Integrated temperature swing adsorption and gas fermentation device

Abstract

Disclosed is an integrated temperature swing adsorption and gas fermentation apparatus comprising: a gaseous feedstock source unit in fluid communication with a first adsorbent bed comprising an adsorbent, the first adsorbent bed further comprising a treated gaseous feedstock outlet; a second adsorbent bed comprising a spent adsorbent and having an effluent outlet, the treated gaseous feedstock outlet of the first adsorbent bed further being in fluid communication with the second adsorbent bed; and a bioreactor of a gas fermentation plant, the bioreactor in fluid communication with the treated gaseous feedstock outlet of the first adsorbent bed and the effluent outlet of the second adsorbent bed, the bioreactor comprising a tail gas stream outlet and a product stream outlet, and the tail gas flow outlet is communicated with fluid of the second adsorption bed. The apparatus may almost completely recover or completely recover the treated gaseous feedstock and eliminate the need for inert regeneration gases.

Description

Technical Field

[0001] This disclosure relates to a method and apparatus for integrating temperature-switching adsorption and gaseous fermentation. The substrate for gaseous fermentation passes through an adsorption device to remove impurities, ensuring safe gaseous fermentation. Background Technology

[0002] Carbon dioxide (CO2) accounts for approximately 76% of global greenhouse gas emissions caused by human activities, with methane (16%), nitrous oxide (6%), and fluorinated gases (2%) making up the remainder (United States Environmental Protection Agency). Most CO2 comes from burning fossil fuels to produce energy, but industrial and forestry practices also release CO2 into the atmosphere. Reducing greenhouse gas emissions, especially CO2, is crucial to halting global warming and the resulting climate and weather changes.

[0003] It has long been recognized that catalytic methods, such as the Fischer-Tropsch process, can be used to convert gases containing carbon dioxide (CO2), carbon monoxide (CO), and / or hydrogen (H2), such as industrial waste gases or syngas or mixtures thereof, into a variety of chemicals, such as ethanol, acetone, and isopropanol. Syngas can also be converted into various chemicals via the Monsanto process, with methanol as the first step. Both the Fischer-Tropsch and methanol synthesis units are optimized for very high capacities. They require well-defined feed gas compositions with low impurities and syngas feed to avoid catalyst poisoning. The Fischer-Tropsch process requires complex and expensive purification equipment to produce high-purity industrial chemicals. Recently, gaseous fermentation has emerged as an alternative platform for the bio-fixation of such gases. C1-fixing microorganisms containing CO2 have been demonstrated to produce CO2-containing bio-fixing gases. 2、 Gases such as CO and / or H2 (e.g., industrial waste gas or syngas or mixtures thereof) are converted into products such as ethanol and 2,3-butanediol.

[0004] Gas fermentation has emerged as an alternative platform for biocapture and conversion in gases containing single-carbon compounds such as carbon monoxide (CO), carbon dioxide (CO2), and / or methane (CH4). Specifically, C1-immobilized microorganisms act as biocatalysts to convert C1-carbon gaseous substrates into valuable fermentation products, such as ethanol or other C1-C4 alcohols.

[0005] Temperature swing adsorption (TSA) can be used to remove contaminants from gaseous feedstocks. When a TSA bed becomes unable to effectively remove the desired impurities to the desired concentration due to the adsorbent approaching its adsorption capacity limit, this is called "saturation," and the adsorbent can be regenerated. An adsorbent bed contains at least one adsorbent selected to remove the target impurities. Additional adsorbents can be added to the adsorbent bed to target multiple impurities. Adsorbent regeneration is achieved by passing heated gas through the adsorbent bed to transfer heat from the regenerated gas to the adsorbent. As the adsorbent temperature increases, impurities are desorbed from the adsorbent because the saturation capacity of the adsorbent decreases with increasing temperature. The regenerated gas flow rate is sufficient to ensure adequate mixing and prevent the regenerated gas from becoming saturated with the desorbed impurities. Typically, an inert gas (such as nitrogen) is used as the regenerated gas. However, the generation of inert gases involves expensive equipment, thus increasing the overall cost. Furthermore, the impurity-loaded inert gas must undergo further treatment before being released into the atmosphere or reused. A typical treatment method is thermal oxidation at high temperatures. Given the inert nature of the regenerated gas, a significant amount of energy is required to heat the impurity-loaded inert gas to the desired thermal oxidation temperature. Alternatively, a portion of the untreated gaseous feedstock can be heated and used as a regeneration gas. However, this reduces the amount of gaseous substrate available for fermentation. Therefore, there is a need for a method and apparatus for regenerating a saturated adsorption bed in addition to regeneration using an inert gas, while retaining the gaseous feedstock available for the process and without loss of regeneration. Utility Model Content

[0006] In one aspect of this disclosure, a method for integrating a TSA process and a gaseous fermentation process comprises (a) providing a TSA process and a gaseous fermentation process, the TSA process comprising at least a first adsorption bed and a second adsorption bed, the first adsorption bed comprising an adsorbent and the second adsorption bed comprising waste or saturated adsorbent, the gaseous fermentation process comprising a bioreactor containing at least one C1 immobilized microorganism in a nutrient solution; (b) passing a gaseous feedstock comprising CO, CO2, H2, CH4 or any combination thereof and at least one contaminant (or impurity) to the first adsorption bed operating at an adsorption temperature, adsorbing the contaminant onto the adsorbent, and producing a treated gaseous feedstock depleted of the contaminant; and (c) passing at least a portion of the treated gaseous feedstock to the gaseous fermentation process to produce a gas comprising gaseous fermentation products and a tail gas stream. The process comprises: (d) first passing at least a portion of the exhaust gas stream to a heater to generate a heated exhaust gas stream, the heated exhaust gas stream being passed from the gaseous fermentation process to the second adsorption bed at a regeneration temperature and through the spent adsorbent to desorb adsorbed contaminants and provide heated regenerated adsorbent, wherein the regeneration temperature is greater than the adsorption temperature; (e) then passing at least a portion of the treated gaseous feedstock from the first adsorption bed to the second adsorption bed and through the regenerated adsorbent to cool the heated regenerated adsorbent to the adsorption temperature and provide an effluent stream from the regenerated bed; and (f) combining the effluent stream from the second adsorption bed with the treated gaseous feedstock from the first adsorption bed, or passing the effluent stream of the treated gaseous feedstock to the gaseous fermentation process, or both. Generally, exhaust gas is the gas and vapor that can be released into the atmosphere from the process after the reaction and treatment have occurred. The process steps (a) through (f) are repeated periodically. In another embodiment, the method further includes a third adsorption bed in standby mode, the third adsorption bed containing regenerated adsorbent. In another embodiment, the method further includes more than three adsorption beds in a standby mode, the more than three adsorption beds containing regenerated adsorbent. In yet another embodiment, the method further includes passing the heated exhaust gas from the gaseous fermentation process through a scrubber before being delivered to the first adsorption bed to remove and recover gaseous fermentation products from the exhaust gas.

[0007] The method further includes (a) adjusting the operating pressure of the first adsorption bed to correspond to the pressure of the gaseous feedstock, and or (b) adjusting the operating pressure of the second adsorption bed to correspond to the pressure of the heated exhaust gas flow from the gaseous fermentation process. The gaseous fermentation process can be operated at a lower pressure relative to the adsorption pressure or at a higher pressure relative to the adsorption pressure.

[0008] In another aspect of this disclosure, a method for integrating a TSA process, a pressure swing adsorption (PSA) process, and a gaseous fermentation process comprises (a) providing a TSA process, a pressure swing adsorption process, and a gaseous fermentation process, wherein the TSA process comprises at least a first TSA adsorption bed and a second TSA adsorption bed, the first TSA adsorption bed comprising a TSA adsorbent and the second TSA adsorption bed comprising TSA waste adsorbent; the pressure swing adsorption process comprises at least a first PSA adsorption bed and a second PSA adsorption bed, the first PSA adsorption bed comprising a PSA adsorbent and the second PSA adsorption bed comprising PSA waste adsorbent; and the gaseous fermentation process comprises a bioreactor containing at least one C1 immobilized microorganism in a nutrient solution; and (b) transferring a gaseous feedstock comprising CO, CO2, H2, CH4, or any combination thereof, and at least one contaminant to the first TSA adsorption bed operating at an adsorption temperature. The process involves: (a) adsorbing the pollutants onto the TSA adsorbent and producing a TSA-treated gaseous feedstock depleted of the pollutants; (b) transferring at least a portion of the treated gaseous feedstock to a first PSA adsorption bed operating at an adsorption pressure, adsorbing CO2 onto the PSA adsorbent, and producing a CO2-depleted PSA-treated gaseous feedstock; (c) transferring the PSA-treated gaseous feedstock to a gaseous fermentation process to produce a gaseous fermentation product stream containing gaseous fermentation products; (d) regenerating the first PSA bed by reducing the operating pressure below the adsorption pressure to produce a CO2-rich PSA purge gas stream; and (e) then transferring at least a portion of the PSA purge gas stream from the second PSA adsorption bed to the second TSA adsorption bed at a desorption temperature to desorb the adsorbed pollutants and provide a TSA purge gas containing the pollutants and CO2. In another embodiment, the gaseous feedstock comprises methane, hydrogen sulfide, and other light hydrocarbons, and the PSA bed adsorbs the methane or other light hydrocarbons (C1-C4). 13 (or hydrogen sulfide). In one embodiment, a compressor is used to increase the pressure of the PSA purge gas to a sufficiently high pressure to overcome the pressure drop of the second TSA bed and associated equipment.

[0009] In another aspect of this disclosure, a method for integrating a temperature swing adsorption (TSA) process, a pressure swing adsorption (PSA) process, and a gaseous fermentation process includes providing a TSA process, a PSA process, and a gaseous fermentation process. The TSA process includes at least a first TSA adsorption bed and a second TSA adsorption bed, the first TSA adsorption bed containing a TSA adsorbent and the second TSA adsorption bed containing spent TSA adsorbent. The PSA process includes at least a first PSA adsorption bed and a second PSA adsorption bed, the first PSA adsorption bed containing a PSA adsorbent and the second PSA adsorption bed containing spent PSA adsorbent. The gaseous fermentation process includes a bioreactor containing at least one C1 immobilized microorganism in a nutrient solution. A gaseous feedstock comprising CO, CO2, H2, CH4, or any combination thereof, and at least one pollutant are also included. The pollutant is transferred to a first TSA adsorption bed operating at an adsorption temperature, whereby the pollutant is adsorbed onto the TSA adsorbent, and a TSA-treated gaseous feedstock depleted of the pollutant is generated. At least a portion of the treated gaseous feedstock is transferred to a gaseous fermentation process to generate fermentation tail gas and a gaseous fermentation product stream containing gaseous fermentation products. At least a portion of the fermentation tail gas is transferred to a first PSA adsorption bed operating at an adsorption pressure, whereby CO2 is adsorbed onto the PSA adsorbent, and a PSA-treated fermentation tail gas and PSA purge gas depleted of CO2 are generated. At a desorption temperature, at least a portion of the PSA purge gas is transferred from the first PSA adsorption bed to a second TSA adsorption bed to desorb the adsorbed pollutant and provide a TSA purge gas containing the pollutant and CO2.

[0010] In another aspect of this disclosure, an integrated TSA and gas fermentation apparatus includes (i) a gaseous feedstock source in fluid communication with a first adsorption bed containing an adsorbent, the first adsorption bed further including a treated gaseous feedstock outlet; (ii) a second adsorption bed containing waste adsorbent and having an effluent outlet, wherein the treated gaseous feedstock outlet of the first adsorption bed is further in fluid communication with the second adsorption bed; and (iii) a bioreactor of the gas fermentation apparatus, the bioreactor being in fluid communication with the treated gaseous feedstock outlet of the first adsorption bed and the effluent outlet of the second adsorption bed, the bioreactor including a tail gas outlet and a product outlet, the tail gas outlet being in fluid communication with the second adsorption bed. The apparatus further includes a third adsorption bed in standby mode, the third adsorption bed containing regenerated adsorbent, the third adsorption bed being in fluid communication with the bioreactor. In one embodiment, a scrubber is in fluid communication with the tail gas outlet of the bioreactor, the scrubber being further in fluid communication with the second adsorption bed. In yet another embodiment, the apparatus further includes a regeneration heater in fluid communication with the tail gas outlet of the bioreactor.

[0011] In another aspect of this disclosure, an integrated TSA, pressure swing adsorption, and gaseous fermentation apparatus comprises: (i) a gaseous feedstock unit fluidly connected to a first TSA adsorption bed containing an adsorbent, the first TSA adsorption bed further comprising a treated gaseous feedstock outlet; (ii) a first PSA adsorption bed containing a PSA adsorbent, the first PSA bed fluidly connected to the treated gaseous feedstock outlet of the first TSA adsorption bed, wherein the first PSA adsorption bed is further fluidly connected to the bioreactor; and (iii) a second PSA adsorption bed containing PSA waste adsorbent, fluidly connected to the treated gaseous feedstock outlet of the first TSA adsorption bed, wherein the second PSA adsorption bed is further fluidly connected to a second TSA adsorption bed containing TSA waste adsorbent. Attached Figure Description

[0012] The accompanying drawings are simplified by removing a large number of devices typically used in processes of this nature, such as internal container components, temperature and pressure control devices, flow control valves, compressors, etc., which are not specifically required to illustrate the performance of this invention. Furthermore, the description of the process of this invention in the embodiments of specific drawings is not intended to limit this disclosure to the particular embodiments. Some embodiments can be described with reference to the method configurations shown in the figures, which relate to both the equipment and methods of performing this disclosure. Any reference to method steps includes a reference to equipment units or devices suitable for performing said steps, and vice versa.

[0013] Figure 1A and 1B This is a schematic flowchart illustrating three TSA beds according to embodiments of the present disclosure.

[0014] Figure 2A and 2B This is a schematic flowchart illustrating two TSA beds and two PSA beds (PSA) according to embodiments of the present disclosure. Detailed Implementation

[0015] In integrated TSA and gas fermentation units, the near-complete or complete recovery of treated gaseous feedstock and the elimination of the need for inert regeneration gas are benefits achieved through the methods and apparatus of this disclosure. For ease of understanding, this disclosure is explained in the context of a TSA oscillating bed unit with two or more TSA beds. A first TSA bed is online and operational, while a second TSA bed is being regenerated or has been regenerated and is ready for service. At a point when the first TSA bed approaches its adsorption capacity or becomes saturated, the first TSA bed is “switched” from service for regeneration, and the second TSA bed is “switched” back to online service. The process continues while at least one TSA bed is in use, while another is being regenerated or ready for service. In this disclosure, a saturated TSA bed is regenerated using a “heated” tail gas stream from the gas fermentation process and then cooled using treated gaseous feedstock from another TSA bed in the TSA oscillating bed unit. Conversely, a feed stream from a PSA bed is used to regenerate the TSA bed. Therefore, regeneration of the TSA bed does not require inert regeneration gas, which is common practice, thus eliminating the cost of obtaining or generating inert regeneration gas. Furthermore, even when used during the regeneration process, the treated gaseous feedstock is almost completely recovered.

[0016] The gaseous fermentation zone of the apparatus includes at least one bioreactor containing at least one C1 immobilized microorganism. The term "bioreactor" includes a fermentation device comprising one or more containers and / or towers or piping arrangements, including continuous stirred tank reactors, immobilized cell reactors, trickle bed reactors, bubble columns, airlift fermenters, static mixers, circulating loop reactors, diaphragm reactors such as hollow fiber membrane bioreactors, or other containers or other devices suitable for gas-liquid contact. A bioreactor may also comprise a device with multiple reactors (stages) connected in parallel or series. For example, a bioreactor may comprise a first growth reactor and a second fermentation reactor for culturing microorganisms, with the output from the growth reactor being fed into the second fermentation reactor, where the second fermentation reactor produces the majority of the fermentation products. In some embodiments, multiple bioreactors in a bioreactor apparatus are stacked on top of each other. Stacking bioreactors increases the flux of the bioreactor apparatus without significantly increasing the land area requirement. In some embodiments, the bioreactor includes a downflow or upflow bioreactor having a mechanism for forming smaller substrate bubbles in a liquid medium and thus substantially increasing the gas-liquid mass transfer rate without increasing energy consumption.

[0017] "C1 immobilized microorganisms" are microorganisms that produce one or more products from a C1 carbon source or substrate. "C1 carbon source or substrate" refers to a single carbon molecule that serves as part or the sole carbon source for the microorganism. For example, a C1 carbon source or substrate may comprise one or more of the following: CO, CO2, CH4, CH3OH, or CH2O2. In one embodiment, the C1 carbon source or substrate comprises one or both of CO and CO2. In addition to C1 compounds, gaseous substrates containing C1 may further comprise other non-carbon components, such as H2, N2, and / or electrons.

[0018] When used in the context of a feed stream flowing into a gaseous fermentation bioreactor (i.e., a gaseous fermenter) or "gaseous fermentation feed," the term "feed" should be understood to encompass any material (solid, liquid, or gaseous) or feed stream that can provide substrates for the gaseous fermenter or bioreactor, either directly or after feed processing.

[0019] Typically, feedstocks for gaseous fermentation include, but are not limited to, industrial waste gas, syngas, biogas, landfill gas, direct air capture gas, or any combination thereof. A portion of the substrate and / or C1 carbon source can be a gas obtained as a byproduct of an industrial process or a gas from another source, such as internal combustion engine exhaust, biogas, landfill gas, direct air capture, combustion, or gas from electrolysis. However, a portion of the substrate and / or C1 carbon source may be syngas produced through pyrolysis, calcination, or gasification. In other words, carbon in solid or liquid materials can be recycled through pyrolysis, calcination, or gasification to produce syngas that can be used as a substrate and / or C1 carbon source in gaseous fermentation. A portion of the substrate and / or C1 carbon source can be natural gas, carbon dioxide from conventional and unconventional gas production, and / or gases containing methane. Gaseous fermentation processes are flexible and can utilize any of these substrates and / or C1 carbon sources.

[0020] In some embodiments, the industrial process for an optional portion of the substrate and / or C1 carbon source is selected from the manufacture of ferrous metal products such as iron and steel production, non-ferrous metal products, petroleum refining, power generation, carbon black production, paper and pulp manufacturing, ammonia production, methanol production, coke manufacturing, petrochemical production, carbohydrate fermentation, cement manufacturing, aerobic digestion, anaerobic digestion, catalytic processes, natural gas extraction, cellulose fermentation, oil extraction, industrial processing of geological reservoirs, processing of fossil resources such as natural gas, coal, and oil, landfill operations, silicon carbide production, or any combination thereof. Examples of specific processing steps within the industrial method include catalyst regeneration, fluid catalytic cracking, and catalyst regeneration. Air separation and direct air capture are other suitable industrial processes. Specific examples in iron and steel and ferroalloy manufacturing include the direct reduction of blast furnace gas, basic oxygen furnace gas, coke oven gas, blast furnace top gas, and residual gases from ironmaking. Other general examples include flue gas from combustion boilers and combustion heaters, such as natural gas, oil or coal-fired boilers or heaters, and gas turbine exhaust. Another example is the combustion of compounds, such as at oil and gas production sites. In these embodiments, substrates and / or C1 carbon sources can be captured from industrial processes using any known method and then released into the atmosphere.

[0021] The substrate and / or C1 carbon source is a syngas known as syngas, which can be obtained from reforming, partial oxidation, plasma, or gasification processes. Examples of gasification processes include coal gasification, refinery residue gasification, petroleum coke gasification, biomass gasification, lignocellulosic material gasification, wood gasification, black liquor gasification, municipal solid waste gasification, municipal liquid waste gasification, industrial solid waste gasification, industrial liquid waste gasification, waste-derived fuel gasification, sewage gasification, sewage sludge gasification, sludge gasification from wastewater treatment, landfill gasification, biogas gasification (such as when biogas is added to enhance the gasification of another material), and gasification of rubber-containing materials, including partial and whole tires. Examples of reforming processes include steam methane reforming, steam naphtha reforming, natural gas reforming, biogas reforming, landfill gas reforming, coke oven gas reforming, pyrolysis waste gas reforming, ethylene production waste gas reforming, 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 waste gas. Examples of municipal solid waste include tires, plastics, waste-derived fuels, and fibers such as shoes, clothing, and textiles. Municipal solid waste may be simple landfill-type waste and may be classified or unclassified. Tires, including those with filed ends, can be a raw material. Examples of biomass can include lignocellulosic materials and microbial biomass. Lignocellulosic materials can include agricultural byproducts, forestry byproducts, and some industrial byproducts. The entire tire can be pyrolyzed to produce syngas.

[0022] Biomass can be produced as a byproduct of nature-based solutions (NBS), and therefore, NBS can provide feedstock for gas fermentation processes. The European Commission defines NBS as nature-inspired and supported solutions that are cost-effective, provide environmental, social, and economic benefits, and contribute to enhanced resilience. Such solutions introduce more and more diverse natural features and processes into cities, landscapes, and seascapes through site-specific, resource-efficient, and systematic interventions. NBS must benefit biodiversity and support the provision of a range of ecosystem services. Solutions that provide both social and overall biodiversity benefits can be achieved through the use of healthy, resilient, and diverse ecosystems (whether natural, managed, or newly created) using NBS. Examples of NBS include natural climate solutions (protecting, restoring, and improving land management, increasing carbon storage in landscapes and wetlands globally, or preventing greenhouse gas emissions), efforts to halt biodiversity loss, socioeconomic impacts, habitat restoration, and health and well-being efforts related to air and water. Biomass produced through NBS can be used as feedstock for gas fermentation processes.

[0023] A portion of the substrate and / or C1 carbon source may be a gas stream containing methane. Such methane-containing gases can be obtained from fossil methane emissions, such as during fracturing, wastewater treatment, livestock, agriculture, and municipal solid waste landfilling. It is also envisioned that methane can be burned to generate electricity or heat, and that C1 byproducts can be used as a substrate or carbon source. The substrate and / or C1 carbon source may be a gas stream containing natural gas.

[0024] Syngas substrates typically contain a large proportion of CO, such as at least about 15 vol% to about 75 vol% CO, about 20 vol% to about 70 vol% CO, about 20 vol% to about 65 vol% CO, about 20 vol% to about 60 vol% CO, and about 20 vol% to about 55 vol% CO. In some embodiments, the syngas substrate comprises about 25 vol% CO, or about 30 vol% CO, or about 35 vol% CO, or about 40 vol% CO, or about 45 vol% CO, or about 50 vol% CO, or about 55 vol% CO, or about 60 vol% CO. In other embodiments, the syngas substrate typically contains a large proportion of CO2, such as at least about 15 vol% to about 75 vol% CO2, about 20 vol% to about 70 vol% CO2, about 20 vol% to about 65 vol% CO2, about 20 vol% to about 60 vol% CO2, and about 20 vol% to about 55 vol% CO2. In some embodiments, the syngas substrate comprises about 25% by volume of CO2, or about 30% by volume of CO2, or about 35% by volume of CO2, or about 40% by volume of CO2, or about 45% by volume of CO2, or about 50% by volume of CO2, or about 55% by volume of CO, or about 60% by volume of CO2.

[0025] C1 immobilized microorganisms can be selected from Clostridium, Moorella, and Pyrococcus Genus (Pyrococcus), Genus (Eubacterium), Genus (Desulfobacterium), Carbon oxidizing thermophile Genus: Carboxydothermus, Acetogenium, Acetobacterium, Anaerobic Acetoanaerobium, Butyribaceterium, Peptostreptococcus (Peptostreptococcus) and its mixtures The microorganisms in the bioreactor can be modified microorganisms derived from naturally occurring or parental microorganisms. A “parental microorganism” is another microorganism from which a microorganism can be derived. Both parental and derived microorganisms are suitable microorganisms. Parental microorganisms can be naturally occurring microorganisms (i.e., wild-type microorganisms) or microorganisms that have been pre-modified (i.e., optimized, mutant, or recombinant microorganisms). Suitable microorganisms can be modified to express or overexpress one or more enzymes that are not expressed or overexpressed in the parental microorganism. Similarly, the microorganisms of this disclosure can be modified to contain one or more genes not present in the parental microorganism. Microorganisms can also be modified to not express or express a lower amount of one or more enzymes expressed in the parental microorganism. According to one embodiment, the microorganisms are selected from or derived from the following: Acetobacterium woodii and Alkalibaculum bacchii), Blautia producta, Butyribacterium methylotrophicum, Clostridium aceticum, Clostridium ethanoliferum *Clostridium carboxidivorans*, *Clostridium clarithii* Clostridium coskatii, Clostridium drakei, Clostridium formic acid acetic acid formicoaceticum), Clostridium ljungdahlii, Clostridium Clostridium ragsdalei, Clostridium scatologenes, and Clostridium mucosae Eubacterium limosum, Moorella thermautotrophica, hot vinegar Moorella thermoacetica, Oxobacter pfennigii, and Rat ovalis (Sporomusa ovata), *Sporomusa silvacetica*, *Sporomusa spheroida* (Sporomusa sphaeroides), Cupriavidus necator, Kewood anaerobic bacteria (Thermoanaerobacter kivui)Or any combination thereof. In one embodiment, the microorganism is selected from or derived from Clostridium ethanoligenin, Clostridium yangniger, or Clostridium ranelii. In one embodiment, the parent microorganism is Clostridium ethanoliferum It was deposited on June 7, 2010, in accordance with the provisions of the Budapest Treaty at the German Collection of Microorganisms and Cell Cultures (Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH (DSMZ)) located at D-38124 Inhoffenstraße 7B, Braunschweig, Germany, with accession number DSM23693. This strain is described in International Patent Application No. PCT / NZ2011 / 000144, publication number WO 2012 / 015317.

[0026] The microorganisms disclosed herein can be cultured with gaseous substrates to produce one or more products. For example, in addition to 2-phenylethanol (WO 2021 / 188190, US 2021 / 0292732) and ethylene, the microorganisms can produce or be engineered to produce ethanol (WO 2007 / 117157, US 7,972,824), acetates (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), butyrates (WO 2008 / 115080, US 8,293,509), and 2,3-butanediol (WO 2009 / 151342, US 8,293,509). 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 / 045807), butadiene (WO 2012 / 024522, US 2012 / 045807), methyl ethyl ketone (2-butanone) (WO 2012 / 024522, US 2012 / 045807 and WO 2013 / 185123, US 9,890,384), and then converted to ethylene ethanol (WO 2012 / 026833, US 2013 / 157,322), acetone (WO 2012 / 115527, US 10,590,406), acetone (WO 2012 / 115527, US 10,590,406), methyl ethyl ketone (2-butanone) (WO 2012 / 024522, US 2012 / 045807 and WO 2013 / 185123, US 9,890,384), ethanol (WO 2012 / 026833, US 2013 / 157,322), acetone (WO 2012 / 115527, US 10,590,406 ... 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), 1-propanol (WO 2014 / 0369152, US 9,284,564), 1-hexanol (WO 2017 / 066498, US 9,738,875), 1-octanol (WO 2017 / 066498, US 9,738,875), and products derived from branched acid salts (WO 2016 / 191625, US 10,174).303), 3-hydroxybutyric acid (WO 2017 / 066498, US 9,738,875), 1,3-butanediol (WO 2017 / 066498, US 9,738,875), 2-hydroxyisobutyrate or 2-hydroxyisobutyric acid (WO 2017 / 066498, US 9,738,875), isobutene (WO2017 / 066498, US 9,738,875), adipic acid (WO 2017 / 066498, US 9,738,875), 1,3-hexanediol (WO2017 / 066498, US 9,738,875), 3-methyl-2-butanol (WO 2017 / 066498, US 9,738,875), 2-buten-1-ol (WO 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 / or monoethylene glycol (WO 2019 / 126400, US 11,555,209).

[0027] In some embodiments, the microbial biomass itself can be considered a product. These products can be further converted to produce at least one component of diesel, jet fuel, sustainable aviation fuel (SAF), and / or gasoline. In some embodiments, ethylene can be catalytically converted into another product, article, or any combination thereof. Furthermore, the microbial biomass can be further processed by any method or combination of methods known in the art to produce single-cell protein (SCP). The fermentation effluent from the bioreactor contains the produced products and the culture medium present in the bioreactor.

[0028] Bioreactors in gaseous fermentation processes operate under suitable conditions to produce products. Specific reaction conditions will depend in part on the specific microorganisms used and the target product. However, generally, it is preferred to operate fermentation at pressures above atmospheric pressure and temperatures suitable for the specific microorganisms used.

[0029] The target product can be separated or purified from the fermentation broth effluent using any method or combination of methods known in the art, including, for example, fractionation, evaporation, pervaporation, stripping, phase separation, and extractive fermentation (including, for example, liquid-liquid extraction). In some embodiments, the target product is recovered from the fermentation broth by continuously removing a portion of the fermentation broth from the bioreactor, separating microbial biomass from the fermentation broth (e.g., by filtration, including membrane removal), and recovering one or more target products from the permeate. Alcohols and / or acetone can be recovered, for example, by distillation. Acids can be recovered, for example, by adsorption onto activated carbon. The separated microbial biomass, such as microbial biomass in the retention, can be returned to the bioreactor. A portion of the cell-free microbial permeate remaining after the removal of the target product can be returned to the bioreactor to recycle the culture medium. Additional nutrients can be added to the recirculated cell-free permeate to replenish the culture medium before recycling to the bioreactor. The product and microbial biomass can be recovered in one operation using vacuum distillation.

[0030] Substrates in gaseous fermentation processes are typically treated to remove fermentation inhibitors before being introduced into a bioreactor. A TSA (Transfer-Alternating Current) device can be used to adsorb selective contaminants from a gaseous feedstock onto an adsorbent at an adsorption temperature. After the adsorbent becomes saturated, the adsorbed contaminants are desorbed from the adsorbent at a desorption temperature, and the TSA bed is thus regenerated and can be reused. Suitable adsorbents used in TSA beds include, but are not limited to, zeolite molecular sieves, activated carbon, silica gel, activated alumina, or any combination thereof. Typical fermentation inhibitors removed by adsorption onto the TSA bed include, but are not limited to, hydrocarbons, oxygen-containing compounds, sulfur compounds, nitrogen compounds, or any combination thereof. Lighter tars with lower boiling points, such as benzene, toluene, ethylbenzene, and xylene (BTEX), can also be removed from the feedstock, if present.

[0031] Referring to a single bed in a TSA device, the steps of the TSA process applied to said single bed include:

[0032] 1) Adsorption steps under adsorption pressure and adsorption temperature;

[0033] 2) An optional decompression step to reduce the pressure to a regeneration pressure that may be lower than the adsorption pressure;

[0034] 3) Desorption steps at desorption temperatures higher than the adsorption temperature;

[0035] 4) The cooling step that returns the TSA bed from the desorption temperature to the adsorption temperature; and

[0036] 5) Pressurization step to return the TSA bed from regeneration pressure to adsorption pressure.

[0037] The adsorption step continues until the adsorbent no longer has sufficient available adsorption capacity to remove the target component to the target concentration. The desorption step continues until the TSA bed has recovered sufficient available adsorption capacity to remove the target component. The adsorption step can be considered as the adsorption mode, while the depressurization, desorption, cooling, and pressurization steps can be considered as the regeneration mode.

[0038] In oscillating bed operation, while the first TSA bed is in the adsorption step and in use, the second TSA bed can undergo depressurization, desorption, cooling, and pressurization steps. However, the third TSA bed can be in standby mode, fully regenerated, and ready for use. Any number of TSA beds can be in active service, regeneration, or standby mode. For simplicity, this disclosure focuses on a two-bed TSA process. However, it should be understood that a three-bed TSA process or even a four-bed TSA process may be advantageous. Furthermore, the regeneration of the TSA beds can occur in the same or opposite flow direction as the adsorption mode.

[0039] refer to Figure 1A and 1B The gaseous fermentation zone includes at least one bioreactor 100, which converts a treated gaseous feedstock 122 to produce at least one target product stream 138, the target product stream comprising at least one product and a tail gas stream, also referred to as a tail gas stream 136 containing at least CO2. The treated gaseous feedstock 122 originates from a feedstock source 102 and optionally a compressor 106, and is subsequently processed using a TSA process comprising adsorbent beds 116, 118, and 120. The TSA process is described in which the regeneration mode of the adsorbent bed occurs in the direction of fluid flow, which is countercurrent to the fluid flow in the adsorption mode. It is contemplated that, in another embodiment, the regeneration mode of the adsorbent bed may occur in the direction of cocurrent fluid flow.

[0040] Feed source 102 provides gaseous feedstock 104. A suitable feedstock source has been described above. Gaseous feedstock 104 is compressed in compressor 106 to produce compressed gaseous feedstock 108. Valves 110, 112, and 114 control the fluid flow of the compressed gaseous feedstock 108, as shown in 108a, 108b, and 108c, to each of the corresponding adsorbent beds 116, 118, and 120. Figure 1A and 1B As depicted, the first adsorbent bed 116 contains an active adsorbent and is in adsorption mode, while the second adsorbent bed 118 contains spent adsorbent, whose adsorption capacity is reduced compared to fresh or regenerated adsorbent. In some embodiments, the spent adsorbent has reached its capacity and cannot adsorb additional pollutants. Figure 1A and 1BThe second adsorbent bed 118 shown is in regeneration mode. The optional third adsorbent bed 120 has been regenerated and is ready for online service (online service of the third adsorbent bed 120 is not shown).

[0041] In one embodiment, when in adsorption mode, the first adsorbent bed 116 operates at an adsorption temperature in the range of about 40°C to about 60°C. In other embodiments, the adsorption temperature may be, for example, about 40°C to about 50°C or about 50°C to about 60°C. When the first adsorbent bed 116 is in adsorption mode, valves 110 and 130 are open, thereby allowing gaseous feedstock 108a to pass through the first adsorbent bed 116 for treatment by adsorbing at least one target pollutant, and producing treated gaseous feedstock 122a depleted of at least one target pollutant. The treated gaseous feedstock is largely delivered as feed stream 122 to the bioreactor 100 in the gaseous fermentation zone. Valves 112 and 114 remain closed to guide gaseous feedstock 108a to the first adsorbent bed 116. Additionally, valves 150a and 124 are closed during adsorption.

[0042] The adsorption capacity of the second adsorbent bed 118 decreases and it is in regeneration mode. Adsorbent with reduced capacity compared to fresh or regenerated adsorbent can be referred to as spent adsorbent. The adsorbent capacity does not necessarily have to reach zero, and regeneration can be performed at any time when the adsorbent capacity decreases. It is advantageous to use the tail gas stream 136 from the bioreactor 100 for adsorbent regeneration in the gaseous fermentation zone. The bioreactor in the gaseous fermentation zone produces the tail gas stream 136 and the target product stream 138. The tail gas stream 136 passes through valve 140 and regeneration heater 142 to heat the tail gas stream 136 and produce a heated tail gas stream 144. The heated tail gas stream 144 passes through the open valve 126 when valves 128 and 124 are closed and reaches the second adsorbent bed 118, thereby providing heated regeneration gas to desorb contaminants from the adsorbent in the second adsorbent bed 118. Additionally, valves 112 and 132 are closed and valve 150b is open.

[0043] The regeneration temperature is higher than the adsorption temperature. In some embodiments, the regeneration temperature is in the range of about 150°C to about 200°C. In various embodiments, the regeneration temperature may be, for example, about 150°C to 160°C, or about 160°C to about 180°C, or about 180°C to about 200°C.

[0044] The effluent stream 146b generated during the regeneration of the second adsorbent bed 118 exits from the TSA bed 118 and is transferred to a thermal oxidizer or other energy recovery or oxidation unit 400. Valve 322 is used to control the flow of the effluent stream 146a. The desorbed compounds from the TSA bed contain trace impurities, such as being rich in volatile organic compounds relative to the feed gas. The thermal oxidizer thermally destroys these trace impurities and typically recovers waste heat to increase the energy of the regeneration gas (i.e., the tail gas stream 160). When the TSA bed 118 is fully regenerated and operational, valves 112 and 132 are open, and valves 126 and 150b are closed.

[0045] Using a heated tail gas stream 144 to regenerate the second adsorbent bed 118 eliminates the requirement to use an inert gas (e.g., nitrogen) for TSA regeneration. Technologies utilizing nitrogen require capital expenditure to produce and store nitrogen, and may subsequently involve processing large quantities of contaminated nitrogen, as well as a low-energy-value dilution tail gas stream. Similarly, regenerating the adsorbent bed from the tail gas stream from the bioreactor is advantageous compared to regeneration from product gases, as typically up to about 10% by volume of the feed gas is lost during regeneration due to the difficulty in recycling the desorbed compounds contained therein without further treatment / separation.

[0046] In some embodiments, the regenerative heater 142 is a flame heater that provides direct heat transfer from fuel combustion. The heat released by fuel combustion enters the open space and is transferred to gas / fluid within ducts arranged along the walls and top of the combustion chamber. In another embodiment, the regenerative heater includes an electric flame heater that uses electricity to increase the temperature of the exhaust gas. Depending on the application, the electric flame heater can be used for both direct and indirect heating. The electric flame heater may include, but is not limited to, immersion heaters, circulating heaters, and electrothermal fluid heaters. In another embodiment, saturated or superheated steam is used for heating. Other heat sources with suitable temperatures are contemplated in these embodiments.

[0047] To cool the second adsorbent bed 118 after regeneration, the treated gaseous feedstock from the first adsorbent bed 116 is in fluid communication with the second adsorbent bed 118. A portion of the treated gaseous feedstock 122a from the first TSA bed 116 passes through the second TSA bed 118 via open valves 132 and 150b, thereby generating an effluent stream 146b connected to the regeneration effluent gas manifold 410. At least a portion of the regeneration effluent gas 410r passes through the desorption cooler 240 via open valve 318 to generate a cooling stream 192, which is compressed by compressor 412 to overcome the pressure drop of the second TSA bed 118 and associated piping and valves. The compressed gas 192 is then incorporated into the product gas manifold 122 via open valve 326, enabling the recovery of product gas used to cool the second adsorbent bed 118, such as... Figure 1A As shown in the diagram. Cooling and further recycling the treated gaseous feedstock from the TSA bed into the feed gas helps achieve nearly 100% feed gas recovery. Figure 1A and 1B A cooling flow conduit integrated with a regeneration flow conduit is shown, but in other embodiments, each function of the conduit may be independent.

[0048] In another embodiment, such as Figure 1B As shown, the cooling regeneration gas is recirculated through the second TSA bed 118 by opening valves 226, 250b, 218, and 426, while valves 124, 128, 150a, 150c, and 322 are closed. Gas recirculation stops once the adsorbent in the second TSA bed 118 approaches its adsorption temperature, and the remaining gas in the second TSA bed 118 is recovered into the product gas manifold once the second TSA bed 118 transitions to the adsorption stage.

[0049] A thermal oxidizer 400 heats trace impurities (such as volatile organic compounds (VOCs)) to a temperature typically above their auto-ignition temperature until they are oxidized. The oxidation process breaks down harmful particles into carbon dioxide, water, and trace amounts of other combustion byproducts. Thermal oxidizers can be selected from direct flame thermal oxidizers, heat recovery oxidizers, regenerative thermal oxidizers, catalytic thermal oxidizers, flameless thermal oxidizers, or any combination thereof. The first type of thermal oxidizer is the direct flame thermal oxidizer. The principle of direct fixed oxidizer operation is to introduce a portion of the combustion process gas flow into the direct thermal oxidizer, where the temperature of the process gas flow is raised to or above the auto-ignition temperature and maintained in the furnace section at this temperature for the required residence time to achieve the desired VOC destruction efficiency. The second type of thermal oxidizer is the regenerative thermal oxidizer (RTO). An RTO uses a ceramic bed that can be heated from a previous oxidation cycle to preheat the input gas to partially oxidize it. The preheated gas enters a combustion chamber, which can be heated by an external fuel source to reach the target oxidation temperature. This type of oxidizer is specifically designed for oxidizing large process airflows with low concentrations of organic compounds, such as low percentages of organic pollutants including VOCs in the process airflow. The third type of thermal oxidizer is the heat recovery oxidizer. Heat recovery oxidizers have primary and / or secondary heat exchangers within the unit. The primary heat exchanger preheats the incoming combustion airflow by recovering heat from the existing clean airflow. This primary heat recovery raises the temperature of the process airflow before it enters the combustion chamber, resulting in lower fuel requirements for the oxidizer unit.

[0050] Based on the above discussion, the method for integrating a TSA process and a gaseous fermentation process includes the following steps: (a) providing a first TSA bed containing an adsorbent and a second TSA bed containing waste adsorbent and a gaseous fermentation process containing a bioreactor; (b) passing a gaseous feedstock and at least one contaminant to the first TSA bed and generating a contaminant-depleted treated gaseous feedstock; (c) passing a portion of the treated gaseous feedstock to the gaseous fermentation process to generate a tail gas stream and a gaseous fermentation product stream; (d) first passing at least a portion of the tail gas stream from the gaseous fermentation process through a heater to heat the tail gas stream to a desired regeneration temperature, and then passing the heated tail gas stream to the second TSA bed. (e) A first TSA bed is used to desorb adsorbed contaminants and provide heated, regenerated adsorbent; (f) at least a portion of the treated gaseous feedstock is then transferred from the first TSA bed to the second TSA bed and through the regenerated adsorbent to cool the heated, regenerated adsorbent to its adsorption temperature and provide a regenerated effluent; (c) the regenerated effluent is cooled and recompressed, and the regenerated effluent from the second TSA bed is combined with the treated gaseous feedstock from the first TSA bed, or the effluent from the treated gaseous feedstock is transferred to a gaseous fermentation process, whereby the cooled regenerated effluent is recycled through the second TSA bed 118 to further cool the regenerated adsorbent, or any combination thereof. While repeating steps (a) through (f), the adsorption switch is periodically switched from the first adsorbent bed to the second adsorbent bed and vice versa, wherein one of the TSA beds contains adsorbent and the other TSA beds contain spent adsorbent. In another embodiment, a third TSA bed 120 containing regenerated adsorbent is maintained in standby mode. If the adsorbents in both the first TSA bed 116 and the second TSA bed 118 are no longer able to adsorb contaminants or support extended regeneration cycles or maintenance requirements, and therefore need to be taken offline, a third TSA bed can be switched on during operation. In such cases, the third TSA bed 120 will be in fluid communication with the bioreactor 100. The third TSA bed 120 will be used to regenerate either the first TSA bed 116 or the second TSA bed 118. When valve 114 is open, the third TSA bed 120 can receive gaseous feedstock.

[0051] In one embodiment, the first TSA bed 116 can be pressurized to correspond to the pressure of the gas fermentation feedstock, such that adsorption occurs at the corresponding pressure. The pressure of the second TSA bed 118 can be reduced (depressurized) to correspond to the pressure of the exhaust gas stream 136 from the gas fermentation process or the pressure of the heated exhaust gas stream 144, such that regeneration occurs at the corresponding pressure.

[0052] In some embodiments, the tail gas stream 136 or heated tail gas stream 144 from the bioreactor 100 passes through a scrubber 146. The scrubber advantageously removes trace product streams, such as ethanol, from the tail gas stream 136 or heated tail gas stream 144. Therefore, passing the tail gas stream 136 or heated tail gas stream 144 through the scrubber 146 avoids additional cleaning of the TSA bed adsorption bed and prevents loss of products that may be included in the tail gas stream 136 generated by the bioreactor 100.

[0053] refer to Figure 2A and 2B According to alternative embodiments, integrated TSA and PSA beds are disclosed. TSA has been discussed above. Pressure Swing Adsorption (PSA) uses a bed of solid adsorbent to separate components, such as contaminants. The bed is then regenerated by depressurization. PSA technology is based on the affinity of gas molecules to the adsorbent material for reversible binding. The corresponding forces acting between gas molecules and the adsorbent material depend on the gas composition, the type of adsorbent material, the partial pressure of the gas components, and the operating temperature. The separation effect is based on the difference in binding forces with the adsorbent material. PSA processes typically operate at constant temperatures and utilize the effects of alternating pressure and species partial pressure to perform adsorption and desorption. Short cycles are possible because no heating or cooling is required. Therefore, the process allows for the economical removal of large amounts of impurities. Adsorption is typically carried out at high pressures (and therefore correspondingly high partial pressures) in the range of about 10 bar to about 40 bar until the equilibrium load is reached. At this point, no further adsorption capacity is available, and the adsorbent material can be regenerated. Such regeneration is achieved by adjusting the pressure to slightly above or below atmospheric pressure, thereby correspondingly reducing the equilibrium load. Therefore, the contaminants on the adsorbent material are desorbed, and the adsorbent material is regenerated. After regeneration is terminated, the pressure increases back to the adsorption pressure level, and the process restarts from the beginning.

[0054] like Figure 2AAs shown, the integrated TSA, PSA, and gaseous fermentation process and apparatus comprises: a first TSA bed 516 containing adsorbent, a second TSA bed 518 containing spent adsorbent (i.e., adsorbent that can no longer adequately adsorb pollutants), a first PSA bed 590 containing PSA adsorbent, a second PSA bed 591 containing spent PSA adsorbent, and a gaseous fermentation process in a bioreactor 610. A gaseous feed source 500 provides a gaseous feed stream 502. The gaseous feed 502 is optionally compressed in a compressor 504 to produce a compressed gaseous feed 506. When the feed inlet valve 510 is open, the compressed gaseous feed 506 enters the first TSA bed 516 to allow the gaseous feed 506 to enter the first TSA bed 516 through an inlet stream 508a for adsorption. For example, the first TSA bed 516 operates at the adsorption temperature described above and adsorbs at least one pollutant from the gaseous feed to produce a pollutant-depleted, TSA-treated gaseous feed 522a. However, the TSA-treated gaseous feedstock may contain excess CO2 or other removable components. A first PSA bed 590 is in fluid communication with a first TSA bed, such that the contaminant-depleted TSA-treated gaseous feedstock 522a enters the first PSA bed 590 through a feed stream 540 and passes through an adsorbent to adsorb CO2 or other components in the first PSA bed 590, producing a first PSA-treated gaseous feedstock 630 enriched with fermentation substrate species such as CO and H2. As used herein, the term "enriched" means that the effluent stream has a higher concentration of a specified component than the influent stream of the vessel. The first PSA bed 590 is in fluid communication with a bioreactor 610, such that the first PSA-treated gaseous feedstock 630 enters the bioreactor 610 through a valve 575a. The bioreactor 610 produces a gaseous fermentation product stream 600 containing, for example, ethanol. Pre-removal of CO2 or other components by the first PSA bed 590 before gaseous fermentation helps enrich the feedstock of the bioreactor 610 with feedstock components favorable for certain gaseous fermentations and can increase the yield of the product in the product stream 620. The spent adsorbent in the second PSA bed 591 is regenerated by reducing the operating pressure, thus forming a PSA repulsive stream 570, which can be used as the regeneration gas for the TSA unit. As previously described, the PSA repulsive stream is heated to the TSA regeneration heater 544 using a suitable heat source. The heated PSA repulsive gas then passes through the spent adsorbent in the second TSA bed 518, thereby transferring heat to the spent adsorbent. As the adsorbent temperature increases, the adsorbed contaminants are desorbed and carried out of the TSA bed by the regeneration gas, thus forming a regeneration effluent stream 546b, which is sent to a thermal oxidizer or other suitable process. Figure 2A As shown, after the adsorbent is heated, the heater 544 needs to be shut off and eventually shut off, thereby allowing the cold PSA repulsive flow to cool the adsorbent to or near the adsorption temperature.

[0055] In another embodiment, the TSA unit is used to remove contaminants from the feed gas, and the PSA unit is used to remove contaminants from the fermentation exhaust gas, such as... Figure 2B As shown in the diagram. In this configuration, the fermentation tail gas stream 580 is optionally sent to a scrubber 440 to recover trace amounts of fermentation products contained in the fermentation tail gas stream 580. The scrubbed tail gas stream 581 is then directed to a PSA unit to remove significant contaminants, such as carbon dioxide, to enrich the concentration of gaseous fermentation substrates (such as CO and H2) before sending the gas to the bioreactor 610. The PSA repulsion stream 570 is used as the regeneration gas for the second TSA bed as described above.

[0056] Unless otherwise specified, the description of ranges in this document is intended only as a shorthand for individually referring to each individual value falling within the range, and each individual value is incorporated into the specification as if described separately herein. For example, unless otherwise stated, any concentration range, percentage range, ratio range, integer range, size range, or thickness range should be understood to include any integer value within the range, and, where appropriate, its fraction (e.g., one-tenth and one-hundredth of an integer).

[0057] Unless otherwise indicated herein or clearly contradicted by the context, all methods described herein may be performed in any suitable order. Unless otherwise stated, the use of any and all instances or exemplary language (i.e., "such") provided herein is intended only to better illustrate this disclosure and does not constitute a limitation on the scope of this disclosure. No language in this specification should be construed as indicating any unclaimed element as necessary for practicing this disclosure.

[0058] Embodiments of this disclosure

[0059] This document describes embodiments of this disclosure. Variations of these embodiments will become apparent to those skilled in the art upon reading the foregoing description, and such variations may be used where appropriate to practice within the scope of this disclosure in ways other than those specifically described herein. Therefore, this disclosure includes all modifications and equivalents of the subject matter described in the claims as permitted by applicable law. Furthermore, unless otherwise specified herein or otherwise clearly contradicted by the context, this disclosure covers any combination of the foregoing elements in all possible variations.

[0060] Example 1. A method for integrating a temperature-switching adsorption process and a gaseous fermentation process, the method comprising:

[0061] (a) Provides a temperature-switching adsorption process and a gaseous fermentation process, wherein the temperature-switching adsorption process comprises at least a first adsorption bed and a second adsorption bed, the first adsorption bed comprising an adsorbent, the second adsorption bed comprising waste adsorbent, and the gaseous fermentation process comprising a bioreactor, wherein the bioreactor contains at least one C1 immobilized microorganism in a nutrient solution.

[0062] (b) A gaseous feedstock comprising CO, CO2, H2, CH4 or any combination thereof and at least one contaminant is passed to a first adsorption bed operating at an adsorption temperature, the contaminant is adsorbed onto the adsorbent, and a treated gaseous feedstock depleted of the contaminant is produced.

[0063] (c) Transferring at least a portion of the treated gaseous feedstock to the gaseous fermentation process to generate a heated exhaust stream and a gaseous fermentation product stream containing gaseous fermentation products.

[0064] (d) First, at least a portion of the heated exhaust gas is transferred from the gaseous fermentation process to the second adsorption bed at a regeneration temperature and through the waste adsorbent to desorb the adsorbed pollutants and provide a heated, regenerated adsorbent, wherein the regeneration temperature is greater than the adsorption temperature.

[0065] (e) Then at least a portion of the treated gaseous feedstock is transferred from the first adsorption bed to the second adsorption bed and through the regenerated adsorbent, such that the heated regenerated adsorbent is cooled to the adsorption temperature and an effluent stream of the treated gaseous feedstock is provided; and

[0066] (f) Combining the effluent stream of the treated gaseous feedstock from the second adsorption bed with the treated gaseous feedstock from the first adsorption bed, or transferring the effluent stream of the treated gaseous feedstock to the gaseous fermentation process, or both.

[0067] Example 2. The method according to Example 1 further includes periodically repeating the process.

[0068] Example 3. The method according to Example 1 or 2 further includes a third adsorption bed in standby mode, the third adsorption bed containing regenerated adsorbent.

[0069] Example 4. The method according to any one of the foregoing embodiments further comprises passing the heated exhaust gas from the gaseous fermentation process through a scrubber before being delivered to the first adsorption bed to remove and recover the gaseous fermentation products from the heated exhaust gas.

[0070] Example 5. The method according to any one of the foregoing examples, wherein the adsorption temperature is in the range of about 40°C to about 60°C.

[0071] Example 6. The method according to any one of the foregoing examples, wherein the regeneration temperature is in the range of about 150°C to about 200°C.

[0072] Example 7. The method according to any one of the foregoing examples, wherein the gaseous feedstock is selected from industrial waste gas, syngas, biogas, landfill gas, direct air capture, or any combination thereof.

[0073] Example 8. The method according to any one of the foregoing examples, wherein the synthesis gas is generated by a reforming process, a partial oxidation process, a gasification process, or any combination thereof.

[0074] Example 9. The method according to any one of the foregoing examples, wherein the industrial gas is obtained from a source selected from: iron and steel manufacturing, non-ferrous product manufacturing, petroleum refining, power generation, carbon black production, paper and pulp manufacturing, ammonia production, methanol production, coke manufacturing, petrochemical production, carbohydrate fermentation, cement manufacturing, aerobic digestion, anaerobic digestion, natural gas extraction, cellulose fermentation, oil extraction, industrial processing of geological reservoirs, processing of fossil resources, or any combination thereof.

[0075] Example 10. The method according to any one of the foregoing examples, wherein the contaminant is selected from at least one of the following: hydrocarbons, oxygen-containing compounds, sulfur compounds, nitrogen compounds, or any combination thereof.

[0076] Example 11. The method according to any one of the foregoing examples, wherein the adsorbent or the waste adsorbent is selected from zeolite molecular sieve, activated carbon, silica gel, activated alumina or any combination thereof.

[0077] Example 12. The method according to any one of the foregoing embodiments further comprises: (a) adjusting the operating pressure of the first adsorption bed to correspond to the pressure of the gaseous feedstock; (b) adjusting the operating pressure of the second adsorption bed to correspond to the pressure of the heated tail gas flow from the gaseous fermentation process; or both (a) and (b).

[0078] Example 13. A method for integrating a temperature swing adsorption process, a pressure swing adsorption process, and a gaseous fermentation process, the method comprising:

[0079] The system provides a temperature swing adsorption (TSA) process, a pressure swing adsorption (PSA) process, and a gaseous fermentation process. The TSA process includes at least a first TSA adsorption bed and a second TSA adsorption bed, the first TSA adsorption bed containing a TSA adsorbent and the second TSA adsorption bed containing spent TSA adsorbent. The PSA process includes at least a first PSA adsorption bed and a second PSA adsorption bed, the first PSA adsorption bed containing a PSA adsorbent and the second PSA adsorption bed containing spent PSA adsorbent. The gaseous fermentation process includes a bioreactor containing at least one C1 immobilized microorganism in a nutrient solution. A gaseous feedstock comprising CO, CO2, H2, CH4, or any combination thereof, and at least one pollutant are passed to the first TSA adsorption bed operating at an adsorption temperature. The pollutant is adsorbed onto the TSA adsorbent, and a TSA-treated gaseous phase depletes the pollutant. The process involves: passing at least a portion of the treated gaseous feedstock to a first PSA adsorption bed operating at an adsorption pressure to adsorb CO2 onto the PSA adsorbent and generate a CO2-depleted PSA-treated gaseous feedstock; passing the PSA-treated gaseous feedstock to a gaseous fermentation process to generate a gaseous fermentation product stream containing gaseous fermentation products; first passing at least a portion of the TSA-treated gaseous feedstock to a second PSA adsorption bed operating at a desorption pressure to desorb CO2 from the PSA waste adsorbent and generate a CO-rich PSA purge gas stream, wherein the desorption pressure is different from the adsorption pressure; and then passing at least a portion of the PSA purge gas stream from the second PSA adsorption bed to the second TSA adsorption bed at a desorption temperature to desorb the adsorbed pollutants and provide a TSA purge gas containing the pollutants and CO2.

[0080] Example 14. A method for integrating a temperature swing adsorption process, a pressure swing adsorption process, and a gaseous fermentation process, the method comprising:

[0081] The system provides a temperature swing adsorption process, a pressure swing adsorption process, and a gaseous fermentation process. The temperature swing adsorption process includes at least a first TSA adsorption bed and a second TSA adsorption bed. The first TSA adsorption bed contains a TSA adsorbent, and the second TSA adsorption bed contains spent TSA adsorbent. The pressure swing adsorption process includes at least a first PSA adsorption bed and a second PSA adsorption bed. The first PSA adsorption bed contains a PSA adsorbent, and the second PSA adsorption bed contains spent PSA adsorbent. The gaseous fermentation process includes a bioreactor containing at least one C1 immobilized microorganism in a nutrient solution.

[0082] A gaseous feedstock comprising CO, CO2, H2, CH4 or any combination thereof and at least one pollutant are passed to a first TSA adsorption bed operating at an adsorption temperature, the pollutant is adsorbed onto the TSA adsorbent, and a TSA-treated gaseous feedstock depleted of the pollutant is produced.

[0083] At least a portion of the treated gaseous feedstock is fed into a gaseous fermentation process to generate fermentation tail gas and a gaseous fermentation product stream containing gaseous fermentation products.

[0084] At least a portion of the fermentation tail gas is transferred to the first PSA adsorption bed operating under adsorption pressure, whereby CO2 is adsorbed onto the PSA adsorbent, and CO2-depleted PSA-treated fermentation tail gas and PSA purge gas are generated.

[0085] At a desorption temperature, at least a portion of the PSA purge gas is transferred from the first PSA adsorption bed to the second TSA adsorption bed to desorb the adsorbed pollutants and provide TSA purge gas containing the pollutants and CO2.

[0086] Example 15. An integrated temperature-switching adsorption and gas fermentation device, comprising:

[0087] A gaseous raw material source unit is in fluid communication with a first adsorption bed containing an adsorbent, the first adsorption bed further including a treated gaseous raw material outlet;

[0088] A second adsorption bed, comprising waste adsorbent and having an effluent outlet, wherein the treated gaseous feed outlet of the first adsorption bed is further in fluid communication with the second adsorption bed; and

[0089] A bioreactor in a gaseous fermentation apparatus, wherein the bioreactor is in fluid communication with the treated gaseous feed outlet of the first adsorption bed and the effluent outlet of the second adsorption bed, the bioreactor comprising a tail gas outlet and a product outlet, the tail gas outlet being in fluid communication with the second adsorption bed.

[0090] Example 16. The apparatus according to Example 15 further includes a third adsorption bed in standby mode, the third adsorption bed containing regenerated adsorbent, the third adsorption bed being in fluid communication with the bioreactor.

[0091] Example 17. The apparatus according to Example 15, wherein the scrubber is in fluid communication with the exhaust gas outlet of the bioreactor, and the scrubber is further in fluid communication with the second adsorption bed.

[0092] Example 18. The apparatus according to any one of Examples 15, wherein each of the variable temperature adsorption bed and the bioreactor is in fluid communication with at least one on-off valve.

[0093] Example 19. The apparatus according to any one of Examples 15, further comprising a regeneration heater in fluid communication with the exhaust gas outlet of the bioreactor.

[0094] Example 20. An integrated temperature swing adsorption, pressure swing adsorption, and gas fermentation device, comprising:

[0095] A gaseous feedstock source unit is in fluid communication with a first TSA adsorption bed containing an adsorbent, the first TSA adsorption bed further including a treated gaseous feedstock outlet;

[0096] A first PSA adsorption bed, comprising a PSA adsorbent, is in fluid communication with the treated gaseous feed outlet of a first TSA adsorption bed, wherein the first PSA adsorption bed is further in fluid communication with the bioreactor; and

[0097] A second PSA adsorption bed, comprising PSA waste adsorbent, is in fluid communication with the treated gaseous feed outlet of the first TSA adsorption bed, wherein the second PSA adsorption bed is further in fluid communication with a second TSA adsorption bed comprising TSA waste adsorbent.

Claims

1. An integrated temperature swing adsorption and gas fermentation apparatus, comprising: i. a gaseous feedstock source unit, said gaseous feedstock source unit in fluid communication with a first adsorption bed comprising an adsorbent, said first adsorption bed further comprising a treated gaseous feedstock outlet; ii. a second adsorption bed, said second adsorption bed comprising spent adsorbent and having an effluent outlet, wherein said treated gaseous feedstock outlet of said first adsorption bed is further in fluid communication with said second adsorption bed; and iii. a bioreactor of a gas fermentation apparatus, said bioreactor in fluid communication with said treated gaseous feedstock outlet of said first adsorption bed and said effluent outlet of said second adsorption bed, said bioreactor comprising a tail gas stream outlet and a product stream outlet, said tail gas stream outlet in fluid communication with said second adsorption bed.

2. The apparatus of claim 1, wherein further comprising a third adsorption bed in standby mode, said third adsorption bed comprising regenerated adsorbent, said third adsorption bed in fluid communication with said bioreactor.

3. The apparatus of claim 1 wherein a scrubber in fluid communication with said tail gas stream outlet of said bioreactor, said scrubber further in fluid communication with said second adsorption bed.

4. The apparatus of claim 1 wherein each of said temperature swing adsorption bed and said bioreactor in fluid communication with at least one on-off valve.

5. The apparatus of claim 1 wherein further comprising a regeneration heater, said regeneration heater in fluid communication with said tail gas stream outlet of said bioreactor.

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