oxidation of biogas, partial oxidation of landfill gas, or partial oxidation of pyrolysis off-gas. Examples of municipal solid waste include tires, plastics, refuse derived fuel, and fibers such as in shoes, apparel, and textiles. Municipal solid waste may be simply landfill-type waste and may be sorted or unsorted. Examples of biomass may include lignocellulosic material and microbial biomass. Lignocellulosic material may include agriculture by-products, forest by-products, and some industrial by-products. Biomass may be created as by-products of “nature-based solutions” (NBS) and thus natured-based solutions may provide feedstock to the gas fermentation process. Nature-based solutions is articulated by the European Commission as solutions inspired and supported by nature, which are cost-effective, simultaneously provide environmental, social, and economic benefits and help build resilience. Such solutions bring more, and more diverse, nature and natural features and processes into cities, landscapes, and seascapes, through locally adapted, resource-efficient, and systemic interventions. Nature-based solutions must benefit biodiversity and support the delivery of a range of ecosystem services. Through the use of NBS healthy, resilient, and diverse ecosystems (whether natural, managed, or newly created) can provide solutions for the benefit of both societies and overall biodiversity. Examples of nature-based solutions include natural climate solutions (conservation, restoration and improved land management that increase carbon storage or avoid greenhouse gas emissions in landscapes and wetlands across the globe), halting biodiversity loss, socio-economic impact efforts, habitat restoration, and health and wellness efforts with respect to air and water. Biomass produced through nature-based solutions may be used as feedstock to gas fermentation processes. As shown, the optional step of a gasification process in the overall gas fermentation process greatly increases suitable feedstocks to the overall gas fermentation process as
compared to gaseous feedstocks alone. Further, incentives achieved may extend beyond items such as carbon credits, and into the natural based solutions space. The substrate and/or C1-carbon source may be a gas stream comprising methane. Such a methane containing gas may be obtained from: fossil methane emissions such as during fracking, wastewater treatment, livestock, agriculture, and municipal solid waste landfills. It is also envisioned that the methane may be burned to produce electricity or heat and the C1 by-products may be used as the substrate or carbon source. The substrate and/or C1-carbon source may be a gas stream comprising natural gas. B. Examples The following examples are given to illustrate the present disclosure. It should be understood that the disclosure is not to be limited to the specific conditions or details described in these examples. Example 1 – Carbon Capture, Utilization, and Storage Gas fermentation technology is operated similarly to traditional brewing. However, instead of using yeast to ferment sugars into alcohol, this gas fermentation process employed a specialized microorganism known as Clostridium autoethanogenum. This C1-fixing microorganism metabolizes carbon and energy from gases, producing alcohol as a result. This microorganism is an obligate anaerobe that lives only in oxygen-free environments. The process begins with an input gas comprising CO and CO2, and optionally hydrogen, being sourced directly from an industrial facility such as a steel or alloy producing facility. The input gas is compressed, for example to <10 barg, to provide enough pressure to run the gas through a pretreatment unit and the bioreactor. To safeguard the biocatalyst, both oxygen and harmful impurities are carefully removed from the input gas. The input gas is then introduced into a gas fermentation process comprising a bioreactor containing the biocatalyst, which is a C1-fixing microorganism. The gas fermentation yields a chemical product such as ethanol, and a single-cell protein. The chemical product and the single-cell protein are the CCU portion, which is continually removed from the fermentation broth and stored. The system is designed to ensure a steady and ongoing flow of gas into the bioreactor and the ethanol product being removed. In one embodiment, system design may be for 6,000 to 10,000 operating hours per year. During this process, un-metabolized CO2 from the input gas is combined with any CO2 that may be generated during fermentation thereby generating an CO2– enriched stream that is removed from the bioreactor. The CO2-enriched stream is also termed the tail gas stream. This is an example of the direct use of industrial off gas
without prior combustion. This is also an example of the direct use of tail gas streams without prior combustion. This example demonstrates economic opportunities according to available renewable energy sources, such as green hydrogen. Depending on the availability, for example, of green hydrogen the carbon may be directed to utilization or sequestration. When the cost of hydrogen is low then carbon can be directed to CCU. When the cost of hydrogen is high then carbon can be directed to CCS. Moving now to the CCS portion of the overall process, the CO2-enriched stream, or tail gas stream, may be purified and converted into a liquid by cryogenic technologies, such as cryogenic liquefaction, which cools the tail gas to very low temperatures. The resulting purified liquid CO2 stream may be stored temporarily on site until transported for sequestration. The input stream is the carbon-dense industrial off-gases from steel and alloy plants, comprising from about 7 to about 80 vol-%, on a dry basis, CO, from about 4 to about 63 vol- %, on a dry basis, H2, from about 2 to about 25 vol-%, on a dry basis, CO2, from about 6 to about 50 vol.- % N2, and less than 2,000 ppm O2 and other inert gases. The input gas, with a volume of from about 12,500 to about 18000 Nm3/h , will be channeled into the gas fermentation system from the steel and alloy facility through hundreds of meters of piping. The implemented methods and systems use biotechnology to capture carbon in industrial emissions, remove carbon monoxide (CO) by metabolism in a gas fermentation process, and leave a concentrated CO2 stream. The concentrated CO2 stream may be purified and optionally stored for transportation for ultimately sequestration or used for purposes such as beverage carbonation. At the same time, carbon is captured and utilized to provide a valuable product, such as low carbon intensity ethanol. Gas fermentation methods and systems will have reduced carbon emissions of ferroalloy off-gas this is passed to the process of this disclosure by 97% in five years, with, for example 27% of the carbon going into fermentation products (carbon capture and utilization) and 70% of the carbon to sequestration. The process of flexible, and the ratio of the amount of carbon directed to CCU versus the amount of carbon directed to CCS may be periodically changed based on numerous factors, such as the cost of green hydrogen, environmental credits, or the selling price of the chemical product. * * * * * The present technology is not to be limited in terms of the particular embodiments described in this application, which are intended as single illustrations of individual aspects of the present technology. Many modifications and variations of this present technology can be made without departing from its spirit and scope, as will be apparent to those skilled in the
art. Functionally equivalent methods and apparatuses within the scope of the present technology, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the present technology. All patents, patent applications, and published references cited herein are hereby incorporated by reference in their entirety. The claims are intended to cover the components and steps in any sequence which is effective to meet the objectives there intended unless the context specifically indicates the contrary. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. For example, any concentration range, percentage range, ratio range, integer range, size range, or thickness range is to be understood to include the value of any integer within the recited range and, when appropriate, fractions thereof (such as one tenth and one hundredth of an integer), unless otherwise indicated. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the disclosure and does not pose a limitation on the scope of the disclosure unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the disclosure. Preferred embodiments of this disclosure are described herein. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the disclosure to be practiced otherwise than as specifically described herein. Accordingly, this disclosure includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the disclosure unless otherwise indicated herein or otherwise clearly contradicted by context. All pressures disclosed herein are absolute unless otherwise stated. All temperatures are Celsius unless otherwise stated. EMBODIMENTS OF THE DISCLOSURE
Embodiment 1. A method of processing greenhouse gas carbon for both utilization and sequestration comprising: a) passing an input gas stream comprising at least greater than 50 vol-%, on a dry basis, CO and 10 vol-%, on a dry basis, CO2 to a fermentation process; b) fermenting under suitable conditions at least a portion of the CO using a C1- fixing microorganism for: 1) generating at least one fermentation product, and 2) generating a tail gas stream comprising at least 60 vol-%, on a dry basis, CO2, wherein the CO2 was present in the input gas stream; c) conditioning the tail gas stream by liquefaction to generate a liquified CO2 stream comprising at least 90 vol-%, on a dry basis, CO2; and d) sequestering the liquified CO2 stream. Embodiment 2. The method according to embodiment 1, wherein the input gas stream further comprises a gas selected from hydrogen, nitrogen, oxygen, other inert gases, or any combination thereof. Embodiment 3. The method according to any of embodiments 1 to 2, wherein the input gas stream is industrial off-gas. Embodiment 4. The method according to any of embodiments1 to 3, wherein the industrial off-gas is from a production process comprising steel or alloy. Embodiment 5. The method according to any of embodiments 1 to 4, wherein the C1- fixing microorganism is Clostridium autoethanogenum. Embodiment 6. The method according to any of embodiments 1 to 5, wherein the at least one fermentation product is selected from ethanol, single-cell protein, or any combination thereof. Embodiment 7. The method according to any of embodiments 1 to 6, wherein liquefaction is cryogenic liquefaction. Embodiment 8. A method for purifying CO2 comprising: a) passing an input gaseous stream comprising from about 50 vol-%, on a dry basis, to 75 vol-%, on a dry basis, CO and from about 10 vol-%, on a dry basis, to 45 vol-%, on a dry basis, CO2 to a gas fermentation process; b) removing the CO by generating at least one fermentation product; c) recovering the CO2 in a concentrated CO2 tail gas stream; d) purifying the CO2 tail gas stream by liquefaction to generate a purified CO2; and e) providing the purified CO2 stream for sequestration.
Embodiment 9. The method according to embodiment 8, wherein the input gas stream further comprises a gas selected from hydrogen, nitrogen, oxygen, other inert gases, or any combination thereof. Embodiment 10. The method according to any of embodiments 8 to 9, wherein the input gas stream is industrial off-gas. Embodiment 11. The method according to any of embodiments 8 to 10, wherein the industrial off-gas is from a production process comprising steel or alloy. Embodiment 12. The method according to any of embodiments 8 to 11, wherein the C1-fixing microorganism is Clostridium autoethanogenum. Embodiment, 13. The method according to any of embodiments 8 to 12, wherein the at least one fermentation product is selected from ethanol, single-cell protein, or any combination thereof. Embodiment 14. The method according to any of embodiments 8 to 13, wherein liquefaction is cryogenic liquefaction. Embodiment 15. A method of capturing carbon for combined utilization and sequestration comprising: a) passing a gas stream comprising CO and CO2 to a gas fermentation process under suitable conditions; b) fermenting at least a portion of the CO using a C1-fixing microorganism to:1) generate at least one fermentation product, and 2) generate an enriched residual CO2 stream comprising about 20-95 vol-%, on a dry basis, CO2; c) conditioning the enriched residual CO2 stream using cryogenic liquefaction to generate a purified CO2 stream comprising greater than 99 vol-%, on a dry basis, CO2; and d) providing the purified CO2 stream for sequestration. Embodiment 16. The method according to embodiment 15, wherein the gas stream comprising CO and CO2 comprises about 20 vol-%, on a dry basis, CO2. Embodiment 17. The method according to any of embodiments 15 to 16, wherein the enriched residual CO2 stream comprises about 86 vol-%, on a dry basis, CO2. Embodiment 18. The method according to any of embodiments 15 to 17, wherein the purified CO2 stream comprises about 99.9 vol-%, on a dry basis, CO2. Embodiment 19. The method according to any of embodiments 15 to 18, wherein the C1-fixing microorganism is Clostridium autoethanogenum. Embodiment 20. An apparatus for both carbon capture and utilization and carbon capture and sequestration comprising: a) a CO/CO2 gas source; b) a gas fermentation process unit in fluid communication with the gas source; c) a gas fermentation product conduit in fluid communication with the gas fermentation process unit; d) a tail gas conduit in fluid
communication with the gas fermentation process unit and a liquefaction unit; and e) a purified CO2 conduit in fluid communication with the liquefaction unit and a sequestration facility. Embodiment 21. A method of processing greenhouse gas carbon for both utilization and sequestration comprising: a) passing an input gas stream comprising at least greater than about 50 vol-%, on a dry basis, CO and at least lower than about 45 vol-%, on a dry basis, CO2 to a fermentation process; b) fermenting under suitable conditions at least a portion of the CO using a C1- fixing microorganism for: 1) generating at least one fermentation product, and 2) generating a tail gas stream comprising at least 60 vol-%, on a dry basis, CO2, wherein the CO2 was present in the input gas stream; c) conditioning the tail gas stream by liquefaction to generate a liquified CO2 stream comprising at least 90 vol-%, on a dry basis, CO2; and d) sequestering the liquified CO2 stream. Embodiment 22. A method for controlling the processing of greenhouse gas carbon for both utilization and sequestration comprising: a) identifying an amount of carbon for utilization; b) determining a composition of an input gas stream to obtain an identified amount of carbon directed to utilization, wherein the input gas stream comprises hydrogen, at least 50 vol-%, on a dry basis, CO, and at least 10 vol- %, on a dry basis, CO2; c) passing the input gas stream to a fermentation process; d) fermenting under suitable conditions at least a portion of the CO using a C1- fixing microorganism for: 1) generating at least one fermentation product, and 2) generating a tail gas stream comprising at least 60 vol-%, on a dry basis, CO2, wherein the CO2 was present in the input gas stream; e) conditioning the tail gas stream by liquefaction to generate a liquified CO2 stream comprising at least 90 vol-%, on a dry basis, CO2; and f) sequestering the liquified CO2 stream. Embodiment 23. The method according to embodiment 22, wherein the determining the composition of the input gas stream is a ratio of CO:CO2.
Embodiment 24. The method according to embodiment 22, wherein cost of H2 is high then the amount of carbon directed for utilization is low and the amount of carbon directed for sequestration is high. Embodiment 25. The method according to embodiment 22, wherein cost of H2 is low then the amount of carbon directed for utilization is high and the amount of carbon directed for sequestration is low.
Claims
CLAIMS: 1. A method of processing greenhouse gas carbon for both utilization and sequestration comprising: a) passing an input gas stream comprising at least greater than about 50 vol-%, on a dry basis, CO and at least greater than about 10 vol-%, on a dry basis, CO2 to a fermentation process; b) fermenting under suitable conditions at least a portion of the CO using a C1- fixing microorganism for: 1) generating at least one fermentation product, and 2) generating a tail gas stream comprising at least 60 vol-%, on a dry basis, CO2, wherein the CO2 was present in the input gas stream; c) conditioning the tail gas stream by liquefaction to generate a liquified CO2 stream comprising at least 90 vol-%, on a dry basis, CO2; and d) sequestering the liquified CO2 stream.
2. The method of claim 1, wherein the input gas stream further comprises a gas selected from hydrogen, nitrogen, oxygen, other inert gases, or any combination thereof.
3. The method of claim 1, wherein the input gas stream is industrial off-gas.
4. The method of claim 3, wherein the industrial off-gas is from a production process comprising steel or alloy.
5. The method of claim 1, wherein the C1-fixing microorganism is Clostridium autoethanogenum.
6. The method of claim 1, wherein the at least one fermentation product is selected from ethanol, single-cell protein, or any combination thereof.
7. The method of claim 1, wherein liquefaction is cryogenic liquefaction.
8. A method for purifying CO2 comprising: a) passing an input gaseous stream comprising from about 50 vol-%, on a dry basis, to 75 vol-%, on a dry basis, CO and from about 10 vol-%, on a dry basis, to 35 vol-%, on a dry basis, CO2 to a gas fermentation process; b) removing the CO by generating at least one fermentation product; c) recovering the CO2 in a concentrated CO2 tail gas stream; d) purifying the CO2 tail gas stream by liquefaction to generate a purified CO2; and e) providing the purified CO2 stream for sequestration.
9. The method of claim 8, wherein the input gas stream further comprises a gas selected from hydrogen, nitrogen, oxygen, other inert gases, or any combination thereof.
10. The method of claim 8, wherein the input gas stream is industrial off-gas.
11. The method of claim 10, wherein the industrial off-gas is from a production process comprising steel or alloy.
12. The method of claim 8, wherein the C1-fixing microorganism is Clostridium autoethanogenum.
13. The method of claim 8, wherein the at least one fermentation product is selected from ethanol, single-cell protein, or any combination thereof.
14. The method of claim 8, wherein liquefaction is cryogenic liquefaction.
15. A method of capturing carbon for combined utilization and sequestration comprising: a) passing a gas stream comprising CO and CO2 to a gas fermentation process under suitable conditions; b) fermenting at least a portion of the CO using a C1-fixing microorganism to: 1) generate at least one fermentation product, and 2) generate an enriched residual CO2 stream comprising about 20-95 vol-%, on a dry basis, CO2; c) conditioning the enriched residual CO2 stream using cryogenic liquefaction to generate a purified CO2 stream comprising greater than 99 vol-%, on a dry basis, CO2; and d) providing the purified CO2 stream for sequestration.
16. The method of claim 15, wherein the gas stream comprising CO and CO2 comprises about 17.5 vol-%, on a dry basis, CO2.
17. The method of claim 15, wherein the enriched residual CO2 stream comprises about 86 vol-%, on a dry basis, CO2.
18. The method of claim 15, wherein the purified CO2 stream comprises about 99.9 vol- %, on a dry basis, CO2.
19. The method of claim 15, wherein the C1-fixing microorganism is Clostridium autoethanogenum.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100317074A1 (en) * | 2007-10-28 | 2010-12-16 | Lanzatech New Zealand Limited | Carbon capture in fermentation |
| US20110239700A1 (en) * | 2009-12-15 | 2011-10-06 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Method of Obtaining Carbon Dioxide From Carbon Dioxide-Containing Gas Mixture |
| US20120003706A1 (en) * | 2010-06-30 | 2012-01-05 | Robert Hickey | Process for Converting a CO and CO2 Feed Gas Stream to Liquid Products by Fermentation |
| US20120052541A1 (en) * | 2009-04-29 | 2012-03-01 | Lanzatech New Zealand Limited | Improved carbon capture in fermentation |
| US20130252299A1 (en) * | 2010-09-11 | 2013-09-26 | Inoeos Commercial Services UK Limited | Process and apparatus for the production of alcohols |
| US20190249315A1 (en) * | 2018-02-12 | 2019-08-15 | Lanzatech, Inc. | Process for improving carbon conversion efficiency |
-
2025
- 2025-05-02 WO PCT/US2025/027618 patent/WO2025240146A1/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100317074A1 (en) * | 2007-10-28 | 2010-12-16 | Lanzatech New Zealand Limited | Carbon capture in fermentation |
| US20120052541A1 (en) * | 2009-04-29 | 2012-03-01 | Lanzatech New Zealand Limited | Improved carbon capture in fermentation |
| US20110239700A1 (en) * | 2009-12-15 | 2011-10-06 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Method of Obtaining Carbon Dioxide From Carbon Dioxide-Containing Gas Mixture |
| US20120003706A1 (en) * | 2010-06-30 | 2012-01-05 | Robert Hickey | Process for Converting a CO and CO2 Feed Gas Stream to Liquid Products by Fermentation |
| US20130252299A1 (en) * | 2010-09-11 | 2013-09-26 | Inoeos Commercial Services UK Limited | Process and apparatus for the production of alcohols |
| US20190249315A1 (en) * | 2018-02-12 | 2019-08-15 | Lanzatech, Inc. | Process for improving carbon conversion efficiency |
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