BREATHING AIR MAINTENANCE AND RECYCLE

This application claims priority to and extends the teachings and disclosures of the following applications: Provisional Application Serial No. 60/771,170 for Oxygen Generation for Space Suit Application, Bruce F. Monzyk et al., filed February 7, 2006; and PCT Application No. PCT/US06/34004, for Power Device and Oxygen Generator, Bruce F. Monzyk et al., filed August 31, 2006; and Provisional Application Serial No. 60/358,448 for Development of Photolytic Pulmonary Gas Exchange, Bruce Monzyk et al., filed February 20, 2002; Provisional Application Serial No. 60/388,977 for Photolytic Artificial Lung, Bruce Monzyk et al., filed June 14, 2002; Provisional Application Serial No. 60/393,049 for Photolytic Oxygenator with Carbon Dioxide Fixation and Separation, Bruce Monzyk et al., filed June 20, 2002; and PCT Application No. PCT/US02/24277 for Photolytic Oxygenator with Carbon Dioxide Fixation and Separation, Bruce Monzyk et al., filed August 1, 2002; Provisional Application Serial No. 60/404,978 for Photolytic Oxygenator with Carbon Dioxide and/or Hydrogen Separation and Fixation, Bruce Monzyk et al., filed August 21, 2002; PCT Application No. PCT/US2003/026012 for Photolytic Oxygenator with Carbon Dioxide and/or Hydrogen Separation and Fixation, Bruce Monzyk et al., filed August 21, 2003; and Provisional Application Serial No. 60/713,079 for Closed Loop Oxygen Generation and Fuel Cell, Paul E. George II et al., filed August 31, 2005.

The disclosures of the above referenced applications are hereby incorporated by reference.

FIELD OF THE INVENTION

The disclosed invention provides for advanced technology for the closed- loop regeneration of a breathing atmosphere and the management of carbon dioxide (CO2) within a closed environment. The photolytically driven electrochemistry (PDEC) technology disclosed herein has broad application both on Earth and in space. This invention is particularly useful in a spacesuit applications and in portable systems such as vehicles, housing, temporary

camps, and the like, where system performance is safety critical. Important parameters provide for reduced mass, volume and power consumption of the system. Large scale applications are also contemplated.

BACKGROUND OF THE INVENTION

Art related to the present invention includes US 6,866,755 to Monzyk et al.; WO 03/011,366 to Monzyk et al.; WO 03/011,445 to Monzyk et al.; WO 03/011,359 Monzyk et al.; WO 03/012,261 to Monzyk et al.; and WO 04/085,708 to Monzyk et al.

BRIEF DESCRIPION OF THE INVENTION

The present invention provides for a single step design for carbon dioxide removal and fixation using a cell incorporating a carbon dioxide selective film for active/passive transport while simultaneously producing oxygen. The invention is useful for outer space and in hazardous environments. Further details of the invention are shown in the following text and Figures.

Broadly, one aspect of the invention provides for a photolytically energized electrochemical cell including a gas flow chamber; a gas permeable membrane adjacent to the chamber; a porous or gas permeable cathode disposed on the membrane; an anode electrically connected to the cathode; and a light activated catalyst layer disposed adjacent to the anode layer.

Typically the electrochemical cell includes a light transparent window disposed on the light activated catalyst; .In some embodiments the electrochemical cell includes an ion conductive membrane disposed between the anode and cathode and typically has a catholyte bordering the cathode and/or a an anolyte bordering the anode. Other embodiments have a gas permeable membrane that is selective for carbon dioxide so as to facilitate the conversion carbon dioxide from a gas flow to carbonaceous materials.

In yet other embodiments a living enclosure has a gas flow connecting the living enclosure to a gas flow chamber of the electrochemical cell. Typically hydrogen ions flow from the cathode to the anode during operation

through an electrolyte or through an anolyte contact with the light activated catalyst and a catholyte in contact with the cathode.

Another broad aspect of the invention includes an air maintenance system including an enclosure for a human or animal; a separator for separating carbon dioxide from a gas flowing from the enclosure; and an electrochemical cell comprising a photolytic anode and a cathode separated by a cation exchange membrane, wherein oxygen for the enclosure is generated at the photolytic anode and carbon dioxide is reduced to a carbonaceous material at the cathode; and a gas flow chamber for receiving gas flow from the separator; and a gas permeable membrane disposed between the gas flow chamber and the cathode, and wherein the cathode allows gas flow to a catholyte. Typically, the air maintenance system has a gas porous or gas permeable cathode.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 is a schematic drawing of a broad overview of the invention showing major mass and energy flows.

Figure 2 is a schematic drawing of a typical PDEC unit for space suit or other applications according to one aspect of the invention.

Figure 3 is a graph depicting space suit carbon dioxide removal rate relationship of PDEC cathode area and cell stack volume (Modeling calculation results). Note that the total output is 25 mg CO2 /second for each calculated data point (equiv. 29 mg 0 ₂ /second.

Figure 4 is a graph depicting space suit oxygen production relationship of PDEC catalyst area and cell stack volume. Note that the total output is 29 mg oxygen/second for each calculated data point (equiv. to 25 mg Cθ2/second.

Figure 5 is a schematic diagram showing one version of a PDEC unit with a gas diffusion cathode. This allows the circulation of gas directly through the cell for removing excess CO ₂ in air

Figure 6 is a schematic diagram of another aspect of the invention showing a PDEC cell with a gas diffusion cathode. Microporous hydrophobic polymers are typically used for the CO ₂ selective film. A typical material is Teflon™. The process is a single step type design for carbon dioxide removal and fixation

Figure 7 is a schematic diagram of another aspect of the invention showing a two-step process for carbon dioxide removal from a gas stream involving capture followed by fixation. A carbon dioxide separator concentrates the carbon dioxide prior to flowing the carbon dioxide through the PDEC cell with the gas diffusion electrode.

DETAILED DESCRIPTION OF THE INVENTION AND BEST MODE

Broadly the present invention provides for the production of oxygen and the removal of carbon dioxide in an enclosed space. The enclosed space is typically a space suit, a portable living area, a hazardous environmental suit, fire fighter suit, vehicles as well as large living areas. The invention is useful for the mass, volume, and power consumption design constraints associated with enclosed living areas such as spacesuits for the Moon, Mars and in-space Extra- Vehicular Activity (EVA), as well as other highly constrained applications such as a portable breathing apparatus for emergency responders, coal miners and closed loop air regeneration systems for confined environments such as space vehicles, submarines, aircraft, battlefield vehicles, and compact, highly reliable, long-life systems that continuously regenerate fuel, food and/or a high-quality breathing atmosphere within a closed environment. With this invention CO ₂ produced by animals or humans is captured and regenerated without the need for lithium hydroxide (LiOH) or lithium oxide (Li ₂ O) canisters or other logistically disadvantageous absorption devices.

Referring now to Figure 1, this figure illustrates the system 100 parameters in a typical black box design. Details for the boxes are as follows. Inhabitants such a as astronauts or other workers produce spent air 110 reduced in oxygen content and enhance in carbon dioxide content. The gases

are sent to an air rejuvenation unit 120 where oxygen is replenished and carbon dioxide removed. Light input 130 and electrical power 140 typically drive the process. Carbon dioxide is typically converted to carbohydrates 160 for later use or treatment. Water 150 is used for oxygen production by the splitting of water. Fresh air 170 enhanced in oxygen content and reduced in carbon dioxide returns to the inhabitants 100.

The present invention uses light energy to simultaneously generate oxygen and electrical energy while removing CO ₂ and water from the breathing atmosphere or a spent fuel gas stream. The invention enables the construction of a device that, when integrated as a closed system, can essentially close the mass balance on the respiration or fuel cell gas maintenance cycle and can be sized to accommodate the maximum expected CO2 and/or H2O production rate of one or more users. For example, astronauts generate about 50 mg/s of carbon as carbon dioxide. As another example the spacesuit application in the Martian environment, the system would use a compact, portable laser or other lamp light source that would require only electrical power (Figure 2). Thus, one aspect of the spacesuit system does not require ambient light (including solar energy) to operate. However, for other applications such as a space vehicle or a habitat module, the system could be configured to use ambient light as the energy source. The lamp or laser could be powered electrically using solar, nuclear reactor, thermal nuclear, wind, battery or other well known in the art means for electricity generation. The system 200 of the invention does not require the use of a sorption canister to absorb carbon dioxide. Important to space travel, moon settlement and/or Martian surface use the technology provides a means of recycling onboard carbon and avoiding carbon losses (e.g. as CO ₂ ). Various embodiments of the system are applicable to: 1) spacesuits, pressurized rovers and habitat modules for the surfaces of Mars and the Moon, 2) orbiting and fn-space transfer vehicles, and 3) a lunar or Martian lander. The system also has great potential as a backup system for a Crew Exploration Vehicle (CEV).

Referring again to Figure 2, inhabitants in enclosed space 202 (may be a space suit, vehicle, or permanent base) produce carbon dioxide and use up

oxygen. The oxygen and carbon dioxide are typically treated in PDEC unit 204 that produces oxygen and removes carbon dioxide. Carbon dioxide typically flows in loop 203 through a gas flow chamber 210 where a gas permeable membrane 211, is adjacent to a gas permeable cathode 212. The carbon dioxide enters cathode chamber 214 where it is converted to higher carbon compounds and exits the unit. Light 219 from power source 220 impinges on photo catalyst 225 where oxygen is produced at the surface from water in the anode chamber 234. An ion permeable membrane 240 separates the anode chamber 234 from the cathode chamber 214 and allows the passage of hydrogen ions as shown. Oxygen from the anode chamber 234 flows to a gas/liquid separator 250 then to storage in a pressurized tank260 and further use by inhabitants in an enclosed space 202. Carbonaceous product 270 is removed from the cathode compartment 214 for later disposition.

In a further aspect of the invention pressurized oxygen is produced by the cell according to the invention.

Figure 3 illustrates an embodiment for a closed loop breathing system for a spacesuit. For the spacesuit application, the system can use ambient light or a compact, portable laser light source that would require only electrical power. Thus, this system does not require ambient light to operate. This is important in hazardous applications such as firefighting or in mine rescue operations. However, the spacesuit, space vehicle, rover, habitat module, and the like can be configured to use ambient light as the energy source. Because the preferred system does not use a sorption canister, CO2 will not be vented to the outside environment and resources are conserved. The system appears applicable to: 1) spacesuits, pressurized rovers and habitat modules for the surfaces of the Moon and Mars, 2) orbiting and in-space transfer vehicles, and 3) a lunar or Martian Lander. The system also has great potential as a backup system for a Crew Exploration Vehicle (CEV).

A breathing atmosphere in a closed environment such as a spacesuit, space vehicle, lunar rover, or lunar habitat module can consist of blends of oxygen (O2), water (H ₂ O), CO2, and inert gases, with the exact ratio and the precise mass a function of the atmospheric pressure inside the closed

environment. Expelled breathing atmosphere within the closed environment, enriched in CO ₂ and reduced in O ₂ , is circulated to the breathing atmosphere regeneration system to capture the CO ₂ and water vapor and to separate them from the O ₂ and inert gas components. Simultaneously, O ₂ is generated and reintroduced into the breathing atmosphere. The output of the system is a refreshed breathing atmosphere that can be delivered to gas storage and then released on demand.

The fully scaled breathing atmosphere regeneration system can be sized to achieve a rate of CO ₂ removal from the helmet equal to the metabolic production rate of CO ₂ , measuring a mean of 25 mg/s, with a minimum of 8 mg/s and a maximum of 50 mg/s. The fully developed system can be targeted to consume less than 50 watts electrical power and be able to operate for extended periods, well beyond the 8-hour requirement currently envisioned for spacesuit systems.

In addition to providing an efficient method of breathing-atmosphere regeneration, the effluents output by the system can be captured for reuse. The CO ₂ and H ₂ O that are separated from the breathing atmosphere can be chemically converted into oxygen and alcohols that can be used as feedstock for a PEM fuel cell. Methanol and ethanol are typical and likely outputs of the air regeneration system since these fuels have the potential for multiple uses on the lunar and Martian surface as feedstock for a fuel cell and as fuel for a rocket. This carbon re-use feature enables true closed-loop recycling of precious resources and greatly reduces the cost and complexity of the logistics necessary for space exploration.

The PDEC-based system can further enable human space exploration, greatly surpassing the capabilities of any existing technology or system currently available. The system is expected to continuously regenerate a breathable atmosphere without the need for LiOH canisters or other absorbers that have limited life and create major logistics problems due to the need to constantly re-supply them. Any requirements associated with the pressure and composition of the outside atmosphere are obviated, because the system eliminates the need to vent CO ₂ gas to the outside environment.

The disclosed PDEC-based system will further enable human space exploration by replacing a consumption/throw-away process with a continuously recycle that typically surpasses the capabilities of other existing technology or system currently available. The disclosed system will continuously regenerate a breathable atmosphere and /or regenerated fuel inside the spacesuit, or other confined spaces without the need for LiOH canisters or other absorbers that have limited life and create major logistics and cost problems due to the need to constantly re-supply them. Requirements associated with the pressure and composition of the outside atmosphere are obviated, for example by back pressure of high CO2 levels in the Martian environment, fire fighting, aboard submarines, aboard rescue craft, and the like because the system eliminates the need to vent CO ₂ gas to the outside environment.

EXAMPLE 1

A spacesuit breathing atmosphere can consist of blends of oxygen (O ₂ ), water (H2O), CO2, and inert gases, with the exact ratio dependent on the use environment and the precise mass and a function of the spacesuit pressure. Expelled breathing atmosphere within the spacesuit helmet, greatly enriched in CO ₂ and somewhat reduced in O ₂ , is circulated to the breathing atmosphere regeneration system of the invention to capture or "fix" at least a portion of the CO ₂ and water vapor and to separate them from the O ₂ and inert gas components. Simultaneously, in series or parallel, O ₂ is generated and reintroduced into the breathing atmosphere. The output of the system is a refreshed breathing atmosphere that is used directly and/or delivered to gas storage and then released to the suit on demand. This O ₂ gas and fixed CO ₂ can also be used for other purposes such as fuel cells.

The fully scaled breathing atmosphere regeneration system is typically sized to achieve a rate of CO ₂ removal from a space suit or a fire fighters suit or a like helmet equal to the catabolic production rate of CO ₂ , measuring a mean of 25 mg/s for space suit applications, with a minimum of 8 mg/s and a maximum of 50 mg/s. The fully developed system typically consumes less than

50 watts electrical power and is able to operate for extended periods of time, well beyond the 8-hour requirement currently envisioned for spacesuit systems.

EXAMPLE 2

In addition to providing an efficient method of breathing-atmosphere regeneration, a unique feature of the invention is that the effluents output by the system are most preferably captured for reuse. The CO2 and H ₂ O that are separated from the breathing atmosphere will be chemically converted into O ₂ and a protonated reduced product that is collected and has future value to the astronaut(s). Such a product includes organic compounds that can be readily used as foodstuffs (e.g., carbohydrates, fatty acids) or fuel (e.g. ether(s), esters, H ₂ , alcohols and the like) for a fuel cell or combustion. This carbon and H re-use feature enables true closed-loop recycling of precious life-support resources and greatly reduces the cost and complexity of the logistics necessary for long distance (e.g. lunar or Mars) space exploration.

The system typically provides for spacesuit requirements for use on the surfaces of the Moon and Mars, as well as in the vacuum of space. The resulting system can also be readily transferred to the other previously mentioned space exploration applications such as rover, habitat module spacecraft, space station, and the like. Typical system level attributes are: Reduced system mass and volume

Continuously sustain CO ₂ removal rate from the breathing atmosphere equivalent to the amount exhausted by an active adult (25 mg/s {range of 8 to 50 mg/s}) from the helmet in a breathing atmosphere vent flow rate of 10 m ³ /hr (40 kPa), with the balance containing mostly O ₂ at a high RH). Operate for 8-hour periods per use in prevailing Mars ambient pressures of 4 to 9 kPa, with operating pressures of up to 40 kPa Consume fewer than 50 watts of continuous electrical power Configurable in a two-failure-tolerant design Operate in low gravitational fields

Operate in a high (95%) CO ₂ partial pressure environment (4 to 9 kPa total ambient pressure)

Accommodate walking, physical exertion, and other bodily motions

Produce a disposable, or preferably reusable, compound from the removed CO ₂ and H ₂ O

The unit is typically re-usable over several years of use.

The quantum and electrochemical efficiencies of the anodic and cathodic chemistries respectively involved with this system determine the design parameters controlling the ultimate size, weight, and power demands of the finished wearable module for the spacesuit application. The anode and cathode assembly construction materials, with associated breathing and product gas handling hardware, have the greatest impact on the system's CO ₂ conversion and O ₂ production performance.

One aspect of the system consists of the following four major subsystems:

1. CO ₂ separation or preconcentration subsystem (optional if using a gas permeable cathode);

2. CO ₂ fixation subsystem (primarily consisting of a cathode for producing H ₂ and/or reducing CO ₂ electrochemϊcally);

3. Photocatalyst subsystem (for O ₂ and electrical current production); and

4. Hardware that integrates these subsystems into an operational system (balance of device).

CO ₂ Separation Subsystem

The CO ₂ separation subsystem extracts the CO ₂ from a gas stream flowing from a source of the carbon dioxide. In a space suit the flow is typically expected be about 10 m ³ /nr (40 kPa) (STP) gas stream flowing from the helmet. This gas stream carries up to 50 mg/s of excess CO ₂ . Several embodiments for separation include CO ₂ separation technology options selected from one or more synergistic combinations of the following options: (1) passive selective polymer membrane; (2) active transport membrane, including

nanoporous electro-deionization (EDI) membrane; (3) microporous support liquid membrane (SLM) based on a non-volatile, amine-based carrier, thin liquid film; and/or (4) a unique non-membrane approach using a gas scrubber design employing a continuously regenerated, immobilized, non-volatile liquid film. The separation options are selected for each application type of the invention based on CO ₂ capture efficiency, CO2 membrane transport rate, and fit to the CO ₂ fixation subsystem. Typically carbon dioxide separation includes pre- concentration of carbon dioxide separation by a method as discussed above .

CO ₂ Fixation Subsystem Development and Cathodes

The primary design requirements for the CO ₂ fixation subsystem focus on the cathode. When the CO ₂ has been separated from the breathing gas, it undergoes fixation to non-CO2 carbonaceous material. Optionally, the CO ₂ can be absorbed for storage in the system to be held until CO ₂ fixation operation is available and powered. Alternatively, the CO ₂ is continuously removed in a non-exhaustible manner by the PDEC-powered CO ₂ fixation module. If power is turned off or lost temporarily, the system will self-reestablish normal function of CO ₂ removal upon power recovery. Surge volume capacities for feed materials and products are selected to provide this surge capacity.

Elements to be considered for the cathode include physical structure and chemical composition. The cathode is typically made from soft metals (tin, zinc, cadmium, lead, graphite, Pt, Pd, Hg, Ag, etc.) that are used monolithicaJly or plated or alloyed to an underlying basis metal. At least one reasonable CO ₂ fixation product material ("reduced carbon compound") is produced.

Table 1 of a related pending application contains examples of such reduced carbon compounds that are effective (refer to PCT Application No. PCT/US06/34004, for Power Device and Oxygen Generator, Bruce F. Monzyk et al., filed August 31, 2006). These candidates fall into four cases: Case I if the direct reduction of CO2( ₉ ) or carbonic acid or CO ₂ ( _aq ) to a C, product; Case II is the electrochemical reduction of a bicarbonate or carbonate ion to a C, product; Case III is the case where the CO ₂ starting material (present as any

Il

combination of CO ₂₍ g), CO ₂ ( _aq ), carbonic acid (HaCO ₃ ), HCO ₃ ^" or CO ₃ ^2" ) reacts with a Cn carbonion generated at the cathode to generate a C _n+ i compound or higher; Case IV is the case where H2 or hydride is formed at the cathode along with hydroxide ion, then the hydroxide ion reacts with the CO ₂ in one or more of its neutral forms (CO ₂ (g), C0 ₂ ( _g) or H2CO ₃ ) and H ₂ O to produce HCO ₃ ^" or CO ₃ ^2" , and where the H ₂ is the product fuel or H ₂ and/or the hydride is allowed to react with a reducable carbonaceous compound, a reducible inorganic material alone or in combination to produce usable foods and fuels that are chemically in reduced and/or hydrogenated states. Table 1 provides examples of such compounds. The compounds of Table 1 are exemplary only and are not to be construed to representing only limits as to the candidate compounds that might be used. Also, two electrochemical cathodic processes: (1) direct capture of CO ₂ by carbanion electrically generated from the cathode and (2) the direct electrochemical reduction of inorganic forms of CO ₂ (e.g., CO ₂ (g), CO ₂ (aq), HCO ₃ ^" (aq), H ₂ CO ₃ (J) _C ), or CO ₃ ⁼ (aq>) to form reduced carbon compounds. Powdered carbon is one reduced carbon that can be formed. Alcohols, aldehydes, esters, ethers, olefins or polymers of these are also desirable reduced carbon products.

Referring now to Figure 5, this figure shows details of one aspect of a PDEC cell using a gas permeable membrane. The system 500 allows the flow of carbon dioxide directly though the system. The system 500 has an enclosure 502 that contains the gas flow chamber 510, cathode chamber 512, and anode chamber 514. One side of the gas flow chamber 512 is bounded by a gas permeable membrane 520, that is adjacent to a permeable cathode 522, that also is one boundary of cathode chamber 512. A permeable membrane (PEM) 524 between the cathode chamber 512 and anode chamber 514. The permeable membrane 524 provides for hydrogen ion flow from the anode chamber 514 to the cathode chamber. A photo catalyst 526 forms the other boundary for the anode chamber 514. Adjacent to the photo catalyst 526 is the anode 528 that is transparent for the purpose of conducting light to the photo catalyst The electrolyte 532 flowing through the cathode chamber 512 may be the same or different from the electrolyte 534 flowing through the anode chamber 514. When the system 500 is in operation light impinging the photo

catalyst 526 splits water in the anode compartment that is in contact with the photo catalyst 526 and produces oxygen that is subsequently used by the astronaut or other user. The hydrogen ion that is produce then migrates to the cathode compartment and to the cathode 522. Gas flow into the gas flow chamber 510 brings carbon dioxide produced by the inhabitants or from other processes . The carbon dioxide flows through the gas permeable membrane 520 through the cathode 522 and reacts at the cathode wall to form higher products that effectively remove the carbon dioxide. The gas flow exits the chamber 510 and can be recirculated to a user since it still contains oxygen and other gases. Typically it can be mixed with oxygen produced in the anode chamber 514. A voltage source 542 (+ and - )that produces a flow of current 540 in addition to light is typically required to drive the reactions.

Referring now to Figure 6 and 7, variants of two fundamentally different versions of the electrochemical gas cathode can be used. Option A is a single- step design concept (Figure 3). Major components of this design include a CO ₂ - selective passive or active membrane to separate the CO ₂ from the helmet purge gas, a photocatalytic anode where O ₂ is generated and returned to the helmet inlet gas, and a cathode that reduces CO2 to carbonaceous materials, preferably useful products (CO2 fixation). A cation exchange membrane separates the electrodes and selectively allows H ⁺ ions from water, generated at the anode, through to migrate to the cathode to participate in the CO ₂ reduction. In a most preferred version of the invention, pressurized O ₂ is generated at the anode. Water is removed when O ₂ is produced and CO ₂ is reduced (and/or H ₂ is produced), providing a means to reduce relative humidity of the breathing air or flue gas exhaust.

The second option, illustrated in Figure 7, is a two-step design. CO ₂ is separated from the helmet gases using an enclosed gas/liquid exchange system. Then the CO ₂ -rich liquid from this unit is carried to a separate cell, where O ₂ generation and CO ₂ reduction/fixation are carried out in a modified electrochemical cell.

Referring again to Figure 6, Figure 6 illustrates a most preferred embodiment of the invention. The figure shows multi-layered stack of materials

designed to convert CO2, for example as contained in breathing air purged from a confined space or other volume of air being, or to be, breathed by one or more humans and or animals. . Such confined breathing situation arise in situation involving space suits, manned space vehicles and manned space station, lunar and Martian space facilities of all types, peoples and animals in confined or quarantined or toxic/fouled air situations such as in welding, in coal, metals, and other mining, large chemical tank cleanout, asphalt production plants and use, and the like, under water applications such as scuba diving, submarines, underwater rescue craft, and under water facilities of all types, in fire fighting and rescue, around chemical spills of trucks, pipelines, rail cars, shipping, and the like, in dusty work areas such as agriculture. In these and similar settings the breathing air needs to be recirculated such to maintain CO2 and relative humidity (RH) levels within safe and comfort levels respectively. The CO2 level of air is about 300 ppm (v/v) (0.03 vol%) and a variable RH of 40-70 %, and often 10 to essentially 100%. However, exhaled air from the human lung is about 4 vol% (40,000 ppm) and is very humid (essentially 100%). Hence air in confined space rapidly accumulates CO2 to beyond safe levels, even at normal breathing rates. Since atmospheric PO2 is already high (PO2=21 vol% at 0.20 atm, and at less pressure, but still >0.05 atm, in space applications), and since the human can function at 02 levels at much lower than 0.2 atm, or much higher, exhaled stale air still contains plenty of 02 for breathing, it is the CO2 level that needs to be controlled closely and kept low, and yet control at low levels is the most difficult to accomplish. Hence the breathing rate is normally controlled by CO2 levels and not 02 levels. The CO2 level being too high is very toxic to humans and animals due to its acidic nature, causing pH of the blood to drop and thereby causing enzymes to fail in their critical reactions in the body. The rise of PCO2 in the breathing space decreases the amount of CO2 that can be exhaled via the lung which then decreases the amount of CO2 that can be exhaled via the lung which then decreases the amount o f CO2 removed from the blood to the lung due to increased CO2 back pressure. Hence in is critical that CO2 be continuously removed to about < 600 ppm, and preferably to < 300 ppm so that it helps

dilute the breathing air in use environment. In addition the PO2 level needs to be maintained at sufficient levels. Figures A illustrates how the invention accomplishes this 02 and CO2 balance in confined breathing space situations without forming or accumulating lithium carbonate waste product. Following below is a description as to how this is accomplished by the invention.

First, the invention consists of a air pump 601 that purges at least a part of the confined breathing air (1-100 m3/hr at 4-100 kPa) enriched in CO2 (for example 500-1000 ppm) and partially depleted in 02 (for example < 0.2 atm, or < 0.01 atm) 602. This purge gas is pumped, using pump 601, which can be the same pump circulating the breathing air within the confined space, to a container within which there is located one, a and preferably more, cells 603. Note that 603 shows one cell or "unit cell". Such cells consist of a multi-layer or laminant of several materials such as electrodes, metal oxides, membranes, as described below, and these unit cells can be used individually but preferably they are combined in parallel as "cell stacks" to further increase productivity so that many unit cells can operate in unison to a achieve very high production rates of 02 and high removal rates for CO2 and of moisture. Such interconnected sets of unit cells are referred to as "cell stacks". Cell stacks can contain 1-10,000 unit cells, but more often contain 1-1000 unit cells (Figures 3 and 4), and most preferably only contain 4-200 unit cells. The number of unit cells used per stack depend on the total amount of CO2 that needs to be processed per unit time (the productivity per unit area of anode 604 and cathode 615 (the "y" axis of the plots of Figure 3 and 4), the desired "x and "y" dimensions of the cell , where any additional productivity per cell stack is obtained by expanding in the V direction by adding more unit cells to the cell stack (Figures 3 and 4). Figure 3 provides the size of the cell stack needed for one human being (25 mg CO2/sec collected and processed). Figure C provides this information for the equivalent amount of O2 production needed for the O2 consumption rate of one human being (29 mg 02/sec).

The specific operation of each unit cell in the cell stack is the same and as follows. The stale air 602 is passed through a narrow gas flow chamber 613 through the cell stack entering at 607. The walls of this gas flow chamber

consist of CO2-selective permeation membrane 605 that removes at least a portion of the CO2 from the stale air stream. CO2 gas separation selectivity by competitive molecular gas diffusion of such membranes is already known by the medical field. Therefore CO2 separation from the inlet gas can be achieved either by the known method of 1) passively by gas phase competitive molecular diffusion, or by known methods using active transport mechanisms. In the later case the CO2 separates by diffusion after chemical sorption reaction to cause its absorption into the membrane's gas or liquid-filled, or solid pores. After sorption, the sorbed species in both cases diffuse away from the high CO2 stale air (concentration gradient driven) to cause permeation of the CO2 species through the membrane away from the gas stream (and hence physically removing CO2 from the gas stream). Once the CO2 sorbed species reaches the other side of the membrane (facing the cathode), then either the CO2 is released as a gas by Perevaporation, or it forms as a solution of one or more of the following species: CO2(aq), H2CO3(aq), HCO3- and/or CO3(2-). The sorption reaction could have also involved formation of these species at the inlet side of the membrane pore, or anywhere within the pores or porosity of the membrane.

Supported liquid membranes with pores filled with non- or low- volatility amines are particularly good active transport reagents. Passive membrane separations require more membrane surface area but are kinetically faster than liquid-filled membranes, but the latter possess much larger sorption factors and selectivities. Hence either membrane type is satisfactory. In this manner the gas continuously being passed through the gas flow chamber becomes depleted in CO2 while O2 and inert gases (normally N2 or Ar) pass right through the unit cell and exits with the exit gas 606.

The exiting gas, now depleted in CO2 and some moisture is at least partially refreshed and can be stored or, more preferably, immediately recycled back to the confined breathing air space as needed to maintain steady and low CO2 concentrations. The ratio of fraction of sweet air sent to storage or to the breathing space is determined by optional proportional valve 609. The product

air can also be recirculated through the cell stack to produce sweet air of even lower CO2 residual.

As is well known in the art, flow rate ratios, and counter-current flowing arrangement, of the stale gas feed flow with respect to the strip catholyte (for active transport), or Perevaporation (passive transport) will enhance gas separation productivity and are so-used in this invention. The fresh air return is 610.

Within the unit cell, the sorbed CO2 is chemically "fixed" at the cathode 615 directly and/or indirectly within the catholyte 611 by reacting with one or more intermediate reducing agents supplied by generation, and preferably regeneration, at the cathode. Suitable cathode and catholyte electrolyte materials have been previously described in our prior application and are included herein by reference.

When CO2(gas) is provide by the CO2-selective diffusion based membrane 605, then the cathode is most preferably of the gas permeable type to allow CO2(g) to flow from the CO2(g) permeable membrane 605, through the pores of the cathode, to the electrochemical active surface 612 facing the anode 604. When the CO2(g) is converted to electrolyte - soluble species, it converts from CO2(g) to CO2(aq), which is in equilibrium with carbonic acid, H2CO3(aq), bicarbonate ion (HCO3-), and carbonate ion (CO3=). Collectively, these carbon species represent fully oxidized carbon, or C(IV), species. At the cathode of the invention, and or within the catholyte of the invention, this carbon is reduced from the oxidation state of C(IV) to compounds of carbon containing the oxidation states of one or more of C(III), C(II), C(I), C(O), C(-I), C(-II), C(-III), and/or C(-IV), including any mixtures of these compounds. These compounds are collectively referred to as "carbonaceous" compounds. Examples of carbonaceous chemical compounds representing thee reduced oxidation states of carbon are provided in our previous application and are usually organic compounds, for example aliphatics, especially oxygenated aliphatics, aldehydes such as paraformaldehyde, formaldehyde, methane, carbohydrates, ethers, esters, formic acid, aromatic compounds, especially oxygenated aromatic compounds, preferably carboxylic compounds and their

salts, alcohols, ketones, and the like. The reduced carbon products can also be inorganic, namely carbon monoxide (CO), graphic carbon and carbenes.

The hydrogen atoms needed for the production of these organic compounds are derived from the proton exchange membrane or positive ion exchange membrane 614 (both represented by PEM) and arise from the water (moisture, or RH) of the stale air and/or provided separately to the aqueous electrolyte, normally via electrolyte surge vessel 617. These reduces carbonaceous compounds are stored or disposed or reused of, preferably as product liquid, but also can be solids and gases. For iπ-space applications, recycle of this material is important as recycled C, H and O values.

The breathing air is also optionally and most preferably refortified with O2(gas) that is co-produced by the unit cell and cell stack of the invention in parallel to the above described CO2 fixation activity and within the same cells. Details describing this 02 production by the photocatalyst are available from our previous patent application. In summary, the photocatalyst anode 604 is illuminated by light from one or more lamps, lasers, or from solar radiation, or by any combination of these, including solar radiation by day and then by powered lamp or laser when dark. For O2 generation the water from anolyte 616 is separated at the photocatalyst using the photolytic energy described into O2(gas), electrons, and hydrogen ions. The high energy of the photons used (UV and visible light) make this transformation energetically possible despite the high thermodynamic stability of water and of CO2. We note that Photosynthesis by green plants also is based on these energetics. All three of the products are used to maintain breathing atmospheres in limited space. The O2 is immediately useful to replace the stale air of depleted O2. The electrons are collected and so represent an electrical current than are supplied to the cathode 615 at a reduction potential sufficient to enable the above referenced electrochemical reduction chemical reactions to occur at cathode 615.

The hydrogen ions released by the photolysis reaction referred to above are formed in the anolyte 616 adjacent to the photocatalyst anode 604 and then they very rapidly transported, by faster-than-diffusion-rates using the well characterized "hopping" mechanism characteristic of this ion, to and through

the PEM 614. From the PEM the H+ ions enter the catholyte 611 and thereby supply H+ ions for chemical reaction within the catholyte 611 and/or at the surface of cathode 612. The conductive, metallic, or graphitic cathode 612 can be a gas permeable as described previously, a screen, or a nonporous solid.

The electrolytes referred to above, 611 and 616, can have a broad range of acceptable compositions and need not be the same fluid but it is most preferred that they are so that two reservoirs and two pumps can be replaced with just one each. The discriminating electrolyte is the catholyte as the anode only require access by water into the photocatalyst. Examples of such electrolytes are the water soluble combinations of cations (hydrogen ion and the following metal ions: alkali, alkaline earth, transition metals, rare earths, gallium, and aluminum), specifically Li, Na, K, Cs, Rb, Mg, Ca, Tl, Fe, Ni, Cu, Zn, Al, Ga, Co, and complexes and chelates of these metal ions.

Anions are selected for these electrolytes from the list hydroxides, oxides, sulfates, chlorides, bromides, organic sulfonates, phosphates, organic phosphonates, borates, carboxylates, including acetates, iodides,

In addition, redox active catalysts are useful in the catholyte formulation, including ferrocyanide ion, ferrocyanide ion, Bipyridyl complexes of ruthenium (Ru), other Ru complexes, oxalates, transaction metal ion complexes of EDTA, NTA, CyDTA, and other aminocarboxylates chelates, and the like. Aminophosphonate chelates are also effective for catalyzing cathodic reactions of the invention.

The electrolyte is useful over a wide range of aqueous concentration liquids and gels of concentrations > 0.0005 molar (M), preferably > 0.005 M and most preferably > 0.05 M. Maximum concentrations are 50-70 wt %.

Although the single-step design is preferable due to its compactness and simplicity, the two-step design concentrates the CO ₂ ZCO ₃ = for the cathode thereby enabling the use of a smaller PDEC cell. As is well known in the art, the sensors, controls, and supporting hardware are added to support the final subsystem design. The design of the CO2 fixation subsystem involves range- finding and down selection of the design option for subsystem refinement.

When the design has been selected, systematic statistical experimental design and the range-finding results from the preliminary design phase are used to identify the best mode of operation of the subsystem and estimates of the associated set points, control windows, and process control requirements. This information is then used to prepare a process schematic of the selected CO ₂ - fixation process with mass balance data. This information serves as input to the final system-level engineering construction activity where energy balances are also added.

In one embodiment shown in Figure 7 the system 700 uses a PDEC unit 500 that operates in conjunction with a carbon dioxide separator 710. The separator 710 concentrates the carbon dioxide and provides for improved performance. A dehumidifier 720 is typically used to remove excess moisture. Photocatalyst Subsystem Development.

The PDEC photocatalyst provides the electro-chemical power source for CO2 fixation, O ₂ production and optional pressurization, and H ₂ O removal from the feed gas stream. Absorption of light energy by the photocatalyst promotes electrons to the conductance band of the catalyst causing an electrical current to flow, and thereby provides the "holes" left behind to oxidize water to O ₂ and to liberate H ⁺ ions. Liberated electrons are then carried via an external or internal conductor to the cathode where they are consumed in reducing CO ₂ to reduced carbon, or "carbonaceous" products with the consumption of the H ⁺ ions. For the spacesuit application, compact size and low power consumption are critical design parameters. Efficiency of the charge separation step within the photocatalyst film determines the critical design parameters by controlling the ultimate size, weight, and power demands of the finished module for the spacesuit (modeled in Figure 5). Specifically, the quantum yield is efficiently designed in, using vacuum thin film fabrication techniques (sputter coating, chemical vapor deposition, epitaxial deposition, etc.) and related fabrication techniques, features and elements that are well established to optimize yields of photon absorption, film adhesion, charge separation, internal electrical conductivity, and energy transformation.

Figures 3 and 4 illustrate the preliminary O2 and CO2 flux relationship for a single spacesuit breathing-gas maintenance application employing the invention. These figures give only the size, in cm ³ , of the cell stack needed to produce the needed amount of O ₂ and fix the needed amount of CO ₂ for one astronaut. This size is the cell stack only and does not include the lamp, pump, or power supply. Note that the size of the cell stack (x-axis) includes both anode and cathode (i.e., both O2 generation and CO2 fixation) volume. Therefore, the projected size of the PDEC device required for maintaining one astronaut is calculated to be reasonable, e.g., < 1000 cc over most of the flux values (y-axis) given. These flux values were selected to remain within realistic values based on actual optimized industrial operations, such as batteries, electro-surface finishing, electroplating, or fuel cells. These plots are useful to help guide development of the specific photocatalyst. The quantum yield (φ) for the modeling calculations of Figures 3 and 4 was assigned a value of 1.0 and so the cell stack size needs to be adjusted linearly for actual measured values.

Balance of System

There may be one or more variations of balance of system to be balanced so that all operate smoothly as an integrated unit. Balance-of-system elements include pumps, sensors, surge vessels, controls, valves, and lines.

System Integration

With the continuous-flow breathing-gas regeneration system in place, a series of statistically designed parametric tests (SDPT) are normally performed. These designs are based on randomized, statistically designed experimentation produced using commercially available computer software (e.g. Design Expert ^® ). The input "factors" for the design are based on the previous component development effort, supplying the factor range values for "high," "low," "center point," and "fixed" value settings for the SDPT. As the first step for the SDPT, an initial set of randomized range finding tests are run at continuous Cθ ₂ -laden breathing-gas flow conditions to verify the input

parameters and confirm that all key parameters are under control. Such data are invaluable for projecting the performance of the CO ₂ mitigation technology with respect to device size, weight, and power requirements.

While the forms of the invention herein disclosed constitute presently preferred embodiments, many others are possible. It is not intended herein to mention all of the possible equivalent forms or ramifications of the invention. It is to be understood that the terms used herein are merely descriptive, rather than limiting, and that various changes may be made without departing from the spirit of the scope of the invention.