Intensification of the synthesis gas generation process using electrolysis.

Abstract

A method and system relating to enhanced synthesis gas production using electrolysis is disclosed. The disclosed method includes collecting an amount of carbon monoxide from a synthesis gas production system operating on an amount of natural gas, feeding the amount of carbon monoxide to a cathode region of an electrolyzer, and using the amount of carbon monoxide and the electrolyzer to produce an amount of a product chemical, the amount of the product chemical being at least one of an amount of a hydrocarbon, an amount of an olefin, an amount of an organic acid, an amount of an alcohol, and an amount of a N-rich organic compound.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Patent Application No. 17 / 980,912, filed November 4, 2022, which claims the benefit of U.S. Provisional Patent Application No. 63 / 322,638, filed March 22, 2022, and U.S. Provisional Patent Application No. 63 / 351,442, filed June 13, 2022, all of which are incorporated by reference in their entirety for all purposes. [Background technology]

[0002] There is an urgent need in our society to reduce the emissions associated with the production of useful fuels and chemicals. Furthermore, there is a need for the widespread adoption of clean-burning fuels (i.e., fuels that do not produce gaseous carbon when burned) to replace the fossil fuels used throughout our society. Therefore, processes to produce dihydrogen gas (hereinafter also referred to as "hydrogen gas") and syngas with low carbon dioxide (CO2) emissions are key technologies for building a sustainable fuel and chemical production platform of the future.

[0003] Hydrogen gas can be used as an energy source in a variety of reactors, including fuel cells and dihydrogen combustion systems. It can also be used in several industrial processes, especially chemical processes. Dihydrogen gas burns cleanly, but requires a large amount of energy to initially produce. The process required to produce this large amount of energy can adversely involve the production of carbon by-products. Dihydrogen gas can be classified based on the environmental impact of its production. Grey hydrogen is dihydrogen produced using a process that releases carbon by-products into the atmosphere, thereby negating to some extent the benefits of using dihydrogen as an alternative to hydrocarbon fuels. Blue hydrogen is dihydrogen produced using a process that produces carbon by-products, but captures and sequesters the carbon by-products rather than releasing them into the atmosphere. Green hydrogen is dihydrogen produced without or with very limited carbon by-product production, such as by using renewable energy sources to power a process that produces dihydrogen by electrolysis of water.

[0004] Syngas is a mixture of dihydrogen (H2) and carbon monoxide (CO) in varying ratios. The gas often also contains CO2 and methane (CH4). Syngas can be used as a feedstock to produce dihydrogen gas, or as a feedstock to produce chemicals and synthetic fuels. Syngas can also be used directly as a fuel for power generation or as a feedstock for internal combustion engines.

[0005] Various technologies are available to produce dihydrogen and syngas. Syngas can be produced by processing various feedstocks that contain carbon and hydrogen atoms, such as natural gas, hydrocarbons, biomass, or certain waste materials. The processes used to produce syngas from these feedstocks can be called syngas generation processes. For example, natural gas can be processed to separate dihydrogen from the methane and other hydrocarbons in the natural gas. The carbon that is left behind combines with oxygen to produce carbon monoxide and carbon dioxide, collectively called carbon oxides. Syngas can be produced in various ratios of dihydrogen gas and carbon oxides, depending on the application for which the syngas is used. In certain applications, this ratio will be zero, as all carbon oxides are removed to produce pure dihydrogen gas. In these applications, blue hydrogen can be produced from syngas using a syngas generation process that first produces syngas in a manner that captures carbon, then separates and captures the carbon oxides from the syngas, and isolates pure dihydrogen gas.

[0006] Currently, blue hydrogen has advantages over green hydrogen, both from an economic standpoint and in terms of the maturity of the relevant technologies. Blue hydrogen also has significant advantages over grey hydrogen with regard to environmental impact. As a result, blue hydrogen is expected to play a key role in the expansion of the global hydrogen power infrastructure due to its scalability and relatively low cost. However, a problem that remains with blue hydrogen is the cost of carbon capture and the low likelihood that such costs will decrease over time. The capture of carbon dioxide from the blue hydrogen process has been reported to add 30%-100% to the final cost of hydrogen gas, bringing the overall cost to approximately $1.40-$2.40 per kilogram of blue hydrogen, compared to grey hydrogen, which can reach prices as low as $1.00 per kilogram. As a result, many of the facilities that produce syngas, or that generate syngas specifically for the production of hydrogen gas, do not have carbon capture and storage facilities and instead simply release the carbon dioxide produced into the atmosphere. Summary of the Invention [Means for solving the problem]

[0007] Disclosed herein are methods and systems relating to the enhancement of a synthesis gas generation process using electrolysis. In certain embodiments, carbon monoxide produced from a synthesis gas production system is collected directly or indirectly for use in an electrolyzer to produce at least one of a hydrocarbon, an olefin, an organic acid, an alcohol, or a N-rich organic compound.

[0008] In certain embodiments of the present invention, a method is provided that includes collecting a quantity of carbon monoxide from a synthesis gas production system, feeding the quantity of carbon monoxide to a cathode region of an electrolyzer, and producing a quantity of a product chemical with the quantity of carbon monoxide and the electrolyzer. In certain embodiments of the present invention, the electrolyzer is a specialized electrolyzer designed for the electrochemical reduction of carbon monoxide as described in the detailed description below. The quantity of product chemical is at least one of a quantity of a hydrocarbon, a quantity of an organic acid, a quantity of an alcohol, a quantity of an olefin, and a quantity of a N-rich organic compound.

[0009] In a particular embodiment of the invention, a system is provided that includes a synthesis gas production system configured to produce a quantity of synthesis gas, a first connection fluidly connected to a synthesis gas output of the synthesis gas production system, a separation system fluidly connected to the first connection and configured to separate a quantity of carbon monoxide from the quantity of synthesis gas, a second connection fluidly connected to the carbon monoxide output of the separation system, and an electrolyzer having a cathode input fluidly connected to the second connection and configured to produce a quantity of product chemical from the quantity of carbon monoxide. The quantity of product chemical is at least one of a quantity of hydrocarbon, a quantity of organic acid, a quantity of alcohol, a quantity of olefin, and a quantity of N-rich organic compound.

[0010] In certain embodiments of the present invention, a method is provided. The method includes providing a quantity of carbon dioxide and a quantity of natural gas to a reforming process. The method also includes collecting a quantity of carbon monoxide from the reforming process. The method also includes providing the quantity of carbon monoxide to a cathode region of an electrolyzer and producing a quantity of product chemical with the quantity of carbon monoxide and the electrolyzer. [Brief description of the drawings]

[0011] [Figure 1] 1 shows a flow chart of a series of methods for enhancing a synthesis gas production system according to certain embodiments of the invention disclosed herein. [Figure 2A] 1 illustrates a system for enhancing a synthesis gas production system in accordance with certain embodiments of the invention disclosed herein. [Figure 2B] 1 illustrates a system for enhancing a synthesis gas production system using recycled dihydrogen gas, according to certain embodiments of the invention disclosed herein. [Figure 3A] 1 illustrates a system for enhancing a synthesis gas production system including a water gas shift reactor, according to certain embodiments of the invention disclosed herein. [Figure 3B] 1 illustrates another system for enhancing a synthesis gas production system including a water-gas shift reactor, in accordance with certain embodiments of the invention disclosed herein. [Figure 4A] 1 illustrates a system for enhancing a synthesis gas production system using a reforming reactor, according to certain embodiments of the invention disclosed herein. [Figure 4B] 1 illustrates a system for enhancing a synthesis gas production system using a gasification reactor, according to certain embodiments of the invention disclosed herein. [Figure 4C] 1 shows a system for enhancing a synthesis gas production system using oxygen collected from the output of an electrolyzer as input to a partial oxidation reactor, according to certain embodiments of the invention disclosed herein. [Figure 4D]FIG. 1 illustrates a system for enhancing a synthesis gas production system using parasitic hydrogen collected from the output of an electrolyzer to enhance the production of dihydrogen by the system, according to certain embodiments of the invention disclosed herein. [Diagram 5] FIG. 1 shows an exploded view of an electrolytic cell that can be utilized in accordance with certain embodiments of the invention disclosed herein. [Figure 6] 1 shows a first set of electrolytic cell reactions that can be utilized in accordance with certain embodiments of the invention disclosed herein. [Figure 7] 1 shows a second set of electrolytic cell reactions that can be utilized in accordance with certain embodiments of the invention disclosed herein. [Figure 8] 1 shows an electrolytic cell using a diaphragm as a separating element according to certain embodiments of the invention disclosed herein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] According to the above summary, methods and systems related to the enhancement of the synthesis gas generation process using electrolysis are disclosed in detail herein. The methods and systems disclosed in this section are non-limiting embodiments of the present invention, are provided for illustrative purposes only, and should not be used to limit the overall scope of the present invention. It should be understood that the disclosed embodiments may or may not overlap with each other. Thus, a part of an embodiment, or a specific embodiment thereof, may or may not be included within the scope of another embodiment or a specific embodiment thereof, and vice versa. Different embodiments from different aspects may be combined or implemented separately. Many different combinations and subcombinations of the representative embodiments shown within the broad framework of the present invention will be apparent to those skilled in the art, but may not be explicitly shown or described and should not be construed as excluded.

[0013] The production of synthesis gas or pure dihydrogen gas may include a synthesis gas generation process that results in the production of carbon monoxide. Carbon monoxide can be produced in a synthesis gas generation reaction in which a mixture of dihydrogen, carbon monoxide, and potentially other chemicals is produced. The other chemicals can include carbon dioxide and other carbon-containing chemicals. The term synthesis gas generation reaction is used in reference to the fact that the feedstock is at least partially converted to synthesis gas. This reaction can be part of a further reaction that achieves a final composition of dihydrogen and carbon monoxide or where all the dihydrogen is separated to form pure dihydrogen gas. According to certain embodiments of the invention disclosed herein, the carbon monoxide product produced during such synthesis gas generation reaction can be collected for certain purposes.

[0014] The collection of carbon monoxide from the syngas generation reaction may be direct collection or indirect collection. In indirect collection, the carbon monoxide from the syngas generation reaction may be piped to a storage tank and then sealed. The tank may then be transported to a location where the carbon monoxide is utilized or stored locally for later use. In contrast, in direct collection, the carbon monoxide from the syngas generation may be piped directly from the reactor or other system where the syngas generation reaction occurs to an electrolyzer or other system where the carbon monoxide is utilized (e.g., one or more intermediate steps may be performed before the carbon monoxide is sent to the electrolyzer). In certain embodiments of the invention, the two systems (e.g., the reactor and the electrolyzer) may be located in a single industrial facility. Indeed, in certain embodiments of the invention, existing syngas or dihydrogen production facilities may be enhanced using the systems disclosed herein to enable the direct collection of carbon monoxide that would otherwise have been directly released into the atmosphere or first converted to carbon dioxide and then released into the atmosphere from those facilities.

[0015] FIG. 1 includes a flow chart 100 of a series of methods for enhancing a syngas production system according to certain embodiments of the invention disclosed herein. Flow chart 100 includes step 101 of collecting a quantity of carbon monoxide from a syngas production system. The syngas production system may operate with a quantity of natural gas, biomass, waste (e.g., biowaste, plastic, waste mixture), or other feedstock. Natural gas may be in liquefied or gaseous form, and the term "gas" as used in the phrase is not meant to limit the state of natural gas to gaseous form, as those skilled in the art will know that natural gas can be transported and processed in liquefied form while still using the term "natural gas" to refer to natural gas (i.e., liquefied natural gas). Throughout this disclosure, the term "fluid" is used to refer to a substance in any physical form, including liquid, gas, supercritical, or a combination of liquid and gas forms.

[0016] The syngas production system can be part of a dihydrogen production line 110 that utilizes a syngas generation process. The syngas production system can include a syngas generation process that produces a quantity of dihydrogen, such as dihydrogen gas, and a quantity of carbon monoxide. The collecting can include collecting the entire quantity of carbon monoxide produced by the syngas production system, or a portion of the quantity of carbon monoxide produced by the syngas production system. The quantity of carbon monoxide can be collected as part of a carbon monoxide-containing stream in which the quantity of carbon monoxide is mixed with other chemicals or impurities. As noted elsewhere herein, the term "amount" of a substance (e.g., an amount of carbon monoxide) is not meant to indicate a separate, distinct, refined physical volume, but is meant to refer to a collection of substances in the same sense that a cup of coffee with a tablespoon of milk contains a "quantity" of milk and that quantity is one tablespoon.

[0017] The collection of carbon monoxide may be direct collection, and all steps of the flowchart 100 may be performed in a single facility. The collection of carbon monoxide may be performed according to a synthesis gas production system. For example, the dihydrogen production line 110 may be in the same facility as the electrolyzer 120, and the carbon monoxide produced by the dihydrogen production line 110 may be collected and fed directly to the electrolyzer 120, or the CO-containing stream may be pretreated by one or more intermediate steps between 110 and 120 before being fed to the electrolyzer. The synthesis gas production system may be fluidly connected to a separation system used to collect the carbon monoxide from the synthesis gas. The fluid connection may be provided via one or more valves, one or more seals, and / or one or more regulators or additional equipment in the piping or other connections that connect the output of the synthesis gas production system to the area where the carbon monoxide is used. Alternatively, the collection of carbon monoxide may be indirect collection, where an area of ​​the process that produces a certain amount of carbon monoxide is fluidly connected to one or more storage tanks that store the carbon monoxide for transport and / or later use. In either case, the machine in which the synthesis gas generation process occurs and the machine in which the carbon monoxide is utilized in the electrolysis process may be located in a single industrial facility such as a refinery, biorefinery, chemical plant, industrial laboratory, waste treatment plant, or other facility. Carbon monoxide can be collected from this process in a variety of ways, as described below.

[0018] In certain embodiments of the invention, carbon monoxide can be separated from the syngas produced by the syngas production system. Carbon monoxide can be separated from the syngas using various approaches, such as membrane separation, cryogenic separation, separation methods based on various physical or chemical properties of the components of the syngas, pressure swing adsorption, temperature swing adsorption, vacuum or vacuum pressure swing adsorption based separation, or absorption based separation. For example, a separation system can be used on the syngas to first cool the syngas to remove impurities, then heat the syngas to evaporate the purified dihydrogen through a membrane that filters the carbon monoxide.

[0019] The systems utilized to perform the above separation steps and processes can take a variety of forms. A separation system can perform one or more of a number of separation / purification steps, including any technology available for the targeted purification / separation. A separation system can include separation units based on, but not limited to, membrane technologies, including but not limited to, high density polymer membranes, ultrafiltration and nanofiltration membranes, facilitated transport membranes, metal membranes, hollow fiber pervaporation membranes, cryogenic technologies, adsorption technologies, including but not limited to, physical adsorption and chemical adsorption technologies, absorption technologies, including physical absorption and chemical adsorption technologies, and operation technologies, including but not limited to, vacuum pressure swing, temperature swing, pressure swing, dry pressure swing, combined pressure and temperature swing, electrical swing, etc. Chemical adsorbents that can be used include, but are not limited to, amine-based adsorbents (solids grafted or impregnated with amines), metal oxides, metal salts, double salts, and hydrotalcites. Physical adsorbents that can be used include, but are not limited to, materials such as carbon-based materials, mesoporous silica, zeolites, zeolitic imidazolate frameworks (ZIF's), metal organic frameworks (MOF's), mixed adsorbents, and the like.

[0020] The crude syngas may have a dihydrogen to carbon monoxide ratio of 1 to 5, depending on the feedstock and the process used to generate the syngas. Approaches used to alter this ratio can be used to generate concentrated streams of dihydrogen and carbon monoxide. In certain embodiments of the invention, the process used to generate carbon monoxide does not need to remove all carbon monoxide from the syngas leaving only pure dihydrogen. In fact, if the goal of the overall process is to produce a syngas with a specific ratio of carbon monoxide to dihydrogen, the collection and separation steps disclosed herein can be tailored to remove only a portion of the carbon monoxide in the syngas product. In these approaches, the process of collecting a quantity of carbon monoxide may include feeding a quantity of syngas from the syngas production system to a separation system and using the separation system to separate a quantity of dihydrogen and a quantity of carbon monoxide from the quantity of syngas, leaving a second quantity of syngas. The separation system may be configured to separate a quantity of carbon monoxide from the quantity of syngas to achieve a target ratio of carbon monoxide to hydrogen in the second quantity of syngas.

[0021] In certain embodiments of the invention, the synthesis gas generation process that produces a certain amount of carbon monoxide can take a variety of forms. Synthesis gas can be produced using a variety of feedstocks and a variety of processes. Processes that produce synthesis gas include reforming techniques, oxidation or partial oxidation (POX) techniques, and gasification of biomass or waste (e.g., biowaste, plastic, or any waste containing carbon-rich molecules). Reforming techniques can be further classified into steam reforming, such as steam methane reforming (SMR), autothermal reforming (ATR), and dry reforming techniques. Some reforming techniques that are in less advanced stages of development also include the use of plasma. The feedstock for reforming and partial oxidation techniques can be natural gas, including methane, or any carbon feedstock, including naphtha and other hydrocarbon fuels. Carbon dioxide can also be used as a co-reactant for the above techniques. The feedstock for gasification techniques can include biomass and / or waste, such as biowaste, plastic, or any waste containing carbon-rich molecules, or any of the above feedstocks.

[0022] The technology and feedstock selected will affect the ratio of carbon to dihydrogen gas ultimately produced. If the production of dihydrogen gas is the goal, SMR is an advantageous approach since it produces the highest dihydrogen to carbon ratio at the output with methane as the input. Throughout this disclosure, examples of natural gas and methane are used as examples of feedstocks for the synthesis gas generation process described herein. However, the other feedstocks mentioned above can be used in their place.

[0023] Equations for the various techniques described in the previous paragraphs are provided below, using methane from natural gas as the feedstock in each example. With specific reference to natural gas and methane, the reforming techniques mentioned above can be referred to as SMR, autothermal reforming, and dry methane reforming (DMR). In SMR, methane from natural gas is heated with steam, often using a catalyst, to produce a mixture of carbon monoxide and dihydrogen. Blue hydrogen can be produced using a process that involves the generation of synthesis gas, using a synthesis gas generation process in the form of SMR. SMR can be performed on a methane gas feedstock, followed by a water gas shift reaction (WGSR), in which carbon monoxide from the synthesis gas reacts with water to produce additional dihydrogen and carbon dioxide gases. The equations for SMR and WGSR are as follows:

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[0024] Gasification involves the thermal treatment of a feedstock at high temperatures without complete combustion, particularly through the controlled introduction of oxygen or steam. Gasification to produce dihydrogen in a synthesis gas production process can be represented by the following equation:

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[0025] FIG. 2A illustrates a system 200 for enhancing a syngas generation process according to certain embodiments of the invention disclosed herein. The system includes a syngas production system 201 configured to produce a quantity of syngas using a syngas generation process. The feedstock 202 can be natural gas, biomass, biowaste, carbon-rich waste, or other feedstock for syngas production as described herein. In embodiments where the feedstock 202 for the syngas production process is at least one of biomass, biowaste, or any carbon-rich waste, the syngas production system 201 can be a gasification system and the syngas generation process performed by the syngas production system can be a gasification process. In embodiments where the feedstock 202 is natural gas, the syngas production system 201 can be a reforming system, such as a steam methane reforming system, a dry reforming system, or an autothermal reforming system, or an oxidation system, such as a partial oxidation system. The syngas production system 201 can be configured to convert the feedstock 202 to syngas 203 using any of the processes described above. The syngas 203 can then be delivered through a first connection 204 to a separation system 205 that can be used to collect carbon monoxide 206 from the syngas 203, such as in step 101 as described above. The first connection 204 can also carry carbon dioxide and other impurities along with the syngas 203. The carbon monoxide 206 can be provided from a carbon monoxide output of the separation system 205 to a second connection 207. The separation system can be designed to separate at least a portion of the carbon monoxide from the syngas and send the low carbon syngas or pure dihydrogen gas 208 out to another pipe or manifold. In the illustrated embodiment, pure dihydrogen gas is produced and sent out to another pipe or connection 211.

[0026] 2A depicts a system in which a particular implementation of the collection of a quantity of carbon monoxide as in step 101 may include step 251 of feeding a quantity of syngas from a syngas production system to a separation system, and step 252 of separating a quantity of dihydrogen and a quantity of carbon monoxide from the quantity of syngas using the separation system. In the illustrated case, the quantity of dihydrogen is pure dihydrogen gas 208 collected in a separate pipe or connection 211. However, in alternative embodiments, depending on the original feedstock of the system, the syngas generation process, and the separation system, the quantity of dihydrogen gas may instead be a low carbon content dihydrogen containing low carbon dihydrogen gas (i.e., dihydrogen gas with a residual amount of carbon). The low carbon dihydrogen gas may then be used as syngas for a particular process requiring a resulting carbon to dihydrogen ratio, or may be further purified.

[0027] The flow chart 100 further includes a step 102 of supplying a quantity of carbon monoxide to the cathode region of the electrolyzer. This step can include providing a quantity of carbon monoxide to the cathode input of the electrolyzer at the cathode input of the electrolyzer. The quantity of carbon monoxide can be mixed with additional fluid to form a cathode input fluid or can be kept pure so that the cathode input fluid is pure carbon monoxide. This step can include transporting a tank of carbon monoxide from the area where it is collected and connecting it to a connection or pipe coupled to the cathode region of the electrolyzer. This step can also include storing the carbon monoxide in a temporary tank until electricity prices drop and then supplying the stored carbon monoxide to the electrolyzer when it becomes more economical. Alternatively, this step can include sending the carbon monoxide directly from the synthesis gas production system to the electrolyzer in the same industrial facility via a connection or pipe. The electrolyzer can have the characteristics described below with reference to Figures 5-7. The connections or pipes may include seals and valves that allow the carbon monoxide to be controllably fed to the electrolyzer as a cathode input fluid. The connections or pipes allow alternative fluids, such as water or other feedstocks, or impurities from the syngas production process, to be mixed with the carbon monoxide to form the cathode input fluid of the electrolyzer. This is illustrated by connection 218, which carries the alternative chemical 217 to the electrolyzer assembly 209. In Figures 2-4, the top of the electrolyzer represents the cathode input to the cathode region of the electrolyzer, and the left side of the electrolyzer represents the anode input to the anode region of the electrolyzer. In certain embodiments of the invention, the contents of connections 218 and 207 may be mixed before being provided to the electrolyzer assembly. The connections or pipes allow the carbon monoxide to be alternatively fed to other systems, such as other electrolyzers or to a water gas shift system. The valves, seals, and any other necessary equipment may be configurable to send the carbon monoxide to one system at a first time and then to a second system at a second time.A connection or pipe may be connected to an accumulation tank or set of tanks located between the syngas production system and the electrolyzer to accumulate excess carbon monoxide when there is a difference in speed between the syngas production system and the electrolyzer. Such an accumulation tank or set of tanks may also be used to temporarily store carbon monoxide during periods of high electricity costs.

[0028] Flowchart 100 further includes step 103 of using the amount of carbon monoxide and an electrolyzer to produce an amount of product chemical. For example, electrolyzer 209 can use carbon monoxide 206 to produce product chemical 216. The amount of product chemical can be at least one of an amount of hydrocarbon, an amount of organic acid, an amount of alcohol, and an amount of N-rich organic compound. Using the illustrated process, the carbon content of the syngas can be reduced, optionally down to the production of pure dihydrogen from the syngas, and the carbon monoxide can be valorized to create useful chemicals that can be used as feedstocks in other industrial processes and other useful applications. The disclosed methods and systems can be used to augment existing syngas production facilities, including facilities that would otherwise vent any excess carbon monoxide, or facilities that use carbon monoxide to obtain additional dihydrogen gas by a water-gas shift reaction and vent carbon dioxide. Using these processes, blue hydrogen production becomes more economically competitive with grey hydrogen production, as the market value of the product chemicals offsets the operating costs of the electrolyzer and the use of carbon monoxide to produce those chemicals eliminates carbon storage costs. In certain embodiments of the invention, the electrolyzer can operate using dihydrogen gas as an input without or with little additional external energy. In certain embodiments of the invention, the dihydrogen gas used for this purpose can be dihydrogen gas separated from the syngas. In an alternative embodiment, as described below, the dihydrogen gas can be dihydrogen gas that is parasitically generated by the electrolyzer and then recycled from the cathode output of the electrolyzer to the anode input of the electrolyzer. For example, system 220 of FIG. 2B shows the circulation of dihydrogen 221 on connection 222 linking the cathode output to the anode input such that the dihydrogen parasitically generated at the cathode output is recycled to be used as an oxidation substrate by being fed to the anode input. In an alternative embodiment, a portion of dihydrogen 208 can be fed to serve as an oxidation substrate instead.

[0029] 2A includes a single separation system and a single electrolytic cell, many different variations are possible. For example, multiple separation systems can be connected in series to separate larger quantities of low carbon dihydrogen syngas at increasing levels of purity, and one or more of the multiple separation systems can be coupled to a single electrolytic cell to supply carbon monoxide. As another example, multiple such separation systems can be coupled to a set of electrolytic cells configured to accept cathode inputs having different levels of carbon monoxide amounts or concentrations.

[0030] The system 200 includes an electrolyzer 209 having a cathode input coupled to a second connection 207 for receiving a quantity of carbon monoxide 206. The electrolyzer is represented by a line at the top of the block as the cathode input and a line at the left side of the block as the anode input. In certain embodiments, the electrolyzer can also include a cathode output and an anode output for receiving output fluids from the cathode and anode regions. In certain embodiments, the electrolyzer can also include a separation region output from a separation region of the electrolyzer, the separation region being located between the cathode and anode regions and providing a method for recovering additional product chemicals. In certain embodiments, chemicals are recovered from both the separation region output and the anode or cathode output. In certain embodiments, multiple chemicals can be recovered from either of these outputs in both liquid and gaseous form. For example, the quantity of product chemicals can include a quantity of gaseous hydrocarbons and a quantity of liquid products including at least one of a liquid organic acid and a liquid alcohol. A quantity of gaseous hydrocarbons can be recovered from the cathode output of the electrolyzer. A quantity of the liquid product may then be recovered by a trap at the cathode output or, if the electrolyser includes a separation zone, via the separation zone output.

[0031] The electrolyzer can receive a certain amount of fluid at the cathode input and another certain amount of fluid at the anode input. The electrolyzer can convert the carbon monoxide received at the cathode input into useful and valuable chemicals by electrolysis. In certain embodiments of the invention disclosed below, additional chemicals such as ammonia, water, electrolyte water, or nitrogen-containing reactants such as steam can be provided to the cathode input along with the carbon monoxide. For example, these additional chemicals can be provided via connection 218 or can be combined with the carbon monoxide at connection 207 before being provided to the electrolyzer assembly 209. In certain embodiments of the invention disclosed below, various chemicals can be provided to the anode region, including one or more of water, electrolyte, oxidation substrate, and dihydrogen gas. The dihydrogen gas can be dihydrogen gas obtained from a syngas generation process or can be dihydrogen gas provided separately. The dihydrogen gas can also be parasitically generated dihydrogen produced in the cathode region that is circulated from the cathode output of the electrolyzer back to the anode input of the electrolyzer. In Figure 2A, the electrolyzer 209 receives water 212 from connection 213 at the anode input and an oxidized substrate 214 from connection 215 at the anode input. In certain embodiments of the invention, an additional chemical, such as water, and an oxidized substrate can be combined and provided to the electrolyzer assembly through a single connection. The water provided to either the anode input or the cathode input can be provided from a water source. The water source can provide a fluid stream that includes water. The water from the water source can be pure deionized water, electrolytic water, or water mixed with any other chemical.

[0032] The product chemicals can be removed from the electrolytic cell from the product chemical output in liquid or gas form. The product chemical output can be fluidly coupled to a separation region of the electrolytic cell. In FIG. 2A, the useful chemicals 216 are removed from the electrolytic cell via a collected output from the cathode output stream from the cathode region. In an alternative embodiment disclosed below, the useful chemicals can be collected via a separation region between the anode and cathode regions of the electrolytic cell.

[0033] Notably, there is no step in Flowchart 100 that uses carbon monoxide to perform a water gas shift to collect more dihydrogen. Indeed, while some of the processes represented by Flowchart 100 can be used in combination with processes that utilize a water gas shift as described below, these processes do not require the use of a water gas shift, and the alternative use of carbon monoxide as a feedstock for the electrolysis process rather than as a feedstock for the water gas shift reaction is an important aspect of certain embodiments of the invention disclosed herein. In these particular embodiments of the invention, carbon monoxide from the entire amount of natural gas used as a feedstock for the syngas generation process is not used in the water gas shift reaction. For example, feedstock 202 may be a quantity of natural gas, and carbon monoxide from the quantity of natural gas cannot be used in the water gas shift reactor. Instead, all of the carbon monoxide may be used as the quantity of carbon monoxide 206. In these embodiments, the syngas production system (e.g., syngas production system 201) may be an SMR reactor, and the SMR process may be performed on a quantity of natural gas. In these embodiments, pure dihydrogen may be the desired output of the system. However, according to certain embodiments disclosed below, the carbon monoxide may be used in the electrolyzer rather than being used in the water-gas shift reactor to produce more dihydrogen. As described below, in an alternative embodiment, at least a portion of the carbon monoxide in connection 204 may be used in the WGS reaction, and another portion of the carbon monoxide in connection 204 may be provided to the electrolyzer assembly.

[0034] The approach of replacing the WGS reaction running on carbon monoxide from the syngas generation process with an electrolyzer running on carbon monoxide from the syngas generation process offers certain advantages. In the syngas generation system where the system is ultimately used to produce dihydrogen, it is important to further increase the ratio of dihydrogen gas to carbon monoxide beyond that produced by the first SMR-driven syngas generation. To this end, a WGS reaction step is added to produce additional H2 from CO according to the following reaction:

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[0035] Suppressing the WGS step and advantageously combining the SMR and CO electrolysis steps to produce valuable carbon-based products counterintuitively reduces the cost of equivalent low-carbon dihydrogen. This is counterintuitive because suppressing the WGS step increases the cost of dihydrogen gas to $1,333 per ton of dihydrogen gas. This is because currently only 3 moles of dihydrogen gas can be produced for the same cost as 4 moles of dihydrogen gas. Most of the process costs come from the SMR step compared to the WGS step, so the costs are effectively the same. However, in certain embodiments, the WGS step is purposefully replaced with a carbon monoxide capture step intended to capture the carbon monoxide generated during the SMR step and provide it to a carbon monoxide electrolyzer to produce high-value carbon-based products. From an economics perspective, this results in the following analysis: The mass of carbon monoxide captured (m(CO)) is a function of the mass of dihydrogen gas produced by the SMR (without the WGS reaction) and is given by the following relationship:

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[0036] A further advantage of certain embodiments of the present invention is that existing facilities for producing dihydrogen gas and syngas already have separate reactors for the syngas generation process described above, so the installation of a separation system and electrolyzer assembly for collecting and separating carbon monoxide only requires connecting the new machine to the existing output of the connection that would otherwise be sent to the WGS reactor. In a typical syngas generation and WGS system, the syngas generation process is an endothermic reaction. For SMRs, it is typically carried out at 800-1000 °C and 20-30 bar in the presence of a nickel-based catalyst. However, the WGS process is exothermic and requires different conditions to be optimized, so it is preferably carried out in a separate reactor. Due to its exothermic nature, the formation of dihydrogen gas by WGS is thermodynamically unfavorable at high temperatures, but as the temperature increases, the reaction becomes kinetically favorable. Thus, to benefit from both thermodynamic and kinetic advantages, WGS is typically carried out in a two-stage process: a first high-temperature shift step (usually carried out at 300-450 °C using an iron oxide-based catalyst) and a low-temperature process (usually carried out at 200-250 °C using a copper-based or copper oxide-based catalyst supported on a mixture of alumina and zinc oxide). In this system, the reactor typically used to perform the two-stage water-gas shift (i.e., low-temperature shift and high-temperature shift) is suppressed and replaced with a separation system that allows separation of dihydrogen and carbon, the latter of which is available for the carbon monoxide electrolysis step using an electrolyzer as discussed later herein. Thus, two separate WGS systems can be replaced with a separation system and a single electrolyzer, which allows the fixed costs of the production line to be maintained or reduced.

[0037] In certain embodiments of the invention, a portion of the carbon monoxide from the original feedstock is sent to the electrolyzer and a portion is sent to the water-gas shift reactor. Figure 3A shows a system 300 in which a feedstock 301 (e.g., natural gas) is fed to a synthesis gas production system in the form of a reforming reactor 302. A portion of that carbon monoxide 303 is then provided via a third connection 211 to a water-gas shift reactor 304 which produces additional dihydrogen gas and carbon dioxide 305 from the carbon monoxide 303 and water 306. Although this approach produces carbon dioxide, certain embodiments of the invention discussed below can be utilized as described below so that this carbon dioxide does not need to be captured and sequestered.

[0038] In a particular embodiment of the invention, the carbon monoxide originating from the original feedstock is sent directly to a water gas shift reactor, and the output of the water gas shift reactor is sent to a separation system where the remaining carbon monoxide can be separated and sent to the electrolyzer. Figure 3B shows a system 310 in which a feedstock 301 is provided to a synthesis gas production system in the form of a reforming reactor 302. All the synthesis gas produced by the reforming reactor 302 is then fed to a water gas shift reactor 311 which also receives a certain amount of water 316. The output 313 of the WGS reactor 311 is in the form of dihydrogen gas mixed with carbon dioxide and carbon monoxide. The output 313 can then be applied to a separation system 312 which supplies carbon monoxide 314 to the electrolyzer 209 along a connection 315, where it can be converted into a useful feedstock in the electrolyzer 209 as described with reference to Figure 2A. In certain embodiments of the invention, the reforming reactor can perform a DMR or ATR reaction using carbon dioxide as an input, and the carbon dioxide produced by the water gas shift reactor 311 can be separated and returned as an input to the reforming reactor 302, as described below.

[0039] In certain embodiments of the invention, the synthesis gas generation process may be a reforming process, such as an autothermal or dry reforming process, such as a DMR process performed on natural gas. These processes have the added advantage from an environmental point of view of using carbon dioxide as an input, thus providing the environmental benefits already mentioned above while recovering the carbon dioxide. These processes may be referred to as carbon dioxide consuming reforming processes and the associated systems may be referred to as carbon dioxide consuming reforming systems. In certain embodiments of the invention, the synthesis gas production system may be a dry methane reforming system, where the dry methane reforming process may be performed on a quantity of natural gas and a quantity of carbon dioxide. The synthesis gas production system may be configured to use both a quantity of natural gas and a quantity of carbon dioxide to produce a quantity of synthesis gas.

[0040] In system 400 of Figure 4A, the syngas production system is a reforming reactor 401, such as a dry methane reforming reactor or an autothermal reforming reactor. Figure 4A also includes a step 410, which may be performed before the start of the steps of flowchart 100, of providing an amount of carbon dioxide for use by the syngas production system. For example, the feedstock 402 may be methane and the reforming reactor 401 may be a DMR reactor that receives both the feedstock 402 and carbon dioxide from a carbon dioxide source 403 on connection 404.

[0041] Carbon dioxide for the dry reforming process can be provided from a variety of carbon dioxide sources. For example, the carbon dioxide source can be captured from a carbon emission process in another industrial process that takes place in the same single industrial facility as the dihydrogen or syngas production line from which carbon dioxide capture is desired. As another example, the dihydrogen production line can include a water gas shift reactor as shown in FIG. 4A, and the carbon dioxide produced from that reaction can be returned as at least a portion of the carbon dioxide source 403. In these embodiments, both the collecting step 101 and the providing step 410 can take place in a single industrial facility. These processes can include connections such as connection 404 that fluidly connects the carbon dioxide output of the carbon dioxide emission source (represented by carbon source 403) to the syngas production system (e.g., reforming reactor 401). In these embodiments, existing connections used to release carbon dioxide can be reused to provide carbon dioxide to the syngas production system, although this can only be done to a certain extent depending on the targeted H2:CO ratio. In an alternative embodiment, the amount of carbon dioxide may be from a carbon dioxide storage tank that stores carbon released at different times or at different facilities, represented by carbon source 403. For example, carbon dioxide source 403 may be a storage tank or a carbon dioxide transportation pipeline.

[0042] In the system 420 of FIG. 4B, the synthesis gas production system is a partial oxidation reactor 453 and the feedstock is a suitable feedstock for a gasification reactor, such as biomass or carbonaceous waste 422. The remaining elements of the system of FIG. 4B can be similar to those referenced with respect to FIGS. 2A, 3 and 4A. In an alternative embodiment, the water-gas shift reactor 302 can be replaced by a Fischer-Tropsch reactor followed by an upgrading reactor to upgrade the crude oil to a usable fuel. Such a system allows for the production of sustainable aviation fuel. Notably, the carbon dioxide produced by the illustrated WGS reactor 302 can be returned as an input to the partial oxidation reactor 453.

[0043] In the system 450 of FIG. 4C, the synthesis gas production system is an oxidation reactor 421, and the feedstock is a suitable feedstock for the oxidation reactor, such as methane 451 and oxygen 452. In the system 450, the oxygen 452 can be oxygen collected from the electrolyzer 209 at the anode output of the electrolyzer. As shown, the oxygen can include additional oxygen provided from a separate source, since the collected oxygen is generally not enough to keep the oxidation reactor adequately fed. The oxygen can be produced when the electrolyzer oxidizes water that is fed to the anode input of the electrolyzer. The oxidation reactor can perform a partial oxidation process. In an alternative embodiment, the oxygen produced by the electrolyzer oxidizing the water that is fed to the anode input can be enriched in a separate process or can be stored separately. The stored oxygen can then be sold, for example, as purified oxygen.

[0044] In system 460 of FIG. 4D, the syngas production system can use the parasitic output of the electrolyzer to increase the concentration of dihydrogen in the produced syngas or to obtain a larger amount of purified dihydrogen. As shown, the electrolyzer 209 produces parasitic dihydrogen 461 at the cathode region of the electrolyzer and outputs it to the cathode output of the electrolyzer, which can be sent via connection 462 to enhance the production of hydrogen by the WGS reactor 302, or any other system utilized to produce dihydrogen in the overall system of which the electrolyzer is a part. The dihydrogen can be separated from the useful product 216, which is also output from the cathode output produced in 216. For example, if the useful product is a fluid, they can be separated via a trap on connection 462, while the gaseous dihydrogen is retained within the connection.

[0045] In certain embodiments of the invention, the synthesis gas production device is advantageously integrated with a carbon monoxide electrolyser comprising a cathode region where the reduction of carbon monoxide occurs according to the following equation 16, and an anode region where the oxidation reaction occurs on an oxidation substrate. The oxidation substrate can be water, dihydrogen gas, a halide, an organic waste, or any other oxidation substrate. For example, the oxidation can involve the oxidation of water or the oxidation of dihydrogen according to the following equations 17 and 18, respectively.

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[0046] The chemicals produced by the electrolytic cell may vary in different embodiments of the invention. The chemicals may be separated using separation elements such as traps for liquid chemicals on the anode or cathode output of the electrolytic cell, or a separation region between the cathode and anode regions with their own output from the electrolytic cell. The produced chemicals may be removed from the electrolytic cell in solid or gas form, from the cathode or anode output stream of the cathode or anode output of the electrolytic cell, or from a separate output from a separation layer. Examples of such separation layers are shown below. A single electrolytic cell may simultaneously produce chemicals in both gas and liquid form. Thus, the amount of chemical produced in a step such as step 103 may include at least one of an amount of hydrocarbon, an amount of organic acid, an amount of alcohol, an amount of olefin, and an amount of N-rich organic compound, where the chemicals are in gas or liquid form. For example, the amount of produced chemical may include an amount of gaseous hydrocarbon and an amount of liquid alcohol. As another example, the amount of produced chemical may include an amount of gaseous hydrocarbon and an amount of organic acid. In certain embodiments, the primary target products are ethylene (in the gas product stream) and acetic acid / acetates (in the liquid product stream).

[0047] In situations such as the production of low-carbon dihydrogen gas where a water-gas shift reaction would otherwise occur, such a system would be particularly advantageous as it could enhance the value of carbon monoxide prior to its conversion to carbon dioxide, which would otherwise occur during the water-gas shift reaction. As a result, the system would enable the production of low-carbon SMR-derived dihydrogen (similar to blue hydrogen) without the need for carbon capture and sequestration facilities. Furthermore, it would enable the co-production of valuable carbon-based feedstocks with a lower carbon footprint than those traditionally produced in petroleum-derived processes (such as, but not limited to, naphtha cracking and ethane dehydration).

[0048] In certain embodiments of the invention, the oxidation substrate is dihydrogen gas, which is provided from a synthesis gas production process. The system can include a second output from a separation system that separates dihydrogen from the synthesis gas, and a connection that fluidly connects the second output of the separation system to an anode region of the electrolyzer. For example, the second output can be drawn from the separation system 205 and connected to connection 215 of FIG. 2A. The process performed by the system can then include separating the second amount of dihydrogen from the amount of synthesis gas. The production of useful chemicals by the electrolyzer using the amount of carbon monoxide can then include providing the amount of carbon monoxide as a cathode input fluid to the cathode region of the electrolyzer, and providing the second amount of dihydrogen as an anode input fluid to the anode region of the electrolyzer.

[0049] A carbon monoxide electrolyzer used according to the present disclosure may comprise one or more electrocatalytic cells arranged on top of or adjacent to each other to increase the surface available for reaction. These may be stacked on top of each other, and such stacks may also be paralleled. The cells may be connected in series or in parallel. Many different cell and stack configurations may be used in electrolyzers according to the present disclosure. Figure 5 shows a diagram of an electrolyzer 500 for illustrative purposes. The methods and systems disclosed herein are generally applicable to electrolyzers capable of receiving an input of carbon, such as carbon monoxide, and electrolyzer 500 is provided as one non-limiting example of such an electrolyzer.

[0050] FIG. 5 includes a diagram of an electrolyzer 500 in the form of a stack according to a particular embodiment of the invention disclosed herein. The electrolyzer assembly 500 includes end plates such as 502, monopolar plates such as 504, rigid bars such as 506, a membrane electrode assembly (MEA) such as 508 or a catalytic core of any form, flow fields such as 510, and bipolar plates such as 512. Again, an example of an MEA is provided, but this is merely an example and electrolyzers with catalytic cores of any form may be used according to the embodiments disclosed herein. Additionally, the stack 500 includes an inlet 514 and an outlet 516 for the anode stream, as well as an inlet 518 for the cathode stream and an outlet 520 for the cathode stream. The plates such as the monopolar plate 504 and the bipolar plate 512 may be part of a cell in the stack. The stack may also include gaskets, seals of any shape and material that are not shown in FIG. 5 for clarity.

[0051] In an electrolysis stack, the subsequent cells can be physically separated by bipolar plates (BPPs), such as bipolar plate 512 in FIG. 5, which ensure mechanical support for each of the electrolysis cells on each side of the BPP. The BPP ensures an electrical series connection between the subsequent electrolysis cells and also allows the introduction / removal of reactants / products, respectively. At the end of the stack, only one side of the plate can be in contact with the terminal cell. It is therefore called a monopolar plate, such as monopolar plate 504 in FIG. 5. At the end of the stack, a current collector can allow connection to an external power source and can be used for electrical monitoring of the stack, among other elements. The stack can be assembled in a stack casing, which allows mechanical support and compression, as well as the supply and transport of reactant and product streams to and from the stack. The stack casing can comprise end plates that ensure electrical insulation of the stack and provide inlets and outlets for the reactant and product streams. Alternatively, depending on the material of the end plates, an insulating plate can be placed between the end plate, such as 502, and the monopolar plate, such as 504, to ensure electrical insulation of the stack and the stack casing.

[0052] The carbon monoxide electrolyzer can take as inputs a cathode input stream (e.g., a carbon monoxide rich stream) and an anode input stream. The cathode input stream can be provided to an inlet, such as inlet 518. The anode input stream can be provided to an inlet, such as inlet 514. The cathode and anode streams can flow through the stack from inlet to outlet and be distributed separately to each cathode and anode region via flow paths, such as flow path 510, in each cell. The anode and cathode streams flow through separate channels on either side of the cell. Alternatively, the cathode and / or anode streams can be provided individually to each cell instead of through a connection across all plates. In this case, each cell has a dedicated fluid inlet and outlet for this cathode and / or anode stream. The nature of the anode stream can be determined by the nature of the targeted oxidation reaction (such as, but not limited to, water oxidation, dihydrogen oxidation, chloride oxidation, halide oxidation, hydrocarbon oxidation, waste organic acid oxidation, etc.). When powered, the carbon monoxide electrolyzer performs simultaneous reduction of carbon monoxide and oxidation of selected oxidation substrates to produce value-added chemicals such as hydrocarbons, organic acids and / or alcohols and / or nitrogen-containing organic products in an output cathode stream separated from an anode stream where the oxidation products are specifically collected. For example, producing chemicals using carbon monoxide and the electrolyzer in step 103 can include supplying a quantity of carbon monoxide as a cathode input fluid to a cathode region of the electrolyzer and supplying a quantity of water as an anode input fluid to an anode region of the electrolyzer.

[0053] In certain embodiments of the present invention, the anode region may include an anode catalyst layer capable of oxidizing a substance to produce products and protons. The catalyst may include one or more of the following: molecular species, single metal site heterogeneous compounds, metal compounds, carbon-based compounds, polymer electrolytes (also called ionomers), metal organic frameworks, metal doped covalent organic frameworks, or any other additives. The molecular species may be selected from metal porphyrins, metal phthalocyanines, or metal bipyridine complexes. The metal compounds may take the form of metal nanoparticles, nanowires, nanopowders, nanoarrays, nanoflakes, nanocubes, dendrites, films, layers, or mesoporous structures. The single metal site compounds may include metal doped carbon-based materials or metal-NC based compounds. Anode catalyst species used for this purpose include, but are not limited to, metals and / or ions of Ir, Co, Cu, Ni, Fe, Pt, Rh, Re, Ru, Pd, Os, Mo, and mixtures and / or alloys thereof. For example, the anode catalyst may be Ni, such that the electrolyzer assembly includes a nickel-based anode. The polyelectrolyte can be selected from the same materials used in the described membranes. The carbon-based compounds can include carbon nanofibers, carbon nanotubes, carbon black, graphite, boron-doped diamond powder, diamond nanopowder, boron nitride, or combinations thereof. The additives can be halide-based compounds including F, Br, I, Cl. The additives can be specially dedicated to modify the hydrophobicity, such as treatment with polytetrafluoroethylene (PTFE) or carbon black.

[0054] The anode catalyst may be deposited on a gas diffusion layer, a porous transport layer, or other support that facilitates diffusion of gas from the interface of the anode to a purified gas stream separated from the cathode stream. The anode region may also include a gas diffusion layer with one or more separators at its boundaries, such as, but not limited to, membranes, polymeric materials, diaphragms, inorganic materials, etc., as described below.

[0055] In certain embodiments of the present invention, the cathode region may comprise a catalyst layer capable of reducing a substance (e.g., carbon monoxide) to produce value-added hydrocarbons / alcohols / organic acids. The catalyst may comprise one or more of molecular species, single metal site heterogeneous compounds, metal compounds, carbon-based compounds, polyelectrolytes (also called ionomers), metal organic frameworks, or metal-doped covalent organic frameworks, or any other additives. The molecular species may be selected from metal porphyrins, metal phthalocyanines, or metal bipyridine complexes. The metal compounds may take the form of metal nanoparticles, nanowires, nanopowders, nanoarrays, nanoflakes, nanocubes, dendrites, films, layers, or mesoporous structures. The single metal site compounds can include metal-doped carbon-based materials or metal-NC-based compounds, and the cathode catalyst can be made of metals or metal ions from metals such as, but not limited to, Cu, Ag, Au, Zn, Sn, Bi, Ni, Fe, Co, Pd, Ir, Pt, Mn, Re, Ru, La, Tb, Ce, Dy, or other lanthanides, and mixtures and / or alloys thereof. For example, the cathode catalyst can include Cu, such that the electrolytic cell assembly includes a copper-based cathode. The polymer electrolyte can be selected from the same materials used for the described membranes. The carbon-based compounds can include carbon nanofibers, carbon nanotubes, carbon black, graphite, boron-doped diamond powder, diamond nanopowder, boron nitride, or combinations thereof. The additives can be halide-based compounds including F, Br, I, Cl. The additives can be specially dedicated to modify hydrophobicity, such as treatment with PTFE or carbon black. The cathode may further include a catalyst layer on a gas diffusion layer, a porous transport layer, or any other support to facilitate diffusion of gas from the stream to the surface of the catalyst and to allow release of non-reacted / product gases. The cathode region may also include a gas diffusion layer with one or more separators at its boundaries, such as, but not limited to, membranes, polymeric materials, diaphragms, inorganic materials, etc., as described below.

[0056] In certain embodiments of the present invention, the porous support of the anode region, the cathode region, or both, can be selected from carbon-based porous supports, metal-based porous materials, or combinations thereof. The carbon-based porous support can be based on carbon fiber, carbon cloth, carbon felt, carbon fabric, carbon paper, molded graphite laminates, and the like, or mixtures thereof. The carbon-based porous support can also be a gas diffusion layer with or without a microporous layer.Such carbon-based supports can be selected, in particular, from the list of Sigracet 39AA, Sigracet 39BC, Sigracet 39BB, Sigracet 39BA, Sigracet 36AA, Sigracet 36BB, Sigracet 35BC, Sigracet 35BA, Sigracet 29BA, Sigracet 28BB, Sigracet 28AA, Sigracet 28BC, Sigracet 25BC, Sigracet 22BB, Sigracet 35BI, Toray papers, Toray THP-H-030, Toray TGP-H-060, Toray TGP-H-090, Toray TGP-H-120, Freudenberg H23C6, Freudenberg H15C13, Freudenberg H15C14, Freudenberg H14C10, Freudenberg H14CX483, Freudenberg H14CX653, Freudenberg H23C2, Freudenberg H23CX653, Freudenberg H24CX483, Freudenberg H23C6, Freudenberg H23C8, Freudenberg H24C5, Freudenberg H23C3, Avcarb MB-30, AvcarbGDS5130, AvcarbGDS2130, AvcarbGDS3250, AvcarbGDS3260, AvcarbGDS2230, AvcarbGDS2240, AvcarbGDS2255, AvcarbGDS2185, AvCar1071, AvCarb1698, AvCarbon1209, AvCarb1185, AvCarb1186, AvCarb7497, AvCarbT1819, AvCarbT1820, AvCarbT1824, AvCarbon1071, AvCarb1698, AvCarbon1209, AvCarb1185, AvCarb1186, AvCarb1186, AvCarbT1819, AvCarbT1820, AvCarbT1824, AvCarbEP40, AvCarbP75, AvCarbEP55, AvCarbonEP40T, AvCarbP75T, AvCarbEP55T, AvCarbMGL190, AvCarbMGL280, AvCarbMGL370.The metal-based porous support can be selected from titanium, stainless steel, Ni, Cu, or any other suitable metal and can be in the form of a mesh, frit, foam or plate of any thickness or porosity.

[0057] In certain embodiments of the present invention, the electrolytic cell may include a separation element to separate certain product chemicals from other chemicals. The separation element may be one or more of a trap on the cathode and / or anode output of the electrolytic cell that separates the liquid output from the gas output. It may also be a more complex system known to those skilled in the art for efficient product separation. The separation element may be a separation region between the anode and cathode regions configured to separate a certain amount of product chemicals from the electrolytic cell. The separation region may be a separation layer. An efficient physical separation of the anode and cathode regions may facilitate the separation of gases released from each section of the reactor. The separator may be an ionically conductive polymer separator, a non-ionically conductive polymer separator, a diaphragm, a ceramic-containing material, a non-charged separator scaffold, a mixed ceramic organic compound separator, or any other separator. Separation may be achieved through the use of ion exchange membranes, which facilitate the diffusion of either anions (in the anion exchange membrane) or cations (in the cation exchange membrane), or bipolar membranes (including mixtures of cation and cation exchange membranes), or other types of separators, such as diaphragms, ceramic-containing materials (especially mixed ceramic / organic compounds), or uncharged separator scaffolds. Anion exchange membranes can include organic polymers with positively charged functional groups, such as, but not limited to, imidazolium, pyridinium, or tertiary amines. This allows the negatively charged hydroxide ions (OH) produced during the reduction of carbon monoxide to be transported through the membrane. -) can easily migrate from the cathode to the anode. The use of this layer also prevents crossover of other gases from the cathode to the separation layer. The cation exchange membrane can include an organic polymer with negatively charged functional groups, such as, but not limited to, sulfonic acid groups. The diaphragm or non-charged separator can be a material derived from an insulating material that can be charged with an ion-conducting electrolyte to facilitate charge transfer between the electrodes. The ceramic-containing material can be a pure ceramic or a mixture of polymer and ceramic materials. The ceramic and polymer mixture can reach higher temperatures than the pure organic polymer and can utilize the ion exchange function of the polymer to pass charge between the electrodes.

[0058] In certain embodiments of the invention, the system can include an electrolyte that provides ions that facilitate ion transport and promote the reaction. In particular, the electrolyte can be a concentrated alkaline solution, such as a solution of a hydroxide-containing salt, such as, but not limited to, potassium hydroxide, sodium hydroxide, or cesium hydroxide, at concentrations such as (0.01 molar (M), 0.05M, 0.1M, 0.2M, 0.5M, 1M, 2M, 3M, 4M, 5M, 6M, 7M, 8M, 9M, and 10M). The use of a concentrated alkaline solution reduces the energy required for the overall reaction. Alkali metal cations (Li, Na, K, Cs, Rb, etc.) can be used as countercations.

[0059] In certain embodiments of the present invention, the flow field may include ladders, single or multiple serpentines, interdigitated patterns, pillars, bioinspired lobes, or mixtures thereof. The electrolytic cell may also include plates, as discussed further in this disclosure.

[0060] 6 and 7 show examples of reactions that can be carried out according to the electrolyzer assembly described herein. In the figures, only a single cell is shown for clarity, but can easily be assembled into multiple cells, such as a stack. In the figures, the carbon monoxide electrolyzer comprises a cathode including a gas diffusion layer and a copper-based catalyst, and an anode including a nickel material in any shape, such as, but not limited to, a foam, a mesh, a deposit on a conductive porous transport layer (PTL), etc. In this case, the carbon monoxide reduction products include one or more of ethylene (C2H4), ethanol (C2H5OH), acetic acid (CH3COOH), propylene (C3H6), propanol (C3H8O), oxalic acid (COOH-COOH), acrylic acid (C2H3COOH), glyoxylic acid (COH-COOH), produced according to the following carbon monoxide reduction reaction: Under neutral / basic conditions:

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[0061] In certain embodiments, the CO stream is mixed with other gaseous or liquid compounds to generate higher value added products at the cathode. In one such embodiment, imines, amines, nitrogen oxides or ammonia are added to react with CO or intermediates formed during its reduction to form amide bonds or N-rich organic compounds such as amino acids and ureas. Examples of such reactions are as follows:

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[0062] In certain embodiments, the oxidation reaction at the anode is selected from the group consisting of reactions that take place in an acidic environment and reactions that take place in a basic environment, including but not limited to, anode reactions in an acidic environment such as:

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[0063] In certain embodiments of the invention, the carbon monoxide electrolyzer comprises one or more membranes selected from anion exchange membranes (such as, but not limited to, commercially available Ionomr®, Orion®, Sustainion®, Piperion®, ionomeric anion exchange membranes), proton exchange membranes (such as, but not limited to, Nafion®, Aquivion®, or commercially available membranes), bipolar membranes (such as, but not limited to, Fumasep® FBM and Xion®). In certain embodiments of the invention, the membranes in the anion exchange membranes are manufactured using nitrogen-bearing monomers. In the example of reactor 600, the electrolyzer comprises an anion exchange membrane, and hydroxides migrate from the cathode to the anode. The oxidation products depend on the oxidation substrate, but the products collected from the cathode output can be any of the generated chemicals listed above. In the example of membrane 602, the electrolyzer comprises a cation exchange membrane, and protons migrate from the anode to the cathode. The oxidation product again depends on the oxidation substrate, but the product collected from the cathode output can be any of the product chemicals listed above.

[0064] In certain embodiments of the invention, the electrolytic cell can include a separation layer. In the example of reactor 601, the carbon monoxide electrolytic cell includes a central separation layer through which electrolyte fluid circulates, allowing for the collection of liquid carbon monoxide reduction products moving from the cathode toward the central separation layer. In certain embodiments, the central separation layer is separated from the cathode by an anion exchange membrane or from the anode by a cation exchange membrane, or both membranes are present. In the example of reactor 601, both membranes are present. In this example, useful products can be collected from both the liquid stream from the separation layer and the gas stream from the cathode output. For example, carbon monoxide can be used in the electrolytic cell to produce one or more of ethylene (C2H4), ethanol (C2H5OH), acetic acid (CH3COOH), propylene (C3H6), and propanol (C3H8O). In certain embodiments, the primary target product is ethylene (in the gas product stream). In another specific embodiment, the primary target products are ethylene (in the gas product stream) and ethanol (in the liquid product stream). In another particular embodiment, the primary target products are ethylene (in the gas product stream) and acetic acid / acetate (in the liquid product stream). For example, in reactor 602, a trap is placed at the cathode output to separate the liquid product from the gas product so that both can be collected. In these examples, the oxidation occurring at the anode can be water / hydroxide oxidation, dihydrogen oxidation, or chloride oxidation. In particular, in the physical system, the trap is placed at a connection to the cathode outlet, such as piping connected to the cathode, and the trap is depicted as being connected to the cathode region for illustrative purposes only.

[0065] The embodiment shown in FIG. 7 is similar to the embodiment of FIG. 6 in terms of the overall theory of the reactor. However, the approach of FIG. 7 operates without the use of an exchange membrane, but instead uses a separation layer to achieve a similar effect. Reactor 700 is similar to reactor 600 in that hydroxide ions migrate from the cathode to the anode, and the generated products can be collected from the cathode output. Reactor 701 is similar to reactor 601 in that the separation layer contains a liquid electrolyte, and useful products can be collected from both the output of the separation layer in liquid form and the output of the cathode region in fluid form. Reactor 702 is similar to reactor 602 in that protons migrate across the separation layer, and useful products can be collected from the output of the cathode.

[0066] In certain embodiments of the invention, a porous membrane may be used in an electrolytic cell as a separation element to achieve separation. The membrane may be saturated with electrolyte, allowing ions to pass between the cathode and anode. Figure 8 shows a reactor 800 in which the separation element is a membrane that allows ions to move from the anode to the cathode and / or ions to move from the cathode to the anode.

[0067] In certain embodiments of the invention, the synthesis gas production system is a biomass gasifier used to produce low carbon dihydrogen. Carbon monoxide is then separated from the dihydrogen produced and fed to a carbon monoxide electrolyzer to produce one or more of the following products containing carbon-nitrogen bonds: ethylene (C2H4), ethanol (C2H5OH), acetic acid (CH3COOH), propylene (C3H6), propanol (C3H8O), or, if nitrogen-containing species such as imines, amines, ammonia, nitrogen oxides are used as inputs to the cathode stream simultaneously with CO, such as amino acids and / or ureas and / or amide-containing organic species. In certain embodiments, the primary target product is ethylene (in the gas product stream). In certain embodiments, the primary target products are ethylene (in the gas product stream) and ethanol (in the liquid product stream). The oxidation occurring at the anode is water / hydroxide oxidation, dihydrogen oxidation, or chloride oxidation.

[0068] In certain embodiments of the invention, the carbon monoxide stream is mixed with at least one other chemical, such as other gaseous or liquid compounds, to generate higher value added products at the cathode of the electrolytic cell. The carbon monoxide stream can be mixed with such additives when the carbon monoxide is fed to the electrolytic cell. In one such embodiment, imines, amines, nitrogen oxides, or ammonia are added to react with the carbon monoxide or intermediates formed during its reduction to form nitrogen-rich organic compounds, such as amide bonds or amino acids. In another embodiment, aromatic or aliphatic acids / aldehydes / alcohols are added to react with the carbon monoxide or intermediates formed during its reduction to form hydrocarbons, alcohols, or organic acids. In another embodiment, aromatic or aliphatic olefins or hydrocarbons are added to react with the carbon monoxide or intermediates formed during its reduction to form hydrocarbons, alcohols, or organic acids. These reactions can be combined with any of the reactors described above. For example, the oxidation occurring at the anode can be water oxidation, hydroxide oxidation, dihydrogen oxidation, or halide oxidation.

[0069] Although the present specification has been described in detail with respect to specific embodiments of the present invention, it will be understood that those skilled in the art, upon understanding the foregoing, will be able to readily conceive of modifications, variations, and equivalents of these embodiments. The disclosure of amounts of chemicals in this disclosure is not meant to refer to physically isolated amounts, as a certain amount of dihydrogen can exist with a certain amount of carbon dioxide in a single physical volume in the form of a certain amount of synthesis gas. Although the examples of the present disclosure are generally directed to the production of dihydrogen, the same approach can be utilized in other industrial processes where carbon monoxide becomes available, such as the steel industry. Furthermore, although the examples of the present disclosure have been generally applied to industrial chemical processes, the same approach is applicable to chemical processing of any scale and scope. Furthermore, although the examples of the present disclosure are generally applied to the supply of carbon monoxide to an electrolytic cell, the approach disclosed herein is more broadly applicable to the supply of any member of the oxocarbon family to an electrolytic cell for the purpose of producing useful chemicals. These and other modifications and variations to the present invention may be implemented by those skilled in the art without departing from the scope of the present invention, which is more particularly set forth in the appended claims.

Claims

1. Collecting (101) a quantity of carbon monoxide (206) from a synthesis gas production system (201); supplying (102) said amount of carbon monoxide (206) to a cathode region of an electrolyser (209, 500); and generating (103) a quantity of product chemical (216) using said quantity of carbon monoxide (206) and said electrolytic cell (209, 500); The method (100), wherein the quantity of product chemicals (216) is at least one of a quantity of hydrocarbons, a quantity of organic acids, a quantity of alcohols, a quantity of olefins, and a quantity of N-rich organic compounds.

2. The method (100) of claim 1, wherein the feedstock (202, 301, 402) for the synthesis gas production system (201) is a quantity of natural gas.

3. The synthesis gas production system (201) includes a gasification process; The method (100) of claim 1, wherein the feedstock (202, 301, 402) for the gasification process is at least one of biomass and waste material (422).

4. Collecting (101) the amount of carbon monoxide (206) comprises: feeding (251) a quantity of synthesis gas from said synthesis gas production system (201) to a separation system (205); and separating (252) the amount of dihydrogen (208) and the amount of carbon monoxide (206) from the amount of synthesis gas (203) using the separation system (205).

5. The synthesis gas production system (201) performs a steam methane reforming process on a certain amount of natural gas to produce a certain amount of synthesis gas; 3. The method (100) of claim 2, wherein the amount of carbon monoxide (206) from the synthesis gas (203) is not used in the water gas shift reaction.

6. The method (100) of claim 1, further comprising providing (401) a quantity of carbon dioxide for use in the synthesis gas production system (201).

7. 7. The method (100) of claim 6, wherein the amount of carbon dioxide is obtained from a water-gas shift reaction performed on a second amount of carbon monoxide (206) from the synthesis gas production system (201).

8. The generating (103) using the amount of carbon monoxide (206) and the electrolytic cell (209, 500) comprises: supplying (102) said quantity of carbon monoxide (206) as a cathode input fluid to a cathode region of said electrolyser (209, 500); and supplying a quantity of electrolyte as an anode input fluid to an anode region of the electrolytic cell.

9. supplying a quantity of oxygen (452) produced by the electrolyzer (209, 500) from an anode output to the synthesis gas production system (201); The method (100) of claim 8, wherein the synthesis gas production system (201) performs one of an oxidation process and a partial oxidation process.

10. providing a quantity of dihydrogen (208); The production (103) of the quantity of product chemical (216) is supplying (103) said quantity of carbon monoxide (206) as a cathode input fluid to a cathode region of said electrolyser (209, 500); and supplying the quantity of dihydrogen (208) as an anode input fluid to an anode region of the electrolyzer (209, 500).

11. said quantity of dihydrogen (208) comprising the parasitic dihydrogen (208) (461) output of said cathode region; 11. The method (100) of claim 10, wherein the parasitic dihydrogen (208) (461) output is circulated from a cathode output of the electrolyzer (209, 500) to an anode input of the electrolyzer (209, 500).

12. The collecting (101) of the amount of carbon monoxide (206) comprises: (i) feeding (251) a quantity of synthesis gas from the synthesis gas production system (201) to a separation system (205); and (ii) separating (252) the quantity of dihydrogen (208) and the quantity of carbon monoxide (206) from the quantity of synthesis gas (203) using the separation system (205).

13. providing a quantity of water (212) as an anode input fluid to an anode region of said electrolyzer (209, 500); The method of claim 1, wherein the electrolytic cell comprises a cathode region having a copper-based catalyst.

14. 10. The method of claim 1, wherein the electrolytic cell comprises at least one separation element selected from an ionically conductive polymer separator, a non-ionically conductive polymer separator, a diaphragm, a ceramic-containing material, a non-charged separator scaffold, and a mixed ceramic-organic compound separator.

15. The method (100) of claim 1, wherein the quantity of product chemicals (216) comprises a quantity of gaseous hydrocarbons and a quantity of liquid alcohol.

16. The method (100) of claim 1, wherein the quantity of product chemicals (216) comprises a quantity of gaseous hydrocarbons and a quantity of organic acids.

17. further comprising mixing the quantity of carbon monoxide (206) with a quantity of at least one additive chemical; 2. The method (100) of claim 1, wherein the quantity of carbon monoxide (206) is already mixed with the quantity of at least one additive chemical when the quantity of carbon monoxide (206) is provided to the electrolyzer (209, 500).

18. The method (100) of claim 17, wherein the quantity of at least one added chemical comprises water (212).

19. the amount of added chemical is one of an imine, an amine, a nitrogen oxide, and ammonia; 20. The method (100) of claim 17, wherein the amount of product chemical (216) is an amount of an amino acid.

20. A synthesis gas production system (201) configured to produce a quantity of synthesis gas; a first connection (204) fluidly connected to a syngas output of the syngas production system (201); a separation system (205) fluidly connected to the first connection (204) and configured to separate a quantity of carbon monoxide (206) from the quantity of synthesis gas (203); a second connection (207) fluidly connected to a carbon monoxide (206) output of said separation system (205); an electrolyser (209, 500) having a cathode input fluidly connected to said second connection (207) and configured to produce a quantity of a product chemical (216) from said quantity of carbon monoxide (206); The quantity of product chemicals (216) of the system (200) is at least one of a quantity of hydrocarbons, a quantity of organic acids, a quantity of alcohols, and a quantity of N-rich organic compounds.

21. The synthesis gas production system (201) is a gasification system; 21. The system (200, 300, 400) of claim 20, wherein a feedstock (202, 301, 402) for the gasification system is at least one of biomass and waste material (422).

22. the synthesis gas production system (201) being one of a methane (451) reforming system and a partial oxidation system; 21. The system (200, 300, 400) of claim 20, wherein the synthesis gas production system (201) is configured to operate with a quantity of natural gas.

23. 21. The system (200, 300, 400) of claim 20, wherein the synthesis gas production system (201) is configured to produce the amount of synthesis gas (203) using a quantity of carbon dioxide.

24. Water sources and 21. The system (200, 300, 400) of claim 20, further comprising a third connection (211) fluidly connecting the source of water (212) to an anode region of the electrolyzer (209, 500) as an anode input fluid.

25. an anode region of the electrolyzer (209, 500) having an anode output and configured to produce a quantity of oxygen (452) while oxidizing the anode input fluid; and a third connection (211) fluidly connecting the anode output of the anode region to the synthesis gas production system (201).

25. The system (200, 300, 400) of claim 24, wherein the synthesis gas production system (201) is configured to perform one of an oxidation process and a partial oxidation process.

26. 21. The system (200, 300, 400) of claim 20, further comprising an anode region of the electrolyzer (209, 500) configured to receive a quantity of dihydrogen (208) from the separation system.

27. a third connection (211) fluidly connected to a cathode output of said cathode region; 21. The system (200, 300, 400) of claim 20, further comprising: an anode region of the electrolyzer (209, 500) having an anode input fluidly connected to the third connection (211) and configured to receive a quantity of dihydrogen (208) from a cathode output via the third connection (211).

28. The electrolytic cell (209, 500) comprises: a cathode region having a copper-based catalyst; and an anode region having at least one of an iridium-based catalyst and a nickel-based catalyst.

29. The electrolytic cell (209, 500) comprises:

21. The system (200, 300, 400) of claim 20, further comprising at least one separation element selected from an ionically conductive polymer separator, a non-ionically conductive polymer separator, a diaphragm, a ceramic-containing material, a non-charged separator scaffold, and a mixed ceramic-organic compound separator.

30. Supplying (401) an amount of carbon dioxide and an amount of natural gas to a reforming process; collecting (101) a quantity of carbon monoxide (206) from the reforming process; supplying (102) said amount of carbon monoxide (206) to a cathode region of an electrolyser (209, 500); and producing (103) a quantity of a product chemical (216) using said quantity of carbon monoxide (206) and said electrolytic cell (209, 500).

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