Apparatus, system and method for direct capture of carbonaceous gases

Abstract

The present disclosure relates to apparatus, systems, and methods for selectively capturing carbon-containing gases from an input gas mixture.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefits of: U.S. Provisional Patent Application Serial No. 63 / 179,778 filed on April 26, 2021; U.S. Provisional Patent Application Serial No. 63 / 305,544 filed on February 1, 2022; and U.S. Provisional Patent Application Serial No. 63 / 318,944 filed on March 11, 2022, the entireties of which are incorporated herein by reference. Technical Field

[0003] The present disclosure relates to selectively capturing carbonaceous gases from an input gas mixture. Specifically, the present disclosure relates to apparatus, systems and methods for selectively capturing carbonaceous gases from an input gas mixture by using an insulator and a medium having an affinity for the carbonaceous gases. Background Art

[0004] Atmospheric carbon dioxide (CO2) concentrations cycled at about 235 ± 50 ppm for about 400,000 years until about 1850. Atmospheric CO2 concentrations are currently about 420 ppm and rising at a rapid annual rate. Increased CO2 concentrations in the atmosphere lead to global planetary climate disruption, habitat loss, and various other threats to our planet. CO2 is considered a stable molecule, making its conversion to a non-greenhouse gas significantly challenging.

[0005] It is known that increased atmospheric concentration levels of CO2 can be mitigated by removing CO2 from the air and / or by reducing the rate at which CO2 is emitted into the atmosphere. Known technologies that have been explored to remove CO2 from the air are expensive, require large amounts of water and energy, and are unattractive for long-term storage of the removed CO2. For example, it is known to use concentrated CO2 produced using air capture membrane technology to make seltzer water, which releases CO2 when consumed.

[0006] As another known example, concentrated CO2 produced by a precipitation / calcination process is currently injected to free up fossil fuels (which have limited storage capacity), leaking back into the air, and releasing CO2 into the air as the fossil fuels are consumed.

[0007] Another known example of mitigating increased CO2 atmospheric concentration levels includes converting CO2 into carbon and oxidizing by molten carbonate electrolysis. Useful products produced by this method include carbon nanomaterials. Carbon nanomaterials, including graphitic carbon nanomaterials, have great potential as material resources, with applications ranging from enhanced composite materials, capacitors, lithium-ion batteries, woven textiles, nanoelectronics and catalysts to the main components of lightweight, high-strength building materials due to their characteristic superior strength, electrical and thermal conductivity, flexibility and durability. However, there are still technical challenges to capture sufficient amounts of CO2, thereby substantially reducing the atmospheric concentration levels of CO2 and the associated negative impacts on our planet. Summary of the invention

[0008] Some embodiments of the present disclosure relate to a system for selectively transferring a carbon-containing gas from an input gas mixture. The system may include an optional permeable insulation that allows a net selective passage of carbon-containing gas at a first temperature from the input gas mixture therethrough, and a plenum for containing a medium at a second temperature that is higher than the first temperature. The medium has a first affinity for carbon in the carbon-containing gas received from the optional insulation, and the medium acts as a carbon sink. When used, the optional insulation may be located between a source of the input gas mixture and the plenum.

[0009] Some embodiments of the present disclosure relate to a method for reducing the carbon-containing gas content of an input gas mixture. The method includes the following steps: providing a medium in fluid communication with a source of the input gas mixture, the medium having an affinity for reacting with the carbon-containing gas of the input gas mixture; establishing a temperature difference whereby the medium has a higher temperature than the input gas mixture; and reacting the medium with the carbon-containing gas so that the medium acts as a carbon sink for reducing the carbon-containing gas content of the input gas mixture.

[0010] Some embodiments of the present disclosure relate to an apparatus for capturing carbon dioxide (CO2) from an input gas mixture. The apparatus comprises: an anode and a cathode located within an electrolytic cell; a molten electrolyte medium located between the anode and the cathode, wherein the molten electrolyte medium defines an upper surface having a first surface area, and wherein the upper surface is in fluid communication with a plenum containing the input gas mixture; and an insulator located between the plenum containing the input gas mixture and the upper surface, wherein the insulator is configured to promote a net selective passage of CO2 through the insulator to the upper surface. The apparatus is configured to selectively heat and electrolytically decompose the captured CO2.

[0011] In some embodiments of the apparatus, the input gas mixture is air and the source of the input gas mixture is the atmosphere of the planet Earth.

[0012] In some embodiments of the device, the input gas mixture is anthropogenic CO2-containing gas, an industrial waste gas stream, gas from an isolated CO2 storage tank, exhaust gas from a factory, exhaust gas from a chemical reactor, exhaust gas from a power plant, exhaust gas from a steam power generation facility, exhaust gas from a pyrolysis reactor, CO2-containing gas products from the combustion of fossil fuels, CO2-containing gas products from the conversion of fossil fuels, CO2-containing gas products from heating, CO2-containing gas products from transportation, CO2-containing gas products from the production of polymers, CO2-containing gas products from the production of plastics, or a combination thereof.

[0013] In some embodiments of the apparatus, the insulation has a surface area between 2 and 100 times greater than a first surface area of ​​an upper surface of the molten electrolyte medium within the electrolytic cell.

[0014] In some embodiments of the apparatus, the apparatus further comprises a housing located between the plenum containing the input gas mixture and the insulation.

[0015] In some embodiments of the apparatus, the insulation and the housing define an insulating compartment having a first end, a second end, and the battery is located between the insulating compartments, and wherein the insulating compartment receives the input gas mixture at the first end.

[0016] In some embodiments of the apparatus, the electrolytic cell comprises at least one metal wall that acts as an anode.

[0017] In some embodiments of the apparatus, the anode and cathode are configured to select the relative amounts of constituent carbon nanostructures within the CNM product.

[0018] In some embodiments of the apparatus, the electrolysis current and voltage are configured to select the relative amounts of the constituent carbon nanostructures within the CNM product.

[0019] In some embodiments of the device, metal salts, metals, or other additives are added to the electrolyte to select the relative amounts of the constituent carbon nanostructures within the CNM product.

[0020] In some embodiments of the apparatus, the electrolyte comprises one or more carbonates to select the relative amounts of constituent carbon nanostructures within the CNM product.

[0021] In some embodiments of the device, the electrolyte is configured to enhance thermal properties that enhance the selective capture of CO 2 from the input gas mixture.

[0022] In some embodiments of the device, the electrolyte can store excess thermal energy.

[0023] In some embodiments of the device, a wind lens or wind focus is used to redirect the input gas mixture through the device.

[0024] In some embodiments of the apparatus, heat is input to drive a heat engine or to drive movement of an input gas mixture.

[0025] Some embodiments of the present disclosure relate to a system for capturing carbon dioxide (CO2) from an input gas mixture. The system includes at least two devices, each of which includes: an anode and a cathode located in an electrolytic cell; a molten electrolyte medium located between the anode and the cathode, wherein the molten electrolyte medium defines an upper surface having a first surface area, and wherein the upper surface is in fluid communication with a gas chamber containing an input gas mixture; and a porous insulator, the porous insulator being located between the gas chamber containing the input gas mixture and the upper surface, wherein the porous insulator is configured to promote the net selective passage of CO2 through the porous insulator to the upper surface. Each device of the system is configured to selectively heat and electrolytically decompose the captured CO2 through an electrolysis process.

[0026] In some embodiments of the system, at least two devices are arranged in a vertical stack to reduce the physical footprint of the system.

[0027] In some embodiments of the system, the system further includes a heat source and an electric current source operatively coupled to each device.

[0028] In some embodiments of the system, the system further comprises a heat source and a current source operatively connected to the at least two devices.

[0029] Some embodiments of the present disclosure relate to a method for directly capturing carbon dioxide (CO2) from an input gas mixture within a plenum containing CO2. The method includes the following steps: establishing fluid communication between the input gas mixture and an outer surface of a porous insulator; selectively capturing CO2 from the input gas mixture by passing the CO2 through the insulator into a second plenum; establishing fluid communication between an inner surface of the porous insulator and an electrolyte medium within the second plenum, wherein the electrolyte medium is configured to enhance the capture of CO2; and collecting a carbon nanomaterial product generated by the captured CO2 from an electrode within the second plenum.

[0030] In some embodiments of the apparatus, system and / or method, the input gas mixture comprises at least one carbon-containing gas.

[0031] In some embodiments of the device, system and / or method, the input gas mixture is air, gas containing anthropogenic CO2, an industrial waste gas stream, gas from an isolated CO2 storage tank, exhaust gas from a factory, exhaust gas from a chemical reactor, exhaust gas from a power plant, exhaust gas from a steam power generation facility, exhaust gas from a pyrolysis reactor, CO2-containing gas products from the combustion of fossil fuels, CO2-containing gas products from the conversion of fossil fuels, CO2-containing gas products from heating, CO2-containing gas products from transportation, CO2-containing gas products from the production of polymers, CO2-containing gas products from the production of plastics, or a combination thereof.

[0032] In some embodiments of the apparatus, system and / or method, the input rate of the input gas mixture or the outlet rate of the input gas mixture is accelerated by changing the pressure between the first side and the second side of the porous insulation using a diaphragm pump.

[0033] In some embodiments of the apparatus, system and / or method, the input rate of the input gas mixture or the outlet rate of the input gas mixture is accelerated by changing the pressure between the first side and the second side of the porous insulation using a blower or a fan.

[0034] In some embodiments of the apparatus, system and / or method, further comprising a compressor mechanism for compressing the input gas mixture to a pressure greater than ambient pressure.

[0035] In some embodiments of the apparatus, systems and / or methods, the input gas mixture is pressurized.

[0036] In some embodiments of the apparatus, system and / or method, the exhaust gas generated in the second plenum is hotter than the input gas mixture.

[0037] In some embodiments of the apparatus, system and / or method, the waste gas generated in the second plenum is oxygen (O 2 ).

[0038] In some embodiments of the apparatus, system and / or method, the exhaust gas product compensates for or enhances the input rate of the input gas mixture and / or CO 2 capture in the internal second medium.

[0039] In some embodiments of the method, the method further comprises the step of transferring thermal energy from the exhaust gas product to the input gas mixture.

[0040] In some embodiments of the apparatus, systems and / or methods, the porous insulation is substantially fully porous and open to the input gas mixture.

[0041] In some embodiments of the apparatus, systems and / or methods, the porous insulation is an open channel insulation that inhibits heat transfer between the second plenum and the input gas mixture.

[0042] In some embodiments of the apparatus, systems and / or methods, the porous insulation may be adjusted to regulate airflow and heat transfer therethrough.

[0043] In some embodiments of the apparatus, system and / or method, the surface area of ​​the porous insulation is between 1 and 100 times greater than the surface area of ​​the inner second medium. In some embodiments of the apparatus, system and / or method, the surface area of ​​the porous insulation is between 2 and 20 times greater than the surface area of ​​the inner second medium.

[0044] In some embodiments of the apparatus, system and / or method, the ratio of the surface area of ​​the porous insulation relative to the surface area of ​​the electrolyte surface of the electrolyte medium is adjustable.

[0045] In some embodiments of the apparatus, systems and / or methods, an inner surface of the porous insulation is in direct contact with the electrolyte medium.

[0046] In some embodiments of the apparatus, systems and / or methods, an inner surface of the porous insulation has a gas space positioned proximate to the electrolyte medium.

[0047] In some embodiments of the method, the method further comprises a third step of positioning a non-porous shell around the porous insulation to define an insulating gas-filled chamber having a first end and a second end, the insulating gas-filled chamber also being referred to as a flow channel, and wherein the insulating gas-filled chamber is configured to receive an input gas mixture at the first end.

[0048] In some embodiments of the apparatus, systems and / or methods, the non-porous housing is an insulator.

[0049] In some embodiments of the apparatus, system and / or method, excess heat generated by the method is used to heat or power an external device.

[0050] In some embodiments of the apparatus, system and / or method, a heat pump or heat engine is used to heat the input gas mixture, the internal second medium, or a combination thereof.

[0051] In some embodiments of the apparatus, system and / or method, Joule heat, industrial waste heat, solar heat, geothermal heat, exhaust heat, or a combination thereof is used to heat the input gas mixture, the internal second medium, or a combination thereof.

[0052] In some embodiments of the apparatus, system and / or method, a vortex tube, a heat pump, a heat engine and a combination thereof are further included to increase the concentration of the carbon-containing gas in the input gas mixture; increase the flow rate of the input gas mixture; or a combination thereof.

[0053] In some embodiments of the apparatus, system and / or method, the insulation is configured to enhance the exhaust flow of exhaust products from the molten electrolyte medium, increase the rate of carbon-containing gas through the insulation, or a combination thereof.

[0054] In some embodiments of the apparatus, system and / or method, the insulation is configured to selectively allow a greater amount of carbon-containing gas to pass therethrough compared to other non-carbon-containing gases that are components of the input gas mixture.

[0055] In some embodiments of the apparatus, system and / or method, the system further comprises one or more displaceable members that are displaced to move their position to direct the flow of gas in a first direction or a second direction within the flow channel, wherein the first direction is toward the input orifice and the second direction is opposite and toward the output orifice.

[0056] Some embodiments of the apparatus, systems and / or methods further include providing a cover configured to regulate the inlet of the captured CO2.

[0057] In some embodiments of the devices, systems and / or methods, one or more components of the selectively captured CO2 are mixed in the electrolyte medium by mechanical mixing, agitation, stirring, convection, bubbling, or a combination thereof.

[0058] In some embodiments of the apparatus, systems and / or methods, the input gas mixture comprises a carbon-containing gas other than CO2 for which the electrolyte medium also has an affinity.

[0059] In some embodiments of the method, the electrolyte medium is a molten electrolyte medium.

[0060] In some embodiments of the method, the method further includes the following additional steps: heating the electrolyte to obtain a molten electrolyte medium; arranging the molten electrolyte medium between the anode and the cathode in the electrolytic cell; selectively heating the CO2 in the input gas mixture with at least the molten electrolyte medium; applying an electric current to the cathode and anode in the cell for electrolytic decomposition (decomposition by an electrolytic process) of the selectively heated CO2; and collecting the carbon nanomaterial product from the cathode in the cell.

[0061] In some embodiments of the method, the method further includes the step of producing an oxygen (O2) product within the molten electrolyte medium.

[0062] In some embodiments of the apparatus, system and / or method, the O 2 product enhances convective currents within the molten electrolyte medium for mixing the molten electrolyte medium.

[0063] In some embodiments of the devices, systems and / or methods, the carbon nanomaterial product includes one or more forms of graphitic nanocarbon, such as, but not limited to, carbon nanotubes, carbon nanoonions, platelets, nanoscaffolds, nanohelices, nanoflowers, nanotrees, nanoribbons, graphene, doped carbon nanomaterials, magnetic carbon nanomaterials, amorphous carbon, or combinations thereof.

[0064] In some embodiments of the apparatus, system and / or method, the morphology of the carbon nanomaterial product can be adjusted by changing the electrolyte medium temperature, CO2 rate, current, voltage, cathode composition, anode composition or electrolyte medium composition.

[0065] In some embodiments of the apparatus, systems and / or methods, the molten electrolyte medium comprises a carbonate.

[0066] In some embodiments of the devices, systems and / or methods, the electrical current is supplied by non-fossil energy sources including, but not limited to, solar, wind, hydroelectric, geothermal, tidal, wave, nuclear, or combinations thereof.

[0067] In some embodiments of the method, the method further comprises the step of activating the electrolyte medium.

[0068] In some embodiments of the devices, systems and / or methods, the electrolyte medium comprises an added oxide.

[0069] In some embodiments of the apparatus, system and / or method, the electrolyte medium is molten and reused to enhance the extent of conversion of CO2 into different chemical species.

[0070] In some embodiments of the apparatus, system and / or method, the electrolyte medium is molten and time-equilibrated to enhance the extent of CO2 conversion.

[0071] In some embodiments of the apparatus, system and / or method, the upper surface of the electrolyte medium is positioned adjacent to the lower surface of the inner second medium to enhance the extent of CO 2 conversion.

[0072] In some embodiments of the apparatus, systems and / or methods, the current is low to enhance the extent of CO2 conversion.

[0073] In some embodiments of the apparatus, system and / or method, the electrolytic cell is metallic to enhance the extent of CO2 conversion.

[0074] In some embodiments of the apparatus, system and / or method, multiple CO2 capture devices are stacked vertically to reduce the horizontal footprint area of ​​the method per unit of input gas mixture processed.

[0075] In some embodiments of the method, the method further comprises continuously repeating steps a, b, c, and d.

[0076] In some embodiments of the method, the method further comprises repeating steps a, b, c and d and replacing the internal medium.

[0077] In some embodiments of the apparatus, system and / or method, wind is used to accelerate the input gas mixture. In some embodiments of the apparatus, system and / or method, a wind lens or wind concentrator is used to redirect the input gas mixture.

[0078] In some embodiments of the apparatus, system and / or method, further comprising a second insulation layer located between a source of the input gas mixture and the first side of the insulation, wherein the second insulation layer is substantially non-porous and / or impermeable to the input gas mixture.

[0079]

[0013] In some embodiments of the apparatus, systems and / or methods, the electrolytic cell includes at least one metal wall that functions as an anode.

[0080] In some embodiments of the apparatus, system and / or method, the electrolytic cell, anode and cathode are each adjusted to form a different carbon nanomaterial or to increase the amount of a desired carbon nanomaterial morphology within the carbon nanomaterial product.

[0081] In some embodiments of the apparatus, system and / or method, the electrolytic cell, anode and cathode are each adjusted to form a different carbon nanomaterial or to increase the amount of a desired carbon nanomaterial morphology within the carbon nanomaterial product.

[0082] In some embodiments of the apparatus, system and / or method, metal salts, metals or other additives are added to the electrolyte to form different carbon nanomaterials or to increase the amount of a desired carbon nanomaterial morphology within the carbon nanomaterial product.

[0083] In some embodiments of the apparatus, systems and / or methods, the electrolyte medium comprises one or more carbonates to form different carbon nanomaterials or to increase the amount of a desired carbon nanomaterial morphology within the carbon nanomaterial product.

[0084] In some embodiments of the devices, systems and / or methods, the electrolyte is conditioned for enhanced thermal performance.

[0085] In some embodiments of the apparatus, systems and / or methods, the electrolyte is adjusted to change the absorption rate of various gases from the input gas mixture.

[0086] In some embodiments of the devices, systems and / or methods, the electrolyte can be used to store excess thermal energy.

[0087] Without being bound by any particular theory, embodiments of the present disclosure provide an economical, scalable, and robust method for selectively capturing carbon-containing gases from an input gas mixture by creating a temperature difference between the input gas mixture and a medium having an affinity for reacting with the carbon-containing gas. In some embodiments, the source of the input gas mixture may be one or more anthropogenic sources of carbon-containing gases, such as CO2. BRIEF DESCRIPTION OF THE DRAWINGS

[0088] Figure 1 Three schematic diagrams of a system according to an embodiment of the present disclosure are shown, wherein Figure 1 A shows the first system; Figure 1 B shows the second system; Figure 1 C shows a third system; and Figure 1 D shows the third system.

[0089] Figure 2 are schematic and experimental data, where Figure 2 A shows a schematic diagram of the electrolytic decomposition of CO2 during the electrolysis process; and Figure 2 B shows the carbon dioxide in air as a function of temperature (D CO2 ) diffusion coefficient and velocity (V CO2 ) data.

[0090] Figure 3 Data and schematics are shown, where Figure 3 A shows a line graph representing data for the experimental rate of CO 2 absorption during an electrolysis reaction in 1 m Li 2 O (mol / kg) in Li 2 CO 3 at 770° C. with three different flow rates; and Figure 3 B is a schematic diagram of a configuration according to an embodiment of the present disclosure.

[0091] Figure 4 Two configurations according to embodiments of the present disclosure are shown, wherein Figure 4 A shows a sealing configuration; Figure 4 B shows an unsealed configuration.

[0092] Figure 5 Three schematic diagrams of a device according to an embodiment of the present disclosure are shown, wherein Figure 5 A shows a first device; Figure 5 B shows a second device; and Figure 5 C shows a third device.

[0093] Figure 6 Two schematic diagrams of a system according to an embodiment of the present disclosure are shown, wherein Figure 6 A shows a top plan view of the first system; and Figure 6B shows a side view of the second system.

[0094] Figure 7 Two schematic diagrams are shown, each representing a method according to an embodiment of the present disclosure, wherein Figure 7 A shows the steps of the first method; and Figure 7 B shows the steps of the second method.

[0095] Figure 8 Scanning electron microscope (SEM) images of a first material used as an insulator according to an embodiment of the present disclosure are shown, wherein panel A has a scale bar of 300 μm, panel B has a scale bar of 100 μm, panel C has a scale bar of 100 μm, panel D has a scale bar of 10 μm, panel E has a scale bar of 10 μm, and panel F has a scale bar of 10 μm.

[0096] Fig. 9 SEM images of a second material used as an insulator according to an embodiment of the present disclosure are shown, wherein panel A has a scale bar of 500 μm, panel B has a scale bar of 100 μm, panel C has a scale bar of 20 μm, panel D has a scale bar of 5 μm, panel E has a scale bar of 1 μm, and panel F has a scale bar of 500 nm.

[0097] Fig.10 A schematic diagram of the device configuration according to an embodiment of the present disclosure and experimental data obtained therefrom are shown, wherein Fig.10 A shows two device configurations; Fig.10 B has an upper panel and a lower panel, each of which shows a device configuration and a line graph depicting changes in percent CO2 (CO2%) over time; Fig.10 C has upper, middle and lower panels, each showing the plant configuration and CO2 content (parts per million (ppm) CO2) over time.

[0098] Fig.11 Surface area enhancement is shown to promote the net selective passage of CO2 through the insulation.

[0099] Fig.12 A schematic diagram of an apparatus configuration for increasing the interaction path length of an input gas with an insulator according to an embodiment of the present disclosure is shown, wherein: Fig.12 A shows a flow channel having an extended length, which may be further extended by one or more ridges and / or valleys defined by the insulation and / or the housing; and Fig.12 B shows the piping for collecting and decomposing the flow of hot exhaust products. DETAILED DESCRIPTION

[0100] Embodiments of the present disclosure relate to one or more devices, one or more systems, and one or more methods that can be used to selectively capture carbon dioxide (CO2) from an input gas. The input gas can be a substantially pure gas, a pure gas, or a combination of different gases, and therefore, the terms "input gas" and "input gas mixture" can be used interchangeably herein. According to embodiments of the present disclosure, the captured CO2 can be subjected to an electrolysis process, also referred to herein as an electrosynthesis process, for producing a carbon nanomaterial (CNM) product from the carbon in the CO2. The terms "carbon nanomaterial product" and "CNM product" are used herein to refer to a collection of one or more forms of nanocarbon, which can also be referred to as nanoscale carbon. The term "nanocarbon" used herein refers to carbon that is arranged in a specific structure (such as a graphite nanocarbon structure) at the nanoscale. Specifically, the CO2 selectively captured from the input gas mixture can be decomposed into carbon and oxygen using a molten electrolyte medium and a variety of electrolysis process configurations. The electrolysis process can transfer carbon from the gas phase to the molten electrolyte medium, the solid CNM product, or both. The CNM product can be a substantially pure or pure carbon nanomaterial (CNM), including carbon nanotubes (CNTs). The CNM product may include one or more morphologies of CNM structures, such as carbon nanotubes, carbon nanoonions, nanoflowers, nanotrees, nanoribbons, sheets, nanoscaffolds, helical carbon nanomaterials, graphene, doped carbon nanomaterials, amorphous carbon, or combinations thereof. Optionally, one or more parameters of the electrolysis process may be adjusted to change the relative amount of a given morphology in the CNM product.

[0101] Figure 1 The embodiment of the present disclosure shows an implementation of the system. Figure 1A shows a system 1000 including a container 1002, which contains a medium 1004 having an affinity for carbon-containing gases in an input gas 1006. The container 1002 may also be more generally referred to as a "plenum", and this term is used herein to refer to any space that can be filled with a substance (whether liquid, gas, solid or a combination thereof). The plenum may be open, closed, substantially sealed to restrict fluid entry or egress, or fluid-tightly sealed to prevent fluid entry or egress. The term "affinity" as used herein refers to the tendency of the medium to absorb, react, chemically bond or combine with carbon-containing gases in the input gas 1006. Therefore, more often, the medium 1004 will, for example, without being bound by any limitation or theory, preferentially absorb, combine or a combination of carbon-containing gases by participating in one or more chemical reactions with carbon-containing gases, one or more electrochemical reactions with carbon-containing gases, react, chemically bond or combine with carbon-containing gases. In some embodiments of the present disclosure, the affinity of the medium 1004 to react with the carbon-containing gas will result in the production of different chemical species. The term "different chemical species" is used herein to refer to chemical species that would not otherwise be produced in the absence of the medium having an affinity to react with the carbon-containing compound.

[0102] Container 1002 is shown in Figure 1 A. Figure 1 A is open to fluidly communicate with a source of input gas 1006. Medium 1004 has a higher temperature than the input gas 1006. The medium also has an affinity for reacting with the carbon-containing gases within the input gas. Figure 1 In A, the input gas is rich in carbon-containing gas, which in this case is CO2. The affinity of the hotter medium 1004 for the carbon-containing gas causes at least a portion, substantially all, or all of the carbon-containing gas to leave the input gas 1006 and enter the medium 1004 within the container 1002. The medium 1004 may also have an affinity for reacting with other gases within the input gas 1006, but the affinity for reacting with carbon-containing gases is higher than the affinity for reacting with gases that do not contain carbon. In this way, the medium 1004 can act as a carbon sink, whereby as the carbon-containing gas enters the medium 1004 and reacts with it, the amount of carbon in the input gas 1006 is reduced, substantially depleted, or completely depleted, while the amount of non-carbon-containing gas in the input gas 1006 is minimally changed or not changed at all.

[0103] Figure 1B shows a system 1000A, which includes a container 1002, a medium 1004, and an insulator 1008 located between the upper surface of the medium 1004 and the source of the input gas 1006. The medium 1004 is hotter than the input gas 1006. The insulator 1008 can be porous and allow carbon-containing gas to pass through. In some embodiments of the present disclosure, the insulator 1008 is permeable to carbon-containing gas and other carbon-free constituent gases of the input gas 1006. In some embodiments of the present disclosure, the insulator 1008 may have a greater carbon-containing gas permeability than the carbon-free gas in the input gas 1006, which means that under the same or substantially similar thermodynamic parameters, a larger net amount of carbon-containing gas will pass through the insulator compared to the carbon-free gas. In some embodiments of the present disclosure, the insulator 1008 may be impermeable or less permeable to the carbon-free gas in the input gas 1006.

[0104] In some embodiments of the present disclosure, the affinity of the medium to react with carbon-containing gases and the permeability properties of the insulation 1008 may work synergistically to deplete the carbon-containing gas content of the input gas 1006 and increase the carbon content of the medium 1004. Figure 1 A, Figure 1 B's medium 1004 may act as a carbon sink.

[0105] Figure 1 C shows a system 1000B having the same Figure 1 1006) with the added feature that the specific input gas is air and the space defined between the interior / lower surface of the insulator 1008 and the upper surface of the medium 1004A is also hotter than the input gas 1006 and may contain enclosed air that is also hotter than the input gas 1006. In system 1000B, the medium 1004A is also hotter than the input gas 1006. For example, the medium 1004A may be a molten carbonate electrolyte that is optionally supplemented with an oxide such that the upper surface of the medium 1004A forms a gas-liquid interface. In system 1000B, the medium 1004A has a high affinity for reacting with carbonaceous gases in the input gas 1006 and a relatively low affinity for reacting with other constituent gases (e.g., nitrogen, oxygen, and water) in the input gas 1006 that do not contain carbon. In some embodiments of the present disclosure, insulation 1008 and medium 1004A can reduce the carbon content of input gas 1006 by promoting the reaction between medium 1004A and carbon-containing gas (such as CO2). In this way, system 1000B acts as a carbon sink by selectively reducing the carbon content of input gas 1006.

[0106] Figure 1D shows a system 1000C having many of the same features as system 1000B, with the additional feature of electrodes 1010A and 1010B immersed in a molten carbonate electrolyte medium 1004A (at a temperature of about 750° C.). When an electric current is applied across the electrodes, the carbon-containing gas (CO2 is converted (or electrolytically decomposed) in this embodiment) is converted, new carbon species are produced, and oxygen is produced. The details of these electrochemical reactions between the medium 1004A and the carbon-containing gas are further discussed below.

[0107] Figure 7 A shows a schematic diagram of the steps of a method 2000 for reducing the carbon-containing gas content of an input gas mixture. The method 2000 includes the steps of: 2002 providing a medium in fluid communication with a source of the input gas mixture, wherein the medium has an affinity for reacting with the carbon-containing gas of the input gas mixture; 2004 establishing a temperature difference whereby the medium has a higher temperature than the input gas mixture; and 2006 reacting the medium with the carbon-containing gas so that the medium acts as a carbon sink for reducing the carbon-containing gas content of the input gas mixture.

[0108] CO2 is rapidly absorbed from the air and spontaneously concentrated by an exothermic reaction with the molten electrolyte medium (by reacting with the oxides in the molten salt). This continuously renews the molten carbonate electrolyte medium, without being bound by any particular theory, as described by the following equations 1, 2 and 3:

[0109] CO2( 气体 )+O2 - fi CO3 2- (Equation 1)

[0110] The electrolysis reaction is according to the following equation (2):

[0111] CO3 2- fi C+O2+O 2- (Equation 2)

[0112] In this process, CO2 is decomposed by molten electrolysis to produce CNM carbon products and hot oxygen, with carbon as the CNM product, as described in equation (3):

[0113] CO2fi CNM 产物 +O2 (Equation 3)

[0114] As shown in Figure 13A, the molten Li2CO3 electrolyte rapidly absorbs and reacts with CO2, but is highly insoluble in the major atmospheric gases N2, O2, and H2 O. The experimental rate of CO2 absorption in 1 m Li2O (mol / kg) Li2CO3 at 770°C is high and significantly faster than required to maintain CO2 decomposition by electrolysis.

[0115] Figure 2 A shows a schematic diagram of the electrolytic decomposition of CO2 in a molten carbonate medium 1004A. The molten Li2CO3 electrolyte medium 1004A has an affinity for carbon and rapidly absorbs and reacts with gaseous CO2, but has a low affinity - at least in part due to being highly insoluble in the major constituent gases of the atmosphere, N2, O2, and H2O. The gray arrows extending into the medium to show the net mass transfer of carbon into the medium 1004A and the yellow arrows with red Xs indicate carbon-enriched atmospheres ( Figure 2 There is a lack of mass transfer of other constituent gases in the input gas mixture of A).

[0116] exist Figure 3 The experimental fast rate of CO2 absorption in a 770°C molten lithium carbonate medium containing one mole of lithium oxide is shown in A. Figure 2 A shows a schematic diagram representing one physicochemical feature of the electrolysis process that results in CO2 from the input gas mixture reacting with the medium 1004A. CO2 is readily absorbed in the electrolyte medium by an exothermic reaction characterized by equations 4a and 4b, and N2, O2, and H2O from the air are highly insoluble in molten Li2CO3. Note that the rapid rate of CO2 reactive absorption is measured after chemical mixing of the oxide with Li2CO3; that is, in a chemical environment rather than an electrochemical environment. In contrast, during the electrolysis process, not only is the oxide formed at the cathode, but O2 is also evolved at the anode ( Figure 2 A and Equation 3) rise to the surface.

[0117] CO3 2- C 纳米材料 +O 2- +O2 (Equation 4a)

[0118] CO2+O 2- fi CO3 2- ;CO2+Li2O fi Li2CO3 ΔH(770℃)=-158,000J / mol

[0119] (Equation 4b)

[0120] With respect to Equation 4a, the high rate of CO2 absorption is due to its exothermic chemical reaction with one of the chemical species in the electrolyte medium. Without being bound by any theory, in the formation of CNM products, the oxide that reacts rapidly with CO2 is driven by chemical equilibrium and by the electrolysis of carbonates.

[0121] Regarding Equation 4b, without being bound by any theory, the oxide reacts exothermically with CO2 to continuously renew the carbonate in the electrolyte medium (such as Li2CO3), where the enthalpy of the reaction is calculated from the enthalpies of the individual reacting species using thermodynamic data available through the NIST web book and NIST-JANAF thermochemical tables.

[0122] The evolved O2 product rises through the electrolyte and enhances the convective current in the electrolyte medium, which aids in mixing of the incident CO2 and increases the reaction rate. Although the reaction rate from air CO2 into the electrolyte is very high, it is lower than that of gas mixtures containing higher CO2 levels (such as flue gas). Alternatively, the rate of reactive absorption of CO2 in a molten carbonate electrolyte medium with oxides, with or without electrolysis, can be further increased under enhanced convection, such as mechanical stirring of the electrolyte or flowing or rotating electrodes, or stirring or bubbling hot gases into the electrolyte.

[0123] Figure 3 A shows that the experimental rate of CO2 absorption in 1 m Li2O (mol / kg) Li2CO3 at 770°C is high and significantly faster than required to maintain CO2 decomposition by electrolysis. Without being bound by any particular theory, the diffusion coefficient of CO2 in air (DCO2) DCO2, combined with a selective CO2 sink for binding, capturing, reacting or consuming CO2 and the lack of solubility of the main constituent gases in air, can promote the separation of CO2 from other components of the input gas mixture and maintain the desired rate of the electrolysis reaction occurring in a molten electrolyte medium (such as Li2CO3 (melting point = 723°C) or other electrolyte medium mixtures of binary or ternary carbonates).

[0124] A further physicochemical feature that allows the CO 2 portion of the input gas mixture to be selectively heated independently of other components of the ambient air is the high conventional rate of diffusion of CO 2 in air (compared to the rate at which CO 2 is consumed during the electrolysis process). Figure 2 B shows the known CO2 diffusion in air over the range of 0 to 400°C extrapolated to the higher temperature domain relevant to CO2 electrolysis as a blue line. The extrapolation uses Fick's Diffusion Laws T(K) 3 / 2 Diffusion coefficient changes exponentially from 20-400°C R2 Fit > 0.9996.

[0125] Diffusion is traditionally described by Fick's laws. Without being bound by a specific theory, a fundamentally equivalent but simpler starting point is the Einstein-Smolokovsky equation that describes the relationship between mean square displacement and diffusion. Species i diffuses in time t <x 2 The resulting Brownian motion mean square displacement is given by Equation 5 in 1, 2, or 3 dimensions:

[0126] <x 2 > =q Di t (Equation 5)

[0127] where q is the dimensionality factor (q = 2, 4 or 6 for diffusion in 1, 2 or 3 dimensions); Di is the diffusion coefficient, and t is time. Note that the molecular motion at the interface can differ from this ideal case.

[0128] This translational displacement is converted into the average diffusion velocity of CO2 <x 2 > / t, as a function of temperature, see Equation 6:

[0129] nCO2= <x 2 > 0.5 / t=(qx D CO2 (T)) 0.5 / t u (Equation 6)

[0130] Where T is the temperature, and t u is the unit time that is consistent with the diffusion coefficient.

[0131] Figure 3 A includes the translational displacement or velocity of CO2 in air, calculated using DCO2 and Equation 6 as a function of temperature. The diffusion coefficient of CO2 (DCO2) and the velocity of CO2 in air (nCO2) are temperature dependent. Figure 2 In B, the DCO2 values ​​are shown in the dark blue dashed line, and the 1-, 2-, or 3-dimensional velocity of CO2 is shown as the red, yellow, and light blue (top) lines, respectively. Figure 2 As shown in A, during the electrolysis, the total moles of gas leaving the electrolyte medium are composed of the O2 product from Equation 1. Similarly, this is the same total moles of gas entering the electrolyte medium as the reactant CO2 in Equation 2. Therefore, to the extent that the gas volume agrees with the ideal molar volume, the volume of CO2 entering from above the electrolyte medium is replaced by the volume of O2 displaced from the electrolyte medium, and there is no net change in the volume of gas above the electrolyte medium. Note that while the volume displaced is the same, O2, as a lighter molecule, will travel faster in the gas phase than CO2.

[0132] Without being bound by any particular theory, the hot O2 produced by the electrolysis process, which may also be referred to as an exhaust product, may itself be used to produce oxidants for various applications, including, but not limited to: disinfectants, for various industrial and oxyfuel processes, etc. In addition, the hot O2 may be used to transfer some of its energy back to the absorbed CO2, or to draw more reactants into the system, such as in a thermomechanical process. Some embodiments of the present disclosure involve decomposing the O2 exhaust product from the electrolytic cell, for example, via a conduit that is in fluid communication with the gas space above the liquid-gas interface of the carbonate electrolyte medium within the electrolytic cell.

[0133] Heat can be retained within the electrolyte medium by adding a porous insulation surrounding the electrolytic cell. It should also be noted that as the electrolysis process proceeds, the air within the gas space of the electrolytic cell (above the upper surface of the electrolyte medium) and the air within the porous insulation will contain an increasing concentration of oxygen.

[0134] The addition of a porous insulator cover above the molten carbonate electrolyte medium allows gaseous CO2 to diffuse from the input gas mixture into the molten lithium carbonate electrolyte medium, which is a further physicochemical feature that the CO2 portion of the input gas mixture can be selectively heated. Without being bound by any theory, in the absence of convection, the maximum rate of CO2 achieved as a reactant for electrolysis is limited by the maximum one-dimensional velocity of CO2 in the direction perpendicular to the insulating surface as the CO2 travels toward the interior of the kiln containing the electrolytic cell. Without being bound by any theory, at 20°C, the one-dimensional average displacement per second and velocity of CO2 in the air captured in the insulation closest to the ambient air side is nCO2-insulator = nCO2(20°C) = 0.56 cm CO2 s -1 .

[0135] When the input gas mixture is air from the atmosphere, CO2 originates from the ambient air and arrives as a reactant in the porous insulation for electrolytic decomposition. The molar volume concentration of CO2 in the ambient air (20*C), V M (CO2 in air), determined by its 0.04% molar concentration and the molar volume of the gas; i.e. V M (CO2 in air) = V M (20℃) / 0.04% CO2=1mol CO2 / 6.0x10 7 cm 3 Air. CO2 / cm2 passing through the external surface area of ​​the porous insulator 2 The molar flux of is given as f(CO2) insulator.

[0136] The average global velocity of air (wind speed) is nair-average = 330 cm / s (= 11.9 kph = 7.4 mph) and has been rising at 0.8% per year since 2010. In the examples, 0.33%, 10%, or 100% of this wind speed range (1, 33, or 330 cm / s) was examined to demonstrate that natural wind, rather than artificial blowers, is sufficient to maintain CO2 for embodiments of the present disclosure. Without being bound by any theory, a 1 cm 2 At the air velocity of the air of the square area of ​​the insulator, to a first degree of approximation the wind will replenish the CO2 depleted by the diffusion mean square displacement at a rate proportional to Z = n air (cm / s) / n CO2. In principle, the air velocity can be increased by a membrane that forces more air through a smaller area or pressurizes the air. The increase in wind speed in turn increases the impact ZxV M The molar concentration of CO2 in the region of (CO2 in air). The CO2 flux is driven by the concentration gradient between the concentration gradient at the outer surface of the insulator and the concentration at the surface of the electrolyte medium. CO2 absorption by the electrolyte medium is rapid during electrolysis; the reaction rate is rapid, accelerating the mass transfer of carbon into the electrolyte medium.

[0137] Without being bound by any theory, heat (-Q) is generated during electrolysis by (i) the heat of reaction of CO2 with Li2O to reform the electrolyte medium at ΔH = -158,000 J / mol (Eq. 4), and (ii) resistive heating from the electrolysis overpotential. 入 ). The released heat of reaction is the exothermic reaction of CO2 with the electrolyzed Li2O, -ΔH (Eq. 4), depending on the number of moles of CO2 consumed. The resistive heating of the products from the electrolysis overpotential h and the electrolysis current. The residual potential for the electrolytic decomposition of CO2 in molten carbonate electrolytes is about 0.8 V and varies with electrolyte medium composition and electrolysis electrodes. The additional overpotential to drive a constant current density I will vary with electrolyte medium composition and electrode composition as well as texturing and has been measured for planar electrodes. The heat loss P from the system is 出 is given by the thermal conductivity, the surface area A of thermal contact, the temperature difference ΔT across the insulator, and the thickness of the insulator. The thermal conductivity k is usually expressed in metric units (W / (mK)), while the thermal resistance R is usually expressed in British units (ft2 hr°F / Btu) and includes the thickness of the insulator in inches.

[0138] P 出 =kAΔT / =AΔT / R (Equation 7)

[0139] The dual features of a material that allows CO2 to enter the kiln and retains heat within the electrolysis chamber is achievable with porous insulators. Such materials have (i) an open porosity (as opposed to closed pores or grains) material, (ii) a high insulation factor, and (iii) temperatures that can withstand electrolysis conditions in the appropriate temperature range. The porosity dependence of thermal conductivity of high temperature refractory materials has been studied. Porous insulators that can withstand high temperatures (>1150°C) are aluminosilicates and calcium aluminosilicate blankets. Examples are various products including "ceramic fiber insulators for furnaces", "alumina silica ceramic fibers", or Related thermal products are often returned to English rather than metric units, with similar available compositions (e.g., 46% Al2O3 and 54% Si2O), thicknesses (0.5, 1, or 2 inches thick), and density ranges (4, 6, or 8 lbs / ft 3 =pcf).

[0140] Even the densest of these alumina-silica fiber blankets is lightweight with high porosity. As an example, the density of 8 pcf (=0.128 g / cm 3 )of The porosity of the solid (non-porous) 固体 =3.2g / cm 3 Density from 46% to 4.0g / cm 3 Density of alumina and 54% is 2.6g / cm 3 The porosity is estimated from the open space (d 空气 =0.001225 g / cm3):

[0141] p = 100% x (d solid - d cerara carpet) / (d solid - air), d air = 0.001225 g / cm 3 p(aluminum silicate 8pcf, example) = 96% (Equation 8)

[0142] A readily available alumina silica fiber, 2 inches thick 8pcf thermal fiber blanket, for 电解 To T 空气 The average thermal coefficient of k = 0.52 W / (mK) (and R = 3.8 ft2 hr F°Btu-1) over a temperature range of 1.5°C, with rated insulation values ​​of k and (R) of 0.028(10), 0.05(5.7), 0.08(3.6), 0.19(2.2)NS 0.20(1.4) at 0°C (extrapolated), 200°C, 400°C, 600°C, and 800°C, respectively. The mathematical convenience of the "R" expression for thermal resistance is the approximate additivity of the insulation layers. Thus, an 8-inch thickness of this insulation instead of 2 inches would have a thickness of approximately 15.2 ft2 hr F°Btu-1.2 R-value of hr F°Btu-1.

[0143] In the outer layer of insulation, a low temperature compatible (cheaper and with a higher R value) porous insulation such as open glass fiber insulation can be used. Such insulation is available from a variety of commercial manufacturers. The example used here is 4 inches thick unfaced Corning 710 fiber insulation with R = 16.7, density 1.5 pcf 0.024 g / cm 3 , and is composed of interwoven glass fibers. -3 The solid glass fiber density of this insulation is p(4 inches C701) = 99%. The insulating capacities of the combined 8 inches of alumina silicate 8 pcf facing outward from the interior of the kiln and the 4 inches of C701 unfaced fiberglass insulation extending to the ambient air will be approximately additive, i.e., they will have an approximate combined R = (15.2 + 16.7) = 31.9 ft 2 hr F°Btu -1 .

[0144] Some embodiments of the present disclosure relate to an apparatus for selectively capturing CO2 from a carbonaceous input gas mixture and producing CNM products from the captured CO2. The apparatus includes a pair of electrodes, a cathode and an anode, defining an inter-electrode space, which inter-electrode space may also be referred to as an electrolysis space, which may receive and contain an electrolyte medium. The apparatus also includes an insulator located between a source of the input gas mixture and the electrolyte medium. The insulator is porous and configured to facilitate the selective capture of CO2 from the input gas mixture. The apparatus may further include a current source, a heat source, a housing containing electrodes and an electrolyte medium and in fluid communication with a source of the carbonaceous input gas mixture.

[0145] Figure 5 A shows an example of a device 10A according to an embodiment of the present disclosure. The device 10A includes a housing 12 for accommodating a cathode 18, which may also be referred to as an electrolysis chamber or electrolysis cell, wherein an anode 16 may form at least a portion of the inner surface of the wall of the housing 12. The two electrodes together define an electrolysis space B therebetween. As will be appreciated by those skilled in the art, the anode 16 may be separated from the wall of the housing 12, optionally. The housing 12 is configured to accommodate an electrolyte medium 21 (in Figure 5A is shown in a molten state, with the upper surface indicated as 21A). The electrolysis space B including the upper surface 21A can be in fluid communication with the plenum D containing the input gas mixture (which contains CO2). The housing 12 can be supported on a base 14 within an insulating housing 20 (such as a kiln), which defines an insulated plenum A. The apparatus 10 also includes an insulator 22, which is located between the electrolysis space B and the plenum D containing the input gas mixture. In some embodiments of the present disclosure, the insulated plenum A can also be in fluid communication with the plenum D containing the input gas mixture.

[0146] The plenum D containing the input gas mixture can be the earth's atmosphere (with a CO2 content of about 420 ppm CO2), or can be a plenum containing a concentrated anthropogenic CO2-containing gas (such as an industrial waste stream or a storage tank of isolated CO2). For example, the plenum D contains or is the source of the input gas mixture, which can be any gas containing CO2 and optionally other carbon-containing gases. For example, the source of the input gas mixture can be various industrial equipment, including but not limited to: cement manufacturing equipment; ironmaking equipment; steel manufacturing equipment; equipment that manufactures or uses one or more of ammonia, ethanol, magnesium, hydrogen, polymers, plastics, glass; wastewater treatment plants; food processing plants. The source of the input gas mixture can also be a chemical reactor, including internal combustion engines and the combustion of carbon-containing materials for heating or cooking. Exhaust gases from power plants, steam power generation facilities, or pyrolysis reactors can also be the source of the input gas mixture. CO2-containing gases emitted from these sources or in the production of any high-carbon covered substances can also contribute to or constitute the input gas mixture. In addition, CO2-containing gas products of burning or converting fossil fuels for heating, transportation, and carbon products such as polymers and plastics may also contribute to or constitute the input gas mixture. The temperature of the input gas mixture may be in the range of about -90°C to about 400°C. For example, if the source of the input gas mixture is the atmosphere, the temperature range may vary between about -90°C and about 75°C. If the source of the input gas is artificial, the temperature range may vary between about 50°C and about 400°C. The housing 12 is configured to be in fluid communication with the plenum D so as to receive the input gas mixture in the inter-electrode space B.

[0147] In some embodiments of the present disclosure, the anode 16 is formed as a planar structure, a wire structure, a mesh, a porous structure, a conductive plate, a flat or folded gasket, a coiled structure, or the anode can form at least a portion of the inner side wall of the housing 12. The anode 16 can be formed of various conductive materials so that the anode 16 can produce oxygen or not. These materials forming the anode include, but are not limited to: any conductive material having a stabilizing layer or establishing a highly stable oxide outer layer that is conducive to oxygen production during the electrolysis reaction process performed according to embodiments of the present disclosure, Ni, Ni alloys, galvanized (zinc-coated) steel, titanium, graphite, iron, and a variety of metals that establish a highly stable oxide outer layer that is conducive to oxygen production. Other examples of suitable materials for forming the anode 16 include nickel alloy 36 (nickel without chromium but with iron), nickel-chromium alloys (nickel-chromium-based alloys) including stainless steels such as SS304 or SS316, and inconel alloys (such as Inconel 600, 625, and 718), alloy C-264 or chromium-nickel alloys (such as ChromelA, B), or co-nucleation of known alloy components to produce high-quality CNTs. Binary and ternary transition metal nucleating agents may also be useful, including but not limited to: Ni, Cr, Sn, In, Fe, and Mo, which may also affect CNM product growth.

[0148] In some embodiments of the present disclosure, a transition metal may be added to the anode 16, which may be dissolved from the anode 16 to migrate to the cathode 18 through the electrolyte medium 21. The added transition metal may act as a nucleating agent, which may be selected from nickel, iron, cobalt, copper, titanium, chromium, manganese, zirconium, molybdenum, silver, cadmium, tin, ruthenium, zinc, antimony, vanadium, tungsten, indium, gallium, or a non-transition metal such as germanium or silicon or a mixture thereof. The transition metal may also be directly introduced into the electrolyte medium 21 as a dissolved transition metal salt to migrate to the cathode 18. It is also possible to add a transition metal nucleating agent directly to the cathode 18.

[0149] In some embodiments of the present disclosure, the cathode 18 is formed as a planar structure, a wire structure, a mesh, a porous structure, a conductive plate, a flat or folded gasket, a sheet, a coiled structure, or the cathode may form at least a portion of the inner side wall of the housing 12. The cathode 18 may be formed of a variety of conductive materials that reflect the need for changes in nucleation sites and CNM products formed on the cathode 18. Such cathode-forming materials include, but are not limited to, any conductive material, galvanized (zinc-coated) steel, titanium, graphite, iron, alloys containing copper and zinc, Monel alloy (Ni 400, a Ni / Cu alloy), Inconel, stainless steel, iron, nickel-chromium alloys, pure Cu, and brass alloys may also be suitable as materials for manufacturing the cathode 18.

[0150] Anode 16 and cathode 18 can be aligned substantially parallel to each other in shell 12 (such as stainless steel shell or shell made of substantially pure or pure alumina). Shell 12 can be made of any material suitable for containing molten electrolyte medium 21 and maintaining the temperature achieved by device 10A. Electrodes can be oriented in any orientation, including but not limited to substantially horizontal or substantially vertical, but spaced apart from each other to define electrolysis space B therebetween. In some embodiments of the present disclosure, electrolysis space B is between about 0.1cm and about 10cm. In some embodiments of the present disclosure, electrolysis space B is about 1cm. As will be understood by those skilled in the art, the size of electrolysis space B will be determined by the scale of device 10A, such as the size of each electrode, the aeration chamber defined in the shell, the amount of applied current and combinations thereof.

[0151] Anode 16 and cathode 18 are operably connected to a current source (not shown) that can provide about 0.001 A / cm 2 With 10A / cm 2 Any source of alternating or direct current (constant or non-constant) with a current density between the electrodes. In some embodiments of the present disclosure, the current density provided between the electrodes is at least 0.02 A / cm 2 , 0.05A / cm 2 , 0.1A / cm 2 , 0.2A / cm 2 , 0.3A / cm 2 , 0.4A / cm 2 , 0.5A / cm 2 , 0.6A / cm 2 , 0.7A / cm 2 , 0.8A / cm 2 , 0.9A / cm 2 , 1.0A / cm 2 or greater. The power used for the current source can be any power source or combination of power sources, including power supplies, solar power sources, etc.

[0152] The heat source (not shown) can be any heat source that raises the temperature within the housing 12 to a temperature that causes the electrolyte medium 21 to transition to a molten phase. For example, the heat source can achieve a temperature of about 500° C. to about 850° C. or higher within the housing 12. In some embodiments of the present disclosure, the heating achieves a temperature between about 700° C. to about 800° C., between about 720° C. to about 790° C., or between about 750° C. to about 780° C. In some embodiments of the present disclosure, the heating achieves a temperature of 749-750° C., 751-752° C., 753-754° C., 755-756° C., 757-758° C., 759-760° C., 761-762° C., 763-764° C., 765-766° C., 767-768° C., 769-770° C., 771-772° C., 773-774° C., 775-776° C., 777-778° C., or 779-780° C. In some embodiments of the present disclosure, the temperature within the housing 12 may be increased to about 800° C. or hotter. In some embodiments of the present disclosure, the heat source is provided or supplemented by the exothermic reaction of CO absorption and conversion to carbonate (mass transfer from gas phase to solid phase CNM product) or the overpotential of the applied electrolysis current.

[0153] In some embodiments of the present disclosure, the electrolyte medium may include a carbonate that can be heated by a heat source until it is transformed into a molten phase. For example, the carbonate may be lithium carbonate or a lithiated carbonate. Molten carbonates such as lithium carbonate (Li2CO3) (having a melting point of 723°C) or carbonates with lower melting points such as LiBaCO3 (having a melting point of 620°C), when containing oxides, include spontaneous oxide formation occurring during melting or as a result of electrolysis or when mixed with highly soluble oxides such as Li2O, Na2O and BaO, maintaining rapid absorption of CO2 from the space above the molten electrolyte medium. Suitable carbonates may include alkali carbonates and alkaline earth carbonates. Alkali carbonates may include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate or francium carbonate or mixtures thereof. Alkaline earth carbonates may include beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate or radium carbonate or mixtures thereof. In some embodiments of the present disclosure, the electrolyte may be a mixed composition, for example, a mixture of alkali metal carbonates and alkaline earth metal carbonates and one or more of oxides, borates, sulfates, nitrates, chlorides, chlorates, or phosphates.

[0154] Embodiments of the present disclosure relate to providing an insulation 22 between the plenum D containing the input gas mixture and the interior of the housing 12 containing the molten electrolyte medium 21. The insulation 22 is configured to facilitate the net selective passage of CO2 from the first side 22C through the insulation 22 to and from the second side 22D. Other gases are prevented from net selectively passing through the insulation because there is no affinity for its consumption due to sinking in the higher temperature medium. In some embodiments of the present disclosure, the insulation 22 is made of a material that promotes the flow of CO2 therethrough and helps maintain the temperature within the insulating housing 20. In some embodiments of the present disclosure, the insulation 22 material has: (i) an open pore structure; (ii) a high insulation factor; and (iii) if applicable, it can withstand the high temperatures achieved within the housing 22 and the insulating housing 20. Non-limiting examples of suitable materials for the insulation 22 include those that can withstand high temperatures (>1150°C), such as: aluminum silicate and calcium aluminum silicate blankets. Examples of readily available materials for use as insulation 22 include, but are not limited to: fibrous or granular permeable batting, mats or blankets; flexible or rigid boards or panels; and permeable rigid blocks or bricks that allow gas to pass through. Some insulation products used in the construction may also be suitable for use as insulation 22, including, but not limited to: low-temperature and medium-temperature insulation (used in outer walls), such as fiberglass, cellulose, cotton or woven fabrics; medium-temperature insulation (used in outer walls or intermediate walls), such as mineral wool; and high-temperature insulation (used in outer walls, intermediate walls or inner walls) cements and ceramics, such as aluminates (including carbonates), silicates (including calcium aluminum silicate), their derivatives and combinations thereof. Examples of various readily available and suitable high-temperature ceramic products include, but are not limited to: "ceramic fiber insulation for furnaces"; "alumina silica ceramic fibers"; or Suitable insulator products may have similar compositions (e.g., about 46% Al2O3 and about 54% Si2O), thicknesses (0.5 inch, 1 inch, or 2 inches thick), and density ranges (4 lbs / ft 3 =pcf, 6pcf or 8pcf).

[0155] Even the densest alumina silica fiber material can be lightweight with high porosity. As an example, 8 pcf density (=0.128 g / cm 3 )of The porosity of the solid (non-porous) 固体 =3.2g / cm 3 Density increased from 46% to 4.0g / cm 3 Density of alumina and 54% is 2.6g / cm 3 The porosity is estimated from the open space (d 空气=0.001225g / cm 3 ): p = 100% x(d 固体 -d 赛拉毯 ) / (d 固体 -d 空气 ), d 空气 =0.001225g / cm 3 , (aluminum silicate 8pcf, example) = 96% (open pores). Readily available 2 inch thick, 8pcf alumina silica fiber, thermal fiber blanket, for 电解 To T 空气 k=0.52W / (mK) (and R=3.8ft 2 hr F°Btu -1 ), with rated insulation values ​​of k and (R) of 0.028 (10), 0.05 (5.7), 0.08 (3.6), 0.19 (2.2), and 0.20 (1.4) at 0°C (extrapolated), 200°C, 400°C, 600°C, and 800°C, respectively. The mathematical convenience of the "R" expression for thermal resistance is the approximate additivity of the insulation layers. Thus, an 8-inch thickness of insulation, rather than a 2-inch thickness, would have a value of approximately 15.2 ft 2 hr F°Btu -1 R value. The porosity and spacing between the insulation fibers in the first material and the second material The scanning electron microscopy is obvious, and each is shown in Figure 8 and Fig. 9 middle. Figure 8 The first material is shown to have fibers having diameters of approximately 5.8 μm (panel D), 4.4 μm (panel E), and 3.3 μm (panel E). Fig. 9 The second material is shown to have fibers having diameters of approximately 2.5 μm (Panel D), 0.49 μm (Panel E), and 0.24 μm (Panel F).

[0156] In some embodiments of the present disclosure, the surface area of ​​the insulator 22 is 1 to 100 times greater than the surface area of ​​the upper surface 21A of the molten electrolyte medium 21. In some embodiments of the present disclosure, the surface area of ​​the insulator 22 is 2 to 20 times greater than the surface area of ​​the upper surface 21A of the molten electrolyte medium 21. In some embodiments of the present disclosure, in order to maximize the net inward CO2 diffusion and minimize the outward heat flow, the surface area of ​​the insulator 22 on the outside (first surface 22C) facing the input gas mixture is greater than the surface area on the inside (second surface 22D) exposed to the higher temperature medium.

[0157] In some embodiments of the present disclosure, the density and / or thickness of the insulation can be subjected to a conditioning process for use with embodiments of the present disclosure. For example, the insulation can be compressed or conditioned by other simple mechanical, chemical or structural means to change, increase or decrease the net passage of carbon-containing gases through the insulation compared to unconditioned insulation.

[0158] Figure 5 B shows an apparatus 10B according to an embodiment of the present disclosure. The apparatus 10B has many features that are similar or identical to the apparatus 10 described above. The main difference between the two apparatuses 10, 10B is that the apparatus 10B has a frame 22A having one or more walls and a ceiling made of insulation 22, which defines an insulated plenum C containing CO2 captured from an input gas mixture in a plenum D outside the frame 22A. These walls and ceiling of the frame 22A increase the surface area for interaction between the input gas and the porous insulation, which can increase the rate of net CO2 diffusion inward (from the first surface 22C through the insulation to the second surface 22D). As Figure 5 B, the plenum A may be in fluid communication or not with the insulated plenum C. Each wall and ceiling of the frame 22A is composed of a 20 cm x 20 cm and 2 inch thick section of the insulator 22. Based on the size of the frame 22A and the volume of the molten electrolyte medium 21 in the cell 12, the second surface 22D of the insulator 22 is spaced a predetermined distance from the upper surface 21A of the molten electrolyte medium 21. In this way, changing the size of the frame 22A can increase or decrease the predetermined distance because the volume of the molten electrolyte medium 21 in the cell 12 can be increased or decreased. The CO2 concentration in the insulated plenum C can be higher than the CO2 concentration in the input gas mixture in the plenum D. In addition, the CO2-containing gas in the insulated plenum C can also be at a higher temperature than the input gas mixture in the plenum D.

[0159] Figure 5C shows a device 10C according to an embodiment of the present disclosure. Device 10C has many features similar or identical to the above-mentioned device 10B. The main difference between the two devices 10B and 10C is that device 10C also includes a shell 24 defining a gas-filled chamber D, and frame 22B is located in gas-filled chamber D. Shell 24 can be constructed of a material that is substantially impermeable to gas and has low thermal conductivity (e.g., refractory bricks). In other words, shell 24 can be made of a material having thermal insulation properties. Shell 24 can define two holes, an input hole 26A at a first end and an output hole 26B at a second end, so that the airflow in gas-filled chamber D moves from input hole 26A into shell 24 and leaves shell 24 via output hole 26B. The gas content of gas-filled chamber D can be substantially the same inside and outside of shell 24. As with device 10B, due to insulation 22, the gas content and properties in plenum D are different from the gas content and properties in insulated plenum C, because the carbon-containing gas moves from plenum D through insulation 22 into plenum C and selectively enters medium 21 through interface 21A on a net basis. Plenum C can have a higher temperature than plenum D. Optionally, housing 24 can also include one or more displaceable members that can move their positions according to whether the input gas mixture enters the housing via input hole 26A or output hole 26B, such as when the direction of wind travel changes or other. The displaceable member can be a sliding door, port, baffle or any other mechanism configured to shift its position to change the direction in which the input gas mixture moves through housing 24. The displaceable member can also be configured to shift its position so as to change the direction in which the input gas mixture moves through housing 24. Additionally or alternatively, the displaceable member can be displaced based on hot spots that occur in any device described herein, so that the input gas mixture is directed toward or away from the hot spot. As shown, the plenum C is in fluid communication with the upper surface 21A of the electrolyte medium 21 within the cell 12. In some embodiments of the present disclosure, the apparatus may include a winding channel between the first surface 22C and the second surface 22D for increasing the contact path length of the input gas mixture with the insulator 22, and thus increasing the contact time.

[0160] Figure 5 Frame 22B shown in C may have one or more walls made of insulation 22, such as a 20 cm x 20 cm and 4 inch thick section of insulation 22, and the same ceiling as frame 22A.

[0161] The apparatus 10A can also be configured to establish a gas pressure differential between the electrolysis space B above the upper surface 21A and the plenum D. The gas pressure in the cell 12 can be lower than the gas pressure in the plenum D, so that the established gas pressure differential can enhance the flow rate of the carbon-containing gas through the insulation 22 and into the cell 12. The pressure differential can be caused by various mechanisms, such as a diaphragm pump that reduces the relative gas pressure in the cell 12 compared to the plenum D. Alternatively or in addition, a blower or fan can also be used to increase the gas pressure in the plenum D.

[0162] In some embodiments of the present disclosure, the apparatuses 10B and 10C are configured to establish a gas pressure differential between the plenum D and the plenum C in order to enhance the movement of the carbon-containing gas through the insulation 22 into the plenum C. For example, the gas within the plenum D may be pressurized to a level greater than the gas pressure within the plenum C. A diaphragm pump, blower, or fan may be used to facilitate the establishment of such a gas pressure differential between the plenum D and the plenum C.

[0163] In some embodiments of the present disclosure, the cell 12 may be configured to mix the gas present between the inner surface 22C of the insulator 22 and the upper surface 21A of the molten electrolyte medium 21. For example, the cell 12 may include one or more mechanisms for mechanical mixing, agitation, stirring, convection, bubbling, or a combination thereof to promote mixing of the gas above the upper surface 21A with the electrolyte medium 21.

[0164] In some embodiments of the present disclosure, the apparatus 10A, 10B and 10C may further include a mechanism for concentrating the input gas mixture. For example, the apparatus 10A, 10B and 10C may further include a vortex tube, a heat pump or a heat engine to increase the concentration of the carbon-containing gas in the input gas mixture.

[0165]

[0013] Certain embodiments of the present disclosure relate to one or more systems configured to selectively capture carbon-containing gases from an input gas mixture and then produce CNM products from the captured gases. Figure 6 Two examples of systems according to embodiments of the present disclosure are shown. Figure 6 A shows a non-limiting example of a system 200A including at least two devices 10D and an assembly 10E. Device 10D represents any device, including devices 10A, 10B, 10C, and combinations thereof, configured to selectively capture CO2 from an input gas mixture using an electrolysis process and produce CNM products therefrom. Assembly 10E represents a heat source and a power source for providing electric current to device 10D. Figure 6 A shows three devices 10D, it should be understood that there may be more or fewer individual devices 10D forming part of the system 200A. Such devices 10D may share a single component 10E, or there may be more than one component 10E in the system 200A.

[0166] Figure 6 B shows a non-limiting example of a system 200B including at least two devices 10D, wherein one device 10D is arranged vertically on another device 10D to form a stack 10F of at least two devices 10D. At least two devices 10D may be operatively coupled to an assembly 10E, or there may be more than one assembly 10E in the system 200B. Figure 6 B shows one stack 10F, it should be understood that the system 200B may include two or more stacks 10F. One or more stacks 10F may be operably coupled to a given component 10E, or each of the one or more stacks 10F may be operably coupled to a dedicated component 10E.

[0167] Some embodiments of the present disclosure relate to one or more methods for selectively capturing carbon-containing gases from an input gas mixture and producing CNM products from the captured gases. In some embodiments of the present disclosure, the methods described herein can be operated using the apparatus and systems described herein, however, the different embodiments of the methods are not limited to such apparatus and systems.

[0168] Figure 7 A schematic diagram representing a method 300 for selectively capturing CO2 from an input gas mixture within a plenum is shown. Method 300 includes the steps of establishing fluid communication 302 between the input gas mixture and the outer surface of the porous insulation; and a step 304 of selectively capturing CO2 from the input gas mixture by passing the CO2 through the insulation into a second plenum. Method 300 further includes a step 306 of establishing fluid communication between the inner surface of the porous insulation and the electrolyte medium within the second plenum, wherein the electrolyte medium is configured to enhance the capture of CO2. Method 300 further includes a step 308 of collecting carbon nanomaterial products produced by the CO2 captured by the electrodes within the second plenum. Method 300 may further include an optional step of removing exhaust products emitted during the CO2 capture process. In some embodiments of the present disclosure, method 300 further includes a step of selectively removing or adding heat to balance the heat generated or required in capturing CO2.

[0169] According to some embodiments of the present disclosure, method 300 may further include a step of establishing a gas pressure difference on the insulation so that the gas pressure of the input gas mixture is higher than the gas captured in the second gas chamber. The gas pressure difference can be established by using a diaphragm pump, a blower or a fan. In addition or alternatively, the input gas mixture can be pressurized to establish a gas pressure difference. In some embodiments of the present disclosure, the exhaust gas generated in the second plenum may be hotter than the temperature of the input gas mixture. In some embodiments of the method, the exhaust gas product is O2. In some embodiments of the present disclosure, the exhaust gas product compensates or enhances the input rate of the input gas mixture and / or the selective capture and movement of CO2 into the second plenum. Some embodiments of method 300 include the step of transferring heat energy from the exhaust gas product to the input gas mixture. In some embodiments of method 300, the porosity of the porous insulation is adjustable to change the rate at which CO2 is selectively captured by moving through the insulation and the rate at which heat can be transferred through the insulation.

[0170] In some embodiments of method 300, the inner surface of the porous insulation may directly contact the electrolyte medium. In other embodiments of method 300, method 300 further includes positioning the inner surface of the porous insulation a predetermined distance from the upper surface of the electrolyte medium.

[0171] Some embodiments of the present disclosure include the method step of positioning a non-porous outer wall medium around a porous insulation body to define an insulating compartment having a first end and a second end, and wherein the insulating compartment is configured to receive an input gas mixture at the first end. Optionally, the non-porous outer wall medium is also an insulation body.

[0172] In some embodiments of the present disclosure, method 300 further includes the step of using the heat generated in the second plenum to heat or power an external device, such as a heat pump or heat engine for heating the input gas mixture, electrolyte medium, or a combination thereof. Additionally or alternatively, Joule heat, industrial waste heat, solar heat, geothermal heat, waste heat, or a combination thereof can be used to heat the input gas mixture, electrolyte medium, or a combination thereof.

[0173] In some embodiments of the present disclosure, method 300 further comprises the step of mixing the gaseous contents of the second plenum with the electrolyte medium by mechanical mixing, agitation, stirring, convection, aeration, or a combination thereof.

[0174] In some embodiments of the present disclosure, method 300 further includes the steps of: heating the electrolyte to obtain a molten electrolyte medium; arranging the molten electrolyte medium between the anode and the cathode in the electrolytic cell within the second gas-filled chamber; selectively heating the CO2 in the input gas mixture with at least the molten electrolyte medium; applying an electric current to the cathode and anode in the cell for electrolytic decomposition of the selectively heated CO2; and collecting the carbon nanomaterial product from the cathode of the cell.

[0175] In some embodiments of the present disclosure, method 300 further includes the step of generating an O2 product in the molten electrolyte medium, wherein the O2 product can enhance convection in the molten electrolyte medium for mixing the molten electrolyte medium.

[0176] In some embodiments of the present disclosure, the CNM product of method 300 includes carbon nanotubes, carbon nano-onions, nanoflowers, nanotrees, nanobelts, sheets, nanoscaffolds, spirals, graphene, doped carbon nanomaterials, magnetic carbon nanomaterials, amorphous carbon, or a combination thereof. In some embodiments of the present disclosure, method 300 further includes the step of selecting the relative amount of the constituent carbon nanostructures within the CNM product by varying the electrolyte medium temperature, CO2 rate, current, voltage, cathode composition, anode composition, or electrolyte medium composition.

[0177] As used herein, the term "selecting the relative amounts of the constituent carbon nanostructures within the CNM product" refers to any step that helps control the morphology of the electrosynthesized CNM product. In some embodiments of the present disclosure, the selected morphology of the CNM may include the following CNM morphologies: carbon nano-onions, carbon nano-scaffolds, carbon nano-spheres, carbon nano-helices, carbon nano-flakes, graphene, or a combination thereof. In some embodiments of the present disclosure, the step of selecting the morphology of the nanomaterial may result in an electrosynthesized CNM product, some, most, substantially all, or all of which is a single CNM morphology. For example, the step of selecting the morphology of the nanomaterial may produce an electrosynthesized CNM product, some, most, substantially all, or all of which is one of the following: nano-carbon onions, nano-carbon scaffolds, nano-carbon spheres, nano-carbon helices, carbon nano-flakes, or graphene.

[0178] In some embodiments of the present disclosure, the step of selecting the nanomaterial morphology comprises applying the current as an alternating current (AC) to the cathode and the anode. For example, an AC electrolysis current can be selected for a CNM product having a nano-onion morphology.

[0179] In another embodiment, the step of selecting the nanomaterial morphology comprises adding ZnO to a molten carbonate electrolyte and applying an AC electrolysis current, which may select a CNM product having a graphene flake morphology.

[0180] In another embodiment, the step of selecting the nanomaterial morphology comprises adding MgO to a molten carbonate electrolyte and selecting an electric current for hollow carbon nanosphere production.

[0181] Transition metal nucleated growth, such as the addition of nickel powder, can result in clearly observable CNT walls. However, when these nucleating additives are intentionally excluded during synthesis, high yield synthesis of nano-onions and graphene is achieved. These differences in the parameters of the electrosynthesis process are just some examples of how electrosynthesized CNM products can be selected.

[0182] In some embodiments of the present disclosure, method 300 further includes the step of supplying current to the battery via non-fossil energy, including but not limited to solar energy, wind energy, hydroelectric energy, geothermal energy, tidal energy, wave, nuclear energy, or a combination thereof.

[0183] In some embodiments of the present disclosure, method 300 further includes one or more of the following steps: activating the molten electrolyte medium by preheating the electrolyte medium, adding an oxide to the electrolyte medium, reusing the electrolyte medium for multiple electrolysis processes, and time balancing the molten electrolyte medium.

[0184] Example

[0185] The examples and experiments described below relate to the direct capture of CO2 from an input gas mixture by the selective net passage of CO2 through a porous insulation, and the production of CNM products from the captured CO2. Without being bound by any particular theory, the selective net passage of CO2 is at least partially due to the medium's affinity for carbon being higher than the medium's affinity for other constituent gases of the input gas mixture. These examples are provided to illustrate embodiments of the present disclosure and are not to be construed in any way as limiting the scope of the present disclosure.

[0186] Example 1 - CO2 passing through an insulator

[0187] Fig.10 A schematic diagram showing the apparatus configuration and data obtained during experiments illustrating the ease with which CO2 flows through the insulation of the present disclosure. Fig.10 A shows a fluid-tight container 100 having a diameter of about 4 inches (1 inch equals about 2.54 cm), which is divided into an upper chamber 100A and a lower chamber 100B by a lower porous, open-channel insulator 122B. Optionally, the upper chamber 100A also includes an upper insulator 122A, which is in fluid communication with air outside the container 100. Unless otherwise specified, the insulators 122A and 122B are each porous insulating partitions, which are 2 inches thick and have a density of 8 lb per cubic foot. The upper chamber 100A receives an input gas mixture via a gas supply line 102. The lower chamber 100B houses a CO2 sensor 104 (such as the type commercially available from CO2meter.com) for measuring and reporting CO2 levels within the lower chamber 100B. The lower chamber 100B initially contains only pure N2 and no CO2.

[0188] Fig.10 B shows two experimental setups, the setup shown in the upper inset receives 100% CO2 into the upper chamber 100A via supply line 102. Fig.10 In the upper small figure of B, the upper chamber 100A includes the upper insulator 122A, while in the lower small figure there is no upper insulator 122A. Fig.10 Sensor 104 in the experimental setup of B is a CO2 sensor with a sensitivity of 0 to 100%. Fig.10 In the lower panel of B, the upper chamber 100A is initially filled with 100% CO2. Fig.10 Each of the upper and lower panels of B also includes a line graph depicting the experimental CO2 levels measured in the lower chamber 100B over time.

[0189] As shown in the thumbnail Fig.10 As shown in FIG. 2B , when an input gas mixture of pure CO2 is introduced into the upper chamber 100A at a flow rate of 1 L / min, the CO2 concentration in the lower chamber 100B increases from 0 to 100% in about 15 minutes, and when the flow is turned off, the CO2 level gradually decreases. Fig.10 As shown in the lower panel of FIG. B, when the upper chamber is filled with 100% CO2, the CO2 concentration in the lower chamber increases from 0 to about 62% in about 24 minutes. CO2 is denser than N2, which can drive the concentration of CO2 in the lower chamber 100B to increase compared to the upper chamber 100A. The relative gas density of N2 and CO2 moles is given by the ratio of their chemical formula weights, 28 / 44=63.6%.

[0190] Fig.10 C shows three experimental setups, two of which received compressed air (with a CO2 level of about 418 ppm) at different flow rates through the supply line 102, and used a CO2 sensor with a sensitivity of 0 to 1%. Fig.10 The upper panel of Figure C shows only the lower chamber 100B, the lower insulation 122B, and the compressed air delivered to the top of the insulation 102 at a rate of 6.2 L / min (equivalent to a wind speed of 330 cm / s). Fig.10 As shown in the upper panel of Figure 1, at 10°C, the CO2 concentration in the chamber increases from 0 (pure N2) to about 410 ppm in about 29 minutes.

[0191] exist Fig.10In the middle panel of C, the experimental setup includes an upper insulator 122A and an upper chamber 100A separated from a lower chamber 100B by a lower insulator 122B. Fig.10 The upper line graph of the middle panel of C shows the CO2 level detected over time in the lower chamber 100A when air was introduced at a rate of 0.624 L / min (equivalent to a wind speed of 33 cm / s). The lower chamber CO2 concentration increased from 0 to about 395 ppm in about 45 minutes. Fig.10 The lower line of the middle panel of C plots the CO2 levels detected over time in the lower chamber 100A when air was introduced at a rate of 6.2 L / min. The bottom chamber CO2 concentration increased from 0 to about 395 ppm in about 10 minutes.

[0192] Without being bound by any specific theory, a thicker porous insulation layer can slow down the rate at which CO2 concentration increases. Interestingly, the opposite is observed to occur. In the same test chamber, a 2-inch insulation layer is replaced by an 8-inch (4 stacked 2-inch layers) insulation that separates the upper chamber from the lower chamber (not shown). The CO2 from air in the upper chamber reaches a level of 395ppm in about 20 minutes or 2.5 minutes at a flow rate of 0.624 or 6.2L air / minute, respectively. Without being bound by any specific theory, the increase in CO2 concentration in the lower chamber 100B observed in a shorter amount of time when using thicker insulation may be related to the substantially reduced height of the lower chamber 100B, which reduces the volume of the lower chamber 100B, thereby allowing a faster replacement of the original N2.

[0193] Fig.10 The lower panel of C shows a further experimental setup, in which the sealed upper chamber 100A is filled with 100% air, and then the CO2 concentration in the lower chamber 100B is increased from 0 to about 240 ppm in about 18 minutes.

[0194] Without being bound by any particular theory, Fig.10 All experimental setups in show CO2 from air or from pure CO2 passing through a porous, open channel insulation.

[0195] For each electrolysis process described subsequently, the theoretical mass change before and after electrolysis was calculated using:

[0196] Q = the measured electrolytic charge applied in ampere-hours (Ah), and

[0197] n = 4; Equation 2 Electrolysis transfer of electrons.

[0198] F = Faraday constant = 96485 c / mol electrons = 26.801 Ah / mol e-.

[0199] FW(C), FW(O2) and FW(CO2) = chemical formula weight of carbon, O2, or CO2: 12.01, 32.00 or 44.01 g / mol, respectively.

[0200] Example 2 - Carbonate Electrolysis in the Absence and Presence of CO2

[0201] The experimental representation consists of two electrolytic configurations. Figure 4 As shown in Figure 4A, in a first configuration 400, an electrolysis chamber 402 containing a molten carbonate electrolyte medium 404 and an electrolysis electrode 406 is sealed by a sealing member 408. The electrolysis chamber 402 is contained in a housing 405 made of a solid insulating material. Air is not allowed to enter the chamber during the electrolysis process, and no additional CO2 is available for renewing the carbonate electrolyte medium 404 during the electrolysis process. A pressure relief valve allows O2 to be released through a tube 410 during the electrolysis process, and the tube 410 extends below the sealing member 408 and above the housing 405. In the absence of added CO2, consistent with Equation 2, the level of the carbonate electrolyte medium decreases within the electrolysis cell 402 during the electrolysis process. The measured mass of the combination of the electrode 406 and the electrolyte medium 404 is measured before and after passing the electrolysis charge, and in the absence of CO2, it is noted that the mass of the combination decreases as oxygen is precipitated.

[0202] Specifically, a CO2-free experiment was conducted by constructing 400 (eg, Figure 4 A):

[0203] Housing: 4" x 6" stainless steel 304 crucible, where the inner wall acts as the anode

[0204] Anode / Electrode: Nichrome C, approximately 6cm x 6cm

[0205] Cathode / Electrode: Brass about 6cm x 6cm

[0206] Electrolyte medium: Li2CO3

[0207] Temperature: 750℃

[0208] Current: 8.4 amperes (current density = 0.2A / cm 2 )

[0209] Electrolysis time: 20 hours

[0210] The combined mass of the cell, electrolyte and electrodes was measured before and after passing an electrolytic charge of 8.4 amps x 20 hours = 168 Ah. 168 Ah can be reduced to 9.6485 x 10 according to Equation 2 using n = 4 and F = 9.6485 x 10 4As is calculated as 1.567 mol of carbonate calculated as mass = Q / nF. In a sealed cell of configuration 400, without replacing CO2, according to equation 2, the loss of O2 is 1.567 mol x 32 g O2mol -1 , the sealed cell should lose about 50 g of mass. After electrolysis in a sealed cell, the measured cell mass loss was about 48 g, amounting to 96% of the theoretical 50 g loss.

[0211] Without being bound by any theory, when the oxide is established according to Equation 3, it may be difficult to precipitate the last remaining small portion of O2, such as developing a competitive equilibrium with O2+oxide or carbonate to form a substance that inhibits the continued release of O2.

[0212] In the second configuration 400A ( Figure 4 B), CO2 from the air is allowed to flow into the electrolysis chamber 402 through the porous insulator 12. Specifically, the top of the electrolysis chamber 402 is unsealed, and the porous insulator 412 has 10 times the surface area of ​​the electrolyte medium 404 as the upper surface exposed within the electrolysis chamber 402. Again using the unsealed configuration 400A (as shown in FIG. Figure 5 The porous top experiment was performed at a current density of 0.2 A / cm2 with the same type of electrodes as cell 402 and the same 750°C Li2CO3 electrolyte medium in stainless steel 304. The cover consisted of a 2-inch thick porous Composition to allow CO2 to pass from the air into the electrolytic cell 402.

[0213] Using the unsealed configuration 400A with the porous insulator 412, consistent with Equation 2 (the sum of Equations 1 and 2), the measured mass of the electrolytic cell 402, the electrode 406, and the carbonate electrolyte medium 404 increases as CO2 is absorbed and reacts to renew the electrolyte 404. With the input CO2, only O2 leaves the system. The electrolytically decomposed CO2 is retained on the cathode as a solid CNM product, and oxygen is precipitated from the anode. During the electrolysis process, it was observed that the outside of the porous insulation remained cool (i.e., close to ambient temperature), and the 48g cell mass loss after the electrolysis process using configuration 400 was avoided.

[0214] Example 3 - Capturing CO2 and Generating CNM Products

[0215] Further experiments were conducted to investigate the capture of CO2 from air and the production of CNM products by decomposing CO2 via electrolysis, with the following operating parameters:

[0216] Housing: 1.2" x 4" x 6" stainless steel 304 crucible, where the inner wall acts as the anode

[0217] Cathode / Electrode: Brass 5cm x 6cm (2 sides active)

[0218] Electrolyte medium: Li2CO3, electrolyte heated for 24 hours before electrode immersion

[0219] Temperature: 750℃

[0220] Current: 2 amperes (current density = 0.04A / cm 2 )

[0221] Electrolysis time: 9 hours

[0222] These experiments involved measuring the mass of the cell before and after electrolysis. The mass of the cell includes the mass of the cell, electrolyte, and electrodes.

[0223] The ambient air temperature was varied from 21° C. to 23° C. The mass was measured using a Radwag R series precision balance with 0.01 g resolution. The mass of the cell was raised adiabatically from a balance platform, but the balance is thermally sensitive, which explains several percent error in the experimental mass variation.

[0224] According to Equations 2 and 3, the theoretical mass gain due to CNM products is: nF x FW(C). This is the same as the theoretical cell mass gain for the full cell (including electrodes and electrolyte) only if there is enough CO2 to renew all consumed carbonates according to Equation 1. The theoretical mass loss due to O2 according to Equation 2 is: nF x FW(O2). This is the same as the theoretical cell mass loss only if there is no CO2 to renew consumed carbonates according to Equation 1.

[0225] Example 3A

[0226] Figure 5 A shows the construction of the apparatus 10A used in the above-mentioned capture and CNM production experiments. The apparatus 10A includes a cell 12, an anode 16 and a cathode 18 forming at least a portion of the inner wall surface of the cell 12. The anode 16 and the cathode 18 define an electrolysis space B in which an electrolyte medium 21 is contained in a molten state, thereby defining an upper surface 21A of the electrolyte medium 21. The cell 12 is supported on an insulated base 14, which is on a scale, such as a Radwag R series precision balance with a resolution of 0.01g, for measuring the mass of the cell. The cell 12 is contained in an insulated gas-filled chamber A of an insulating housing 20. The insulation 22 is a 2-inch thick insulated body 20 having a density of 8 pcf. The device 10A is placed in a plenum D of ambient air such that the upper surface 21A is in fluid communication with the plenum D through a portion of the insulator 22 .

[0227] Electrolysis experiments can be analyzed for the relative reaction due to the ingress and decomposition of CO2 (the reaction of Eq. 3, net of Eq. 1 and Eq. 2), rather than just carbonate decomposition (Eq. 2), compared to all CO2 absorbed (Eq. 3), or compared to when all CO2 is blocked. The latter results in a mass loss of O2 evolution (Eq. 2). This is measured as, Dm 池 , the change of cell quality before and after electrolysis.

[0228] The degree of advantage of CO2 decomposition compared to carbonate decomposition is expressed here in two different ways. The first, expressed in Equations 9a and 9b, is Dm relative to the measured electrolytic charge converted to carbon (CO2 absorption) or to the negative mass expected from oxygen evolution (carbonate decomposition). 池 The second measurement in Equation 10 is the percentage of CO2 absorbed compared to the CO2 required for electrolysis. This is determined by Dm relative to the electrolytic charge converted to carbon plus oxygen (CO2). 池 Combined with the possible maximum O2 loss, equations 4a, 4b and 5 are given as follows:

[0229] DC=100x Dm 池 / (nF x FW(C) (Equation 9a)

[0230] DO2=-100x Dm 池 / (nF x FW(O2) (Equation 9b)

[0231] DCO2=100x(Dm 池 +(nF x FW(O2)) / (nF x FW(CO2) (Equation 10)

[0232] For the open configuration of apparatus 10A, the expected result is net electrolysis without sufficient CO2 input, based on the loss of cell mass for insufficient CO2, see Equation 11:

[0233] Li2CO3→CNM 产物 (y)+Li2O(y)+O2↑;

[0234] y = gas remaining in the pool; ↑ = gas leaving the pool (Eq. 11)

[0235] For the configuration of apparatus 10A, which has minimal inlet for CO2 to enter the cell; i.e., only through a small portion of the porous insulator, whose primary function is to allow the electrolysis waste gas products of O2 to leave the cell; the observed results were a forecell mass of 2262.50 g and a postelectrolysis cell mass of 2257.50 g. The postelectrolysis mass loss was about 5 g less than the forecell mass.

[0236] Theoretical mass of O2 lost with minimal CO2 input:

[0237] 32.00 g mol-1 O2 x 2A x 9h / 4F = 5.37 g loss (as O2 precipitates)

[0238] The change in oxygen DO2 was about 93% (indicating oxygen production).

[0239] The theoretical mass of CO2 is:

[0240] 44.01g mol-1CO2 x 2A x 9h / 4F=7.38g

[0241] The change in CO2, DCO462, is about 5% (indicating only a small 46 uptake of CO2). Without being bound by any particular theory, the CNM product is retained at the cathode where n(e-)=4, but the anode produces O2 which is evolved from the cell 12.

[0242] Example 3B

[0243] Figure 5 B shows a second apparatus 10B, which was also used in the above capture and CNM production experiments. The insulation 22 used was also 2 inches thick with a density of 8 pcf. but now has a larger surface area consisting of multiple walls and ceilings located between the source of the gas input mixture and the electrolyte surface 21A for enhancing the entry and absorption of CO2 into the electrolyte medium 21. Figure 5 For the device shown in B, the expected result is net electrolysis, where diffusion of CO2 through the insulation causes an increase in cell mass due to at least partial renewal of the carbon within the electrolyte medium 21, according to equations 12, 13 and 14:

[0244] Li2CO3→C CNT (y) + Li2O(y) + O2↑(gas output); y = pool retention (Equation 12)

[0245] CO2(air)+Li2O(y)→Li2CO3 (Equation 13)

[0246] Net: CO2(air) → C CNT (y)+O2↑ (Equation 14)

[0247] For the open configuration of the device 10B with frame 22A, the observed results were 2137.67g of forecell mass and 2138.81g of post-electrolysis cell mass. In contrast to the measured mass loss produced in Example 3A, this embodiment resulted in a measured mass increase, and the post-electrolysis mass was about 1.14g higher than the forecell mass. The theoretical mass increase as C is:

[0248] 12.01 g mol-1C x 2A x 9h / 4F = 2.01 g obtained (as CNM product)

[0249] The change DC of carbon compared to theory is about 57%.

[0250] In addition, the change in CO2, DCO2, is about 88% compared to the theoretical mass of CO2 calculated in Example 3A. Without being bound by any particular theory, the Li2CO3 within the electrolyte medium 21 is renewed by carbon from the CO2 held in the cell 12. The CNM product remains on the cathode 18, where n(e-)=4, accounting for the increase in cell mass.

[0251] Example 3C

[0252] Figure 5 C shows a third apparatus 10C used in the above capture and CNM production experiments. The insulation 22 is a 2 inch thick sheet with a density of 8 pcf. The sheet has an extended surface and now forms a channel for air flow. The net contact of the porous insulation with the air and its CO2 can be improved by allowing the air to flow through the channel formed by the solid insulation wall and the inner wall of the porous insulation. For the device 10C with the housing 24 and the frame 22B, the expected result is net electrolysis, similar to Example 2B.

[0253] For the open configuration of device 10C, the observed results were a forecell mass of 2241.13 g and a post-electrolysis cell mass of 2243.16 g. The post-electrolysis mass was about 2.03 g higher than the forecell mass. The change in carbon, DC, was about 101%, and the change in CO2, DCO2, was about 100%. Without being bound by any theory, the rate at which CO2 diffuses through the insulation increases approximately linearly with decreasing insulator thickness, and the insulator increases approximately linearly with decreasing insulator density. Therefore, using a comparable insulator with a thickness of 0.5 inches instead of 2 inches but 4 pcf instead of 8 pcf can increase the sustainable current at high DCO2 to about 16 amps instead of 2 amps.

[0254] Without being bound by any particular theory, the increased cell mass may have been caused because the Li2CO3 within the electrolyte medium 21 was at least partially renewed by the CO2 drawn into the cell 12, and the carbon from the CO2 was retained in the cell 12 for use in producing the CNM product. The increased cell mass is due to an increase in the CO2-derived CNM product within the aeration chamber D, then the aeration chamber C, and finally the electrolysis space B.

[0255] Example 4 - Media Activation

[0256] Activation of the electrolyte medium may be required to initiate consumption of the captured CO2 from the input gas mixture. At 750°C, equilibrium is reached with pure Li2CO3 in equilibrium with a concentration of approximately 0.3 molar Li2O in Li2CO3, with no measured mass change for pure Li2CO3 mixed with 0.33 molar Li2O over a period of 4 hours. Thus, without being bound by any theory, equilibrium is maintained according to Equation 15:

[0257]

[0258] This consumption can be driven by CO2 moving from the gas phase into the molten lithium carbonate electrolyte medium, such as by Equation 1 and electrolytic consumption. Without being bound by any theory, if CO2 is not consumed, then the electrolyte medium is consumed and not renewed by CO2 according to Equation 2. According to Equation 2 (rather than according to the net value of Equation 1 and Equation 2), the electrolyte medium can electrolytically decompose and lose weight as oxygen evolves.

[0259] In an embodiment without electrolyte activation, molten Li2CO3 contained in a high purity alumina (Al2O3) crucible is inert to CO2 absorption during electrolysis in a molten electrolyte. Specifically, fresh, molten Li2CO3 exhibits the need to be activated to trigger incident gas phase continuous electrolytic consumption of CO2 in air into the molten electrolyte. In one embodiment, molten lithium carbonate open to hot air in a high purity alumina (Al2O3) crucible is inert to CO2 absorption during electrolysis, with or without metal (12.5% ​​cast iron). Specifically, between a NiCr C anode and a Muntz brass cathode, at 750° at 0.2 A / cm 2 After 4 hours of electrolysis, the fresh electrolyte showed good carbon deposition on the cathode, as expected from Equation 2, but the total mass of the cell measured before and after electrolysis decreased, rather than growing as expected for sufficient CO2 uptake. The change in CO2 is based on the oxygen-free uptake shown in Equation 1 or the CO2 that is renewed with each carbonate electrolyte.

[0260] In repeated 4-hour electrolysis in the cell, when the same electrolyte was reused (which can be considered in the first stage of equilibrium activation), CO2 was marginally absorbed (as measured by a 3% rise in CO2). This 3% indicates that CO2 began to continuously activate the electrolyte, which was not complete to renew the carbonates during the electrolysis. However, the pure Li2CO3 electrolyte was substantially activated when the electrolyte was heated at 750°C for 24 hours (equilibrium time) before electrode immersion and electrolysis. This activation step increased the change in CO2 to about 81%. Similarly, mixing Li2CO3 with sufficient Li2O (5wt%) in a stainless steel 304 (rather than alumina) crucible without waiting for any equilibrium after the electrolysis time increased the change in CO2 to about 99% in the fresh molten electrolyte, indicating almost complete CO2 absorption. As in the electrolysis in pure Li2CO3 without any time equilibrium activation, fresh Li2CO3 mixed with 10wt% Na2CO3 or with 3 and 1.3wt% CaO showed no mass-based evidence of CO2 uptake during the 4-hour electrolysis. The electrolyte can be adjusted by metal salts, metals or other additives to affect the CO2 uptake rate and CNM products.

[0261] Two other examples of electrolyte-activated absorption of CO2 are noted here. Reuse of electrolyte, which can provide longer time for electrolyte equilibrium, presumably leads to the observed increase in CO2 absorption, and particularly after electrolysis in 750°C Li2CO3 with 1 wt% Li2O, the change in CO2 increased from 38% to 91% upon reuse of electrolyte. Second, the upper surface of the electrolyte relative to the top of the cell and close to the inward flow of CO2 is directly related to the observed measured CO2 change. When the gas phase interacts with the electrolysis electrodes immersed in a low level of electrolyte (below the top of the cell), very low CO2 change values ​​are observed, suggesting a "dead zone" that is depleted of CO2 just above the upper surface of the molten electrolyte medium. Without being bound by any theory, the dead zone can be related to the flow of gas that leaves (rises from the surface) during electrolysis but does not enter the gas phase CO2 during electrolysis. In one case, it was observed that this depletion was so significant that the electrolyte decomposition exceeded that attributed to Equation 2, electrolysis was apparently occurring above the surface of the electrolyte medium and the CO2 concentration was so low that without being bound by any theory, carbonates could further decompose according to Equation 11. This further carbonate decomposition may result in further mass loss and CO2 evolution rather than CO2 being used by the electrolyte to produce CNM products. In the case of electrolysis with low electrolyte in the crucible, the change in CO2 was measured to be -39%.

[0262] Example 5 - Regulating the input airflow

[0263] Directing or enhancing the input gas flow (e.g., by directing wind, adding additional fans, blowers, wind lenses, wind focusing elements, or driving convection) over a porous insulator separated from the electrolyte medium can also affect the consumption of carbon-containing input gas (such as CO2 in air) by the electrolysis process. Thus, as a related example, using a Figure 5 The configuration in C used an electrolyte medium containing 750°C Li2CO3 and 1 wt% Li2O equilibrated in a stainless steel 304 crucible for 24 hours. Afterwards, the electrolysis process occurred at air velocities of 0 m / s, 1.5 m / s, or 2.5 m / s, and the changes in CO2 were 38%, 89%, and 100%, respectively. The higher wind speed case showed essentially complete CO2 absorption.

[0264] Note that in another example, the combined presence of (i) air blast, (ii) metal crucible and (iii) low level of added Li2O (31 / 3 wt%) but using fresh electrolyte rather than time equilibration still resulted in a relatively low CO2 absorption of about 8%.

[0265] Example 6 - Adjusting the current density

[0266] The electrolysis current density, Jelectrolysis, can also affect the magnitude of the CO2 change. A higher J requires a larger CO2 inflow rate. Thus, under the previous conditions, at an incident air velocity of 2.5 m / s, when Jelectrolysis is 0.042 A / cm 2 When J 电解 0.15A / cm 2 At the same air velocity, the CO2 absorption was measured to be 55%.

[0267] Example 7 - Insulation Surface Area Increase

[0268] The net passage of CO2 through the insulation 22 and the absorption rate of CO2 into the medium 21 can be increased by increasing the surface area of ​​the first side 22C of the insulation 22 (for example, by shaping the first side 22C). Maintaining the substantially flat second side 22D of the insulation 22 can have the additional benefit of minimizing heat flow outward from the plenum C. Increasing the surface area of ​​the first side 22C can be achieved by a variety of known shaping techniques, such as but not limited to: macroscopic (geometric), microscopic (surface roughening) and nanoscale techniques / methods, such as bonding molecular components to the first side 22C. For example, the effective surface area of ​​the first side 22C of the insulation 22 can be increased by adding a "loose fill" layer, blowing in fiberglass, borate-coated cellulose or ceramic insulation. The layer can be loosely distributed on the first side 22C and then confined by a flat or shape-molded mesh to maximize the surface area of ​​the first side 22C.

[0269] Another example of a contoured first side 22C is a macroscopic "dimpled" surface enhancement. Fig.11 As shown. The first side 22C can be shaped by various methods to form a plurality of recesses 500, and the plurality of recesses 500 define a plurality of inter-recess channels 502 therebetween. Fig.11 The depressions 500 shown in the figure are convex, meaning that they extend away from the second side 22D, they can also be concave and extend toward the second side 22C, or a combination thereof. The plurality of inter-depression channels 502 together define a convoluted inter-depression flow path 506 along which an input gas mixture can flow. The plurality of depressions 502 also define an over-depression flow path 508 along which an input gas mixture can flow through the convex or concave depressions instead of or in addition to flowing within the inter-depression channels 502 in contact with the permeable insulation.

[0270] The surface area of ​​the two-dimensional first side 22C can also be enhanced by macroscopic, microscopic or nanoscale methods. Non-limiting examples of methods for microscopic surface area enhancement include roughening the first side 22C by mechanical, physical, optical, electrical, electrochemical or thermal methods. The microscopic and nanoscale increase in surface area can also be achieved by chemical treatment of the first side 22C, such as chemical deposition on the first side 22C, or chemical reaction, or chemical or electrochemical etching.

[0271] Without being bound by any particular theory, increasing the surface area of ​​the first side 22C by macroscopic methods, microscopic methods, or any combination thereof can increase the net selective passage of CO2 from the first side 22C to the second side 22D and into the medium 21 by providing chemical affinity, physical affinity, or both for CO2 to enter the insulation 22. In turn, the increased net passage of CO2 through the insulation 22 can increase the amount and / or rate at which CO2 is absorbed into the medium 21.

[0272] Example 8 - Adjusting the flow path between the insulation and the shell

[0273] Fig.12 A shows a device 10D having many similarities to the device 10C (in Figure 5 C) wherein the device 10D defines an extended / longer path length of a flow channel 26C defined between the inner surface 24B of the housing 24 and the first side 22C of the insulator 24. The housing 24 has an outer surface 24A that can take a variety of different shapes to facilitate integration of the device into one or more systems described herein. The flow channel 26C begins at the input aperture 26A and ends at the output aperture 26B. Fig.12As shown in FIG. 2A , the inner surface 24B may define one or more ridges 24C extending away from the outer surface 24A and toward the first side 22C. The inner surface 24B may also define one or more valleys 24D extending away from the first side 22C and toward the outer surface 24A.

[0274] Additionally or alternatively, first side 22C of insulation 22 may define one or more ridges 22E extending toward inner surface 24B and away from second side 22D. First side 22C may also define one or more valleys 22F extending away from inner surface 24B and toward second side 22D.

[0275] The presence of ridges and / or valleys defined by the inner surface 24B of the shell 24, the first side 22C of the insulation 22, or both within the flow channel 26C can enhance the net selective passage of CO2 through the insulation 22 and into the medium 21 by increasing the distance that the input gas mixture flows along the first side 22C. The flow channel 26C can be tortuous, causing the flow of the input gas mixture within the flow channel 26C to change direction one or more times as it moves from the input aperture 26A (wherein the input gas mixture can have substantially the same composition gases as the input gas mixture at the source) through the first side 22C of the insulation layer 22 to exit through the output aperture 26B (wherein the gas in the flow channel 26C will be depleted of carbon-containing gases, such as CO2, and optionally supplemented with exhaust gases generated in the cell 12, such as hot O2. The change in direction imposed by the tortuous flow channel 26C may induce turbulence and / or extend the flow path length within the input gas mixture. Each of the turbulent flow and the greater flow path length can enhance the interaction of the input gas mixture with the first side 22C of the insulator 22 and enhance the net selective passage of the carbon-containing gas to exit the flow channel 26A and enter the plenum C and ultimately the media 21, as compared to the case where the first side 22C and the inner surface 24B are substantially flat or smooth. Various channels or passages that maximize such interactions are contemplated herein, and Fig.12 A shown flow channel 26C is not limiting. It is obvious to those skilled in the art that the path length of the gas input channel through the permeable insulation can be increased or extended in various mechanical and geometric configurations. In further embodiments, the input gas mixture can be compressed by a compressor so as to flow through the first side 22C at a pressure higher than ambient pressure to promote CO2 to flow inward to the higher temperature medium.

[0276] Fig.12 A shows the O2 waste gas product of the electrolysis process forming an emission stream (see Fig.12A), the exhaust flow passes from the second side 22D of the insulator 22 to the first side 22C to mix with the CO2-depleted input gas toward the output hole 26B. Above the surface 21A of the medium 21, the precipitation of the O2 electrolysis waste gas products occurs in the area near the anode 16, which can promote the local collection of such waste gas products. A variety of methods for collecting the O2 electrolysis waste gas products and separating them from the input gas mixture can be envisioned by those skilled in the art, and without limitation, the method for collecting and separating the waste gas products is shown in Fig.12 In B.

[0277] Fig.12 B shows that the exhaust stream of O2 waste gas products is collected in the exhaust duct 30 and separated from the CO2-depleted input gas leaving the device 10D through the exhaust port 26C. The exhaust duct 30 provides fluid communication between the plenum C and the plenum D. Alternatively, the exhaust duct 30 can be coupled to a transport and / or storage system (not shown) for providing fluid communication between the plenum C and a system that facilitates further use of the oxygen waste gas products. The exhaust duct X can be made of various materials that will withstand the chemical and temperature environment in the plenum C, including the hot waste gas products in the exhaust stream X. In some embodiments of the present disclosure, the exhaust duct 30 can guide the exhaust stream X of the hot oxygen waste gas products through an optional heat exchanger 32, which can extract some, most, substantially all or all of the heat energy from the oxygen waste gas products in the exhaust duct 30. The heat exchanger 32 can transfer the collected heat energy to the plenum B, the plenum C, or both. The benefits of collecting and separating the hot O2 exhaust product are that: (i) some or all of the heat can be returned to the device via the heat exchanger 32; and (ii) the high purity O2 product can be involved in various useful industrial and / or oxy-fuel processes. The skilled person will appreciate that the use of the exhaust duct 30 and optional heat exchanger 32 is not limited to use with the device 10D. Collecting and separating the hot exhaust stream can be used in various devices described herein, and these devices can be used in various systems and methods described herein.

[0278] In some embodiments of the present disclosure, the insulation 22 may be adjusted so as to preferentially or selectively allow a greater flow of carbon-containing gases through the insulation 22 than other constituent gases of the input gas mixture. For example, the molecular structure of the permeable insulation may be chemically adjusted so as to selectively allow carbon-containing gases to pass more easily than the ease of passage of other non-carbon-containing constituent gases or combinations thereof when the insulation 22 is not so adjusted. For example, the insulation 22 may be adjusted so that certain non-carbon-containing gases may be absorbed or adsorbed onto the insulation, and therefore, these non-carbon-containing gases do not enter the plenum C to be absorbed by the medium 21. In some embodiments of the present disclosure, the insulation may be adjusted to incorporate a molecular sieve that selects gases that may pass through the insulation more easily than other constituent gases as components of the input gas mixture.

[0279] Without being bound by any particular theory, the above examples demonstrate the selective capture of CO2 from an input gas mixture and the use of the carbon therein to produce CNM products. The experiment was observed from start to finish, including measuring the cell mass before electrolysis and measuring the cell mass after electrolysis. The calculated values ​​were compared with the experiments. The results were verified. The experiments showed that the cell could obtain a stable rate without heating all of the input gas mixture. The porous insulation with a higher temperature medium with a high CO2 affinity allows a net selective passage / diffusion of CO2, which is at least one mechanism by which CO2 is selectively captured from an input gas mixture. For CO2 / N2 mixtures across the porous insulation, both surface adsorption and pore size affect CO2 diffusion. The porous structure of the insulation promotes the interaction of the electrolyte medium with the captured CO2 gas. The high affinity of the molten electrolyte for CO2 provides a net selective transfer from the gas phase above the upper surface of the electrolyte medium into the electrolyte medium. The experiments and examples described herein demonstrate that different configurations can affect the extent to which CO2 is absorbed within the cell. The experiments demonstrated configurations and operating conditions where CO2 was depleted and where sufficient CO2 from the air was present for the given operating conditions of the cell.

[0280] As supported by the equations presented above in this article, CO2 can be rapidly absorbed and spontaneously concentrated from the input gas mixture by an exothermic reaction with the electrolyte medium (by reaction with oxides in the molten salt of the electrolyte medium). The reaction of CO2 with the electrolyte medium can continuously renew the carbonate electrolyte medium, as described by Equation 1. The experimental results are consistent with the expected mass increase or loss according to the equation (as described in Section 2). As described by the total net equation (Equation 3), an increase in the mass of the cell is observed due to carbon accumulation on the cathode (in the form of CNM products). Hot O2 generated from electrolysis can also be used. System features that can enhance the degree of conversion of CO2 into cathode-related CNM products during molten carbonate electrolysis include, but are not limited to: increased air or wind speed, use of lower current density, change in porosity insulation, adjustment of the spacing between the insulation and the upper surface of the electrolyte medium, activation of the electrolyte by increased equilibrium time, electrolyte reuse, increased oxide concentration, positioning the upper surface of the electrolyte medium closer to the inner surface of the insulation, use of a metal electrolytic cell, or a combination of these features.

Claims

1. A system for selectively delivering a carbon-containing gas from an input gas mixture, the system comprising: (a) an insulator that permits net passage therethrough of the carbon-containing gas at a first temperature from the input gas mixture; (b) a gas-filled chamber, (c) an anode and a cathode located within the plenum; as well as (d) a molten electrolyte medium contained in a plenum between the anode and the cathode, the molten electrolyte medium being at a second temperature greater than the first temperature, the molten electrolyte medium having a first affinity for carbon in the carbon-containing gas received from the insulation, and the molten electrolyte medium acting as a carbon sink, wherein the molten electrolyte medium defines a surface having a first surface area, and wherein the upper surface is in fluid communication with a source of the input gas mixture; wherein the insulation promotes the net passage of the carbon-containing gas therethrough to the surface of the molten electrolyte medium, wherein the system is configured to selectively heat and electrolytically decompose the carbon-containing gas to produce different chemical species, and Wherein, the insulation is located between the source of the input gas mixture and the inflation chamber.

2. The system according to claim 1, wherein: The first affinity for carbon includes: the molten electrolyte medium chemically reacting with the carbon-containing gas received from the insulator; electrochemically reacting with the carbon-containing gas received from the insulator; absorbing the carbon-containing gas received from the insulator, combining with the carbon-containing gas received from the insulator, or any combination thereof.

3. The system according to claim 1, wherein: The first affinity for carbon includes the molten electrolyte medium producing a different chemistry than the carbon-containing gas received from the insulation.

4. The system according to claim 2, wherein: The first affinity for carbon includes the molten electrolyte medium producing a different chemistry than the carbon-containing gas received from the insulation.

5. The system according to claim 1, wherein: The carbon-containing gas is carbon dioxide (CO2).

6. The system according to claim 1, wherein: The input gas mixture is air, anthropogenic CO2-containing gas, an industrial waste gas stream, gas from isolated CO2 storage tanks, exhaust gas from factories, exhaust gas from chemical reactors, exhaust gas from power plants, exhaust gas from steam power generation facilities, exhaust gas from pyrolysis reactors, CO2-containing gas products from burning fossil fuels, CO2-containing gas products from converting fossil fuels, CO2-containing gas products from heating, CO2-containing gas products from transportation, CO2-containing gas products from the production of polymers, or a combination thereof.

7. The system according to claim 1, wherein: The insulation is permeable.

8. The system according to claim 1, wherein: The insulation is porous.

9. The system according to claim 7, wherein: The insulation is porous.

10. The system according to claim 1, wherein: The insulation includes fiberglass, cellulose, cotton, woven textiles, mineral wool, cement, carbonates, calcium aluminates, calcium silicates, aluminum silicates, chemical derivatives thereof, and combinations thereof.

11. The system according to claim 1, wherein: The molten electrolyte medium has a second affinity for other gas components of the input gas mixture.

12. The system according to claim 11, wherein: The first affinity is greater than the second affinity.

13. The system of claim 1, wherein: The first temperature is between -90°C and 75°C.

14. The system of claim 1, wherein: The first temperature is between 50°C and 400°C.

15. The system of claim 1, wherein: The second temperature is between 400°C and 850°C.

16. The system of claim 1, wherein: The carbon-containing gas includes CO2.

17. The system of claim 1, wherein: The first affinity for carbon includes: the molten electrolyte medium chemically reacting with the carbon-containing gas received from the insulator; electrochemically reacting with the carbon-containing gas received from the insulator; absorbing the carbon-containing gas received from the insulator and combining with the carbon-containing gas received from the insulator.

18. The system of claim 16, wherein: The different chemical species is elemental carbon.

19. The system of claim 16, wherein: The different chemical substance is nanocarbon.

20. The system of claim 16, wherein: The different chemical substance is graphite nanocarbon.

21. The system of claim 1, wherein: The insulation defines a surface area that is between 1 and 100 times greater than the first surface area of ​​the molten electrolyte medium.

22. The system of claim 1, wherein: The insulation includes a first side adjacent to the source of the input gas mixture, wherein the first side has a larger surface area than an opposing second side adjacent to the molten electrolyte medium.

23. The system of claim 22, wherein: The macro-pathway includes depressions such that the first side defines a plurality of depressions.

24. The system of claim 1, wherein: The system further includes a housing located between the insulation and the source of the input gas mixture, wherein the housing and the insulation define a flow passage for passing the input gas mixture along a first side of the insulation.

25. The system of claim 24, wherein: The housing, the insulation, or both define one or more ridges, one or more valleys, or both for increasing the length of the flow channel.

26. The system of claim 1, further comprising a conduit providing fluid communication between a source of an exhaust stream of exhaust products and an exterior of the system.

27. The system of claim 1, wherein: The thickness, density, or both of the insulation are adjusted to increase the net passage rate of the carbon-containing gas through the insulation.

28. The system of claim 1, wherein: The input gas mixture is a CO 2 -containing product gas from the production of plastics.

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