No, 62/144,018, filed April 7, 2015, the contents of which are incorporated into the present application by reference

A. Field of the Invent on

[0002] The invention relates to membrane carbonation-photobioreactor systems.

The invention also relates to systems that selectively remove gases from atmospheric air, particularly carbon dioxide (CO?.), and release them into controlled environments.

B. Background of the Invention

[0003] Two and a half billion years ago, photosynthetic microorganisms completely transformed our planet by using solar energy to capture huge amounts of C0 ₂ from the atmosphere for growth and releasing oxygen (O2). Today, these microaigae have the potential to produce fuels and products with significant economic value. Key to making microalgal technologies economically attractive is increasing the per-area productivity so that capital costs are offset by a large income stream. Despite atmospheric CO2 levels rising at an alarming rate from anthropogenic fossil fuel combustion, current levels (~ 400 ppmv) present a significant limitation for technologies that rely on microalgal growth. One way to increase microalgal productivity is to deliver CO2 at a concentration much higher than that in atmospheric air.

[0004] The present application focuses on systems and methods that utilize one or more C0 ₂ sorbent substrates and a swing cycle, e.g., a moisture swing cycle, to increase the partial pressure of the C0 ₂ in a gaseous feedstock, which is delivered through a membrane into a bioreactor, such as a membrane carbonation photobioreactor. Such systems and processes offer an effective means for concentrating and capturing CO?, obtained from air and delivering the concentrated C0 ₂ into a photobioreactor through a membrane.

[0005] One aspect of the present disclosure relates to a system comprising a membrane bioreactor and moisture swing sorption (MSS) module where the MSS module supplies at least a portion of the gaseous feedstock to the bioreactor.

[0006] The terms "a" and "an" are defined as one or more unless this disclosure explicitly requires otherwise.

[0007] The terms "substantially," "approximately" and "about" are defined as being largely but not necessarily wholly what is specified (and include wholly what is specified) as understood by one of ordinary skill in the art. In any disclosed embodiment, the term "substantially," "approximately," or "about" may be substituted with "within [a percentage] of what is specified, where the percentage includes 0.1, 1, 5, and 10 percent.

[0008] The terms "comprise" (and any form of comprise, such as "comprises" and

"comprising"), "have" (and any form of have, such as "has" and "having"), "include" (and any form of include, such as "includes" and "including") and "contain" (and any form of contain, such as "contains" and "containing") are open-ended linking verbs. As a result, any of the present devices, systems, and methods that "comprises," "has," "includes" or "contains" one or more elements possesses those one or more elements, but is not limited to possessing only those one or more elements. Likewise, an element of a device, system, or method that "comprises," "has," "includes" or "contains" one or more features possesses those one or more features, but is not limited to possessing only those one or more features. Additionally, terms such as "first" and "second" are used only to differentiate structures or features, and not to limit the different structures or features to a particular order.

[0009] Furthermore, a structure that is capable performing a function or that is configured in a certain way is capable or configured in at least that way, but may also be capable or configured in ways that are not listed,

[0010] The feature or features of one embodiment may be applied to other embodiments, even though not described or illustrated, unless expressly prohibited by this disclosure or the nature of the embodiments.

[0011] Any of the present devices, systems, and methods can consist of or consist essentially of— rather than comprise/include/contain/have— any of the described elements and/or features and/or steps. Thus, in any of the claims, the term "consisting of or "consisting essentially of can be substituted for any of the open-ended linking verbs recited above, in order to change the scope of a given claim from what it would otherwise be using the open-ended linking verb.

[0012] Details associated with the embodiments described above and others are presented below.

BRIEF DESCRIPTION OF THE DRAWINGS

[0013] The following drawings illustrate by way of example and not limitation. For the sake of brevity and clarity, every feature of a given structure may not be labeled in every figure in which that structure appears. Identical reference numbers do not necessarily indicate an identical structure. Rather, the same reference number may be used to indicate a similar feature or a feature with similar functionality, as may non-identical reference numbers.

[0014] FIG, 1A illustrates a schematic of an embodiment in accordance with the present disclosure.

[0015] FIG. IB illustrates a schematic of a collector and a regeneration unit in accordance with the present disclosure.

[0016] FIG. 2 il lustrates the moisture-swing process with a quaternary amine sorbent. As shown in A), a wet resin binds a single C0 ₂ as a carbonate ion (CO : } for every two quaternary amines. B) As the resin dries, some quaternary amines bind with a hydroxide and others with a bicarbonate ion (HC0 ₃ ^~ ). C) If the dried resin is exposed to C0 ₂ , a bicarbonate ion can form by the hydroxide ion reacting with COT. D) Exposing the dried resin to moisture after it has been exposed to C0 ₂ , the water causes a release of CO2 and regenerates the wet resin to (A).

[0017] FIG. 3 shows isotherms of the equilibrium partial pressure (P) of CO? over a resin as function of the fraction (S) of the C0 ₂ binding sites occupied. P is 500 times larger for the wet resin than the dry resin. Data are fit to Langmuir isotherms, i.e., P --- PoS/ (1— S), where Po is a material property.

[0018] FIG. 4 illustrates a schematic of a second embodiment in accordance with the present disclosure. [0019] FIG. 5 illustrates schematic of two 5-L membrane carbonation photobioreactor co-systems set-up at the bench scale. The components include as follows: (1) CO?, gas cylinder, (2) Pressure gauge, (3) Peristaltic pumps, (4) Magnetic stirrers, (5) Reservoir bottle for medium solution, (6 and 7) Photobioreactor vessels, (8) Light source, (9) Reservoir bottles for effluent, (10 and 11) Membrane Carbonation modules.

DETAILED DESCRIPTION OF THE INVENTION

[0020] Referring now to the drawings and more particularly to FIG. 1A, shown there and designated by the reference numeral 100 is a first embodiment of an atmospheric C0 ₂ enrichment and delivery (ACED) system configured to concentrate CO? from air and transfer the C0 ₂ to an algae culture through a membrane system configured for diffusion- driven delivery of the C0 ₂ . In the embodiment shown, system 100 comprises: (i) a collector 10 configured to capture CO? from air; (ii) a regeneration unit 20 configured to receive collector 10 within an enclosure, to regenerate collector 10 by causing it to release the captured C0 ₂ ; and to retain the released C0 ₂ in the form of dissolved C0 ₂ ; (hi) a storage- extraction unit 30 comprising a storage tank to store at least a portion of the released C0 ₂ from the regeneration unit 20 and configured to selectively extract the C0 ₂ from the storage tank for delivery to a bioreactor 40; (iv) a bioreactor 40 containing an algae-containing liquid; and (v) a membrane system 50 comprising one or more membranes configured for diffusion- driven delivery of a gas across the membranes to the liquid. Membrane system 50 is configured so that one side of each membrane interfaces with a gas flow comprising C0 ₂ from regeneration unit 20 and/or storage-extraction unit 30 and the other side of the membrane interfaces with a portion of the algae-containing liquid. In some embodiments, such a configuration can allow higher than ambient concentrations of C0 ₂ be delivered to an algae culture to boost productivity and do so in a more cost-effective way than delivery through traditional methods, such as gas sparging.

[0021] In some embodiments, collector 10 comprises a sorbent configured to selectively (or preferentially) capture CO? from air through the binding action of the sorbent, and regeneration unit 20 is configured to cause the captured CO? to be released from the sorbent thereby regenerating collector 10. In some embodiments, collector 10 comprises a sorbent that is attached to or coated on a substrate.

[0022] Collector 10 and/or regeneration unit 20 can be configured such that the collector can alternate between two environments, a first being one where collector 10 is exposed to outdoor/ambient air and the second being one where collector 0 is isolated from outdoor/ambient air (e.g., disposed within an enclosure of regeneration unit 20 which can be sealed). Collector 0 can be configured to move between at least two positions, namely, out of and into the regeneration unit 20, or an enclosure of regeneration unit 20 can be configured to move between at least two positions. For example, as shown in FIG. IB, collector 10 can be coupled to a hoist 1 1 comprising a motor 12. Hoist 11 is configured to move collector 10 between a position that is within the enclosure 22 of regeneration unit 20 and a position where collector 10 is exposed to ambient/outdoor air, external to the enclosure 22. Enclosure 22 can comprise a cover 24 that is configured to move between two positions so that the enclosure can be opened to receive collector 10 and closed to seal enclosure and recover the absorbed CO?. As shown, cover 24 can also be coupled to hoist 1 and configured to move with collector 10.

[0023] In other embodiments, collector 10 does not move between two positions but the enclosure of regeneration unit 20 is configured to move between two positions, such that the collector is disposed within the enclosure or disposed outside of the enclosure. And yet still in other embodiments, regeneration unit 20 can be configured to have one or more walls or sections of walls that form the enclosure and that move between two positions such that collector 10 disposed therein is exposed to outdoor/ambient air when the walls or section of walls are in a first position and the collector is isolated from outdoor/ambient air (e.g., the enclosure is sealed) when the walls are in a second position.

[0024] In some embodiments, the released CO?, released in the regeneration unit

20, is transferred to membrane system 50. In some embodiments, the released C0 ₂ is transferred to the storage tank of storage-extraction module 30. Storage-extraction unit 30 is configured to produce a gas stream comprising a C0 ₂ concentration higher than ambient concentration with at least a portion of the CO? obtained from the solution in the storage tank. This gas stream is then fed to bioreactor 40 through membrane system 50. Through membrane system 50, the CO?, is delivered by diffusion to the algae-containing liquid as needed. Of the CO? delivered to the microalgae, some fraction may be directly taken from the regeneration unit 20, storage-extraction unit 30, air, and/or other sources that were available at a specific site, such as an exhaust gas stream.

[0025] In some embodiments, the storage tank of extraction-storage unit 30 is included to account for discrepancies between the C0 ₂ pressure delivered by regeneration unit 20 and the C0 ₂ demand of the microalgal growth system. The C0 ₂ delivered by the regeneration subsystem 20 will fluctuate with temperature and humidity conditions, whereas the C0 ₂ demand of the bioreactor 40 varies with the seasons, temperature, and light levels. The extract! on- storage unit 30 ensures the C0 ₂ released from regeneration unit 20 is always actively taken up, even if the algae demand is not sufficient, and there is always a reliable CO ₂ supply for the microalgal growth system, even if atmospheric conditions were not conducive for capturing sufficient amounts of C0 ₂ .

[0026] As mentioned above, collector 10 is exposed to air and preferentially sorbs

C0 ₂ . Collector 10 is able to capture C0 ₂ through the action of a sorbent. For example, in some embodiments, polystyrene anion exchange resins, which are functionaiized with quaternary ammonium ions, are used as the sorbent to capture atmospheric C0 ₂ and to selectively release the CO?, using a wet-dry cycle, as shown in Fig. 2. This wet-dry cycle is in the following referred to as a moisture swing. Functionaiized polystyrene anion exchange resins can contain about 0.5, 1 , 1.5, 2, 2.5, 3, 3.5, 4 moles of quaternary ammonium ions per kilogram, or any value therebetween. In the loaded state, the charge of the quaternary ammonium ion is balanced by a bicarbonate ion (HC0 ₃ ^~ ). In the unloaded state the charge of two quaternary ammonium ions is balanced by a carbonate ion (CQ ₃ ^2'" ). As shown in FIG. 2(A), the unloaded state still binds C0 ₂ , and, when compared to the state where all ions have been exchanged with hydroxide, it could still be considered half full. However, these states which contain less inorganic carbon than the carbonate state cannot be reached with a moisture swing. When an unloaded resin (FIG. 2(B)), holding one carbon per two quaternary ammonium ions, is exposed to ambient air with low relative humidity, it dries and loads up with atmospheric C0 ₂ until the anions are nearly all bicarbonates (FIG. 2(C)). When the loaded resin is wetted or exposed to sufficient humidity within regeneration unit 20, the state holding one carbon for every two cations is preferred and the equilibrium shifts from bicarbonate to carbonate releasing C0 ₂ from the sorbent (e.g., 2HC0 ₃ ^~ C0 ₃ ^2~ + CO? + H ₂ 0) where it is captured into a contained environment for collecting the C0 ₂ . In some embodiments, a sweep gas flows through the regeneration unit 20 to carry the released CO? to the storage-extraction unit and/or bioreactor 40. In some embodiments, the sweep gas is air.

[0027] The sorbent of collector 10 can be a porous material For example, the sorbent can be a membrane-type or sheet-like material that contains small active sorbent materials in its pores. In some embodiments, the sorbent of collector 10 comprises a felt-like material that comprises an ion-exchange material in a powder or fibrous form. In some embodiments, the felt-like material is disposed within a plurality of air-permeable baffles akin to a down blanket or quilt.

[0028] Fig. 3 shows that, at fixed temperature and loading, the equilibrium partial pressure of C0 ₂ over the resin increases 500 fold as the relative humidity changes from 21% to 100%, using moisture to swing the CCh partial pressure over the resin. In some embodiments, a plurality of collectors 10 can be used in system 100. In some embodiments, the regeneration unit 20 is configured to have a counter flow design where, a counter flow of a sweep gas advances from a first collector disposed in unit 20 to a second collector disposed in unit 20 and so on. The first collector holds less sorbed CO?, than the second collector, and, similarly, when present, the second collector holds less sorbed C0 ₂ than a third collector. With a counter flow design, the last collector encountered by the sweep gas before the sweep gas exits the regeneration unit 20 is at the start of its regenerating process and thus holds the highest concentration of CO?.. The first collector encountered by the sweep gas after entering the regeneration unit 20 is at the end of its regenerating process and thus holds the lowest concentration of CO?. The air in contact with each unit contains less CO? than the equilibrium partial pressure over the unit and thus CO _? is released from each unit. However, the exit partial pressure of CO? will exceed the equilibrium partial pressure over the first nearly empty unit. In some embodiments, each collector 10 can advance through the regeneration process by way of a conveyor that moves opposite from the direction of the sweep gas. In some embodiments, the CO2 partial pressure in a continuous gas stream can be amplified to 5000 Pa, or more than 100 times higher than in ambient air.

[0029] Regeneration unit 20 comprises one or more enclosures configured to receive one or more collector 10 and can be configured to regenerate the sorbent and cause release of CO? from the sorbent by causing one or more of a humidity increase, a temperature increase, and a pressure decrease at the surface of the sorbing substrate while within an enclosure of the regeneration unit. In some embodiments, regeneration unit 20 can comprise a buffer tank that comprises an aqueous solution that is applied to the sorbing substrate of collector 10, thereby regenerating the substrate and yielding a storage solution that can have a higher ratio of bicarbonate to carbonate than the initial solution. The storage solution is transferred to storage tank of storage-extraction unit 30. In some embodiments, CO? from the sweep gas is transferred to the storage solution, such as through a gas exchange membrane or a trickle bed exchanger or similar device. [0030] In some embodiments, the storage solution has a lower pH than that of the initial aqueous solution. In some embodiments, the aqueous solution can comprise carbonate to bicarbonate ratio greater than or about 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, or 100 or any value therebetween. In some embodiments, the aqueous solution can comprise bicarbonate to carbonate ratio greater than or about 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, or 100 or any value therebetween. In embodiments, regeneration unit 20 can regenerate the sorbing substrate by applying water at about neutral pH to release bicarbonate and cause a decrease in the pH of the aqueous solution. [0031 ] In some embodiments, storage-extraction unit 30 comprises at least one pump and one or more storage tanks for holding the storage solution and is configured to extract C0 ₂ from the storage tank solution for release into a gas stream either via a shift in pressure, temperature, or a combination thereof. The C0 ₂ concentration in the gas stream can be varied by the degree of the shift in pressure, temperature, or a combination thereof. In some embodiments, a gas stream can comprise CO?, at 3% to 5%. Once the storage solution is effectively spent as a source of C0 ₂ , it can be transferred to the buffer tank to be used as the aqueous solution to regenerate the sorbent. In some embodiments, storage-extraction unit 30 is configured to maintain a headspace above the bicarbonate/carbonate solution and to pump the gas from the headspace. A gaseous flow passes through the headspace having a C0 ₂ partial pressure that is lower than the vapor pressure of CO? for the carb onate/bi carb onate sol uti on .

[0032] In some embodiments, collector 10 comprises a composite material comprising a sorbing surface. The sorbing surface can be adapted to impede salt build-up on the surface, which may occur as a result of repeat regeneration cycles. For example, the composite material can comprise a hydrophobic surface. In particular, a composite material comprising the sorbent can have a porous hydrophobic material disposed on the surface. The porous hydrophobic coating can comprise a polyolefin (e.g., a flashspun high-density polyethylene fibers such as Tyvek*), a fluoropolymer (e.g., polytetrafluoroethylene (PTFE) such as Teflon ^® ), or a fluoropolymeric membrane (e.g., an expanded PTFE). The hydrophobic coating can be applied by vapor deposition, brush, dip or spray coating, or any method used to apply these hydrophobic coatings,

[0033] The surface area, shape, and dimensions of the sorbing surface of each collector 10 and the number of collectors 10 can depend on the C0 ₂ requirements of the algae culture being fed. In some embodiments, collector 10 comprises a wind-facing area that is at or less than 1 m ² . In some embodiments, collector 10 comprises a wind-facing area that is at or less than 0 m ² .

[0034] Bioreactor 40 comprises a reservoir configured to retain a culture of phototrophic microorganisms (such as an algae culture) in the reservoir and a membrane carbonation system 50 comprising one or more membranes configured for diffusion-driven delivery of C0 ₂ . Bioreactor 40 can be open or closed. In Fig, 1A, the C0 ₂ from the storage tank is delivered to an open pond bioreactor via pathway 4a and/or delivered to a closed photobioreactor system via pathway 4b. In some embodiments, the one or more membranes are located in the lower light area of the reservoir. In some embodiments, a portion of the reservoir is blocked from a light source, and the one or more membranes are contained within the portion blocked from light. For example, the membrane system is placed near the middle of a closed photobioreactor, at the deeper levels of an open bioreactor, or behind a light shield, filter, or reflector in bioreactor 40 or in a separate enclosure through which the algae- containing media in bioreactor 40 is circulated. In some embodiments, the one or more membranes comprise a plurality of hollow fiber membranes through which the C0 ₂ - containing gas flows. In some embodiments, the one or more membranes are a non-porous polypropylene tubes. In some embodiments gas flows in one end of the hollow fiber membranes that are closed at the other end. In other embodiments, a hollow fiber membrane is not closed at the other end and after the gas stream passes through the membrane in contact with the liquid medium, it is returned back to the storage tank for further enrichment and then circulated through the hollow fiber membrane again. In some embodiments, the tubes have an outer diameter of about 100 μηι to 500 μιη, such as 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 425, 450, 500 μτη, or any value or range therebetween. In some embodiments, each membrane can have a lumen diameter of 50 urn to 150 μηι, such as 54, 58, 62, 66, 70, 74, 78, 80, 85, 90, 100, 1 10, 120, 130, 140, 150 μιη or any value or range therebetween. In some embodiments, each membrane can have an outer diameter of about 200 μτη and a lumen diameter of 67 μηι. In some embodiments, each membrane can have an apparent C0 ₂ diffusivity of 10 ^"4 m7d to 10 ^"6 m d, such as about 10 ^"5 m7d. [0035] The conditions of the liquid media and of the membrane system are such to facilitate diffusion of C0 ₂ across the membrane at a rate substantially equivalent to the rate at which the culture consumes CO?. Such conditions include the pH of the liquid media, the specific surface area of the membrane, the surface area of the membranes contacting the liquid media, and the partial pressure of the CO?, on the one side of the membrane. For example, in some embodiments, the pH of the liquid media in bioreactor 40 is maintained between 7 to 10. For example, the pH of the liquid media is between 8.5 to 9.5 or between 8.8 to 9.2. In some embodiments, the pH of the liquid media is maintained at about a pH of 9, In other embodiments, the pH is greater than 10, such as 10,5, 10.7, 11 or any value or range therebetween, or less than 7, such as 6, 5, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.5, 0 or any value or range therebetween, to accommodate phototrophic microorganisms that favor those pH conditions. In some embodiments, the one or more membranes have a membrane specific surface area at or less than 25 m ^"1 , 20 m ^'1 , 18 m ^"1 , 15 m ^'1 , 12 m ^"1 , 5 m I m ^"1 , 0.5 m ^'1 or any value or range therebetween. In some embodiments, the surface area of membranes interfacing with the fluid is between 0.005 to 0.025 m ² per L of algae-containing liquid. In some embodiments, the gaseous flow received by the membrane system comprises between 3% and 5% C0 ₂ , between 5% and 10% C0 ₂ , between 10% and 30% C0 ₂ , between 30% and 50% C0 ₂ , between 50% and 80% C0 ₂ , or between 80% and 100% C() ₂ , In some embodiments, the CO? transfer efficiency into the liquid media is at least 80%, 85%, 90%, 95%, 98%>, 99%, or 99.9%. Transfer efficiency, is the percentage of the C0 ₂ that moves across the membrane wall and into the reactor fluid rather than escaping to a gas phase.

[0036] In some embodiments, the concentration of dissolved inorganic carbon

(DIG) in the liquid media is maintained at or below 10 mg DIC/'L, such as at about 9.5, 9. 8,5, 8, 7.5, 7, 6.5, 6, 5.5, 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1, or any value or range therebetween. In some embodiments, the concentration of DIC is maintained above 10 mg DIC/L, such as 1 1, 12, 13, 14, 15, 17.5, 20 or 25, or any value or range therebetween. In some embodiments, the concentration of DIC in the liquid media is maintained between 5 and 7 mg DIC/L. In some embodiments, the C0 ₂ concentration within the membranes is monitored continuously with infrared gas analyzers.

[0037] Referring now to FIG. 4, shown therein and designated by the reference numeral 200 is a second embodiment of an ACED system configured to concentrate C0 ₂ from air and transfer the C0 ₂ to an algae culture through a membrane system configured for diffusion-driven delivery of the C0 ₂ . Embodiment 200 is substantially similar to embodiment 100 described above, except that that system 200 further comprises a compressor 60 configured to compress C0 ₂ , extracted from the storage solution and/or released from the substrate during regeneration, to gas pressures at or greater than 1, 2, 3, 4 or 5 atm, or any value therebetween. Such a compressor can be used to increase the partial pressure of the CO?, for efficient delivery to bioreactor 40 through membrane system 50. In some embodiments, a gaseous flow from the headspace above the storage tank would flow into the compressor. In some embodiments, the gas produced during the regeneration process can flow into the compressor.

EXAMPLE:

[0038] By way of example, a study was conducted to demonstrate the effectiveness of C0 ₂ taken up by an algae culture with a diffusion-delivery membrane system. Fig. 5 illustrates the experimental set-up. Membrane loops were placed near the middle of the photobioreactor so that they were not illuminated and did not accumulate significant biofilm. The systems were operated continuously to grow Synechocystis sp. PCC6883 with a modest external light intensity of 44 W/nT (-220 ^/m ² -sec), CO2 pressure of about 1 atm, and different membrane specific surface areas < 0.2 m ^"1 . Long-term performance at a pH controlled to near 9 demonstrated that CO2 off-gas was zero, and at least 95% of the delivered CO2 was invested into organic products of photosynthesis, with < 5% in DIC in the effluent liquid. Thus, membrane carbonation delivered CO2 with no waste and allowed good control at a suitable pH.

[0039] The above specification and examples provide a complete description of the structure and use of an exemplary embodiment. Although certain embodiments have been described above with a certain degree of particularity, or with reference to one or more individual embodiments, those skilled in the art could make numerous alterations to the disclosed embodiments without departing from the scope of this invention. As such, the illustrative embodiments of the present ACED systems and methods are not intended to be limited to the particular forms disclosed. Rather, they include all modifications and alternatives falling within the scope of the claims, and embodiments other than the one shown may include some or all of the features of the depicted embodiment. For example, components may be combined as a unitary structure and/or connections may be substituted. Further, where appropriate, aspects of any of the examples described above may be combined with aspects of any of the other examples described to form further examples having comparable or different properties and addressing the same or different problems. Similarly, it will be understood that the benefits and advantages described above may relate to one embodiment or may relate to several embodiments. [0040] The claims are not to be interpreted as including means-plus- or step-plus- function limitations, unless such a limitation is explicitly recited in a given claim using the phrase(s) "means for" or "step for," respectively.