System for removing impurities from gas stream

Abstract

A method and system for generating a fermentable gas stream from a gas source containing one or more impurities that may be detrimental to a fermentation process is provided. To produce the fermentable gas stream, the gas stream passes through a series of specially ordered removal beds. The removal bed removes and / or converts various impurities found in the gas stream that may have a harmful effect on a downstream removal bed and / or an inhibitory effect on downstream gas fermentation microorganisms. At least a portion of the fermentable gas stream may be able to be passed to a bioreactor containing gaseous fermentation microorganisms.

Description

Technical Field

[0001] The present invention relates to systems and methods for removing impurities from gas streams. In particular, the present invention relates to removing impurities from gas streams that may be detrimental to C1 stationary microorganisms in subsequent removal beds and / or downstream fermentation processes. Background Art

[0002] The following discussion is provided to assist the reader in understanding the present disclosure, and it is not admitted that the following discussion describes or constitutes prior art thereof.

[0003] Mitigating the impending climate change requires a major transformation of the manufacturing industry and a greater reliance on biotechnology. Sustainable sources of fuels and chemicals are currently insufficient to significantly replace reliance on fossil carbon. Biotechnology uses the power of biology to create new products that improve the quality of life and the environment. Gas fermentation has emerged as a powerful biotechnology advancement as an alternative platform for biological fixation of such gases as CH4, CO, CO2 and / or H2 into sustainable fuels and chemicals. Specifically, gas fermentation technology can produce ethanol, aviation fuel, chemicals and various other products using a wide range of raw materials including gasified carbonaceous materials such as municipal solid waste or agricultural waste or industrial waste gases such as waste gases from steel manufacturing, refineries and petrochemical processes. Gas fermentation alone can replace 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 can be fully realized. The present disclosure advances the science of scaling up production and reducing barriers to the continued commercialization of gas fermentation.

[0004] Gas fermentation processes can be used to produce target materials from gaseous substrates or other input materials, particularly carbon-based materials. For example, specific biological systems can be used to perform gas fermentation. Such methods and systems are alternatives to traditional methods and have important benefits that help address climate change. C1 fixed microorganisms that fix carbon dioxide (CO2) and / or carbon monoxide (CO) can alleviate the impact of dependence on fossil carbon because these microorganisms can convert gaseous carbon into useful fuels and chemicals.

[0005] Industrial processes may output gases that contain large amounts of carbon-based materials. Chemical processing plants and refineries typically burn and vent carbon-rich sources into the atmosphere or otherwise discard them as a traditional standard operation. Currently, the main alternative for chemical processing plants and refineries is to engage in some form of carbon capture and storage ("CCS"). CCS can involve finding permanent underground repositories, such as depleted oil wells or sealed saline formations, to permanently store gaseous carbon.

[0006] In addition, there is currently a large amount of "above ground" carbon that can be recovered from carbon in waste to carbon in newly produced chemicals through a gas fermentation process. Waste can be gasified into syngas, which in turn becomes the feedstock for a gas fermentation process to produce newly produced chemicals, thereby recovering carbon. This cycle is carbon capture and utilization ("CCU"), not CCS.

[0007] The wide range of industries that generate these gas streams always introduce impurities due to process variables and trace elements in the process feedstock. These impurities may affect the downstream conversion performance of the gas fermentation microorganisms. For example, single nitrogen-containing species such as hydrogen cyanide (HCN), ammonia (NH3), nitrogen oxides (NO x ) and other known enzyme inhibiting gases such as acetylene (C2H2), ethylene (C2H4), BTEX (benzene, toluene, ethylbenzene, xylene) and oxygen (O2). Sulfur compounds in the gas such as hydrogen sulfide (H2S), carbonyl sulfide (COS), carbon disulfide (CS2) and sulfur oxide (Sox) compounds such as SO2 and SO3 can in turn have a negative impact on catalyst-based scrubbing systems. The same is true for synthesis gas produced from carbonaceous waste materials. Even more variability can be found in synthesis gas.

[0008] For many impurity compounds, there are commercially available removal systems; however, these systems have not been used for microbial gas fermentation. As a downstream process, microbial gas fermentation is a relatively new alternative to conventional catalytic conversion technology and has relatively specific impurity restrictions. In order to ensure successful non-inhibitory gas fermentation, treatment of these gases must be completed to protect the F1 stationary microorganisms.

[0009] There are three major problems with cleaning gas for gas fermentation, including (1) excessive consumption of the reactant compounds desired for microbial fermentation; (2) reaction to form other undesirable compounds that will act as inhibitors to the microorganisms; and (3) reducing the inhibitory compounds in the feed stream to sufficiently low levels to ensure successful, uninhibited gas fermentation.

[0010] In industry, there are situations where existing equipment used for one method may be modified to accommodate technological advances or reused for another method. The goal is usually to minimize capital expenditures by using existing equipment rather than building new equipment. Current gas processing methods can use three or more heat exchangers, and three, four or more separate containers, each containing materials for reacting and or removing impurities from the source gas. In the case of transformation, the desired number of containers and heat exchangers is usually not available. Therefore, it is necessary to merge several traditional gas processing steps into one container. However, the challenge is that the combined steps need to operate at the same temperature because they are co-located in the same container. Typically, adsorbents require lower temperatures and catalysts require relatively high temperatures. It is necessary to select adsorbents and catalysts that perform their functions at the same temperature when co-located in the same container. Since all materials are co-located in a single container operating at a common temperature, only one heater or heat exchanger is required.

[0011] Therefore, there remains a need for an invention that strategically processes gas streams and or syngas from industrial or other processes to provide a suitable gas as a feedstock for a downstream fermentation process. Summary of the invention

[0012] The present disclosure provides a method for removing impurities from an input gas stream to produce a fermentable gas stream, the method comprising:

[0013] a. heating the input gas stream to a temperature effective for the deoxygenation catalyst and below the reduction temperature of the sulfur guard bed material to produce a heated input gas stream;

[0014] b. contacting the heated input gas stream in a container with:

[0015] i. a hydrolysis catalyst bed for removing hydrogen cyanide to less than 1 ppm of hydrogen cyanide and / or removing carbonyl sulfide to less than 1 ppm of carbonyl sulfide;

[0016] ii. an optional sulfur guard bed, the optional sulfur guard bed containing materials effective to remove and / or react sulfur-containing compounds, the optional sulfur guard bed being positioned in juxtaposition with or downstream of the hydrolysis bed; and

[0017] iii. a deoxygenation catalyst bed, the deoxygenation catalyst bed being positioned downstream of the sulfur guard bed;

[0018] c. wherein the fermentable gas stream comprises less than about 100 ppm oxygen, less than about 1 ppm acetylene, and less than about 1 ppm hydrogen cyanide.

[0019] In one embodiment, the method further comprises contacting the heated input gas stream with a hydrocarbon removal adsorbent bed in the vessel positioned upstream of the hydrolysis catalyst bed, or contacting the input gas stream with a hydrocarbon removal adsorbent bed in a module upstream of the heating and the vessel.

[0020] In one embodiment, the hydrolysis catalyst bed and the sulfur guard bed are a physical mixture forming a combined hydrolysis and sulfur guard bed.

[0021] In one embodiment, the method further comprises passing at least a portion of the fermentable gas stream into a bioreactor, wherein the bioreactor contains a culture comprising a fermentation broth and at least one C1 immobilized microorganism.

[0022] In one embodiment, at least a portion of the input gas stream is syngas and / or producer gas.

[0023] In one embodiment, the method further comprises measuring the concentration of impurities in the input gas stream and / or the fermentable gas stream.

[0024] In one embodiment, the input gas flow includes CO, CO2, H2 or any combination thereof.

[0025] In one embodiment, the sulfur guard bed material is zinc oxide or copper and zinc oxide supported on alumina.

[0026] In one embodiment, the deoxygenation catalyst comprises copper supported on alumina, silica, titania, ceria, lanthanum oxide, carbon, silica-alumina or zeolite.

[0027] In one embodiment, the hydrocarbon removal adsorbent is activated carbon.

[0028] In one embodiment, the hydrolysis bed and the sulfur guard bed are a combined hydrolysis and sulfur guard bed comprising bifunctional zinc oxide on an alumina support or copper and zinc oxide on an alumina support.

[0029] In one embodiment, the hydrolysis bed and the sulfur guard bed are a combined hydrolysis and sulfur guard bed comprising bifunctional zinc oxide on an alumina support or copper and zinc oxide on an alumina support.

[0030] The present disclosure provides a system for removing impurities from a gas stream, comprising:

[0031] a. a heating device, the heating device having a heating device gas inlet and a heating device gas outlet;

[0032] b. A container having a container gas inlet in fluid communication with the heating device gas outlet and a container fermentable gas outlet, wherein the single container contains at least three beds, the at least three beds comprising:

[0033] i. a hydrolysis catalyst bed, the hydrolysis catalyst bed comprising alumina;

[0034] ii. an optional sulfur guard bed comprising zinc oxide or copper and zinc oxide on an alumina support, the optional sulfur guard bed being positioned in juxtaposition with or downstream of the hydrolysis catalyst bed;

[0035] iii. a deoxygenation catalyst bed located downstream of the sulfur guard bed, wherein the deoxygenation catalyst comprises copper supported on alumina, silica, titania, ceria, lanthanum oxide, carbon, silica-alumina or zeolite; and

[0036] c. A bioreactor having a bioreactor gas inlet in fluid communication with the vessel fermentable gas outlet and a bioreactor fermentation broth output, wherein the bioreactor comprises at least one C1 immobilized microorganism.

[0037] In one embodiment, the system further comprises at least one monitoring device, wherein the at least one monitoring device is in communication with the gas inlet of the container, the fermentable gas outlet of the container, or both.

[0038] In one embodiment, the vessel further comprises a hydrocarbon removal bed comprising activated carbon positioned in the vessel upstream of the hydrolysis catalyst bed.

[0039] In one embodiment, the system further comprises a hydrocarbon removal module comprising activated carbon and having a hydrocarbon removal module gas inlet and a hydrocarbon removal module gas outlet, the hydrocarbon removal module gas outlet being in fluid communication with the heating device gas inlet.

[0040] The present disclosure provides a method for modifying a gas processing system, the method comprising:

[0041] a. Co-locate the following in a repurposed container:

[0042] i. a hydrolysis catalyst bed for removing hydrogen cyanide to less than 1 ppm of hydrogen cyanide and / or removing carbonyl sulfide to less than 1 ppm of carbonyl sulfide;

[0043] ii. an optional sulfur guard bed, the optional sulfur guard bed containing materials effective to remove and / or react sulfur-containing compounds, the optional sulfur guard bed being positioned in juxtaposition with or downstream of the hydrolysis bed; and

[0044] iii. a deoxygenation catalyst bed, the deoxygenation catalyst bed being positioned downstream of the sulfur guard bed.

[0045] In one embodiment, the method further comprises connecting a recycling heating device upstream of the recycling container.

[0046] In one embodiment, the method further comprises connecting a hydrocarbon removal module comprising activated carbon upstream of the reuse heating device.

[0047] As described above, the present disclosure provides a method for producing a fermentable gas stream from an input gas stream, wherein the input gas stream includes CO, CO2, H2 or a combination thereof, wherein the method includes: passing the input gas stream into a hydrolysis bed, wherein at least one impurity of the gas stream is removed and / or converted to provide a post-hydrolysis gas stream; passing the post-hydrolysis gas stream into a sulfur protection bed or an acid gas removal bed, wherein at least one additional impurity of the gas stream is removed and / or converted to produce an acid gas-depleted stream; passing the acid gas-depleted stream into a deoxygenation bed, wherein at least one additional impurity is removed and / or converted to produce a fermentable gas stream.

[0048] In at least one embodiment, the at least one impurity removed is a microbial inhibitor and / or a catalyst inhibitor.

[0049] In embodiments, at least one or more of the impurities removed and / or converted by the hydrolysis bed is carbonyl sulfide (COS) and / or hydrogen cyanide (HCN).

[0050] The impurities removed and / or converted by the acid gas removal bed may be selected from the group consisting of carbon dioxide (CO2), hydrogen sulfide (H2S), and hydrogen cyanide (HCN).

[0051] In an embodiment, at least one or more of the impurities removed and / or converted by the deoxygenation bed are oxygen (O 2 ) and / or acetylene (C 2 H 2 ).

[0052] In certain examples, the hydrolysis bed is bypassed and the input gas stream is delivered to the acid gas removal bed.

[0053] The method may further comprise a catalytic hydrogenation bed. In embodiments utilizing a catalytic hydrogenation bed, the acid gas depleted stream is passed to a catalytic hydrogenation bed prior to being passed to the deoxygenation bed, wherein at least one impurity from the acid gas depleted stream is removed and / or converted prior to being passed to the deoxygenation bed. At least one impurity removed and / or converted by the catalytic hydrogenation bed is acetylene (C2H2).

[0054] The method may comprise at least one additional bed selected from the group consisting of a particulate removal bed, a chloride removal bed, a tar removal bed, a hydrogen cyanide removal bed, an additional acid gas removal bed, a temperature module, and a pressure module.

[0055] In certain instances, the additional acid gas removal bed is a pressure swing adsorption (PSA) bed or a temperature swing adsorption bed (TSA).

[0056] In an example, the method includes a monitoring device for measuring the level of impurities in the gas stream. The one or more monitoring devices can be placed before and / or after one or more beds. In some cases, the method can bypass one or more beds depending on the level of one or more impurities in the gas stream.

[0057] The method may include a hydrogen cyanide removal bed capable of receiving the post-deoxygenated gas stream. The hydrogen cyanide removal bed may remove at least a portion of the hydrogen cyanide from the gas stream before the gas stream is passed into the bioreactor.

[0058] Prior to being passed into the bioreactor, the impurity level may be reduced to a predetermined level so that the gas stream is fermentable. In an embodiment, the predetermined impurity level includes no more than 100 parts per million (100 ppm) of oxygen (O2), 1 part per million (1 ppm) of hydrogen cyanide (HCN), and 1 part per million (1 ppm) of acetylene (C2H2). In some cases, the predetermined impurity level includes no more than 100 parts per billion (100 ppb) of hydrogen cyanide (HCN).

[0059] The bioreactor may contain a culture comprising a fermentation broth and one or more microorganisms. In an embodiment, the one or more microorganisms are C1 fixed bacteria or carboxydotrophic bacteria.

[0060] Instead of or prior to passing the treated gas stream to a bioreactor, the method can send the treated gas stream to a carbon capture unit.

[0061] In certain embodiments, the method can receive a gas stream from one or more sources. At least a portion of the gas stream can be derived from an industrial source. Additionally, at least a portion of the gas stream can be syngas. Additionally, at least a portion of the gas stream can be producer gas.

[0062] In an embodiment, the present invention provides a method for producing a fermentable gas stream, wherein the method includes treating a gas stream in a gas treatment process to remove one or more undesirable impurities from the gas stream, the gas stream including CO, CO2 or H2, wherein the steps of treating the gas stream include: passing the gas stream into a hydrolysis bed, wherein at least one impurity in the gas stream is converted to provide a post-hydrolyzed stream; passing the post-hydrolyzed stream into an acid gas removal bed, wherein at least one additional impurity in the stream is removed to provide an acid gas depleted stream; and passing the acid gas depleted stream into a deoxygenation bed, wherein at least one additional impurity is converted to provide a fermentable gas stream.

[0063] The fermentable gas stream may include depleted levels of oxygen (O2), hydrogen cyanide (HCN), and acetylene (C2H2) compared to the input gas stream prior to passing through the process.

[0064] In one embodiment, the fermentable gaseous stream comprises less than 100 parts per million (ppm) oxygen (O2).

[0065] In one embodiment, the fermentable gaseous stream comprises less than 1 part per million (1 ppm) of hydrogen cyanide (HCN).The fermentable gaseous substrate may comprise less than 100 parts per billion (100 ppb) of hydrogen cyanide (HCN).

[0066] In one embodiment, the fermentable gaseous stream comprises less than 1 part per million (1 ppm) of acetylene (C2H2).

[0067] In various embodiments, the method utilizes one or more dedicated catalysts to produce a fermentable gas stream from an input gas stream. The dedicated catalyst can be used to reduce oxygen to less than 100 ppm, acetylene to less than 1 ppm, and hydrogen cyanide to less than 1 ppm. In some cases, the dedicated catalyst includes reduced copper metal on a high surface area catalyst such as silica, alumina, titania, cerium dioxide, lanthanum oxide, silica-alumina, carbon, or many other materials known to those skilled in the art. In some cases, the dedicated catalyst used is alumina-supported copper (I). In some cases, the dedicated catalyst includes sulfided alumina-supported copper (I) so that the dedicated catalyst is sulfur-resistant. In some cases, the dedicated catalyst includes alumina-supported copper (II). In some cases, the dedicated catalyst includes sulfided alumina-supported copper (II) so that the dedicated catalyst is sulfur-resistant. The dedicated catalyst may include sulfided alumina-supported copper when treating an input gas stream with a high sulfur content.

[0068] In various embodiments, the method receives an input stream comprising various impurities at various levels. In some cases, the input gas stream comprises up to 7000ppm of oxygen, up to 700ppm of acetylene and up to 60ppm of hydrogen cyanide, which may represent gases received from a steel mill. In some cases, the input stream comprises up to 10,000ppm of oxygen, up to 1500ppm of acetylene and up to 500ppm of hydrogen cyanide, which may represent gas streams (biomass or municipal solid waste) or processed coke oven gas from a gasification process. The input gas stream may comprise up to 7000ppm of oxygen, up to 700ppm of acetylene and up to 60ppm of hydrogen cyanide. The input gas stream may comprise up to 10000ppm of oxygen, up to 1500ppm of acetylene and up to 500ppm of hydrogen cyanide. The input gas stream may include up to 7000 ppm oxygen, up to 700 ppm acetylene, and up to 60 ppm hydrogen cyanide, or the input gas stream may include up to 10000 ppm oxygen, up to 1500 ppm acetylene, and up to 500 ppm hydrogen cyanide.

[0069] The method may consume less than 10% of the carbon monoxide in the input gas stream. In some cases, the method may be performed under pressure. For example, the method may be performed under a pressure of at least 138 kPag.

[0070] At least a portion of the fermentable gas stream may be provided to a bioreactor containing a culture of C1 stationary microorganisms. The C1 stationary microorganisms are typically carboxydotrophic bacteria. The carboxydotrophic bacteria may be selected from the group consisting of Moorella, Clostridium, Ruminococcus, Acetobacterium, Eubacterium, Butyribacterium, Oxobacter, Methanosarcina, and Desulfotomaculum.

[0071] The carboxydotrophic bacteria may be ethanologenic Clostridium.

[0072] In some cases, the industrial source may be selected from the group consisting of: ferrous metal product manufacturing such as steel mill manufacturing, non-ferrous metal product manufacturing, petroleum refining, coal gasification, power generation, carbon black production, ammonia production, methanol production, and coke production.

[0073] In some cases, the syngas source is selected from the group consisting of: gasification of coal or refinery residues, gasification of biomass or lignocellulosic materials, reforming of natural gas, and gasification of municipal or industrial solid waste.

[0074] The present disclosure provides a method for removing impurities from an input gas stream to produce a fermentable gas stream, the method comprising:

[0075] a. heating the input gas stream to a temperature effective for the deoxygenation catalyst and below the reduction temperature of the sulfur guard bed material to produce a heated input gas stream;

[0076] b. contacting the heated input gas stream in a first container with:

[0077] i. a hydrolysis catalyst bed for removing hydrogen cyanide to less than 1 ppm of hydrogen cyanide and / or removing carbonyl sulfide to less than 1 ppm of carbonyl sulfide;

[0078] ii. a first sulfur guard bed, the first sulfur guard bed containing a material effective to remove sulfur-containing compounds and / or react sulfur-containing compounds, the first sulfur guard bed being positioned in juxtaposition with the hydrolysis bed or positioned downstream of the hydrolysis bed;

[0079] c. contacting the effluent from the first container in a second container with:

[0080] i. a second sulfur guard bed, the second sulfur guard bed containing a material that is effective in removing sulfur-containing compounds and / or reacting sulfur-containing compounds;

[0081] ii. a deoxygenation catalyst bed, the deoxygenation catalyst bed being positioned downstream of the sulfur guard bed;

[0082] d. wherein the fermentable gas stream comprises less than about 100 ppm oxygen, less than about 1 ppm acetylene, and less than about 1 ppm hydrogen cyanide.

[0083] The method may further comprise contacting the heated input gas stream with a hydrocarbon removal adsorbent bed located upstream of the hydrolysis catalyst bed in the vessel, or contacting the input gas stream with a hydrocarbon removal adsorbent bed in a module upstream of the heating and the vessel.

[0084] The hydrolysis catalyst bed and the first sulfur guard bed may be a physical mixture forming a combined hydrolysis and sulfur guard bed.

[0085] The method may further comprise passing at least a portion of the fermentable gas stream to a bioreactor, wherein the bioreactor contains a culture comprising a fermentation broth and at least one C1 immobilized microorganism.

[0086] At least a portion of the input gas stream may be syngas and / or producer gas.

[0087] The method may further comprise measuring the concentration of impurities in the input gas stream and / or the fermentable gas stream.

[0088] The input gas stream may include CO, CO2, H2, or any combination thereof.

[0089] The first and or second sulphur guard bed materials may be zinc oxide or copper and zinc oxide supported on alumina.

[0090] The deoxygenation catalyst may include copper supported on alumina, silica, titania, ceria, lanthanum oxide, carbon, silica-alumina, or zeolites.

[0091] The hydrocarbon removal absorbent may be activated carbon.

[0092] The hydrolysis bed and the first sulfur guard bed may be a combined hydrolysis and first sulfur guard bed comprising bifunctional zinc oxide on an alumina support or copper and zinc oxide on an alumina support.

[0093] The present disclosure further provides a system for removing impurities from a gas stream, comprising:

[0094] a. a heating device, the heating device having a heating device gas inlet and a heating device gas outlet;

[0095] b. a first container having a first container gas inlet in fluid communication with the heating device gas outlet and a first container gas outlet, wherein the first container contains at least two beds, the at least two beds comprising:

[0096] i. a hydrolysis catalyst bed, the hydrolysis catalyst bed comprising alumina;

[0097] ii. a first sulfur guard bed comprising zinc oxide or copper and zinc oxide on an alumina support, the first sulfur guard bed being positioned juxtaposed with or downstream of the hydrolysis catalyst bed;

[0098] c. a second container having a second container gas inlet in fluid communication with the first container gas outlet and a second container fermentable gas outlet, wherein the second container contains at least two beds, the at least two beds comprising:

[0099] i. a second sulfur guard bed, the second sulfur guard bed comprising zinc oxide or copper and zinc oxide on an alumina support;

[0100] ii. a deoxygenation catalyst bed located downstream of the second sulfur guard bed, wherein the deoxygenation catalyst comprises copper supported on alumina, silica, titania, ceria, lanthanum oxide, carbon, silica-alumina or zeolite; and

[0101] d. A bioreactor having a bioreactor gas inlet in fluid communication with the second vessel fermentable gas outlet and a bioreactor fermentation broth output, wherein the bioreactor comprises at least one C1 immobilized microorganism.

[0102] The system may further include at least one monitoring device in communication with the container gas inlet, the container fermentable gas outlet, or both.

[0103] The system may further include a hydrocarbon removal bed comprising activated carbon positioned in the vessel upstream of the hydrolysis catalyst bed.

[0104] The system may further include a hydrocarbon removal module including activated carbon and having a hydrocarbon removal module gas inlet and a hydrocarbon removal module gas outlet in fluid communication with the heating device gas inlet. BRIEF DESCRIPTION OF THE DRAWINGS

[0105] The following detailed description is merely exemplary in nature and is not intended to limit the various embodiments or the application and use of the various embodiments. In addition, it is not intended to be bound by any theory presented in the previous background technology or the following detailed description. The drawings are simplified by deleting a large number of devices commonly used in processes of this nature, which are not specifically required to illustrate the performance of the present invention. In addition, the description of the process of the present disclosure in the embodiments of specific drawings is not intended to limit the present invention to specific embodiments. Some embodiments can be described with reference to the method configuration shown in the figure, and the figure relates to both the equipment and method for performing the present disclosure. Any reference to the method includes reference to the equipment unit or equipment suitable for performing the steps, and vice versa.

[0106] Figure 1 A process flow diagram is shown depicting the location of hydrocarbon removal beds, hydrolysis beds, sulfur guard beds, and deoxygenation beds all located within a common vessel, according to one embodiment of the present disclosure.

[0107] Figure 2 A process flow diagram is shown depicting the location of the hydrolysis bed, sulfur guard bed, and deoxygenation bed all located within a common vessel in accordance with one embodiment of the present disclosure.

[0108] Figure 3A process flow diagram is shown depicting the location of a hydrocarbon removal bed, a hydrolysis bed, and a first sulfur guard bed all located within a first common vessel, and a second sulfur guard bed and a deoxygenation bed both located within a second common vessel, according to one embodiment of the present disclosure.

[0109] Figure 4 A process flow diagram is shown depicting the location of a hydrolysis bed and a first sulfur guard bed, both located within a first common vessel, and a second sulfur guard bed and a deoxygenation bed, both located within a second common vessel, according to one embodiment of the present disclosure. DETAILED DESCRIPTION

[0110] The present disclosure provides systems and methods for improving carbon capture and increasing overall production yields in oil refining and chemical manufacturing facilities by integrating microbial fermentation into existing oil and gas infrastructure, wherein the microbial fermentation converts a carbon source that would otherwise be emitted to the atmosphere or discarded into one or more products. More specifically, the present disclosure relates to systems and methods for incorporating gas fermentation into oil and gas production and refining and chemical complexes to convert various feedstocks, waste gases and other gaseous byproducts into useful products such as ethylene, ethanol, etc.

[0111] The present disclosure provides systems and methods for improving carbon capture and utilization by integrating a series of impurity removal / reaction beds, wherein impurities can be removed from an input gas, wherein the impurities can inhibit downstream removal beds and / or downstream gas fermentation processes. The selection of adsorbents and catalysts is identified, and the order in which the adsorbents and catalysts are placed is provided. Two or more adsorbents and or catalysts can be co-located as beds within a single vessel.

[0112] definition

[0113] It should be understood that the terms used herein are only for the purpose of describing specific embodiments and are not intended to be limiting. Unless otherwise defined, the technical terms and scientific terms used herein have the meanings commonly understood by those of ordinary skill in the art. Unless otherwise stated, based on the guidance provided herein, materials and / or methods known to those of ordinary skill in the art can be used to implement the methods described herein.

[0114] As used herein, the singular terms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Unless explicitly stated otherwise, reference to an object in the singular is not intended to mean "one and only one," but rather "one or more."

[0115] As used herein, "about" when used with a numerical value means the numerical value and ±10% of the numerical value. For example, "about 10" should be understood as both "10" and "9-11".

[0116] Furthermore, 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 a combination when interpreted in the alternative form ("or").

[0117] The term "substrate comprising carbon monoxide" and similar terms should be understood to encompass, for example, any substrate in which carbon monoxide can be used for growth and / or fermentation of one or more bacterial strains.

[0118] The term "gaseous substrate comprising carbon monoxide" encompasses any gas containing carbon monoxide. The gaseous substrate may contain a significant proportion of CO, such as at least about 5% to about 100% CO by volume.

[0119] The term "C1 carbon" and similar terms should be understood to refer to a carbon source suitable for use by microorganisms, specifically a carbon source for the gas fermentation process disclosed herein. C1 carbon can include but is not limited to carbon monoxide (CO), carbon dioxide (CO2), methane (CH4), methanol (CH3OH) and formate (HCOOH).

[0120] The term "substrate comprising carbon dioxide" and similar terms should be understood to encompass, for example, any substrate in which carbon dioxide is available for growth and / or fermentation of one or more bacterial strains.

[0121] The term "gaseous substrate comprising carbon dioxide" encompasses any gas containing carbon dioxide. The gaseous substrate may contain a significant proportion of CO2, such as at least about 5% to about 100% CO2 by volume.

[0122] The term "cosubstrate" refers to a substance that, while not necessarily serving as the primary source of energy and material for product synthesis, can be used in product synthesis when added to, for example, a primary substrate.

[0123] When referring to passing industrial waste gases or gases into a bioreactor, the term "directly" is used to mean that no or minimal processing or treatment steps, such as cooling and particulate removal, are performed on the gas before it enters the bioreactor (note: anaerobic fermentation may require an oxygen removal step).

[0124] As used herein, the terms "fermentation", "fermentation process", "fermentation reaction" and similar terms are intended to encompass both the growth phase and the product biosynthesis phase of the process. As further described herein, in some embodiments, a bioreactor may include a primary bioreactor and a secondary bioreactor.

[0125] As used herein, the term "nutrient medium" is to be understood as a solution added to a fermentation broth which contains nutrients and other components suitable for the growth of a microbial culture.

[0126] As used herein, the term "primary bioreactor" or "first reactor" is intended to encompass one or more reactors that may be connected in series or in parallel with a secondary bioreactor. Primary bioreactors typically produce products (e.g., ethylene, ethanol, acetate, etc.) from gaseous substrates using anaerobic or aerobic fermentation.

[0127] As used herein, the term "secondary bioreactor" or "secondary reactor" may encompass any number of additional bioreactors that may be connected in series or in parallel with the primary bioreactor. Any one or more of these additional bioreactors may also be connected to an additional separator.

[0128] The term "stream" is used to refer to a flow of material entering, passing through, and leaving one or more stages of a process, such as material fed to a bioreactor. The composition of a stream may change as it passes through a particular stage. For example, as a stream passes through a bioreactor.

[0129] The term "feedstock" when used in the context of a stream flowing into a gas fermentation bioreactor (i.e., a gas fermentor) or a "gas fermentation feedstock" should be understood to encompass any material (solid, liquid or gas) or stream that can provide a substrate and / or a C1 carbon source to the gas fermentor or bioreactor, either directly or after processing of the feedstock.

[0130] The terms "waste gas" or "waste stream" may be used to refer to any gas stream that is either directly discharged, combusted without additional value capture, or combusted for energy recovery purposes.

[0131] The term "synthesis gas" or "syngas" refers to a gaseous mixture containing at least one carbon source, such as carbon monoxide (CO), carbon dioxide (CO2), or any combination thereof, and optionally hydrogen (H2), which can be used as a feedstock for the disclosed gas fermentation process and can be produced from a variety of solid and liquid carbonaceous materials.

[0132] The term "gasification" and the like should be interpreted as the process of converting organic or fossil fuel based carbonaceous materials into carbon monoxide (CO), hydrogen (H2) and carbon dioxide (CO2).

[0133] The term "producer gas" should be interpreted as meaning a gas stream typically used as an energy source for generating heat and / or electricity.

[0134] When used in connection with a fermentation process, the terms "increased efficiency," "increased efficiency," and the like include, but are not limited to, increasing the growth rate of a microorganism catalyzing the fermentation, growth and / or product productivity at increased product concentrations, the volume of desired product produced per volume of substrate consumed, the rate or level of production of a desired product, and the relative proportion of a desired product produced compared to other byproducts of the fermentation.

[0135] As used herein, "a gaseous substrate comprising carbon monoxide," "a gas stream comprising carbon monoxide," and the like encompass any gas containing carbon monoxide. The gas stream may contain a significant proportion of CO, such as at least about 5% to about 100% CO by volume.

[0136] Although substrate does not need to contain any hydrogen, according to the method of the present invention, H2 existence should not be harmful to the formation of product and / or by-product.In an embodiment, the existence of hydrogen causes the overall efficiency of alcohol production.For example, in an embodiment, gas stream can include H2:CO molar ratio at about 2:1 or 1:1 or 1:2.In one embodiment, gas stream includes about 30 volume % or less H2, 20 volume % or less H2, about 15 volume % or less H2 or about 10 volume % or less H2.In ​​other embodiments, gas stream includes low concentration H2, for example, less than 5 volume % or less than 4 volume % or less than 3 volume % or less than 2 volume % or less than 1 volume %, or substantially free of hydrogen.Gas stream can also contain some CO2, for example, about 1 volume % to about 80 volume % CO2 or 1 volume % to about 30 volume % CO2.In one embodiment, gas stream includes less than or equal to about 20 volume % CO2. In embodiments, the gas stream includes less than or equal to about 15 vol. % CO 2 , less than or equal to about 10 vol. % CO 2 , less than or equal to about 5 vol. % CO 2 , or is substantially free of CO 2 .

[0137] "Gas stream" refers to any stream of substrate that can be passed, for example, from one bed to another, from a bed to a bioreactor, and / or from a bed to a carbon capture unit.

[0138] As used herein, "reactant" refers to a substance that participates in and undergoes changes during a chemical reaction. In an embodiment, the reactant includes but is not limited to CO, CO2 and / or H2.

[0139] As used herein, "microbial inhibitor" refers to one or more impurities that slow down or prevent a specific chemical reaction or other process comprising microbial fermentation. In an embodiment, microbial inhibitors include but are not limited to oxygen (O2), hydrogen cyanide (HCN), acetylene (C2H2) and BTEX (benzene, toluene, ethylbenzene, xylene).

[0140] As used herein, "catalyst inhibitor", "sorbent inhibitor", etc. refers to one or more substances that reduce the rate of a desired chemical reaction or prevent a desired chemical reaction. In an embodiment, the catalyst and / or sorbent inhibitor may include, but is not limited to, hydrogen sulfide (H2S) and carbonyl sulfide (COS).

[0141] "Removal beds," "purification beds," "treatment beds," and the like encompass technologies capable of converting and / or removing microbial inhibitors and / or catalyst inhibitors from a gas stream.

[0142] As used herein, the terms "impurities," "contaminants," and the like refer to reactants, microbial inhibitors, and / or catalyst inhibitors that may be present in a gas stream.

[0143] The term "treated gas" refers to a gas stream that has been passed through at least one removal bed and has had one or more impurities removed and / or converted.

[0144] As used herein, the terms "predetermined level", "predetermined impurity level" and the like refer to the amount of one or more impurities that are considered acceptable in a gas stream. The predetermined levels described herein are identified by performing microbial tolerance experiments.

[0145] As used herein, the terms "fermentable gaseous substrate", "fermentable gas stream" and the like refer to a gas stream that contains a predetermined level of impurities and that is capable of being used as a carbon source by a C1 fixing microorganism.

[0146] As used herein, the term "carbon capture" refers to the utilization or sequestration of carbon compounds containing CO2 and / or CO from a stream comprising CO2 and / or CO, and performing any of the following:

[0147] converting CO2 and / or CO into products; or

[0148] Convert CO2 and / or CO into substances suitable for long-term storage; or

[0149] Capturing CO2 and / or CO in materials suitable for long-term storage;

[0150] or a combination of these processes.

[0151] The term "bioreactor" includes a fermentation unit consisting of one or more containers and / or towers or piping arrangements, including a continuous stirred tank reactor (CSTR), an immobilized cell reactor (ICR), a trickle bed reactor (TBR), a bubble chromatography column, an airlift fermenter, a static mixer, a recycle loop reactor, a membrane reactor such as a hollow fiber membrane bioreactor (HFMBR), or other containers or devices suitable for gas-liquid contact. The reactor can be suitable for receiving a fermentable gas stream comprising CO, or CO2, or H2, or a mixture thereof. The reactor can include multiple reactors (stages) connected in parallel or in series. For example, the reactor can include a first growth reactor for culturing bacteria and a second fermentation reactor to which the fermentation broth from the growth reactor can be fed and in which most of the fermentation product can be produced.

[0152] "Nutrient media" or "nutrient medium" is used to describe bacterial growth medium. Generally, this term refers to a medium containing nutrients and other components suitable for the growth of microbial cultures. The term "nutrient" includes any substance that can be used in the metabolic pathways of microorganisms. Exemplary nutrients include potassium, vitamin B, trace metal ions, and amino acids.

[0153] The term "fermentation broth" or "broth" is intended to encompass a mixture of components comprising a nutrient medium and a culture or one or more microorganisms. It should be noted that the term microorganism and the term bacteria are used interchangeably throughout this document.

[0154] As used herein, the term "acid" includes both carboxylic acids and associated carboxylate anions, such as a mixture of free acetic acid and acetate present in the fermentation broth described herein. The ratio of molecular acid to carboxylate in the fermentation broth depends on the pH of the system. Additionally, the term "acetate" includes both acetate alone and a mixture of molecular or free acetic acid and acetate, such as a mixture of acetate and free acetic acid present in the fermentation broth as described herein.

[0155] As used herein, the term "acid gas" is a class of gases that contain a mixture of impurities in amounts that render the gas acidic. Acid gases may contain significant amounts of hydrogen sulfide (H2S) and / or carbon dioxide (CO2). In addition, acid gases may contain a proportion of carbonyl sulfide (COS), hydrogen chloride (HCl), hydrogen fluoride (HF), and / or hydrogen cyanide (HCN).

[0156] The term "desired composition" is used to refer to the desired levels and types of components in a substance (e.g., a gas stream). More specifically, a gas is considered to have a "desired composition" if it contains specific components (i.e., CO and / or CO2) and / or contains specific levels of specific components and / or is free of specific components (i.e., contaminants that are harmful to microorganisms) and / or is free of specific levels of specific components. When determining whether a gas stream has a desired composition, more than one component may be considered. The gas stream that can be fed to a bioreactor is fermentable so that the gas stream has a desired composition.

[0157] Unless the context requires otherwise, the phrases "fermentation," "fermentation process," or "fermentation reaction" and the like as used herein are intended to encompass both the growth phase of gaseous substrates and the product biosynthesis phase.

[0158] A "microorganism" is a microscopic organism, especially a bacterium, archaea, virus or fungus. The microorganism of the present invention is typically a bacterium. As used herein, references to "microorganisms" should be considered to include "bacteria".

[0159] "Parent microorganism" is a microorganism used to generate the microorganism of the present invention. The parent microorganism can be a naturally occurring microorganism (i.e., a wild-type microorganism) or a microorganism that has been previously modified (i.e., a mutant or recombinant microorganism). The microorganism of the present invention can be modified to express or overexpress one or more enzymes that are not expressed or overexpressed in the parent microorganism. Similarly, the microorganism of the present invention can be modified to contain one or more genes that the parent microorganism does not contain. The microorganism of the present invention can also be modified to not express or express one or more enzymes of a lower amount expressed in the parent microorganism. In one embodiment, the parent microorganism is ethanologenic Clostridium, Clostridium young's or Clostridium ragsdalei. The parent microorganism may be Clostridium ethanologenum LZ1561, which was deposited on June 7, 2010 under the terms of the Budapest Treaty at Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH (DSMZ), D-38124 Inhoffenstraβe 7B, Braunschweig, Germany, on June 7, 2010, and has the same deposit number DSM 23693. This strain is described in International Patent Application No. PCT / NZ2011 / 000144, published as WO 2012 / 015317.

[0160] The term "derived from" indicates that a nucleic acid, protein or microorganism is modified or transformed from a different (i.e., parent or wild-type) nucleic acid, protein or microorganism, thereby producing a new nucleic acid, protein or microorganism. Such modifications or adaptations generally comprise insertion, deletion, mutation or substitution of a nucleic acid or gene. Typically, the microorganism of the present invention is derived from a parent microorganism. In one embodiment, the microorganism of the present invention is derived from ethanologenic Clostridium, Yondahl Clostridium or Rassler Clostridium. In one embodiment, the microorganism of the present invention is derived from ethanologenic Clostridium LZ1561, which is deposited under DSMZ accession number DSM23693.

[0161] "Wood-Ljungdahl" refers to the Wood-Ljungdahl carbon fixation pathway as described by Ragsdale, Biochim Biophys Acta, 1784: 1873-1898, 2008. "Wood-Ljungdahl microorganism" predictably refers to a microorganism containing the Wood-Ljungdahl pathway. In general, the microorganism of the present invention contains a natural Wood-Ljungdahl pathway. In this article, the Wood-Ljungdahl pathway can be a natural, unmodified Wood-Ljungdahl pathway, or it can be a Wood-Ljungdahl pathway with a certain degree of genetic modification (e.g., overexpression, heterologous expression, knockout, etc.), as long as it still has the function of converting CO, CO2 and / or H2 into acetyl-CoA.

[0162] "C1" refers to a single carbon molecule, such as CO, CO2, CH4 or CH3OH. "C1 oxide" refers to a single carbon molecule that also includes at least one oxygen atom, such as CO, CO2 or CH3OH. "C1 carbon source" refers to a carbon molecule that is part of or the sole carbon source for the microorganism of the present invention. For example, the C1 carbon source can include one or more of the following: CO, CO2, CH4, CH3OH or CH2O2. The C1 carbon source can include one or both of CO and CO2. A "C1 fixed microorganism" is a microorganism that is capable of producing one or more products from a C1 carbon source. Typically, the microorganism of the present invention is a C1 fixed bacteria.

[0163] "Anaerobes" are microorganisms that do not require oxygen to grow. If oxygen is present above a certain threshold, the anaerobic bacteria may have adverse reactions or even die. However, some anaerobic bacteria can tolerate low levels of oxygen (i.e., 0.000001-5% oxygen). Typically, the microorganisms of the present invention are anaerobic bacteria.

[0164] "Acetogens" are obligate anaerobes that use the Wood-Jungdahl pathway as their primary mechanism for energy conservation and synthesis of acetyl-CoA and acetyl-CoA-derived products such as acetate (Ragsdale, Biochim Biophys Acta, 1784: 1873-1898, 2008). Specifically, acetogens use the Wood-Jungdahl pathway as a mechanism for (1) synthesis of acetyl-CoA from CO2 reduction, (2) a terminal electron acceptance and energy conservation process, and (3) CO2 fixation (assimilation) in cellular carbon synthesis (Drake, "Acetogenic Prokaryotes", The Prokaryotes, 3rd ed., p. 354, New York, NY, 2006). All naturally occurring acetogens are C1-fixing, anaerobic, autotrophic, and non-methane oxidizing. Typically, the microorganisms of the present invention are acetogens.

[0165] An "ethanologen" is a microorganism that produces or is capable of producing ethanol. Typically, the microorganism of the present invention is an ethanologen.

[0166] "Autotrophs" are microorganisms that are able to grow in the absence of organic carbon. In contrast, autotrophs use inorganic carbon sources, such as CO and / or CO2. Typically, the microorganisms of the present invention are autotrophs.

[0167] A "carboxydotroph" is a microorganism that is able to utilize CO as the sole source of carbon and energy. Typically, the microorganism of the present invention is a carboxydotroph.

[0168] "Methanotrophs" are microorganisms that can utilize methane as a sole source of carbon and energy. In certain embodiments, the microorganisms of the present invention are methanotrophs or are derived from methanotrophs. In other embodiments, the microorganisms of the present invention are not methanotrophs or are not derived from methanotrophs.

[0169] "Substrate" refers to the source of carbon and / or energy of the microorganism of the present invention. Usually, the substrate is gaseous and includes a C1 carbon source, such as CO, CO2 and / or CH4. The substrate can include a C1 carbon source of CO or CO+CO2. The substrate can further include other non-carbon components, such as H2, N2 or electronics.

[0170] The term "cosubstrate" refers to a substance that, while not necessarily serving as the primary source of energy and material for product synthesis, can be used in product synthesis when added to, for example, a primary substrate.

[0171] Substrate and / or C1 carbon source can be the gas obtained as the by-product of industrial process or the gas from another source, such as internal combustion engine exhaust, biogas, landfill gas, direct air capture, combustion or the gas from electrolysis.Substrate and / or C1 carbon source can be the synthesis gas generated by pyrolysis, torrefaction or gasification.In other words, the carbon in solid or liquid material can be recycled by pyrolysis, torrefaction or gasification, to produce the synthesis gas used as substrate and / or C1 carbon source in gas fermentation.Substrate and / or C1 carbon source can be natural gas.Substrate and / or C1 carbon source carbon dioxide from conventional and unconventional gas production.Substrate and / or C1 carbon source can be the gas comprising methane.Gas fermentation process is flexible, and any substrate and / or carbon source in these substrates and / or C1 carbon sources can be used.

[0172] In certain embodiments, the industrial process of substrate and / or C1 carbon source is selected from the manufacture of ferrous metal products such as steel manufacturing, manufacture of 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 process, natural gas extraction, cellulose fermentation, oil extraction, industrial processing of geological reservoirs, processing natural gas, coal, fossil resources such as oil, or any combination thereof. Examples of specific processing steps within industrial methods 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 direct reduction of blast furnace gas, alkaline oxygen furnace gas, coke oven gas, iron furnace top gas and residual gas from iron smelting. Other general examples include flue gases 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, the substrate and / or C1 carbon source may be captured from the industrial process using any known method and then discharged into the atmosphere.

[0173] The substrate and / or C1 carbon source can be a synthesis gas referred to as synthesis gas, which can 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 materials, 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 fuels, gasification of sewage, gasification of sewage sludge, gasification of sludge from wastewater treatment, gasification of landfill gas, gasification of biogas, such as when biogas is added to enhance the gasification of another material. Examples of reforming processes include reforming of steam methane, reforming of steam naphtha, reforming of natural gas, reforming of biogas, reforming of landfill gas, reforming of coke oven gas, reforming of pyrolysis waste gas, reforming of ethylene production waste 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 exhaust gases. Examples of municipal solid waste include tires, plastics, refuse-derived fuels, and fibers such as in shoes, clothing, and textiles. Municipal solid waste may be simple landfill type waste and may be classified or unclassified. Examples of biomass may include lignocellulosic materials and microbial biomass. Lignocellulosic materials may include agricultural byproducts, forestry byproducts, and some industrial byproducts.

[0174] Biomass can be produced as a byproduct of "nature-based solutions" (NbS), and NbS can therefore provide feedstock for the gas fermentation process. The European Commission refers to NbS as solutions inspired and supported by nature that are cost-effective, provide environmental, social and economic benefits, and contribute to resilience. Such solutions introduce more and more diverse natural and natural features and processes into cities, landscapes and seascapes through locally appropriate, resource-efficient and systemic interventions. Nature-based solutions must benefit biodiversity and support the provision 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 benefits of both society and overall biodiversity. Examples of nature-based solutions include natural climate solutions (protecting, restoring and improving land management, increasing carbon storage in landscapes and wetlands around the world or avoiding greenhouse gas emissions), stopping biodiversity loss, socio-economic impact efforts, habitat restoration, and health and well-being efforts in air and water. Biomass produced by nature-based solutions can be used as a feedstock for the gas fermentation process.

[0175] As shown in the figure, the optional step of gasification in the overall gas fermentation process greatly increases the suitable feedstock for the overall gas fermentation process compared to gaseous feedstock alone. Further, the incentives achieved may extend beyond projects such as carbon credits and into the realm of nature-based solutions.

[0176] The substrate and / or C1 carbon source can be a gas stream comprising methane. Such methane-containing gases can be obtained from fossil methane emissions, such as during fracking, wastewater treatment, livestock, agriculture, and municipal solid waste landfills. It is also contemplated that methane can be burned to generate electricity or heat, and the C1 byproduct can be used as a substrate or carbon source. The substrate and / or C1 carbon source can be a gas stream comprising natural gas.

[0177] The composition of the substrate can have a significant impact on the efficiency and / or cost of the reaction. For example, the presence of oxygen (O2) can reduce the efficiency of the anaerobic fermentation process. Depending on the composition of the substrate, it may be necessary to treat, scrub or filter the substrate to remove any undesirable impurities (such as toxins, undesirable components, microbial inhibitors or dust particles) and / or increase the concentration of the desired component.

[0178] In certain embodiments, the fermentation is performed in the absence of a carbohydrate substrate such as sugars, starch, lignin, cellulose, or hemicellulose.

[0179] Microorganisms contained in the bioreactor can be cultured with a feedstock and produce one or more gaseous fermentation products. In addition to 2-phenylethanol (WO 2021 / 188190, US 2021 / 0292732), the microorganism can produce or can be engineered to produce 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 WO2017 / 066498, US 9,738,875), butyrate (WO 2008 / 115080, US 8,293,509), 2,3-butanediol (WO 2009 / 151342, US 7,972,824). 8,658,408 and WO 2016 / 094334, US 10,590,406), lactic acid esters (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), ethanol which is then converted to ethylene (WO 2012 / 026833, US 2013 / 157,322), 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, US10,913,958), fatty acids (WO 2013 / 191567, US 9,347,076), 2-butanol (WO 2013 / 185123, US 9,890,384), 1,2-propylene glycol (WO 2014 / 036152, US 9,284,564), 1-propanol (WO 2014 / 036154, US 9,284,564), 2014 / 0369152, US 9,284,564), 1-hexanol (WO 2017 / 066498, US 9,738,875), 1-octanol (WO 2017 / 066498, US 9,738,875), products derived from chorismates (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), isobutylene (WO 2017 / 066498, US 9,738,875), adipic acid (WO 2017 / 066498, US 9,738,875), 1,3-hexanediol (WO 2017 / 066498, US 9,738,875), 3-methyl-2-butanol (WO 2017 / 066498, US 9,738,875), 2-butene-1-ol (WO 2017 / 066498, US 9,738,875), isovalerate (WO 2017 / 066498, US 9,738,875), isopentanol (WO 2017 / 066498, US 9,738,875) and / or monoethylene glycol (WO 2019 / 126400, US 11,555,209). In certain embodiments, the microbial biomass itself can be considered a product. One or more of these products can be further converted to produce at least one component of diesel, jet fuel and / or gasoline. ,

[0180] A "natural product" is a product produced by a microorganism that has not been genetically modified. For example, ethanol, acetate, and 2,3-butanediol are natural products of Clostridium ethanologenum, Clostridium ljungdahlii, and Clostridium raginsii. A "non-natural product" is a product produced by a genetically modified microorganism, but not by the non-genetically modified microorganism from which the genetically modified microorganism was derived.

[0181] "Selectivity" refers to the ratio of the output of target product and the output of whole fermentation products produced by microorganism.Microorganism of the present invention can be engineered to produce product with specific selectivity or minimum selectivity.In one embodiment, target product accounts for at least about 5 mass %, 10 mass %, 15 mass %, 20 mass %, 30 mass %, 50 mass % or 75 mass % of all fermentation products produced by microorganism of the present invention.In one embodiment, target product accounts for at least 10 mass % of whole fermentation products produced by microorganism of the present invention, so that microorganism of the present invention is at least 10 mass % to the selectivity of target product.In another embodiment, target product accounts for at least 30 mass % of whole fermentation products produced by microorganism of the present invention, so that microorganism of the present invention is at least 30 mass % to the selectivity of target product.

[0182] Cultivation is usually carried out in a bioreactor. The term "bioreactor" includes a culture / fermentation device composed of one or more containers, towers or piping arrangements, such as a continuous stirred tank reactor (CSTR), an immobilized cell reactor (ICR), a trickle bed reactor (TBR), a bubble column, an airlift fermenter, a static mixer or other containers or other devices suitable for gas-liquid contact. In certain embodiments, the bioreactor may include a first growth reactor and a second culture / fermentation reactor. Substrate may be provided to one or two or more such reactors. As used herein, the terms "culture" and "fermentation" are used interchangeably. These terms cover both the growth phase and the product biosynthesis phase of the culture / fermentation process.

[0183] Cultivation is usually maintained in an aqueous medium containing nutrients, vitamins and / or minerals sufficient to allow microbial growth. The aqueous medium can be an anaerobic microbial growth medium, such as a minimal anaerobic microbial growth medium. Suitable culture media are well known in the art.

[0184] Cultivation / fermentation should be carried out under the appropriate conditions for producing the target product desirably. Cultivation / fermentation is usually carried out under anaerobic conditions. The reaction conditions to be considered include pressure (or partial pressure), temperature, gas flow rate, liquid flow rate, culture medium pH, culture medium redox potential, stirring rate (if using a continuous stirred tank reactor), inoculum level, the maximum gas substrate concentration for ensuring that the gas in the liquid phase will not become a restriction, and the maximum product concentration for avoiding product inhibition. Specifically, the introduction rate of the substrate can be controlled to ensure that the concentration of the gas in the liquid phase will not become a restriction, because under the condition of gas restriction, the product may be consumed due to cultivation.

[0185] Operating a bioreactor under boost allows to increase the rate of gas mass transfer from gas phase to liquid phase. Therefore, culture / fermentation can be carried out under a pressure higher than atmospheric pressure. Similarly, since a given gas conversion rate is partly a function of substrate retention time and retention time indicates the required volume of a bioreactor, using a pressurized system can greatly reduce the volume of required bioreactor, and therefore reduce the capital cost of culture / fermentation equipment. This then means that when the bioreactor is maintained at an elevated pressure rather than atmospheric pressure, retention time can be reduced, and the retention time is defined as the liquid volume in the bioreactor divided by the input gas flow rate. Optimal reaction conditions will depend in part on the microorganism used. However, usually, fermentation can be operated under a pressure higher than atmospheric pressure. Similarly, since a given gas conversion rate is partly a function of substrate retention time and realizes the desired retention time and then indicates the required volume of a bioreactor, using a pressurized system can greatly reduce the volume of required bioreactor, and therefore reduce the capital cost of fermentation equipment.

[0186] The target product can be separated or purified from the fermentation broth using any method or combination of methods known in the art, including, for example, fractionation, vacuum distillation, evaporation, pervaporation, gas stripping, phase separation, and extractive fermentation (including, for example, liquid-liquid extraction). In certain embodiments, the target product is recovered from the fermentation broth by continuously removing a portion of the fermentation broth from the bioreactor, separating the microbial cells from the fermentation broth (preferably by filtration), and recovering one or more target products from the fermentation broth. Alcohol and / or acetone can be recovered, for example, by distillation. Acids can be recovered, for example, by adsorption on activated carbon. The separated microbial cells can be returned to the bioreactor. The cell-free permeate remaining after the removal of the target product can also be returned to the bioreactor. Additional nutrients (such as vitamin B) can be added to the free permeate before it is returned to the bioreactor to supplement the culture medium.

[0187] describe

[0188] Specifically in the case of a limited number of containers, various beds are merged together in the container, all operating under common operating parameters can be successfully achieved. Various gas impurities can be gradually converted and / or removed from the gas stream, and in the case where the impurities may be harmful to the downstream beds, the impurities are removed and / or converted from those beds upstream, and then other gas impurities are allowed to be removed subsequently, and the fermentable gas stream is fed to the bioreactor later, where the gas can be processed by gas fermentation microorganisms to produce useful products. The conversion and / or removal of these impurities is achieved without consuming the desired compound and without producing other undesirable compounds. In an embodiment, the fermentable gas stream can be introduced into a carbon capture device for storage.

[0189] In an embodiment, an input gas stream is continuously passed to the following beds to treat the following: (1) optional hydrocarbon removal; (2) hydrolysis; (3) optional sulfur compound removal; (4) optional catalytic hydrogenation; and (5) deoxygenation. Each bed can be utilized to remove and / or convert one or more impurities in the gas stream. Since many deoxygenation catalysts are sulfur sensitive, a sulfur removal bed may be advantageous and therefore included and positioned upstream of the deoxygenation catalyst bed. Two or more beds may be positioned within a single vessel. Depending on vessel availability, two, three, four, or all five beds may be positioned within a single vessel. Co-positioning within a single vessel is often referred to as a stacked bed configuration.

[0190] The challenge of co-locating two or more beds of different materials in the same vessel is that all beds will be subject to the same operating conditions. The specific material selected must not be affected by the treatment of one of the beds in the series. As an example, a particular deoxygenation catalyst operates best in a reduced form. The remaining beds co-located in the same vessel with the deoxygenation catalyst must remain substantially unaffected by the reduction temperature and reducing gas required to reduce the deoxygenation catalyst.

[0191] Hydrocarbon Removal Bed

[0192] In one embodiment, the hydrocarbon removal bed can be used to remove hydrocarbons such as BTEX. Suitable adsorbents for the hydrocarbon removal bed can be silica, alumina, silica-alumina, activated carbon or any combination thereof. The input gas is contacted with the adsorbent, and one or more hydrocarbons are adsorbents and are thus removed from the gas stream. The adsorbent can be in the form of a fixed bed, and the bed can be operated in a static mode, a temperature swing adsorption mode or a pressure swing adsorption mode.

[0193] In some embodiments, the hydrocarbon removal bed may be a pressure swing adsorption (PSA), which is an adiabatic process for purifying gas to remove accompanying impurities by adsorption through a suitable adsorbent contained in a container in a fixed bed at high pressure. Regeneration of the adsorbent is accomplished by countercurrent decompression and purging at low pressure with previously recovered treated gas. In order to obtain a continuous product stream, at least two adsorbers may be provided so that at least one adsorber receives, processes and sends a treated gas stream to another treatment bed, and at least one adsorber is used to perform the regeneration of one or more adsorbers that send the treated gas stream to another treatment bed. Those skilled in the art can easily select common adsorbents according to the type of impurities to be adsorbed and removed. Suitable adsorbents include zeolite molecular sieves, activated carbon, silica gel or activated alumina. Combinations of adsorbent beds may be used on top of each other, thereby dividing the contents of the adsorbent into a plurality of different regions. PSA involves swings in parameters such as pressure, temperature, flow rate and composition of the gas phase and adsorbed phase. Gas purification or separation using PSA typically occurs at near ambient inlet temperatures, thereby selectively adsorbing the components to be removed. Ideally, the adsorption should be sufficiently reversible to enable regeneration of the adsorbent at ambient-like temperatures. Additionally, the adsorption can be performed so as to avoid or at least minimize the production of undesirable compounds.

[0194] In some embodiments, the hydrocarbon removal bed can be a temperature swing adsorption (TSA), which is a technique for purifying gas to remove accompanying impurities by means of adsorption through a suitable adsorbent contained in a container in a fixed bed at an adsorption temperature. The regeneration of the adsorbent is completed by countercurrent flow at a second desorption temperature and optionally purging with previously recovered treated gas at the desorption temperature. In order to obtain a continuous product stream, at least two adsorbers can be provided so that at least one adsorber receives, processes and sends a treated gas stream to another treatment bed, and at least one adsorber is used to perform the regeneration of one or more adsorbers that send the treated gas stream to another treatment bed. Those skilled in the art can easily select common adsorbents according to the type of impurities to be adsorbed and removed. Suitable adsorbents include zeolite molecular sieves, activated carbon, silica gel or activated alumina. Combinations of adsorbent beds can be used on top of each other, thereby dividing the contents of the adsorber into multiple different regions. TSA involves swings in parameters such as pressure, temperature, flow rate and composition of the gas phase and adsorption phase. Ideally, adsorption should be fully reversible to achieve regeneration of the adsorbent. Additionally, the adsorption may be performed such that the production of undesirable compounds is avoided or at least minimized.

[0195] Hydrolysis bed

[0196] Hydrogen cyanide (HCN) and carbonyl sulfide (COS) are two expected impurities that first chemically react with water before they can be successfully removed from the gas stream. In applications utilizing high sulfur gas streams, it may be necessary to convert COS to hydrogen sulfide (H2S) because many commercial processes are not efficient at removing sulfur in the form of COS. This conversion occurs according to the following reaction:

[0197]

[0198] This conversion can be achieved using any technology capable of converting COS to H2S. In various embodiments, the hydrolysis bed utilizes a metal oxide catalyst to perform the conversion. In embodiments, the conversion is performed using an alumina catalyst. The alumina can be any form of alumina or silica-alumina, such as gamma alumina, theta alumina, delta alumina, and alpha alumina.

[0199] In an embodiment, the hydrolysis step may comprise a multi-bed approach for converting COS and removing H2S. In an embodiment, the first bed utilizes a conversion bed, thereby converting COS to H2S. Examples of such conversion beds include BASF SELEXSORB TM COS. In an embodiment, the second bed utilizes an iron-based sorbent, such as a high capacity, non-hazardous granular media sold under the trade name "AxTrap 4001," which removes H2S.

[0200] In embodiments, the gas stream is fed to a hydrolysis bed to convert and / or remove one or more impurities from the gas stream. In some cases, the hydrolyzed gas stream is depleted in at least one impurity selected from the group consisting of: COS and / or HCN.

[0201] Sulfur guard bed

[0202] A sulfur guard bed, also known as an acid gas removal bed, refers to a process for separating hydrogen sulfide (H2S) and / or carbon dioxide (CO2) and other sulfur-containing compounds or acid gases from a gas stream. A sulfur guard bed is optional, particularly in embodiments where the gas feedstock contains almost no sulfur compounds. In embodiments where a sulfur guard bed is used, the material selected for the sulfur guard bed will be exposed to the same temperature as the deoxygenation catalyst bed. Therefore, the material selected for the sulfur guard bed is a material that does not undergo reduction at the temperature of the deoxygenation catalyst bed. In some cases, the sulfur guard bed utilizes a zinc oxide (ZnO) catalyst to remove hydrogen sulfide (H2S) from a gas stream. In other cases, the sulfur guard bed utilizes copper and zinc oxide that can be composited with one or more aluminas. The resulting composite adsorbent can be considered a combined adsorbent or a loaded adsorbent. A temperature of about 600°C is required to reduce zinc oxide. The deoxygenation catalyst bed operates at a temperature below 600°C, and therefore ZnO or copper and zinc oxide supported on alumina are particularly suitable choices for adsorbents for the sulfur guard bed.

[0203] An optional carbon dioxide adsorption bed or additional acid gas removal bed may be used after the original sulfur guard bed. The carbon dioxide adsorption bed is used to remove carbon dioxide (CO2) from the gas stream to bring the carbon dioxide level within a desired range. In these embodiments, the treated gas from the sulfur guard bed may be sent to the carbon dioxide adsorption bed before being sent to the optional catalytic hydrogenation bed. In embodiments where the optional catalytic hydrogenation bed is bypassed or not used, the treated gas from the sulfur guard bed may be sent directly to the deoxygenation bed.

[0204] In embodiments, the gas stream is fed to an acid gas removal bed to convert and / or remove one or more impurities from the gas stream. In some cases, the acid gas depleted stream is depleted in at least one impurity selected from the group consisting of carbon dioxide (CO2), hydrogen sulfide (H2S), and hydrogen cyanide (HCN).

[0205] In one embodiment, the hydrolysis catalyst bed and the sulfur guard bed can be mixed into a physical mixture and used as a single bed. Optionally, a hydrocarbon removal adsorbent can also be present in the physical mixture. In another embodiment, the hydrolysis catalyst functionality and the sulfur guard functionality can be combined into a single composite and used as a combined functional bed in a container. An example of a bifunctional functional composite material is zinc oxide on alumina, silica, or silica-alumina.

[0206] Catalytic hydrogenation bed

[0207] Acetylene (C2H2) acts as a microbial inhibitor. To remove acetylene, a catalytic hydrogenation bed can be utilized. Catalytic hydrogenation is treatment with hydrogen in the presence of a catalyst such as, but not limited to, nickel, palladium, or platinum. There is no universal catalyst suitable for acetylene hydrogenation. The choice of catalyst depends largely on the gas composition and operating conditions. In an embodiment, palladium is used as a catalyst. In an embodiment, palladium on alumina (Pd / Al2O3) is used as a catalyst. An example of such a catalyst is BASF TM R 0-20 / 47.

[0208] Inhibitors reduce the activity of palladium. Sulfides represent potential palladium inhibitors. Compounds such as hydrogen sulfide (H2S) or carbonyl sulfide (COS) adsorb on palladium and may change the reaction site. In embodiments, known palladium inhibitors are removed and / or converted prior to catalytic hydrogenation.

[0209] In embodiments, a catalytic hydrogenation bed may be unnecessary for acetylene removal. In addition to being removed by the catalytic hydrogenation bed, acetylene may be removed from the gas stream by certain deoxygenation beds. In embodiments where a catalytic hydrogenation bed is not required, the catalytic hydrogenation bed may be bypassed and / or not included in the process. An example of when a catalytic hydrogenation bed is unnecessary is when the acetylene level is low enough that the acetylene can be effectively removed by other beds. In embodiments where the acetylene level is low enough, the gas stream may be passed from the acid gas removal bed to the deoxygenation bed, thereby bypassing the catalytic hydrogenation bed.

[0210] In an embodiment, the gas stream is fed to a catalytic hydrogenation bed to convert and / or remove one or more impurities from the gas stream. In some cases, at least acetylene (C2H2) in the post-hydrogenation stream is depleted.

[0211] Deoxygenation bed

[0212] Oxygen (O2) can be a microbial inhibitor. Therefore, the oxygen in the gas stream may need to be reduced to an acceptable level. In order to reduce the oxygen level in the gas stream, a deoxygenation bed can be utilized. The reduction in oxygen levels can be achieved by any suitable means. In an embodiment, the deoxygenation bed utilizes a catalytic process, whereby oxygen (O2) is reduced to carbon dioxide (CO2) or water (H2O). In an embodiment, the catalyst used in the deoxygenation bed is copper-containing. Copper can be in a reduced form. Copper can be compounded with other elements such as elements in IUPAC Group 8, IUPAC Group 9 and / or IUPAC Group 10, such as iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), platinum (Pt), palladium (Pd), osmium (Os), iridium (Ir) to form a catalyst. The molar ratio of copper to another element can be as high as about 1:1. An example of such a catalyst is BASF PURISTARTM R 3-15 or BASF CU 0226S.

[0213] In an embodiment, a deoxygenation bed can be used to effectively reduce the acetylene level in the gas stream, thereby allowing the catalytic hydrogenation step to be bypassed. A significant difference between the removal of acetylene by a catalytic hydrogenation bed and the removal of acetylene by a deoxygenation bed is the production of ethane (C2H6). Compared with the removal of acetylene by a catalytic hydrogenation bed, the removal of acetylene by a deoxygenation bed produces a larger amount of ethane. However, due to the robust nature of the microorganisms used in the gas fermentation process, the ethane levels produced by the deoxygenation bed are not harmful to the microorganisms, and therefore, in an embodiment, the catalytic hydrogenation bed can be bypassed.

[0214] Another significant difference between the catalytic hydrogenation bed and the deoxygenation bed is the production of methanol (CH3OH). Methanol may be produced when any copper-based deoxygenation bed is utilized. In the case of acetylene removal using a copper-based deoxygenation bed, this removal process produces a greater amount of methanol relative to the removal process using a catalytic hydrogenation bed. However, due to the robust nature of the microorganisms used in the subsequent gas fermentation process, the methanol levels produced by the deoxygenation bed are not harmful to the microorganisms, and therefore, in embodiments, the catalytic hydrogenation bed can be bypassed.

[0215] In addition to the impurities mentioned above, certain deoxygenation beds may be used to effectively reduce mercury (Hg). Not all gas streams contain mercury (Hg). However, the process is designed to effectively process gas streams from a variety of sources, some of which may contain mercury (Hg). Therefore, in certain cases where the gas stream contains mercury (Hg), deoxygenation beds may be used to effectively remove mercury (Hg) from the gas stream. When mercury (Hg) is removed from the gas stream by the deoxygenation beds, the mercury (Hg) in the post-deoxygenation stream may be depleted.

[0216] In embodiments, the gas stream is fed to a deoxygenation bed to convert and / or remove one or more impurities from the gas stream. In some cases, at least oxygen (O2) and / or acetylene (C2H2) in the post-deoxygenation stream is depleted. In various cases, in addition to oxygen (O2) and / or acetylene (C2H2), mercury (Hg) in the post-deoxygenation stream is depleted.

[0217] In certain embodiments, the catalyst traditionally used for hydroprocessing can be used as a deoxygenation catalyst. Such catalysts are metal catalysts, such as molybdenum and tungsten promoted by nickel and cobalt. The catalyst metal can be impregnated on a carrier material providing a significant surface area. The carrier material can be aluminum oxide, silicon dioxide, magnesium oxide, zirconium oxide and zeolite. These carriers have high surface area and pore size, so that they can withstand operating pressure and temperature conditions, and support the desired reaction. The catalyst shape can include cylindrical, hollow, trilobate, spherical and quadrilobate. These catalysts are activated by partial or complete sulfidation. When selecting a material for sulfiding the catalyst, care should be taken to avoid producing sulfur-containing byproducts, which are gas fermentation inhibitors. Such sulfur-containing byproducts may be difficult to remove from the gas stream, and may be passed into a bioreactor and damage microorganisms. For example, although liquid dimethyl disulfide (DMDS) may be easy to handle and inject, using DMDS to activate metal-based catalysts may produce sulfur-containing byproducts, such as H2S, CS2, COS. Although H2S is easily removed from the gas stream, CS2 and COS are difficult to remove and may be passed into the bioreactor in the treated gas stream. These sulfur-containing compounds, especially CS2, are harmful to gas fermentation microorganisms. H2S can be used instead of DMDS to activate the metal catalyst. Using H2S to activate the metal catalyst will not lead to the production of sulfur-containing byproducts such as CS2 and COS, and thus eliminates potential fermentation inhibitors. Instead of the DMDS liquid holder and metering pump, a pressurized H2S source or cylinder and mass flow controller can be used to control the injection of H2S into the system to activate the deoxygenation catalyst. Another source of suitable H2S is the tail gas from the fermentation reactor. For example, the tail gas from the gas fermentation bioreactor may contain H2S, which can then be used for catalyst activation.

[0218] Gas Sampling and Analysis Systems

[0219] In order to manage, maintain and optimize the process, robust analytical monitoring and control technologies may be required. Such instrumentation may include, but is not limited to, gas sampling systems and data logging / reporting software tools.

[0220] Analysis of the composition of the gas stream is a key element of gas processing. Analysis of the gas stream provides a measurement and determination of which impurities need to be converted and / or removed from the gas stream. In order to ensure that the gas stream has the desired composition, it may be necessary to measure the impurities in the gas stream at multiple points. These measurements may be achieved by any suitable means and may be completed in a continuous and / or periodic manner, which may include online automatic monitoring. In an embodiment, the gas stream may be measured before and / or after being passed to different removal beds.

[0221] In embodiments, the gas stream is measured prior to being passed to one or more removal beds. In some cases, the measurement of impurities present in the gas stream prior to being passed to the one or more removal beds determines which removal beds will be utilized. In embodiments, the determination of whether to utilize a hydrolysis bed depends at least in part on the measurement of carbonyl sulfide (COS) present in the gas stream. In embodiments, the determination of whether to utilize a catalytic hydrogenation bed depends at least in part on the measurement of acetylene (C2H2) present in the gas stream. In embodiments, the determination of whether to utilize a hydrogen cyanide removal bed depends at least in part on the measurement of hydrogen cyanide (HCN) present in the gas stream.

[0222] The impurities present in the gas stream may vary based on various factors. In certain embodiments, the impurities present in the gas stream may vary based on the source of the gas stream. For example, the gas stream from a gasification process may have different impurity levels based on changes in the material fed to the gasifier. In certain embodiments, the impurities present in the gas stream may vary based on gasifier operation. For example, when a plugging occurs in the gasifier, the gas stream from the gasification process may have different impurity levels.

[0223] In certain cases, the gas stream is obtained from a mixture of two or more sources. In various embodiments, the composition of the gas stream can be measured before, during, and / or after the sources are mixed.

[0224] In certain cases, the gas stream can be processed before, during and / or after the mixing source. In certain cases, the composition of the gas stream is measured in order to analyze and determine which removal beds are necessary. This determination can be based at least in part on one or more impurities present in the gas stream. In at least one case, the composition of these gases may fluctuate over time, resulting in changes in the proportion of impurities. These fluctuations may affect the performance of the treatment process. In this way, it may be necessary to adjust the treatment process in response to changes in the composition. In various cases, this adjustment of the treatment process includes removing, bypassing and / or adding one or more removal beds. The selection of which removal bed to remove, bypass and / or add may depend at least in part on the specific impurities present. In certain cases, one or more impurities that were not present previously or that were present but below the detection level can be measured subsequently, and then this may require the addition of one or more removal beds. In certain cases, increasing the proportion of carbonyl sulfide (COS) and / or hydrogen cyanide (HCN) may require the addition of a hydrolysis bed, while reducing the proportion of carbonyl sulfide (COS) and / or hydrogen cyanide (HCN) may allow the removal of a hydrolysis bed. In some cases, increasing the proportion of carbon dioxide (CO2), hydrogen sulfide (H2S) and / or hydrogen cyanide (HCN) may require the addition of an acid gas removal bed, while decreasing the proportion of carbon dioxide (CO2), hydrogen sulfide (H2S) and / or hydrogen cyanide (HCN) may allow the removal of the acid gas removal bed. In some cases, increasing the proportion of acetylene (C2H2) may require the addition of a catalytic hydrogenation bed, while decreasing the proportion of acetylene (C2H2) may allow the removal of the catalytic hydrogenation bed. In some cases, increasing the proportion of oxygen (O2) and / or acetylene (C2H2) may require the addition of a deoxygenation bed, while decreasing the proportion of (O2) and / or acetylene (C2H2) may allow the removal of the deoxygenation bed.

[0225] For online measurement, each measuring point can be connected to a steel pipe to facilitate the transmission of the airflow through the monitoring device. In an embodiment, the airflow is regulated by a pump device to provide a pressurized airflow to the measuring device. In an embodiment, the airflow is pressurized to between twenty pounds per square inch and thirty pounds per square inch (138-207 kPa). In an embodiment, different measuring devices are used to measure different impurities.

[0226] In an embodiment, the level of C2H2 and the level of HCN in the gas stream are monitored by a spectrometer. In some cases, in addition to C2H2 and / or HCN, the spectrometer will monitor the level of one or more of NH3, CO2 and / or H2S. In an embodiment, the spectrometer is configured to measure in periodic increments at various sampling points.

[0227] In an embodiment, hydrocarbons, BTEX, naphthalene and oxygenates dimethyl ether, diethyl ether, acetaldehyde, tetrahydrofuran, methyl ethyl ketone, acetone, methanol and ethanol are measured by a gas chromatograph. In an embodiment, the chromatograph is configured to measure at periodic increments at different sampling points.

[0228] In an embodiment, nitrogen and sulfur in a gas stream are measured by an apparatus comprising oxidative pyrolysis using ultraviolet fluorescence (UVF) technology and chemiluminescence technology. In an embodiment, the apparatus is configured to measure at periodic increments at different sampling points.

[0229] In an embodiment, major impurities and / or trace impurities in a gas stream are measured by a gas chromatograph. Major impurities and / or trace impurities may include, but are not limited to, hydrogen, nitrogen, oxygen, methane, carbon monoxide, carbon dioxide, and hydrogen sulfide. In an embodiment, the apparatus is configured to perform measurements at different sampling points in periodic increments.

[0230] In an embodiment, the various measurement devices may be connected to a software application, whereby the data collected by the measurement devices is interpreted and stored in a database. In a particular embodiment, the data is parsed into an easily interpretable format, such as a spreadsheet.

[0231] Special catalyst

[0232] A dedicated catalyst comprising copper supported on alumina can be used to treat a fermentable gas stream and produce a fermentable gas stream from various gas sources. Such gases can be derived in whole or in part from a combination of gases, synthesis gas and / or producer gas from one or more industrial processes. Specifically, it was found that this dedicated catalyst can reduce oxygen, acetylene and hydrogen cyanide so that the oxygen in the fermentable gas stream is less than about 100ppm, acetylene is less than about 1ppm and hydrogen cyanide is less than about 1ppm. In various cases, the copper used for this catalyst is copper (I). In various cases, the copper used for this catalyst is reduced copper. The catalyst can be reduced by contacting with a hydrogen and nitrogen mixture at a desired temperature. The dedicated catalyst can be used as the only catalyst in gas treatment, or the dedicated catalyst can be used as a deoxygenation catalyst.

[0233] In order to process input gases with high sulfur content, a sulfided version of the special catalyst can be used. Sulfidation is achieved by passing a gas including a sulfiding agent through a reduced form of the special catalyst. Such reduction and sulfidation can be performed according to the prior art. In one embodiment, the sulfidation produces a sulfided alumina-supported copper (I) catalyst. In one embodiment, the sulfidation produces a sulfided alumina-supported copper (II) catalyst. When present in a gas stream, the copper sulfide catalyst may be particularly useful in reducing mercury (Hg) levels because copper sulfide is known to be an effective mercury adsorbent.

[0234] This catalyst is referred to hereinafter as an exemplary deoxygenation catalyst, however, it should be understood that this particular catalyst can be used to remove more pollutants than just oxygen.

[0235] Overview

[0236] The details of the present disclosure are particularly suitable for the removal of pollutants because the amount of material converted by the catalyst is very low compared to bulk conversion operations. Therefore, the capacity level of the adsorbent is manageable and the exothermic temperature change is also manageable. Likewise, the target output level is also very low.

[0237] In an embodiment, a treated fermentable gas stream is fed to a bioreactor containing at least one C1 fixed microorganism. The C1 fixed microorganism is capable of converting a treated fermentable C1-containing gas stream into useful chemicals and products by gas fermentation. In order to provide a non-inhibitory fermentable gas stream to the bioreactor, the gas stream needs to contain a predetermined impurity level or less impurities. In an embodiment, the impurities of interest include oxygen (O2), hydrogen cyanide (HCN), acetylene (C2H2), BTEX (benzene, toluene, ethylbenzene, xylene) and sulfur (H2S and COS). In various embodiments, the oxygen (O2) level needs to be less than one hundred parts per million (100ppm) to be at a predetermined level. In various embodiments, hydrogen cyanide (HCN) needs to be less than one part per million (1ppm) to be at a predetermined level. Hydrogen cyanide (HCN) can be less than one hundred parts per billion (100ppb) to be at a predetermined level. In various embodiments, acetylene (C2H2) needs to be less than one part per million (1ppm) to be at a predetermined level. In various embodiments, BTEX needs to be below thirty parts per million (30 ppm) to be at a predetermined level. In various embodiments, sulfur (H2S and COS) needs to be below one part per million (1 ppm) to be at a predetermined level. In embodiments, all impurities must be at their predetermined levels to constitute the predetermined impurity level.

[0238] The system may include additional beds before the hydrolysis bed and after the deoxygenation bed. These additional beds may include, but are not limited to, particulate removal beds, chloride removal beds, tar removal beds, hydrogen cyanide removal beds, and additional acid gas removal beds that can remove organic matter. In some cases, a bed composed of activated carbon is used to remove undesirable organic compounds. In some cases, these organic compounds can be formed by one or more removal beds. In an embodiment, the gas is fed into the system into the beds in the following order: (1) particulate removal bed, (2) chloride removal bed, (3) tar removal bed, (4) hydrolysis bed, (5) acid gas removal bed, (5) catalytic hydrogenation bed, (6) deoxygenation bed, (7) hydrogen cyanide removal bed, and (8) additional acid gas removal bed. The beds can be arranged in modules or containers, and one or more beds can be co-located in a single module or container. It is also conceivable to use a repeated series of beds / containers in a lead-lag manner, where one series of beds / containers is used while another series is restored to operating conditions. The two are switched periodically so that the recovered system is in use while the spent system is being recovered. It is also contemplated that multiple series of beds / vessels may be used.

[0239] The particle removal bed may include any suitable bed capable of removing particles from a gas stream. Particles are often associated with line blockage. To avoid line blockage, a particle removal bed may be utilized. In an embodiment, the particle removal bed is a baghouse. The baghouse may be of any suitable type, including but not limited to mechanical shakers, reverse gas, and pulse engines. In certain embodiments, the particle removal bed is used before other beds.

[0240] The chloride removal bed may include any suitable bed capable of removing chlorides from a gas stream. Chlorides are often associated with corrosion in gas purification processes. To avoid corrosion, a chloride removal bed may be utilized. In an embodiment, the chloride removal bed is a caustic scrubber capable of removing hydrogen chloride (HCl). In an embodiment, the chloride removal bed is a cyclone capable of removing ammonium chloride (NH4Cl).

[0241] The tar removal bed may include any suitable bed capable of removing tar from a gas stream. Tar may include, but is not limited to, heavy hydrocarbons such as naphthalene, which are often associated with line plugging. To avoid line plugging, a tar removal bed may be utilized. In an embodiment, the tar removal bed is an adsorption device. In some cases, the adsorption device includes activated carbon.

[0242] The hydrogen cyanide removal bed may include any suitable bed capable of removing hydrogen cyanide from a gas stream. Hydrogen cyanide is often associated with inhibition of microorganisms. To avoid microbial inhibition, a hydrogen cyanide removal bed may be utilized. In an embodiment, the hydrogen cyanide removal bed is a copper treated activated carbon device.

[0243] The additional acid gas removal bed may include any suitable bed capable of removing carbon dioxide from the gas stream. High levels of carbon dioxide may dilute the gas stream, thus requiring a larger bioreactor and / or additional fermentation train. To avoid dilution of the gas stream with carbon dioxide, an additional acid gas removal bed may be utilized. In an embodiment, the additional acid gas removal bed is a PSA bed that may utilize calcium hydroxide.

[0244] The system may include one or more temperature modules to increase or decrease the temperature of the airflow. These temperature modules may be placed before and / or after other modules to increase or decrease the temperature of the airflow between the modules. The temperature module may include any suitable module capable of increasing or decreasing the temperature of the airflow. In an embodiment, the temperature module is a shell and tube heat exchanger. The shell and tube heat exchanger includes a shell, wherein a tube bundle is provided within the shell. The shell and tube heat exchanger can regulate the temperature of the airflow by passing a fluid (e.g., water) through the shell while passing the airflow through the tube bundle. Heat is transferred between the airflow and the fluid through the tube wall.

[0245] The system may include a pressure module to increase or reduce the pressure of the airflow. These pressure modules may be placed before and / or after other modules. The pressure module may include any suitable module that can increase or reduce the pressure of the airflow. In an embodiment, the pressure module is a compressor. The compressor can increase the pressure of the airflow to a value suitable for airflow transmission. In an embodiment, the pressure module is a valve. The valve can reduce the pressure of the airflow to a value suitable for airflow transmission.

[0246] In a retrofit situation, where limited vessels or temperature modules are available, at least two or more beds can be co-located in a single vessel, and a single temperature module such as a heat exchanger can be used to bring the single vessel to a common operating temperature for all beds contained therein. In one example, the hydrocarbon removal bed, the hydrolysis bed, the sulfur guard bed, and the deoxygenation bed are all co-located in a single vessel. In another example, the hydrocarbon removal bed is located in a separate module, while the hydrolysis bed, the sulfur guard bed, and the deoxygenation bed are co-located in a single vessel. In both examples, the specialized copper-based catalyst discussed above can be used in the deoxygenation bed, or another deoxygenation catalyst can be used.

[0247] When multiple beds are co-located in a single container, all beds must be operated at a common temperature. This can be challenging because the adsorbent and catalyst typically operate at different temperatures. When using the specialized copper-based catalyst discussed above, the catalyst may need to be reduced before use. Therefore, the catalyst may need to reach 150°C to 200°C or 225°C or 250°C to reduce the copper component. Because all beds are located in the same container, the other beds should withstand the same temperature as the reduction temperature of the deoxygenation catalyst without changing form. A favorable choice for the sulfur guard bed is a zinc oxide adsorbent because zinc oxide is only reduced at temperatures far above the reduction temperature of the deoxygenation catalyst. If the zinc oxide is reduced, it will no longer absorb sulfur and no longer serve as a sulfur guard bed. In other words, the method operates at a temperature below the reduction temperature of the sulfur guard bed adsorbent.

[0248] Since typical deoxygenation catalysts are not always tolerant to sulfur, a sulfur guard bed may be positioned upstream of the deoxygenation catalyst to protect the deoxygenation catalyst from exposure to sulfur compounds.

[0249] Separate beds co-located or stacked within a single vessel may be separated from each other by screens. It is advantageous to use different particle sizes for different beds so that screening can be used to replace spent adsorbent after the vessel is unloaded. The catalyst can be separated from the spent adsorbent and potentially regenerated and reused. It is also contemplated that various catalysts may be mixed in a single bed, provided that the sulfur guard bed is located upstream of the deoxygenation catalyst.

[0250] Removing the stacked beds from the container may involve using gravity to allow one or more beds to flow out of the container or using a vacuum to pull one or more beds out of the container. The beds may be made up of separate containers that can be removed from the container individually and regenerated, reloaded with fresh material, or simply placed back into the container after the other beds have been regenerated or reloaded. The unloading of the spent adsorbent may be designed to be completed in one work shift at an industrial plant along with the other beds within the container. Each bed may be of a different particle size so that the spent adsorbent is easily separated from the catalyst by sieving when unloaded from the container. The catalyst can then be reloaded and reused. Fresh adsorbent may be reloaded to replace the spent adsorbent. The recovered catalyst is not required to be of high purity, in other words, it is acceptable if the screening technique results in a certain percentage of catalyst being mixed from one bed into another.

[0251] To aid in fluid distribution, ceramic balls can be placed on top of the container.

[0252] In an alternative arrangement of a stacked bed system, the different beds may be arranged in nested baskets so that each bed may be removed from the vessel and the basket containing spent adsorbent may be emptied and reloaded with fresh adsorbent without loss of catalyst in the other baskets. The vessel in this embodiment would operate with concentric radial flow of gas. The innermost basket may contain the hydrolysis catalyst, the middle concentric basket may be zinc oxide, and the outer concentric baskets may be a dedicated copper-based deoxygenation catalyst.

[0253] In another embodiment, the two functionalities can be combined into a single material, or the two materials can be physically mixed to form a single bed. For example, the hydrolysis function and the sulfur adsorption function can be combined into a single bifunctional material, such as zinc oxide supported on an alumina support. A single vessel can contain two beds, a combined hydrolysis and sulfur guard bed such as zinc oxide supported on an alumina support, followed by a deoxygenation bed using a deoxygenation catalyst such as a specialized copper-based catalyst.

[0254] In one embodiment, the adsorbent or catalyst beds are arranged in an advantageous order. The hydrolysis bed is positioned upstream of the sulfur guard bed so that the sulfur-containing compounds are converted to a reduced form of sulfur by the hydrolysis catalyst, such as alumina, before contacting the sulfur guard bed and being adsorbed by the sulfur guard bed material, such as zinc oxide. The sulfur guard bed is positioned upstream of the deoxygenation catalyst bed so that the sulfur-containing compounds are removed before the gas contacts the deoxygenation catalyst, which is often susceptible to sulfur poisoning.

[0255] In another embodiment, the vessel may be extended outwardly near the deoxygenation bed without heating the input gas. The reaction occurring at the hydrolysis bed may be exothermic and thus automatically heat that portion of the vessel. Heat need only be applied to the portion of the vessel downstream of the hydrolysis bed.

[0256] In another embodiment, a screen or other physical barrier may be used over the sulfur guard bed in the vessel so that the bed positioned above the physical barrier remains within the vessel when the spent adsorbent is unloaded from the vessel under gravity. Multiple physical barriers may be used to control gravity removal of different beds. The retained bed may be removed by vacuum or gravity.

[0257] Figure 1A system for selectively removing impurities from an input gas stream 104 is shown, the system comprising a hydrocarbon removal bed 110, a hydrolysis bed 112, a sulfur guard bed 114, a deoxygenation bed 116, and a bioreactor 150. The hydrocarbon removal bed 110, the hydrolysis bed 112, the sulfur guard bed 114, and the deoxygenation bed 116 are all contained within a vessel 106. The gas stream may originate from any industrial, producer, and / or syngas source 102. Prior to entering the vessel 106, the input gas may be heated to an operating temperature of the vessel 106, which may be from about 175°C to about 250°C, or from about 200°C to 300°C, or from about 300°C to 500°C, or 550°C. The input gas stream 104 is fed from the industrial, producer, and / or syngas source 102 to a heater 124, which may be a heat exchanger. The heated input gas 122 is passed to the vessel 106. In vessel 106, the input gas sequentially contacts a hydrocarbon removal bed 110, a hydrolysis bed 112, a sulfur protection bed 114, and a deoxygenation bed 116.

[0258] Contact with a hydrogen removal bed containing an adsorbent such as activated carbon results in one or more hydrocarbons being adsorbed by the activated carbon and removed from the gas stream. Contact with a hydrolysis bed 112 converts at least one impurity in the gas stream to provide a post-hydrolysis gas stream. Hydrogen cyanide (HCN) and carbonyl sulfide (COS) are two contemplated components that may chemically react with water and be removed from the gas stream. If COS is present, it is advantageous to convert COS to hydrogen sulfide (H2S), which may then be removed in a subsequent sulfur guard bed 114.

[0259] Now that the HCN has been removed and the COS has been converted to H2S, the gas is passed to a sulfur guard bed 114 where the H2S is adsorbed and removed from the gas. The gas is then passed to a deoxygenation bed 116 where oxygen (O2) is reduced to carbon dioxide (CO2) or water (H2O) and thereby removed from the gas. The treated gas exits the vessel 106 into a treated gas stream 118 which is passed to a bioreactor 150 for fermentation. The bioreactor may contain C1 immobilized microorganisms capable of producing products and post-fermentation gaseous substrates from the gas stream.

[0260] In one embodiment, hydrocarbon removal bed 110 comprises activated carbon, hydrolysis bed 112 comprises hydrolysis catalyst, sulfur guard bed 114 comprises zinc oxide, and deoxygenation bed 116 comprises the unsulfided special copper-based deoxygenation catalyst discussed above. This selection of materials is surprisingly effective because the other materials in the bed except deoxygenation bed 116 are not affected by the reducing gas and reduction temperature required to reduce the special copper-based deoxygenation catalyst. In addition, under the operating conditions of the method, zinc oxide will not be reduced to zinc. If zinc oxide is reduced to zinc, it will become ineffective in adsorbing sulfur-containing compounds, and then the deoxygenation catalyst may be weakened by the sulfur-containing catalyst. If the deoxygenation catalyst cannot fully remove enough oxygen, the anaerobic microorganisms in the fermentation bioreactor may be damaged.

[0261] Go to Figure 2 , the system is similar to Figure 1 , except that the hydrocarbon removal bed is not located in the vessel, but rather in a module upstream of the vessel. The hydrocarbon removal bed module 110 may be upstream of the heating device 124, such as Figure 2 as shown, or may be downstream of the heating device 124 (not shown). Figure 2 A system for selectively removing impurities from an input gas stream 104 is provided, the system comprising a hydrocarbon removal bed 110, a hydrolysis bed 112, a sulfur guard bed 114, a deoxygenation bed 116, and a bioreactor 150. The hydrolysis bed 112, the sulfur guard bed 114, and the deoxygenation bed 116 are all contained within a vessel 106. The hydrocarbon removal bed 110 is positioned upstream of the vessel 106. The input gas stream may originate from any industrial, generator, and / or syngas source 102. The input gas stream 104 is contacted with a hydrocarbon removal adsorbent in the module 110 to remove hydrocarbons from the input gas stream and produce a hydrocarbon-depleted input gas stream 111. In one embodiment, the hydrocarbon removal adsorbent is activated carbon. Prior to entering the vessel 106, the hydrocarbon-depleted input gas 111 may be heated in a heating device 124 to an operating temperature of the vessel 106, which may be about 175°C to about 250°C, or about 200°C to 300°C, or about 300°C to 500°C, or 550°C. The heating device 124 can be a heater or a heat exchanger. It is advantageous to reuse readily available heating devices. The heated input gas 123 is passed into the container 106. In the container 106, the input gas sequentially contacts the hydrolysis bed 112, the sulfur protection bed 114, and the deoxygenation bed 116.

[0262] Contact with a hydrogen removal bed containing an adsorbent such as activated carbon results in one or more hydrocarbons being adsorbed by the activated carbon and removed from the gas stream. Contact with a hydrolysis bed 112 converts at least one impurity in the gas stream to provide a post-hydrolysis gas stream. Hydrogen cyanide (HCN) and carbonyl sulfide (COS) are two contemplated components that may chemically react with water and be removed from the gas stream. If COS is present, it is advantageous to convert COS to hydrogen sulfide (H2S), which may then be removed in a subsequent sulfur guard bed 114.

[0263] Now that the HCN has been removed and the COS has been converted to H2S, the gas is passed to a sulfur guard bed 114 where the H2S is adsorbed and removed from the gas. The gas is then passed to a deoxygenation bed 116 where oxygen (O2) is reduced to carbon dioxide (CO2) or water (H2O) and thereby removed from the gas. The treated gas exits the vessel 106 into a treated gas stream 118 which is passed to a bioreactor 150 for fermentation. The bioreactor may contain C1 immobilized microorganisms capable of producing products and post-fermentation gaseous substrates from the gas stream.

[0264] In one embodiment, hydrocarbon removal bed 110 comprises activated carbon, hydrolysis bed 112 comprises a hydrolysis catalyst such as alumina, sulfur guard bed 114 comprises zinc oxide, and deoxygenation bed 116 comprises the unsulfided specialized copper-based deoxygenation catalyst discussed above. This selection of materials is surprisingly effective because the materials in the beds other than deoxygenation bed 116 are not affected by the reducing gas and reducing temperature required to reduce the specialized copper-based deoxygenation catalyst.

[0265] As previously discussed, in one embodiment, the hydrolysis bed 112 and the sulfur guard bed 114 can be a physical mixture and combined into a single bed. In another embodiment, the functions of the hydrolysis catalyst and the sulfur sorbent can be combined into a composite material, such as zinc oxide on an alumina support, and the composite material is used as a single bed that performs the functions of both beds 112 and 114.

[0266] Figure 3 Similar to Figure 1 , except that vessel 106 is replaced by two vessels, a first vessel 106a and a second vessel 106b. The first vessel 106a contains a hydrocarbon removal bed 110, a hydrolysis bed 112 including a hydrolysis catalyst, and a first sulfur guard bed 114a. The second vessel 106b contains a second sulfur guard bed 114b and a deoxygenation bed 116. The adsorbents in the sulfur guard beds 114a and 114b can be the same or different. The effluent from the first vessel 116a is passed to the second vessel 106b via line 125.

[0267] Figure 4 Similar to Figure 2, except that vessel 106 is replaced by two vessels, a first vessel 106a and a second vessel 106b. The first vessel 106a contains a hydrolysis bed 112 including a hydrolysis catalyst and a first sulfur guard bed 114a. The second vessel 106b contains a second sulfur guard bed 114b and a deoxygenation bed 116. The adsorbents in the sulfur guard beds 114a and 114b can be the same or different. The effluent from the first vessel 116a is passed to the second vessel 106b via line 125.

[0268] Example 1

[0269] The gas cleaning system is configured to receive a mixed gas stream. The mixed gas stream is designed to represent a stream received from a steel mill. The gas cleaning system integrates the following beds in the following order: (i) a hydrolysis bed, (ii) an acid gas removal bed, (iii) a catalytic hydrogenation bed, and (iv) a deoxygenation bed. The hydrolysis bed consists of a bed of gamma-alumina adsorbent (BASF F-200). The acid gas removal bed consists of a bed of zinc oxide adsorbent (RCI ZOP-116). The catalytic hydrogenation bed consists of a palladium alumina catalyst (BASF R0-20 / 47). The deoxygenation bed consists of a copper catalyst (BASF CU0226S).

[0270] Prior to testing the substrates, the hydrogenation catalysts were reduced in 1 vol% H2 at 120°C under N2 for at least 12 hours. The deoxygenation catalysts were reduced in 1 vol% H2 at 250°C under N2 for at least 12 hours.

[0271] The following table illustrates the composition of the mixed gas stream fed to the gas cleaning system.

[0272] Compound hydrogen 6.8% by volume Carbon monoxide 30.6% by volume carbon dioxide 18.4% by volume Nitrogen 43.0% by volume water 4500ppm oxygen 6700ppm Acetylene 500ppm Hydrogen cyanide 60ppm

[0273] In addition to the above compounds, trace levels of methane and dimethyl ether were detected in the mixed stream. These compounds are impurities in the intake gas.

[0274] The following table illustrates these rates of gas flow feed and the inlet temperature of each bed. The pressure of each bed is 345 kPag.

[0275]

[0276]

[0277] This configuration successfully produced a fermentable gas stream. Removal of the targeted pollutants was achieved. The following table illustrates the composition of the fermentable gas stream.

[0278] Compound oxygen 0.50ppm Acetylene 0.062ppm Hydrogen cyanide <0.010ppm

[0279] Trace amounts of methane were detected in the fermentable gas stream. However, the amount of methane in the outlet stream was similar to the amount of methane detected in the inlet stream, so no methane production was detected. Trace amounts of ethane and ethylene were detected. Ethane and ethylene are products from acetylene removal and not microbial inhibitors. No other impurities were detected in the outlet stream using this configuration. No microbial inhibitors were formed using this configuration.

[0280] The outlet concentration of CO was 30.1 vol%. This outlet concentration corresponds to 2.6% of the input CO consumption, which is well below the maximum consumption of 10%.

[0281] Example 2

[0282] Similar to Example 1, a gas cleaning system is configured to receive a mixed gas stream. The mixed gas stream is designed to represent a stream received from a steel mill. The gas cleaning system integrates the following beds in the following order: (i) a hydrolysis bed, (ii) an acid gas removal bed, and (iii) a deoxygenation bed. The hydrolysis bed consists of a bed of gamma-alumina adsorbent (BASF F-200). The acid gas removal bed consists of a bed of zinc oxide adsorbent (RCI ZOP-116). The deoxygenation bed consists of a copper catalyst (BASF CU0226S).

[0283] The following table illustrates the composition of the mixed gas stream fed to the gas cleaning system.

[0284] Compound hydrogen 6.8% by volume Carbon monoxide 30.6% by volume carbon dioxide 18.4% by volume Nitrogen 43.0% by volume water 4500ppm oxygen 6700ppm Acetylene 500ppm Hydrogen cyanide 60ppm

[0285] In addition to the above compounds, trace levels of methane were detected in the mixed stream. These compounds are impurities in the intake gas.

[0286] The following table illustrates these rates of gas flow feed and the inlet temperature of each bed. The pressure of each bed is 345 kPag.

[0287] bed <![CDATA[Gas hourly space velocity (GHSV) -1 > Bed inlet temperature (℃) hydrolysis 2000 200 Acid gas removal 370 20 deoxidation 4000 200

[0288] This configuration successfully produced a fermentable gas stream. Removal of the targeted pollutants was achieved. The following table illustrates the composition of the fermentable gas stream.

[0289] Compound oxygen 0.45ppm Acetylene 0.065ppm Hydrogen cyanide <0.010ppm

[0290] Trace amounts of methane were detected in the fermentable gas stream. However, the amount of methane in the outlet stream was similar to the amount of methane detected in the inlet stream, so no methane production was detected. Trace amounts of ethane and ethylene were detected. Ethane and ethylene are products from acetylene removal. Trace amounts of dimethyl ether and acetaldehyde were detected. Dimethyl ether and acetaldehyde are not microbial inhibitors. No microbial inhibitors were formed using this configuration.

[0291] The fermentable gas stream was passed to an organic compound removal bed to remove trace amounts of dimethyl ether and acetaldehyde. The flow rate of the gas stream to the organic compound removal bed was such that the gas hourly space velocity was 370 h / min. -1 .

[0292] The outlet concentration of CO was 29.8 vol%. This outlet concentration corresponds to 4.0% of the input CO consumption, which is well below the maximum consumption of 10%.

[0293] In addition to running the gas cleaning system at 345 kPag, using this configuration and this gas composition, the pressure was increased so that the pressure per bed was 690 kPag to evaluate how pressure might affect the system.

[0294] It was found that at increased pressure (690 kPag per bed), the configuration successfully produced a fermentable gas stream. Removal of the targeted contaminants was achieved. The following table illustrates the composition of the fermentable gas stream.

[0295] Compound oxygen 0.41ppm Acetylene 0.076ppm Hydrogen cyanide <0.010ppm

[0296] Trace amounts of methane were detected in the fermentable gas stream. However, the amount of methane in the outlet stream was similar to the amount of methane detected in the inlet stream, so no methane production was detected. Trace amounts of ethane and ethylene were detected. Ethane and ethylene are products from acetylene removal and are not microbial inhibitors. Trace amounts of dimethyl ether and acetaldehyde were detected. Dimethyl ether and acetaldehyde are not microbial inhibitors. No impurities were detected in the outlet stream using this configuration.

[0297] The fermentable gas stream was passed to an organic compound removal bed to remove trace amounts of dimethyl ether and acetaldehyde. The flow rate of the gas stream to the organic compound removal bed was such that the gas hourly space velocity was 370 h / min. -1 .

[0298] The outlet concentration of CO was 29.8 vol%. This outlet concentration corresponds to 3.3% of the input CO consumption, which is well below the maximum consumption of 10%.

[0299] Example 3

[0300] The gas cleaning system is configured to receive a mixed gas stream. The mixed gas stream is designed to represent a stream received from a steel mill. The gas cleaning system integrates the following beds in the following order: (i) a hydrolysis bed, (ii) an acid gas removal bed, (iii) a catalytic hydrogenation bed, (iv) a deoxygenation bed, and (v) an organic compound removal bed. The hydrolysis bed consists of a bed of gamma-alumina adsorbent (BASF F-200). The acid gas removal bed consists of a bed of zinc oxide adsorbent (RCI ZOP-116). The catalytic hydrogenation bed consists of a palladium alumina catalyst (BASF R0-20 / 47). The deoxygenation bed consists of a copper catalyst (BASF Cu0226S).

[0301] Prior to testing the substrates, the hydrogenation catalysts were reduced in 1 vol% H2 at 120°C under N2 for at least 12 hours. The deoxygenation catalysts were reduced in 1 vol% H2 at 250°C under N2 for at least 12 hours.

[0302] The following table illustrates the composition of the mixed gas stream fed to the gas cleaning system.

[0303] Compound hydrogen 6.2% by volume Carbon monoxide 27.6% by volume carbon dioxide 16.2% by volume Nitrogen 49.1% by volume water 2400ppm Hydrogen sulfide 40.0ppm Carbonyl sulfide 4.0ppm oxygen 6000ppm Acetylene 550ppm Hydrogen cyanide 20ppm

[0304] In addition to the above compounds, trace levels of methane were detected in the mixed stream. These compounds are impurities in the intake gas.

[0305] The following table illustrates these rates of gas flow feed and the inlet temperature of each bed. The pressure of each bed is 690 kPag.

[0306] bed <![CDATA[Gas hourly space velocity (GHSV) -1 > Bed inlet temperature (℃) hydrolysis 2000 200 Acid gas removal 370 20 Catalytic hydrogenation 5500 120 deoxidation 4000 200 Organic matter removal 370 20

[0307] This configuration successfully produced a fermentable gas stream. Removal of the targeted pollutants was achieved. The following table illustrates the composition of the fermentable gas stream.

[0308] Compound oxygen 0.38ppm Acetylene 0.168ppm Hydrogen cyanide <0.030ppm

[0309] Trace amounts of methane were detected in the fermentable gas stream. However, the amount of methane in the outlet stream was similar to the amount of methane detected as an impurity in the inlet stream, so no methane production was detected. Trace amounts of ethane and ethylene were detected. Ethane and ethylene are products from acetylene removal and not microbial inhibitors. Using this configuration, no other impurities were detected in the outlet stream. No microbial inhibitor bed was formed using this configuration of modules.

[0310] The outlet concentration of CO was 26.6 vol%. This outlet concentration corresponds to 3.8% of the input CO consumption, which is well below the maximum consumption of 10%.

[0311] Example 4

[0312] The gas cleaning system was configured to receive a mixed gas stream similar to Example 3. The mixed gas stream was designed to represent a stream received from a steel mill. The gas cleaning system incorporated the following beds in the following order: (i) a hydrolysis bed, (ii) an acid gas removal bed, (iii) a deoxygenation bed, and (iv) an organic compound removal bed. The hydrolysis bed consisted of a bed of gamma-alumina adsorbent (BASF F-200). The acid gas removal bed consisted of a bed of zinc oxide adsorbent (RCI ZOP-116). The deoxygenation bed consisted of a copper catalyst (BASF Cu0226S).

[0313] The following table illustrates the composition of the mixed gas stream fed to the gas cleaning system.

[0314]

[0315]

[0316] In addition to the above compounds, trace levels of methane were detected in the mixed stream. These compounds are impurities in the intake gas.

[0317] The following table illustrates these rates of gas flow feed and the inlet temperature of each bed. The pressure of each bed is 690 kPag.

[0318] bed <![CDATA[Gas hourly space velocity (GHSV) -1 > Bed inlet temperature (℃) hydrolysis 2000 200 Acid gas removal 370 20 deoxidation 4000 200 Organic matter removal 370 20

[0319] This configuration successfully produced a fermentable gas stream. Removal of the targeted pollutants was achieved. The following table illustrates the composition of the fermentable gas stream.

[0320] Compound oxygen 0.34ppm Acetylene 0.073ppm Hydrogen cyanide <0.010ppm

[0321] Trace amounts of methane were detected in the fermentable gas stream. However, the amount of methane in the outlet stream was similar to the amount of methane detected as an impurity in the inlet stream, so no methane production was detected. Trace amounts of ethane and ethylene were detected. Ethane and ethylene are products from acetylene removal and not microbial inhibitors. Using this configuration, no other impurities were detected in the outlet stream. No microbial inhibitor bed was formed using this configuration of modules.

[0322] The outlet concentration of CO was 26.2 vol%. This outlet concentration corresponds to 4.9% of the input CO consumption, which is well below the maximum consumption of 10%.

[0323] Example 5

[0324] Similar to Example 2, the gas cleaning system is configured to receive a mixed gas stream. The mixed gas stream has a higher concentration of microbial inhibitors. The concentration is within the expected range for biomass or municipal solid waste gasification or treated coke oven gas. The gas cleaning system integrates the following beds in the following order: (i) hydrolysis bed, (ii) acid gas removal bed, (iii) deoxygenation bed and (iv) organic compound removal bed. The hydrolysis bed consists of a bed of gamma-alumina adsorbent (BASF F-200). The acid gas removal bed consists of a bed of zinc oxide adsorbent (RCI ZOP-116). The deoxygenation bed consists of a copper catalyst (BASF Cu 0226S).

[0325] Prior to testing the substrates, the deoxygenated catalysts were reduced in 1 vol% H2 at 250 °C under N2 for at least 12 h.

[0326] The following table illustrates the composition of the mixed gas stream fed to the gas cleaning system.

[0327] Compound hydrogen 4.1% by volume Carbon monoxide 17.8% by volume carbon dioxide 10.7% by volume Nitrogen 66.3% by volume water 2000ppm oxygen 7600ppm Acetylene 860ppm Hydrogen cyanide 280ppm

[0328] In addition to the above compounds, trace levels of methane were detected in the mixed stream. This compound is an impurity in the intake gas.

[0329] The following table illustrates these rates of gas flow feed and the inlet temperature of each bed. The pressure of each bed is 690 kPag.

[0330] bed <![CDATA[Gas hourly space velocity (GHSV) -1 > Bed inlet temperature (℃) hydrolysis 2000 200 Acid gas removal 370 20 deoxidation 4000 200 Organic matter removal 370 20

[0331] This configuration successfully produced a fermentable gas stream. Removal of the targeted pollutants was achieved. The following table illustrates the composition of the fermentable gas stream.

[0332] Compound oxygen 0.46ppm Acetylene 0.040ppm Hydrogen cyanide <0.010ppm

[0333] Trace amounts of methane were detected in the fermentable gas stream. However, the amount of methane in the outlet stream was similar to the amount of methane detected as an impurity in the inlet stream, so no methane production was detected. Trace amounts of ethane and ethylene were detected. Ethane and ethylene are products from acetylene removal and not microbial inhibitors. Using this configuration, no other impurities were detected in the outlet stream. No microbial inhibitor bed was formed using this configuration of modules.

[0334] The outlet concentration of CO was 16.6 vol%. This outlet concentration corresponds to 6.8% of the input CO consumption, which is well below the maximum consumption of 10%.

[0335] Example 6

[0336] The gas cleaning system is configured to receive a mixed gas stream. The mixed gas stream is designed to represent the stream received from a steel mill. The gas cleaning system incorporates only one bed. The bed consists of a copper catalyst (BASF Cu0226S).

[0337] Prior to testing the substrates, the deoxygenated catalysts were reduced in 1 vol% H2 at 250 °C under N2 for at least 12 h.

[0338] The following table illustrates the composition of the mixed gas stream fed to the gas cleaning system.

[0339] Compound hydrogen 7.0% by volume Carbon monoxide 31.6% by volume carbon dioxide 18.5% by volume Nitrogen 41.9% by volume water 4500ppm oxygen 5900ppm Acetylene 490ppm Hydrogen cyanide 20ppm

[0340] In addition to the above compounds, trace levels of methane were detected in the mixed stream. This compound is an impurity in the intake gas.

[0341] The gas flow was supplied at a rate corresponding to a gas hourly space velocity of 4000 hr-1. The bed inlet temperature was 200°C. The bed pressure was 690 kPag.

[0342] This bed successfully produced a fermentable gas stream. Removal of the target pollutants was achieved. The following table illustrates the composition of the fermentable gas stream.

[0343] Compound oxygen 0.41ppm Acetylene 0.060ppm Hydrogen cyanide <0.010ppm

[0344] Trace amounts of methane were detected in the fermentable gas stream. However, the amount of methane in the outlet stream was similar to the amount of methane detected as an impurity in the inlet stream, so no methane production was detected. Trace amounts of ethane and ethylene were detected. Ethane and ethylene are products from acetylene removal and are not microbial inhibitors. Methanol was detected in the fermentable gas stream. Methanol is not a microbial inhibitor. No other impurities were detected in the outlet stream using this configuration. No microbial inhibitor bed was formed using this configuration of modules.

[0345] The outlet concentration of CO was 30.2 vol%. This outlet concentration corresponds to 4.2% of the input CO consumption, which is well below the maximum consumption of 10%.

[0346] Example 7

[0347] The gas cleaning system is configured to receive a mixed gas stream. The mixed gas stream is designed to represent the stream received from a steel mill. The gas cleaning system incorporates only one bed. The bed consists of a copper catalyst (BASF Cu0226S).

[0348] Prior to testing the substrate, the catalyst was reduced in 1 vol% H2 at 250°C under N2 for at least 12 hours. After catalyst reduction, the catalyst was sulfided using a gas stream of 1 vol% H2S and 5 vol% H2 under N2. The catalyst was sulfided at 220°C for 18 hours.

[0349] The following table illustrates the composition of the mixed gas stream fed to the gas cleaning system.

[0350] Compound hydrogen 6.1% by volume Carbon monoxide 27.2% by volume carbon dioxide 16.0% by volume Nitrogen 49.8% by volume water 2400ppm Hydrogen sulfide 39ppm Carbonyl sulfide 4.0ppm oxygen 6200ppm Acetylene 550ppm Hydrogen cyanide 19ppm

[0351] In addition to the above compounds, trace levels of methane were detected in the mixed stream. This compound is an impurity in the intake gas.

[0352] The gas flow was supplied at a rate corresponding to a gas hourly space velocity of 2000 hr-1. The bed inlet temperature was 280°C. The bed pressure was 690 kPag.

[0353] This bed successfully produced a fermentable gas stream. Removal of the targeted pollutants was achieved. The following table illustrates the composition of the fermentable gas stream.

[0354] Compound oxygen 0.42ppm Acetylene 0.581ppm Hydrogen cyanide 0.011ppm

[0355] Trace amounts of methane were detected in the fermentable gas stream. However, the amount of methane in the outlet stream was similar to the amount of methane detected as an impurity in the inlet stream, so no methane production was detected. Trace amounts of ethane and ethylene were detected. Ethane and ethylene are products from acetylene removal and are not microbial inhibitors. Acetaldehyde was detected in the fermentable gas stream. Acetaldehyde is not a microbial inhibitor. No other impurities were detected in the outlet stream using this configuration. No microbial inhibitor bed was formed using this configuration of modules.

[0356] The outlet concentration of CO was 26.9 vol%. This outlet concentration corresponds to 1.0% of the input CO consumption, which is well below the maximum consumption of 10%.

[0357] Example 8

[0358] Similar to Example 7, the gas cleaning system is configured to receive a mixed gas stream. The mixed gas stream includes a higher concentration of microbial inhibitors. The concentration is within the expected range for biomass or municipal solid waste gasification or processed coke oven gas. The gas cleaning system incorporates only one bed. The bed consists of a copper catalyst (BASF Cu0226S).

[0359] The following table illustrates the composition of the mixed gas stream fed to the gas cleaning system.

[0360] Compound hydrogen 3.8% by volume Carbon monoxide 16.4% by volume carbon dioxide 9.1% by volume Nitrogen 69.6% by volume water 2200ppm Hydrogen sulfide 40ppm Carbonyl sulfide 4ppm oxygen 6600ppm Acetylene 1060ppm Hydrogen cyanide 400ppm

[0361] In addition to the above compounds, trace levels of methane were detected in the mixed stream. This compound is an impurity in the intake gas.

[0362] The gas flow was supplied at a rate corresponding to a gas hourly space velocity of 1000 hr-1. The bed inlet temperature was 300°C. The bed pressure was 690 kPag.

[0363] This bed successfully produced a fermentable gas stream. Removal of the targeted pollutants was achieved. The following table illustrates the composition of the fermentable gas stream.

[0364] Compound oxygen 3.1ppm Acetylene 0.960ppm Hydrogen cyanide 0.280ppm

[0365] Trace amounts of methane were detected in the fermentable gas stream. However, the amount of methane in the outlet stream was similar to the amount of methane detected as an impurity in the inlet stream, so no methane production was detected. Trace amounts of ethane and ethylene were detected. Ethane and ethylene are products from acetylene removal and are not microbial inhibitors. Acetaldehyde was detected in the fermentable gas stream. Acetaldehyde is not a microbial inhibitor. No other impurities were detected in the outlet stream using this configuration. No microbial inhibitor bed was formed using this configuration of modules.

[0366] The outlet concentration of CO was 15.9 vol%. This outlet concentration corresponds to 3.0% of the input CO consumption, which is well below the maximum consumption of 10%.

[0367] It should be understood that the foregoing examples given for illustrative purposes should not be construed as limiting the scope of the present disclosure. Although only a few exemplary embodiments of the present disclosure are described in detail above, it will be readily appreciated by those skilled in the art that many variations of the subject matter in the exemplary embodiments are possible without substantially departing from the novel teachings and advantages of the present disclosure. Therefore, all such modifications are intended to be included within the scope of the present disclosure as defined by the appended claims and all equivalents thereof. Further, it should be recognized that many embodiments may be envisioned in the design of a given system that do not achieve all the advantages of some embodiments, however the lack of a particular advantage should not be construed as necessarily meaning that such embodiments are outside the scope of the present disclosure.

[0368] Although the foregoing text sets forth a detailed description of many different embodiments of the present disclosure, it should be understood that the scope of the present disclosure is defined by the words of the claims set forth at the end of this patent. The detailed description is to be construed as merely exemplary and does not describe every possible embodiment of the present disclosure, as it would be impractical, if possible, to describe every possible embodiment. Many alternative embodiments may be implemented using current technology or technology developed after the filing date of this patent, which still fall within the scope of the claims defining the present disclosure.

[0369] Therefore, without departing from the spirit and scope of the present disclosure, many modifications and changes may be made to the techniques and structures described and illustrated herein.Therefore, it should be understood that the methods and apparatus described herein are illustrative only and do not limit the scope of the present disclosure.

[0370] All references (including publications, patent applications and patents) cited herein are hereby incorporated by reference to the same extent as if each reference was individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein. The reference to any prior art in this specification is not, and should not be taken as, an admission that the prior art forms part of the common general knowledge in the field of endeavor in any country.

[0371] Unless otherwise specified herein or explicitly contradicted by the context, the use of the terms "a / an" and "said" and similar references in the context of describing the present invention (especially in the context of the following claims) should be interpreted as covering both the singular and the plural. Unless otherwise indicated, the terms "include", "have", "include" and "contain" should be interpreted as open terms (i.e., meaning "including but not limited to"). The term "consisting essentially of..." limits the scope of the composition, process or method to specific materials or steps, or to those materials or steps that have no substantial effect on the basic and novel characteristics of the composition, process or method. The use of alternatives (i.e., "or") should be understood to mean one, two or any combination thereof in the alternatives. As used herein, the term "about" means ±20% of the indicated range, value or structure, unless otherwise specified. As used herein, the term "substantially" means to a large extent or to a certain extent and is of great significance.

[0372] Unless otherwise specified herein, references to numerical ranges herein are intended only to be used as a shorthand method of referring to each individual value falling within the range, and each individual value is incorporated into this specification as if it were individually quoted herein. For example, unless otherwise indicated, any concentration range, percentage range, ratio range, integer range, size range, or thickness range should be understood to include the value of any integer within the stated range and, where appropriate, its fraction (such as one tenth and one hundredth of an integer). Unless otherwise specified, percentages are mass %.

[0373] Unless otherwise specified herein or explicitly contradicted with the context, all methods described herein may be performed in any suitable order. The use of any and all examples or exemplary language (i.e., "such as") provided herein is intended only to better illustrate the present invention, without limiting the scope of the present invention, unless otherwise indicated. Any language in this specification should not be interpreted as indicating any unclaimed element as necessary for practicing the present invention.

[0374] Selected embodiments of the present invention are described herein. After reading the above description, variations of those embodiments may become apparent to those of ordinary skill in the art. It is contemplated that the skilled person will adopt these variations when appropriate, and intends to practice the present invention in a manner different from that specifically described herein. Therefore, where permitted by applicable law, the present invention includes all modifications and equivalents to the subject matter recited in the appended claims. In addition, unless otherwise specified herein or otherwise clearly contradictory to the content, the present invention encompasses any combination of the above elements in all possible variations thereof.

[0375] Unless the context dictates otherwise, all ranges described herein should be interpreted as being inclusive of their endpoints, and open ranges should be interpreted as including commercially practical values. Similarly, unless the context dictates otherwise, all numerical lists should be interpreted as including intermediate values.

[0376] Reference to the range of values ​​herein is intended only to serve as a simplified method for referring to each individual value falling within the range individually. Unless otherwise specified herein, each individual value is incorporated into this specification as if each individual value is quoted individually herein. Unless otherwise specified herein or explicitly contradicted with the context, all methods described herein may be carried out in any suitable order. The use of any and all examples or exemplary language (e.g., "such as") provided relative to some embodiments herein is intended only to better illustrate the present disclosure, and is not intended to limit the scope of the present disclosure claimed otherwise. Any language in this specification should not be interpreted as indicating any unclaimed element as being indispensable for practicing the present disclosure.

[0377] The grouping of alternative elements or embodiments of the present disclosure disclosed herein should not be construed as limiting. Each group member can be cited and protected individually or with other members in the group or other elements found herein in any combination. For convenience and / or patentability reasons, one or more members in a group can be included in or deleted from a group. When any such inclusion or deletion occurs, the description described in this article is considered to contain the group of modification, thereby satisfying the written description of all Markush groups (Markush group) used in the appended claims.

[0378] It is obvious to those skilled in the art that, without departing from the inventive concept herein, in addition to those modifications already described, more modifications are also possible herein. Therefore, except in the spirit of the appended claims, the subject matter of the present invention is not limited. In addition, when interpreting both the specification and the claims, all terms should be interpreted in a manner as broad as possible consistent with the context. Specifically, the terms "comprises" and "comprising" should be interpreted as referring to elements, components or steps in a non-exclusive manner, thereby indicating that the mentioned elements, components or steps can exist, or use, or combine with other elements, components or steps not explicitly mentioned. In the case where the specification claims refer to at least one of something selected from the group consisting of A, B, C... and N, the text should be interpreted as requiring only one element in the group, rather than A plus N or B plus N, etc.

[0379] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. Although any methods and materials similar or equivalent to those described herein can also be used to practice or test the present invention, a limited number of exemplary methods and materials are described herein.

[0380] It must be noted that, as used herein and in the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0381] Unless the context requires otherwise, throughout the specification and claims, the words "comprise," "comprising," and the like are to be interpreted in an inclusive sense rather than in an exclusive or exhaustive sense, that is, in an inclusive but not limited sense.

[0382] Example

[0383] Example 1. A method for removing impurities from an input gas stream to produce a fermentable gas stream, the method comprising:

[0384] a. heating the input gas stream to a temperature effective for the deoxygenation catalyst and below the reduction temperature of the sulfur guard bed material to produce a heated input gas stream;

[0385] b. contacting the heated input gas stream in a container with:

[0386] i. a hydrolysis catalyst bed for removing hydrogen cyanide to less than 1 ppm of hydrogen cyanide and / or removing carbonyl sulfide to less than 1 ppm of carbonyl sulfide;

[0387] ii. a sulfur guard bed containing a material effective to remove and / or react sulfur-containing compounds, the sulfur guard bed being positioned juxtaposed with or downstream of the hydrolysis bed; and

[0388] iii. a deoxygenation catalyst bed, the deoxygenation catalyst bed being positioned downstream of the sulfur guard bed;

[0389] c. wherein the fermentable gas stream comprises less than about 100 ppm oxygen, less than about 1 ppm acetylene, and less than about 1 ppm hydrogen cyanide.

[0390] Embodiment 2. The method according to embodiment 1 further comprises contacting the heated input gas stream with a hydrocarbon removal adsorbent bed located upstream of the hydrolysis catalyst bed in the container, or contacting the input gas stream with a hydrocarbon removal adsorbent bed in a module upstream of the heating and the container.

[0391] Embodiment 3. The method according to embodiment 1 or 2, wherein the hydrolysis catalyst bed and the sulfur guard bed are a physical mixture forming a combined hydrolysis and sulfur guard bed.

[0392] Embodiment 4. The process according to any one of embodiments 1 to 3, wherein the hydrolysis catalyst bed and the sulfur guard bed are a physical mixture forming a combined hydrolysis and sulfur guard bed.

[0393] Embodiment 5. The method of any one of embodiments 1 to 4, further comprising passing at least a portion of the fermentable gas stream to a bioreactor, wherein the bioreactor contains a culture comprising a fermentation broth and at least one C1 immobilized microorganism.

[0394] Embodiment 6. The method according to any one of embodiments 1 to 5, wherein at least a portion of the input gas stream is synthesis gas and / or producer gas.

[0395] Embodiment 7. The method of any one of embodiments 1 to 6, wherein the method further comprises measuring the concentration of impurities in the input gas stream and / or the fermentable gas stream.

[0396] Embodiment 8. The method according to any one of embodiments 1 to 7, wherein the input gas flow comprises CO, CO2, H2 or any combination thereof.

[0397] Embodiment 9. The method according to any one of embodiments 1 to 8, wherein the sulfur guard bed material is zinc oxide or copper and zinc oxide supported on alumina.

[0398] Embodiment 10. The method of any one of embodiments 1 to 9, wherein the deoxygenation catalyst comprises copper supported on alumina, silica, titania, ceria, lanthanum oxide, carbon, silica-alumina, or zeolite.

[0399] Embodiment 11. The method of any one of embodiments 1 to 10, wherein the hydrocarbon removal adsorbent is activated carbon.

[0400] Embodiment 12. A method according to any one of embodiments 1 to 11, wherein the hydrolysis bed and the sulfur guard bed are a combined hydrolysis and sulfur guard bed, and the combined hydrolysis and sulfur guard bed comprises bifunctional zinc oxide on an alumina support or copper and zinc oxide on an alumina support.

[0401] Embodiment 13. A method according to any one of embodiments 1 to 12, wherein the hydrolysis bed and the sulfur guard bed are a combined hydrolysis and sulfur guard bed, and the combined hydrolysis and sulfur guard bed comprises bifunctional zinc oxide on an alumina support or copper and zinc oxide on an alumina support.

[0402] Embodiment 14. A device comprising:

[0403] a. a heating device, the heating device having a heating device gas inlet and a heating device gas outlet;

[0404] b. A container having a container gas inlet in fluid communication with the heating device gas outlet and a container fermentable gas outlet, wherein the single container contains at least three beds, the at least three beds comprising:

[0405] i. a hydrolysis catalyst bed, the hydrolysis catalyst bed comprising alumina;

[0406] ii. a sulfur guard bed comprising zinc oxide or copper and zinc oxide on an alumina support, the sulfur guard bed being positioned in juxtaposition with the hydrolysis bed or positioned downstream of the hydrolysis bed;

[0407] iii. a deoxygenation catalyst bed located downstream of the sulfur guard bed, wherein the deoxygenation catalyst comprises copper supported on alumina, silica, titania, ceria, lanthanum oxide, carbon, silica-alumina or zeolite; and

[0408] c. A bioreactor having a bioreactor gas inlet in fluid communication with the vessel fermentable gas outlet and a bioreactor fermentation broth output, wherein the bioreactor comprises at least one C1 immobilized microorganism.

[0409] Embodiment 15. The apparatus of embodiment 14, further comprising at least one monitoring device, the at least one monitoring device being in communication with the container gas inlet, the container fermentable gas outlet, or both.

[0410] Embodiment 16. The apparatus of any one of embodiments 14 to 15, wherein the vessel further comprises a hydrocarbon removal bed comprising activated carbon positioned in the vessel upstream of the hydrolysis catalyst bed.

[0411] Embodiment 17. An apparatus according to any one of embodiments 14 to 16, further comprising a hydrocarbon removal module, the hydrocarbon removal module comprising activated carbon and having a hydrocarbon removal module gas inlet and a hydrocarbon removal module gas outlet, the hydrocarbon removal module gas outlet being fluidically connected to the heating device gas inlet.

[0412] Embodiment 18. A method for modifying a gas processing system, the method comprising:

[0413] a. Co-locate the following in a repurposed container:

[0414] i. a hydrolysis catalyst bed for removing hydrogen cyanide to less than 1 ppm of hydrogen cyanide and / or removing carbonyl sulfide to less than 1 ppm of carbonyl sulfide;

[0415] ii. a sulfur guard bed containing a material effective to remove and / or react sulfur-containing compounds, the sulfur guard bed being positioned juxtaposed with or downstream of the hydrolysis bed; and

[0416] iii. a deoxygenation catalyst bed, the deoxygenation catalyst bed being positioned downstream of the sulfur guard bed.

[0417] Embodiment 19. The method according to embodiment 18, further comprising connecting a reuse heating device upstream of the reuse container.

[0418] Embodiment 20. The method according to any one of embodiments 18 to 19, further comprising connecting a hydrocarbon removal module including activated carbon upstream of the reuse heating device.

[0419] Example 21. A method for removing impurities from an input gas stream to produce a fermentable gas stream, the method comprising:

[0420] a. heating the input gas stream to a temperature effective for the deoxygenation catalyst and below the reduction temperature of the sulfur guard bed material to produce a heated input gas stream;

[0421] b. contacting the heated input gas stream in a first container with:

[0422] i. a hydrolysis catalyst bed for removing hydrogen cyanide to less than 1 ppm of hydrogen cyanide and / or removing carbonyl sulfide to less than 1 ppm of carbonyl sulfide;

[0423] ii. a first sulfur guard bed, the first sulfur guard bed containing a material effective to remove sulfur-containing compounds and / or react sulfur-containing compounds, the first sulfur guard bed being positioned in juxtaposition with the hydrolysis bed or positioned downstream of the hydrolysis bed;

[0424] c. contacting the effluent from the first container in a second container with:

[0425] i. a second sulfur guard bed, the second sulfur guard bed containing a material that is effective in removing sulfur-containing compounds and / or reacting sulfur-containing compounds;

[0426] ii. a deoxygenation catalyst bed, the deoxygenation catalyst bed being positioned downstream of the sulfur guard bed;

[0427] d. wherein the fermentable gas stream comprises less than about 100 ppm oxygen, less than about 1 ppm acetylene, and less than about 1 ppm hydrogen cyanide.

[0428] Embodiment 22. The method according to embodiment 21 further comprises contacting the heated input gas stream with a hydrocarbon removal adsorbent bed located upstream of the hydrolysis catalyst bed in the container, or contacting the input gas stream with a hydrocarbon removal adsorbent bed in a module upstream of the heating and the container.

[0429] Embodiment 23. The method of embodiment 21, wherein the hydrolysis catalyst bed and the first sulfur guard bed are a physical mixture forming a combined hydrolysis and sulfur guard bed.

[0430] Embodiment 24. The method of any one of embodiments 21 to 23, wherein the hydrolysis catalyst bed and the first sulfur guard bed are a physical mixture forming a combined hydrolysis and sulfur guard bed.

[0431] Embodiment 25. The method of any one of embodiments 21 to 24, further comprising passing at least a portion of the fermentable gas stream to a bioreactor, wherein the bioreactor contains a culture comprising a fermentation broth and at least one C1 immobilized microorganism.

[0432] Embodiment 26. The method of any one of embodiments 21 to 25, wherein at least a portion of the input gas stream is syngas and / or producer gas.

[0433] Embodiment 27. The method of any one of embodiments 21 to 26, wherein the method further comprises measuring the concentration of impurities in the input gas stream and / or the fermentable gas stream.

[0434] Embodiment 28. The method of any one of embodiments 21 to 27, wherein the input gas stream comprises CO, CO2, H2, or any combination thereof.

[0435] Embodiment 29. The method according to any one of embodiments 21 to 28, wherein the first and or second sulfur guard bed material is zinc oxide or copper and zinc oxide supported on alumina.

[0436] Embodiment 30. The method of any one of embodiments 21 to 29, wherein the deoxygenation catalyst comprises copper supported on alumina, silica, titania, ceria, lanthanum oxide, carbon, silica-alumina, or zeolite.

[0437] Embodiment 31. The method of any one of embodiments 21 to 30, wherein the hydrocarbon removal adsorbent is activated carbon.

[0438] Embodiment 32. A method according to any one of Embodiments 21 to 31, wherein the hydrolysis bed and the first sulfur guard bed are a combined hydrolysis and first sulfur guard bed, and the combined hydrolysis and first sulfur guard bed comprises bifunctional zinc oxide on an alumina support or copper and zinc oxide on an alumina support.

[0439] Embodiment 33. A method according to any one of Embodiments 21 to 32, wherein the hydrolysis bed and the first sulfur guard bed are a combined hydrolysis and first sulfur guard bed, and the combined hydrolysis and first sulfur guard bed comprises bifunctional zinc oxide on an alumina support or copper and zinc oxide on an alumina support.

[0440] Embodiment 34. A device comprising:

[0441] a. a heating device, the heating device having a heating device gas inlet and a heating device gas outlet;

[0442] b. a first container having a first container gas inlet in fluid communication with the heating device gas outlet and a first container gas outlet, wherein the first container contains at least two beds, the at least two beds comprising:

[0443] i. a hydrolysis catalyst bed, the hydrolysis catalyst bed comprising alumina;

[0444] ii. a first sulfur guard bed comprising zinc oxide or copper and zinc oxide on an alumina support, the first sulfur guard bed being positioned juxtaposed with or downstream of the hydrolysis bed;

[0445] c. a second container having a second container gas inlet in fluid communication with the first container gas outlet and a second container fermentable gas outlet, wherein the second container contains at least two beds, the at least two beds comprising:

[0446] i. a second sulfur guard bed, the second sulfur guard bed comprising zinc oxide or copper and zinc oxide on an alumina support;

[0447] ii. a deoxygenation catalyst bed located downstream of the second sulfur guard bed, wherein the deoxygenation catalyst comprises copper supported on alumina, silica, titania, ceria, lanthanum oxide, carbon, silica-alumina or zeolite; and

[0448] d. A bioreactor having a bioreactor gas inlet in fluid communication with the second vessel fermentable gas outlet and a bioreactor fermentation broth output, wherein the bioreactor comprises at least one C1 immobilized microorganism.

[0449] Embodiment 35. The apparatus of embodiment 34, further comprising at least one monitoring device in communication with the container gas inlet, the container fermentable gas outlet, or both.

[0450] Embodiment 36. The apparatus of Embodiment 34 or 35, wherein the vessel further comprises a hydrocarbon removal bed comprising activated carbon positioned in the vessel upstream of the hydrolysis catalyst bed.

[0451] Embodiment 37. An apparatus according to any one of embodiments 34 to 36, further comprising a hydrocarbon removal module, the hydrocarbon removal module comprising activated carbon and having a hydrocarbon removal module gas inlet and a hydrocarbon removal module gas outlet, the hydrocarbon removal module gas outlet being fluidly connected to the heating device gas inlet.

[0452] Embodiment 39. A method of modifying a gas processing system, the method comprising:

[0453] a. Co-locate the following in a first re-use container:

[0454] i. a hydrolysis catalyst bed for removing hydrogen cyanide to less than 1 ppm of hydrogen cyanide and / or removing carbonyl sulfide to less than 1 ppm of carbonyl sulfide; and

[0455] ii. a first sulfur guard bed, the first sulfur guard bed containing a material effective to remove sulfur-containing compounds and / or react sulfur-containing compounds, the first sulfur guard bed being positioned in juxtaposition with the hydrolysis bed or positioned downstream of the hydrolysis bed;

[0456] b. Co-locate the following in a second re-purposed container:

[0457] i. a second sulfur guard bed, the second sulfur guard bed containing a material effective to remove and / or react sulfur-containing compounds; and

[0458] ii. a deoxygenation catalyst bed, the deoxygenation catalyst bed being positioned downstream of the second sulfur guard bed.

[0459] Embodiment 39. The method of embodiment 38 further comprises connecting a reuse heating device upstream of the reuse container.

[0460] Embodiment 40. The method according to embodiment 38 or 39 further comprises connecting a hydrocarbon removal module including activated carbon upstream of the reuse heating device.

Claims

1. A system for removing impurities from a gas stream, characterized in that It includes: a heating device having a heating device gas inlet and a heating device gas outlet; A single container having a single container gas inlet in fluid communication with the heating device gas outlet and a single container fermentable gas outlet, wherein the single container contains at least three beds, the at least three beds comprising: a hydrolysis catalyst bed, the hydrolysis catalyst bed comprising alumina; a sulfur guard bed comprising zinc oxide or copper and zinc oxide on an alumina support, the sulfur guard bed being positioned in juxtaposition with or downstream of the hydrolysis catalyst bed; a deoxygenation catalyst bed positioned downstream of the sulfur guard bed, wherein the deoxygenation catalyst comprises copper supported on alumina, silica, titania, ceria, lanthanum oxide, carbon, silica-alumina or zeolite; or a first vessel having a first vessel gas inlet in fluid communication with the heating device gas outlet and a first vessel gas outlet, wherein the first vessel contains at least two beds, the at least two beds comprising: a hydrolysis catalyst bed, the hydrolysis catalyst bed comprising alumina; a first sulfur guard bed comprising zinc oxide or copper and zinc oxide on an alumina support, the first sulfur guard bed being positioned in juxtaposition with or downstream of the hydrolysis catalyst bed; and a second container having a second container gas inlet in fluid communication with the first container gas outlet and a second container fermentable gas outlet, wherein the second container contains at least two beds, the at least two beds comprising: a second sulfur guard bed comprising zinc oxide or copper and zinc oxide on an alumina support; a deoxygenation catalyst bed positioned downstream of the second sulfur guard bed, wherein the deoxygenation catalyst comprises copper supported on alumina, silica, titania, ceria, lanthanum oxide, carbon, silica-alumina or zeolite; and A bioreactor having a bioreactor gas inlet in fluid communication with the single vessel fermentable gas outlet or the second vessel fermentable gas outlet and having a bioreactor fermentation broth output, wherein the bioreactor comprises at least one C1 immobilized microorganism.

2. The system according to claim 1, characterized in that It further comprises at least one monitoring device in communication with the single container gas inlet or the first container gas inlet, the container fermentable gas outlet or the second container fermentable gas outlet or both.

3. The system according to claim 1, characterized in that The single vessel or the first vessel further comprises a hydrocarbon removal bed comprising activated carbon positioned in the single vessel or the first vessel upstream of the hydrolysis catalyst bed.

4. The system according to claim 1, characterized in that It further comprises a hydrocarbon removal module comprising activated carbon and having a hydrocarbon removal module gas inlet and a hydrocarbon removal module gas outlet, the hydrocarbon removal module gas outlet being in fluid communication with the heating device gas inlet.

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