The subject matter disclosed herein generally relates to systems for generating and providing inert gas, oxygen, and/or power such as may be used on vehicles (e.g., aircraft, military vehicles, heavy machinery vehicles, sea craft, ships, submarines, etc.) or stationary applications such as fuel storage facilities.
It is recognized that fuel vapors within fuel tanks can become combustible or explosive in the presence of oxygen. An inerting system decreases the probability of combustion or explosion of flammable materials in a fuel tank by maintaining a chemically non-reactive or inerting gas, such as nitrogen-enriched air, in the fuel tank vapor space, also known as ullage. Three elements are required to initiate combustion or an explosion: an ignition source (e.g., heat), fuel, and oxygen. The oxidation of fuel may be prevented by reducing any one of these three elements. If the presence of an ignition source cannot be prevented within a fuel tank, then the tank may be made inert by: 1) reducing the oxygen concentration, 2) reducing the fuel concentration of the ullage to below the lower explosive limit (LEL), or 3) increasing the fuel concentration to above the upper explosive limit (UEL). Many systems reduce the risk of oxidation of fuel by reducing the oxygen concentration by introducing an inerting gas such as nitrogen-enriched air (NEA) (i.e., oxygen-depleted air or ODA) to the ullage.
A system for providing inert gas to a protected space is disclosed. The system is onboard an aircraft that includes a pressurized cabin or cockpit space. The system includes an airflow path including an inlet and an outlet, and the inlet is in operative fluid communication with the pressurized cabin or cockpit space. A carbon dioxide separator is configured for separating carbon dioxide from air, and includes an inlet in operative fluid communication with the airflow path outlet, and a carbon dioxide outlet. The system also includes an inert gas flow path from the carbon dioxide outlet to the protected space.
In some aspects, the carbon dioxide separator can include a sorbent for carbon dioxide arranged to remove carbon dioxide from the airflow path and to transfer carbon dioxide to the inert gas flow path.
Also disclosed is a method inerting an aircraft protected space. According to the method, carbon dioxide in air from a pressurized cabin or cockpit space is removed, and the removed carbon dioxide is directed to the protected space.
In some aspects, the method further includes generating inert gas in addition to the removed carbon dioxide, and directing the inert gas and the carbon dioxide to the protected space.
In any one or combination of the foregoing aspects, the method further includes contacting the air from the pressurized cabin or cockpit space with a carbon dioxide sorbent to form a loaded sorbent. Carbon dioxide is removed from the loaded sorbent to form de-loaded sorbent, and the removed carbon dioxide is directed to the protected space.
In any one or combination of the foregoing aspects, the method further includes contacting the de-loaded sorbent with the air from the pressurized cabin or cockpit space to form loaded sorbent, and repeating said removing and contacting to recycle the sorbent.
In any one or combination of the foregoing aspects, the method further includes electrochemically transforming an electrochemically active agent in the loaded sorbent from a first compound having a first sorption capacity for carbon dioxide to second compound having a second sorption capacity for carbon dioxide that is less than the first sorption capacity, thereby releasing carbon dioxide.
In some of any of the above aspects including a sorbent, the sorbent can remove carbon dioxide from the airflow path by absorption.
In some of any of the above aspects including a sorbent, the sorbent can remove carbon dioxide from the airflow path by adsorption.
In some of any of the above aspects including a sorbent, the carbon dioxide separator includes a first fluid contactor in operative fluid communication with the airflow path. A second fluid contactor is in operative fluid communication with the inert gas flow path. A fluid flow path is arranged to transport a fluid comprising the sorbent in a loop from the first fluid contactor to the second fluid contactor, and from the second fluid contactor to the first fluid contactor.
In some of any of the above aspects including a sorbent, the carbon dioxide separator includes a first fluid contactor including the sorbent therein. A gas flow path is arranged to alternately: (a) to transport air from the airflow path to the first fluid contactor in a carbon dioxide capture mode, and (b) to transport carbon dioxide from the rom the first fluid contactor to the inert gas flow path.
In some aspects including the above-mentioned alternatively arranged gas flow path, the gas flow path is further arranged to alternately: (a) transport carbon dioxide from the from the second fluid contactor to the inert gas flow path when the first fluid contactor is in the carbon dioxide capture mode, and (b) to transport air from the airflow path to the second fluid contactor when the first fluid contactor is not in the carbon dioxide capture mode.
In any one or combination of the above aspects including a sorbent, the sorbent can include an amine, an alkaline or alkaline earth, a quinone, a molecular sieve, or a metal organic framework sorbent.
In any one or combination of the above aspects, the carbon dioxide separator can include an electrochemical cell comprising an anode and a cathode separated by a separator comprising an ion transfer medium. An anode fluid flow path is in operative fluid communication with the anode between an anode fluid flow path inlet and an anode fluid flow path outlet, and a cathode fluid flow path in operative fluid communication with the cathode between a cathode flow path inlet and a cathode fluid flow path outlet. A sorption fluid flow path is disposed from the cathode fluid flow path outlet to the anode fluid flow path inlet. The sorption fluid flow path includes an absorber in operative fluid communication with the airflow path inlet. A desorption fluid flow path is disposed from the anode fluid flow path outlet to the cathode fluid flow path inlet, said desorption fluid flow path including a desorber in operative fluid communication with the carbon dioxide outlet. A working liquid is disposed in the sorption and desorption fluid flow loops comprising an electrochemically active agent that reversibly transforms from a first compound to a second compound at the anode, and from the second compound to the first compound at the cathode. The first compound has a greater sorption capacity for carbon dioxide relative to a carbon dioxide sorption capacity of the second compound.
In any aspects including the electrochemical cell, the electrochemically active agent can include a quinone selected from the benzoquinone, naphthoquinone, anthraquinone, or a combination comprising any of the foregoing.
In any one or combination of aspects including the electrochemical cell, the electrochemically active agent can include a sulfonic acid group.
In any one or combination of aspects including the electrochemical cell, the electrochemically active agent comprises benzoquinone disulfonic acid.
In any one or combination of the foregoing aspects, the system can further include an inert gas generator on the inert gas flow path.
Also disclosed is an aircraft including an aircraft body, a protected space including a fuel tank, an engine, a pressurized cabin or cockpit space, and the system according to any one or combination of the foregoing aspects.
The following descriptions should not be considered limiting in any way. With reference to the accompanying drawings, like elements are numbered alike:
A detailed description of one or more aspects of the disclosed apparatus and method are presented herein by way of exemplification and not limitation with reference to the Figures.
Although shown and described above and below with respect to an aircraft, aspects of the present disclosure are applicable to on-board systems for any type of vehicle or for on-site installation in fixed systems. For example, military vehicles, heavy machinery vehicles, sea craft, ships, submarines, etc., may benefit from implementation of aspects of the present disclosure. For example, aircraft and other vehicles having fire suppression systems, emergency power systems, and other systems such as the electrochemical systems as described herein, and may include the redundant systems described herein. As such, the present disclosure is not limited to application to aircraft, but rather aircraft are illustrated and described as example and explanatory aspects for implementation of aspects of the present disclosure.
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In some aspects, the inert gas delivered to the protected space can have an oxygen content of less than 12% by volume. In some aspects, the air remaining after removal of carbon dioxide by the carbon dioxide separator 3 can be returned to the cabin and/or cockpit from an air outlet of the carbon dioxide separator. As shown in the example embodiment of
The carbon dioxide separator can be any type of device or system for separation of carbon dioxide from air. Examples of such devices/systems include but are not limited to sorbent-based separators, including sorbents that remove CO2 by absorption (e.g., forming a solution with CO2) and sorbents that remove CO2 by adsorption. Examples of CO2 sorbents that can absorb CO2 include but are not limited to amines (e.g., monoethanol amine, hindered amines, amine blends with other solvents), K2CO3, alkali or alkali earth bases (e.g., LiOH, CaOH2), quinones. Examples of CO2 sorbents that can adsorb CO2 include but are not limited to CFCMS (carbon fiber composite molecular sieve), solid amine adsorbents (e.g., HSC, HSC+, HSG), metal organic framework sorbents, molecular sieves (e.g., zeolite, activated carbon). Other materials can act as a sorbent by reacting with carbon dioxide in a reversible chemical reaction (e.g., a metal oxide that forms a carbonate) that is released when the reaction is reversed. Separators based on sorbents can include a capture stage that absorbs or adsorbs the CO2, and a release stage that releases CO2 from the sorbent. In some aspects, the sorbent can be a fluid (e.g., a liquid sorbent, or a solid sorbent dissolved in or dispersed as particles in a carrier liquid (e.g., water) that flows in a loop between a capture stage where it contacts CO2-containing air from the cabin or cockpit space, and a release stage where it contacts a gas stream to be directed to the protected space and regenerates the sorbent. Capture of CO2 by the sorbent and release of CO2 from the sorbent can be promoted by varying the temperature or pressure (higher temperatures and lower pressures typically favor release whereas lower temperatures and higher pressures typically favor capture, also referred to as pressure swing or temperature swing), or both pressure and temperature. Other variations such as chemical modifications to the sorbent, or application of an electric field can also be used. Additional disclosure regarding carbon dioxide separators and sorbents can be found in The CO2 economy: Review of CO2 capture and reuse technologies, E. Koytsoumpa et al., The Journal of Supercritical Fluids, 132, February 2018, or Separation of CO2 From Flue Gas: A Review, D. Aaron and C. Tsouris, Separation Science and Technology, 40:1-3, 321-348, 2005, the disclosures of both of which are incorporated herein by reference in their entirety. CO2 separators not based on sorbents can also be used, including but not limited to separators that refrigerate the CO2-containing gas under pressure to condense the CO2 or form CO2-containing hydrates, or membrane separators.
An example embodiment of a CO2 separator with a fluid sorbent is schematically shown in
An example embodiment of a CO2 separator with a stationary sorbent is schematically shown in
In some embodiments, the sorbent can be chemically or electrochemically altered between capture and discharge or release stages in order to change the affinity of the sorbent for carbon dioxide. In some aspects, an electrochemical CO2 separator can be used, such as disclosed in US patent application publication no. US 2019/0030485 A1, the disclosure of which is incorporated herein by reference in its entirety.
Although the arrangement of such reactors or cells may be varied, the anode 24 in this example includes an anode flow path inlet 24a and an anode flow path outlet 24a. The cathode 26 includes a cathode flow path inlet 26a and a cathode flow path outlet 26b. There is an ion exchange membrane 28 that separates the anode 24 and the cathode 26. For example, a proton exchange membrane 28 may be comprised of a perfluorinated sulfonic acid polymer or other ion-exchange material that is adapted to conduct protons and substantially block migration of larger molecules, as well as being non-conductive to electrons (i.e., is an electrical insulator). A single cell is shown, but the electrochemical reactor may consist of multiple cells, which may be arranged in a stack using interconnects and endplates as known to those skilled in the art. Similarly, the reactor 22 may comprise several stacks that can be electrically connected in series or in parallel by those skilled in the art.
The separator 20 includes a sorption flow path 30 and a desorption flow path 32. The sorption flow path 30 serves to collect, or absorb, carbon dioxide from a mixed gas stream, represented at G1, and the desorption flow path 32 serves to discharge carbon dioxide as an essentially pure stream, represented at G2, which may also contain water vapor. The sorption flow path 30 includes a line 30a that is fluidly connected with the cathode flow path outlet 26b and the anode flow path inlet 24a. The sorption flow path 30 includes a carbon dioxide absorber 30b, which will be explained further below. The desorption flow path 32 includes a line 32a that is fluidly connected the anode flow path outlet 24b and the cathode flow path inlet 26a. The desorption flow path 32 includes a carbon dioxide desorber 32b, which will also be described below.
The separator 20 also includes a working liquid 34 for circulation through the electrochemical reactor 22 via the sorption flow path 30 and desorption flow path 32. The working liquid 34 is closed in the system. That is, the working liquid is not consumed in the process or removed from the separator 20. A small portion of the working liquid 34 may be lost to evaporation over time, and can be readily replaced as needed. As will be appreciated, the absorber 30b and a desorber 32b in the illustrated example are external to the electrochemical reactor 22. Alternatively, the absorber 30b and desorber 32b can be combined into the electrochemical reactor 22, with the electrochemical reactor 22 configured for two-phase flow (e.g., the gas streams G1/G2 and the working liquid 34).
The working liquid 34 includes an electrochemically active agent (e.g., quinone), which can be dissolved in a carrier solvent such as water or an alcohol. A solvent is not needed in all instances, but some quinones may be solids at temperatures at which the system is operated, in which case, a solvent such as water or an alcohol can be used. Quinone alone has low solubility in water. In order to increase solubility, and thus the concentration of useable dissolved quinone in an aqueous working liquid 34, the quinone is functionalized with one or more ionic groups. An aqueous working liquid 34 is relatively non-volatile, non-flammable, and non-corrosive in comparison to other working fluids often used in electrolytic cells. For example, in some aspects an aqueous working liquid 34 can be free of strong acids, such as sulfuric acid, which often serve as electrolytes in other types of working fluids. In this regard, in some aspects, an aqueous working liquid 34 can include only water, the quinone, and impurities.
In some aspects, the separator 20 can include one or more pumps 38 and valves 39 to transport the working liquid 34 through the sorption flow path 30, electrochemical reactor 22, and desorption flow path 32.
The cathode 26 of the electrochemical reactor 22 is operable, with an input of electric power via the electrical flow path 27, to electrochemically reduce the quinone of the working liquid 34, to the corresponding hydroquinone thereby electrochemically activating the quinone for carbon dioxide capture in the carbon dioxide collector 30b. The anode 24 of the electrochemical reactor 22 is operable to electrochemically oxidize the hydroquinone of the working liquid 34, back to the corresponding quinone thereby electrochemically deactivating the quinone and releasing carbon dioxide as gas.
The electrochemical reactions in the electrochemical reactor 22 can be characterized by the equation: Quinone (“Q”)+2H++2e−→Hydroquinone (“QH2”) at the cathode, and QH2→Q+2H++2e− at the anode. The electrons are driven by the power source through the external flow path 27, and the protons are transported though the membrane 28 to the anode.
The carbon dioxide absorber 30b is configured to expose the working liquid 34 to the mixed gas stream G1 that contains carbon dioxide. Although not limited, in this example the carbon dioxide absorber 30b includes a gas bubbler 30c that is operable to release bubbles of the mixed gas G1 into the working liquid 34. The working liquid 34 that is activated in the cathode 26 flows to the carbon dioxide absorber 30b. The activated quinone (i.e., the hydroquinone) has an affinity to bond with carbon dioxide to which it is exposed. The working liquid 34 with captured carbon dioxide then flows into the anode 24 of the electrochemical reactor 22, where the quinone is deactivated to release the captured carbon dioxide as gas. The carbon dioxide desorber 32b is configured to emit the carbon dioxide gas, as the pure stream G2. For instance, the carbon dioxide desorber 32b may include an open passage to siphon off the gaseous carbon dioxide or a membrane that is selectively permeable to carbon dioxide.
In further aspects, the quinone of the working liquid 34 is selected from benzoquinones, naphthoquinones, anthraquinones, or combinations thereof. For example, a benzoquinone can be 1,4 benzoquinone or 1,2 benzoquinone, but the latter may be more favorable for functionalization. The functionalization is chosen to both enhance the solubility of the quinone, as well as provide ionic conductivity when it is dissolved in water.
In other aspects, the functionalized quinone can include ionic groups, such as one or more sulfonic acid groups. Examples of functionalized quinones include but are not limited to 1,2 hydrobenzoquinone disulfonic acid or 2,7 anthraquinone disulfonic acid. The 1,2 benzoquinone disulfonic acid has a higher reduction-oxidation potential than anthraquinone (approximately 0.8V versus 0.2V, as determined against a reversible hydrogen electrode). Therefore, the 2,7 anthraquinone disulfonic acid is more susceptible to oxidation in the presence of free oxygen, whereas the 1,2 benzoquinone disulfonic acid does not readily form an oxide in the presence of oxygen. Thus, 1,2 benzoquinone disulfonic acid may provide a more stable, electrochemically active aqueous working liquid 34.
The ionic group, such as the sulfonic acid group, enhances solubility of the quinone in water. As an example, an aqueous working liquid 34 has a concentration of the functionalized quinone of 1 mol/L to 3 mol/L (moles per liter). In some aspects, the concentration may be greater than 1 mol/L, such as at least 2 mol/L or even 4 mol/L. An aqueous working liquid 34 thus has a high quinone concentration in comparison to the relatively low solubility of quinones dissolved in dilute acids (typically, 1 mol/L or less). The high concentration allows an aqueous working liquid 34 to adsorb more carbon dioxide per liter and it also enhances diffusion of the quinone in the electrochemical reactor 22, thus increasing reaction efficiency.
In addition to enhancing solubility in water, the sulfonic acid groups also serve as an ionic carrier, i.e., make the working liquid 34 an electrolyte. Thus, the quinone molecules have dual functionality as both the electroactive specie and as an ionic conductor. As a result of this functionalization of the quinone, a separate electrolyte, such as an acid, a base, or ionic liquid, need not be used.
The separator 20 may also represent a method for separating carbon dioxide. Such a method may include dissolving the electrochemically active agent of quinone in water to form an aqueous working liquid 34 by functionalizing the quinone with the one or more ionic groups. In the cathode 26 of the electrochemical reactor 22, the quinone of the working liquid 34 is electrochemically activated for sorption of carbon dioxide. The activated quinone is then exposed to the mixed gas stream G1 that contains carbon dioxide. The quinone captures a least a portion of the carbon dioxide. The quinone is then electrochemically deactivated in the anode 24, to release the captured carbon dioxide as the pure carbon dioxide gas stream G2. This pure, or water saturated carbon dioxide stream can be used for purposes in addition to providing an inert gas, such as the carbonation of water to make soda, as is well known by those skilled in the art.
In some aspects, the inert gas systems described herein can provide a technical effect of promoting generation inert gas with a reduced payload footprint (i.e., overall inert gas system weight) by capturing and utilizing an additional source inert gas in the form of carbon dioxide exhaled by passengers and crew.
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The term “about” is intended to include the degree of error associated with measurement of the particular quantity based upon the equipment available at the time of filing the application.
The terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting of the present disclosure. As used herein, the singular forms “a”, “an”, “the”, or “any” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising,” when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, element components, and/or groups thereof.
While the present disclosure has been described with reference to an exemplary embodiment or aspects, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the present disclosure. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the present disclosure without departing from the essential scope thereof. Therefore, it is intended that the present disclosure not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this present disclosure, but that the present disclosure will include all aspects falling within the scope of the claims.