DIRECT AIR CAPTURE AND CONCENTRATION OF CO2 USING ADSORBENTS
20240001286 ยท 2024-01-04
Inventors
Cpc classification
B01D53/0462
PERFORMING OPERATIONS; TRANSPORTING
B01D53/0476
PERFORMING OPERATIONS; TRANSPORTING
International classification
Abstract
This disclosure provides an apparatus and method for capturing CO2 from air, particularly from air having a temperature equal to or less than 0 oC, and/or a humidity less than 5 g of H2O per kg of air, using adsorbents. The apparatus includes an enclosure having an internal volume that contains a CO2 adsorbent bed, and a vacuum source, an input air source, and heater coupled to the enclosure such that the contents, pressure, and temperature of the interior volume of the enclosure can be controlled. Adsorbents for capturing CO2 comprise a zeolite, metal organic framework, covalent organic framework, silica, or alumina. The method provides for flowing input air into an interior volume of an enclosure containing CO2 adsorbent material, heating the CO2 adsorbent material to release the trapped CO2 and collecting it, and re-equilibrating the pressure of the enclosure.
Claims
1. An CO.sub.2 direct air capture apparatus, comprising: a. an enclosure defining an interior volume; b. a CO.sub.2 adsorbent bed contained within the interior volume of the enclosure; c. a vacuum source coupled to the enclosure; d. a source of input air coupled to the enclosure; and e. a heater capable of heating the interior volume of the enclosure; wherein the interior volume of the enclosure is configured to be selectively isolated from one or more components of the apparatus to enable selective control of the contents, pressure, and temperature of the interior volume of the enclosure, and wherein the input air has a temperature equal to less than 0 C., or a humidity equal to or less than 5 g of H.sub.2O per kg of air, prior to entering the enclosure.
2. The CO.sub.2 direct air capture apparatus of claim 1, further comprising a drying means located between the source of input air and the enclosure, whereby the drying means is configured to remove water from the input air prior to the input air entering the interior volume of the enclosure.
3. The CO.sub.2 direct air capture apparatus of claim 1, wherein the CO.sub.2 adsorbent bed comprises a zeolite, metal organic framework, covalent organic framework, silica, or alumina CO.sub.2 adsorbent.
4. The CO.sub.2 direct air capture apparatus of claim 1 wherein the vacuum source is further coupled to a second enclosure to collect and concentrate the CO.sub.2.
5. The CO.sub.2 direct air capture apparatus of claim 1, further comprising a fan capable of controlling or directing the flow of air or gas within the enclosure.
6. A method of CO.sub.2 direct air capture, comprising: a. flowing a source of input air into an interior volume of an enclosure containing a CO.sub.2 adsorbent bed, wherein the input air has a temperature equal to or less than 0 C., or a humidity equal to or less than 5 g of H.sub.2O per kg of air; b. heating the CO.sub.2 adsorbent bed and applying a vacuum source to the interior volume of the enclosure to permit extraction of the CO.sub.2 from within the enclosure; and c. equilibrating the pressure of the enclosure by permitting an influx of air or gas until the interior volume of the enclosure returns to about atmospheric pressure.
7. The method of claim 6, wherein the source of input air passes through a drying means prior to entering the enclosure.
8. The method of claim 6, wherein the vacuum source is applied prior to heating the CO.sub.2 adsorbent bed, to permit extraction of non-CO.sub.2 components of the input air from the interior volume of the enclosure prior to extracting the CO.sub.2 from the adsorbent.
9. The method of claim 6, wherein the air or gas used to equilibrate the pressure in the enclosure passes through a drying means prior to entering the enclosure.
10. The method of claim 6, wherein the drying means is regenerated using air heated by the residual heat of the CO.sub.2 adsorbent bed.
11. The method of claim 6, wherein the CO.sub.2 adsorbent bed comprises a zeolite, metal organic framework, covalent organic framework, silica, or alumina CO.sub.2 adsorbent material.
12. The method of claim 6, wherein the pressure of the interior volume of the enclosure when the CO.sub.2 is extracted is between 0-0.25 atm.
13. The method of claim 6, wherein the pressure of the interior volume of the enclosure when the CO.sub.2 is extracted is between 0-0.1 atm.
14. The method of claim 6, wherein the CO.sub.2 adsorbent bed is heated to a temperature of about 75-275 C. during the extraction of CO.sub.2.
15. The method of claim 6, wherein the process is configured to be continuously cycled to extract CO.sub.2 from a continual source of input air.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] The accompanying drawings illustrate embodiments of the invention:
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DETAILED DESCRIPTION
[0038] One or more embodiments of the invention will now be described by way of example. It will be apparent to persons skilled in the art that a number of variations and modifications can be made without departing from the scope of the invention as defined in the claims.
TVSA Cycle in Accordance With the Invention
[0039]
[0040] ambient air utilizing a temperature vacuum-swing adsorption TVSA cycle (1). This method relies upon dry input air, either from atmospheric conditions or after having been subject to a subsequent drying means such as condensation, crystallization, desiccation, adsorption, membranes, or other absorption method to extract atmospheric water. Input air preferably remains in a dried state below a dew point of 40 C. (at ambient or near ambient conditions), and in a further preferred embodiment remains in a dried state below a dew point(s) of 45 C., 50 C., 55 C., 60 C., 65 C., 70 C., 75 C., or 80 C. (each at ambient or near ambient conditions).
[0041] In a preferred embodiment, the TVSA cycle (1) generally comprises the following steps: [0042] a. An adsorption step (2) where the adsorbent is used to capture the approximately 420 ppm of CO.sub.2 from the dry ambient air at near ambient cold conditions between 0 C. and 80 C.; [0043] b. A blowdown step (3) which removes the weakly adsorbed components that are on the adsorbent by applying a vacuum; [0044] c. An evacuation step (4) which desorbs the CO.sub.2 that is on the adsorbent by increasing the temperature and applying a vacuum. The vacuum also removes the CO.sub.2 from the column as a product stream. [0045] d. A pressurization step (5) which pressurizes the adsorbent to adsorption pressures of the adsorption step (2) with dry air;
[0046] After the pressurization step (5), the cycle is repeated. By repeating the TVSA cycle (1), further concentration of CO.sub.2 can be achieved from the initial input air.
[0047]
[0048] flows dry air over the adsorbent in a CO.sub.2 adsorbent bed (10), preferably by using a fan (11) located either upstream or downstream of the CO.sub.2 adsorbent bed (10). This dry input air contains CO.sub.2 concentrations equal to that of atmospheric levels (approximately 420 ppm as of 2021 with CO.sub.2 increasing rapidly year-over-year and being of greater concentration near CO.sub.2 emitting sources). If the input air contains pollutants above acceptable limits (based upon either worker safety or component compatibility), they will need to be removed prior to this step by using materials such as activated carbons or zeolites which do not interact significantly with CO.sub.2.
[0049] Dry input air, containing approximately 420 ppm of CO.sub.2, flows over the adsorbent which is located in the CO.sub.2 adsorbent bed (10). The CO.sub.2 is captured via adsorption onto the adsorbent's surface. The air flowing over the adsorbent would be at near ambient conditions of temperature and pressure of the input air. In a preferred embodiment, the input air has a temperature of about 0 C., 1 C., 2 C., 3 C., 4 C., 5 C., 6 C., 7 C., 8 C., 9 C., 10 C., 11 C., 12 C., 13 C., 14 C., 15 C., 16 C., 17 C., 18 C., 19 C., 20 C., 21 C., 22 C. 23 C., 24 C., 25 C., 26 C., 27 C., 28 C., 29 C., 30 C., 31 C., 32 C., 33 C., 34 C., 35 C., 36 C., 37 C., 38 C., 39 C., 40 C., 41 C., 42 C., 43 C., 44 C., 45 C., 46 C., 47 C., 48 C., 49 C., 50 C., 51 C., 52 C., 53 C., 54 C., 55 C., 56 C., 57 C., 58 C., 59 C., 60 C., 61 C., 62 C., 63 C., 64 C., 65 C., 66 C., 67 C., 68 C., 69 C., 70 C., 71 C., 72 C., 73 C., 74 C., 75 C., 76 C., 77 C., 78 C., 79 C., or 80 C., or any range or combination of those temperatures. It is further preferred embodiment, the method takes place in a climate with an annual mean temperature of about 0 C., 1 C., 2 C., 3 C., 4 C., 5 C., 6 C., 7 C., 8 C., 9 C., 10 C., 11 C., 12 C., 13 C., 14 C., 15 C., 16 C., 17 C., 18 C., 19 C., 20 C., 21 C., 22 C. 23 C., 24 C., 25 C., 26 C., 27 C., 28 C., 29 C., 30 C., 31 C., 32 C., 33 C., 34 C., 35 C., 36 C., 37 C., 38 C., 39 C., 40 C., 41 C., 42 C., 43 C., 44 C., 45 C., 46 C., 47 C., 48 C., 49 C., 50 C., 51 C., 52 C., 53 C., 54 C., 55 C., 56 C., 57 C., 58 C., 59 C., 60 C., 61 C., 62 C., 63 C., 64 C., 65 C., 66 C., 67 C., 68 C., 69 C., 70 C., 71 C., 72 C., 73 C., 74 C., 75 C., 76 C., 77 C., 78 C., 79 C., or 80 C. (or any range or combination thereof).
[0050] The adsorption step (2) can operate at atmospheric pressures between 30 and 120 kPa, and at CO.sub.2 concentrations between 10 to 10,000 ppm. Air exiting from the CO.sub.2 adsorbent bed (10) would contain significantly less CO.sub.2 than the input air up until the CO.sub.2 adsorbent bed (10) begins to reach its adsorption capacity. The adsorption step (2) proceeds until the adsorbent bed (10) reaches its target adsorption capacity. In a preferred embodiment, target adsorption capacity is measured from a feedback loop measuring the exiting CO.sub.2 concentration from the CO.sub.2 adsorbent bed (10). In another preferred embodiment, the target adsorption capacity is preconfigured via predictive modelling based upon based the adsorbent's characteristics, and the input air's flow rate and temperature.
[0051] In a preferred embodiment, the CO.sub.2 adsorbent bed (10) is designed to have a low
[0052] pressure drop across the bed (in the direction of air flow), and in a preferred embodiment the pressure drop across the CO.sub.2 adsorbent bed (10) would be below 2000 Pa. In a more preferred embodiment the pressure drop would be below 500 Pa. These low pressure drops can be achieved by using monolithic adsorbent structures, structured adsorbent packing, or packed beds filled with large pellets with the packed bed having a low length over diameter ratios.
[0053] In a preferred embodiment, the ratio of the length of the CO.sub.2 adsorbent bed (10) over the diameter of the CO.sub.2 adsorbent bed (10) is less than 10, less than 9, less than 8, less than 7, less than 6, less than 5, less than 4, less than 3, less than 2, or less than 1 for adsorbent pellets between 1 mm and 100 mm in diameter. In a more preferred embodiment, the diameter of the adsorbent pellets is 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 11 mm, 12 mm, 13 mm, 14 mm, 15 mm, 16 mm, 17 mm, 18 mm, 19 mm, 20 mm, 21 mm, 22 mm, 23 mm, 24 mm or 25 mm (or any ranger or average of values therein), with length over diameter ratios less than 2, less than 1.9, less than 1.8, less than 1.7, less than 1.6, less than 1.5, less than 1.4, less than 1.3, less than 1.2, less than 1.1, less than 1, less than 0.9, less than 0.8, less than 0.7, less than 0.6, less than 0.5, less than 0.4, less than 0.3, less than 0.2, less than 0.1, and any ranges, combinations, or averages thereof.
[0054] The size and scale at which the invention can be carried out can be tailored to best account for the available space and desired throughput of the system. In a preferred embodiment, the CO.sub.2 adsorbent bed (10) is fully contained within a larger enclosure, such as a tank or container, and the remaining steps of the method are carried out by altering the pressure, temperature, or air sources within the enclosure.
[0055] In alternative embodiments, the enclosure is comprised of a series of tanks or containers linked together. In a further alternative embodiment, the enclosure containing the adsorbent bed (10) is configured as a cylindrical column or tube (or series of columns or tubes), which optimizes the interaction between the input air and the CO.sub.2 adsorbent material. In a further embodiment, the CO.sub.2 adsorbent bed (10) can be isolated via rotation of a rotating/moving conduit gate valve. In another embodiment, the CO.sub.2 adsorbent bed (10) can be rotated/moved in order to be isolated.
[0056]
[0057] After isolating the CO.sub.2 adsorbent bed (10) from the input air, a vacuum source such as a vacuum pump (15) is connected to the CO.sub.2 adsorbent bed (10). In a preferred embodiment, the vacuum pump (15) is connected to the CO.sub.2 adsorbent bed (10) by a gate, valve, or baffle. The vacuum pump (15) reduces the pressure within the CO.sub.2 adsorbent bed (10) to below ambient pressures. The degree to which the pressure is reduced during this step determines the purity of the final CO.sub.2 product stream. The lower the pressure during the blowdown step (3), the higher the final purity of the CO.sub.2 product stream. In a preferred embodiment, the blowdown step (3) occurs at 0.0000001, 0.000001, 0.00001, 0.0001, 0.001, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or 1 atm pressure, and any range or combination or average thereof. In a particularly preferred embodiment a high purity CO.sub.2 product stream can be obtained having a CO.sub.2 concentration above 90%, above 91%, above 92%, above 93%, above 94%, above 95%, above 96%, above 97%, above 97.5%, above 98%, above 98.5%, above 99%, above 99.5%, or above 99.9%. In a particularly preferred embodiment, the blowdown step (3) occurs at a pressure between 0-0.1 atm and achieves a CO.sub.2 concentration above 99%.
[0058] By reducing the pressure within the CO.sub.2 adsorbent bed (10), the weakly adsorbed components of the input air (predominantly composed of N.sub.2, O.sub.2, and Ar) are removed from the CO.sub.2 adsorbent bed (10) while keeping the bulk of the CO.sub.2 on the adsorbent. In a preferred embodiment, this stream of air, (being rich in N.sub.2, O.sub.2 and Ar), can be stored in a buffer tank for later use.
[0059] In an alternative embodiment, where the target concentration of the CO.sub.2 product stream is acceptable without the requirement of removing the N.sub.2, O.sub.2, and Ar, from the CO.sub.2 adsorbent bed (10) using a vacuum, the blowdown step (3) can be omitted and the method proceeds from the adsorption step (2) straight to the evacuation step (4).
[0060]
[0061] The heater (16) can apply heat to the CO.sub.2 adsorbent bed (10) via any acceptable electrical, chemical, sensible, radiative, heat exchange, or other generally known heating means, and may heat the inner area of the CO.sub.2 adsorbent bed (10) via an immersion heater or heat exchanger, or alternatively heat the exterior or other portion of the enclosure, and thereby conduct, convey, or radiate heat to the CO.sub.2 adsorbent bed to indirectly heat the CO.sub.2 adsorbent material. In a preferred embodiment, the heater (16) utilizes heat from an alternative source, such as utilizing waste heat from a separate source to facilitated CO.sub.2 capture. In a preferred embodiment, the CO.sub.2 adsorbent bed (10) is heated using pressurized CO.sub.2 flowing between the heater (16) and CO.sub.2 adsorbent bed (10). In a particularly preferred embodiment, this heated CO.sub.2 is obtained from previous operation of the TVSA cycle (1).
[0062] In a preferred embodiment, a vacuum source is also used to remove the CO.sub.2 from the CO.sub.2 adsorbent bed (10). Once the bed is sufficiently heated, a vacuum pump (15) would be turned on to reduce the pressure within the CO.sub.2 adsorbent bed (10). In a preferred embodiment, the heating of the CO.sub.2 adsorbent bed (10) and the reduction of pressure can occur simultaneously. In a further preferred embodiment, the pressure of the CO.sub.2 adsorbent bed (10) is reduced to between 0 to 0.25 atm, to extract as much of the CO.sub.2 from the CO.sub.2 adsorbent bed (10) as possible. As the evacuation step (4) is occurring, a purified stream of CO.sub.2 exits the vacuum pump (15) and can be collected for further use. This CO.sub.2 stream can be as high as 99.999% pure. In a further embodiment, the CO.sub.2 can be used in a sequestering process, enabling long-term removal of CO.sub.2 from the atmosphere.
[0063]
TVSA Cycle Further Incorporating Desiccation and Filtration in Accordance With the Invention
[0064]
[0065] In a preferred embodiment, the TVSA cycle with desiccation and filtration generally
[0066] comprises the following steps: [0067] a. An adsorption step (6) where the adsorbent is used to capture the approximately 420 ppm of CO.sub.2 from ambient air at near ambient conditions between 80 and 0 C.; [0068] b. A blowdown step (7) which removes the weakly adsorbed components that are on the adsorbent by using the vacuum; [0069] c. An evacuation step (8) which desorbs the CO.sub.2 that is on the adsorbent by increasing the temperature and applying the vacuum. The vacuum also removes the CO.sub.2 from the column as the product stream; [0070] d. A pressurization step (9) where the adsorbent is pressurized to adsorption pressures with dry air; and [0071] e. A waterbed regeneration step (17) where air is flown from the adsorbent to a desiccant to use the sensible heat of the adsorbent to desorb and regenerate the desiccant.
[0072] After the waterbed regeneration step (17), the method is repeated with the adsorption step (6). By incorporating the waterbed regeneration step (17), significant energy savings are achieved by decreasing the energy required to regenerate the desiccant.
[0073] This TVSA cycle with desiccation and filtration relies upon many of the same principles discussed in respect of the previously-described TVSA cycle. As such, focus of this section will only be placed upon additional elements or particular areas of focus, and reference to the previous discussion of the adsorption, blowdown, evacuation, and pressurization steps of the TVSA cycle (1) are intended to be incorporated herein.
[0074]
[0075] Input air passes first through a particulate filter (12) to remove any solids that may be present within the air stream that will accumulate in the system. These solids can be particulate matter, ice crystals, or any other materials that are greater than 1 m which are airborne and may negatively impact the function of the adsorbent. The filtering of these particulates from the input air can be achieved using a known technology such as grates, electrostatic, or fiber filters. In a preferred embodiment, the filtering is done in-line with the remaining step in the method.
[0076] Filtered air is then passed through a water capture bed (13) comprising a desiccant that removes water from the air. This water capture bed (13) can be filled with any of several known desiccants such as silica gel, 3A (a zeolite that is also often described as a molecular sieve), activated carbons, aluminas, or certain metal organic frameworks (MOFs). In a preferred embodiment, the desiccant contained within the water capture bed (13) does not adsorb CO.sub.2 in significant quantities (for example, 0.1 mmol.sub.CO2/g.sub.desiccant@0 C.) at a partial pressure of 0.0004 atm CO.sub.2 and removes water from the input air at near ambient conditions.
[0077] The resulting dried air then flows into the CO.sub.2 adsorbent bed (10) in a similar way to
[0078] the previously described adsorption step (2) from
[0079]
[0080]
[0081]
[0082] In a preferred embodiment, this reverse flow of air for the pressurization step (9) and waterbed regeneration step (17) acts to ensure the apparatus is regenerated between cycles, while ensuring water is not able to enter the CO.sub.2 adsorbent bed (10). This permits the method to be cycled with minimal downtime and at reduced energy cost. During the evacuation step (8), the CO.sub.2 adsorbent bed (10) is heated to desorb the CO.sub.2. Much of this heat is retained by the CO.sub.2 adsorbent bed (10) (i.e. as sensible heat), and needs to be cooled before the method can be repeated. During the pressurization step (9) and the waterbed regeneration step (17), dry air flows into the CO.sub.2 adsorbent bed (10) at a slow rate so that it can be heated by this sensible heat of the CO.sub.2 adsorbent bed (10). This heated dry air can then be exhausted through the water capture bed (13). The desiccant is regenerated using the heat from this warm air. In appropriate circumstances, the heater (16) or an additional heater (not shown) can be operated during the waterbed regeneration step (17) to ensure that a sufficient supply of warm air is available to regenerate the water capture bed (13).
[0083] In another preferred embodiment, once the water capture bed (13) has been regenerated, the flow of air can be reversed and air from inside the CO.sub.2 adsorbent bed (10) can be allowed to exhaust through the water guard (14), acting to regenerate the water guard (14) for future use. In an alternative embodiment, the regeneration can be aided by the heater (16) or an additional heater placed (not shown) configured so as to further heat the flow of air between the water guard (14) and the CO.sub.2 capture bed (10).
[0084] In a preferred embodiment, care is taken to ensure that no water is in the input air for
[0085] the pressurization step (9) and waterbed regeneration step (17) by using dried air that has been stored from another step in the method or the exhaust air from the adsorption step (6) of a parallel method. By taking care to ensure no water is in the input air, the water guard (14) can be omitted from the design as no water is required to be removed prior to input air being fed into the CO.sub.2 capture bed (10).
[0086] In a preferred embodiment, the alternative flow of air through the various cycles is controlled by the fan (11), which in a particularly preferred embodiment is located at the most downstream portion of the system relative to the input air used in the adsorption step (6).
[0087] Under either method described above, modifications can be made to the implementation of the invention. For example, in a preferred embodiment there are multiple machines performing the method simultaneously, but at offset steps, such that dry air from the first method can be immediately used as input air in the second method. Alternatively, the steps need not be directly linked, such that the various steps are operated only during their most optimal time, such as overnight for the adsorption step (2 or 6) when cold temperatures are most desired, which is then held until the day when temperatures have increased to perform the heating steps of the evacuation step (4 or 8) when higher temperatures are desired. This would be expected to provide a further reduction in the cost per ton to capture and concentrate CO.sub.2, balanced only against the desired throughput.
[0088] In preferred embodiments, the methods described above are carried out in facilities located at, or in close proximity to, clean energy sources such as wind, solar, hydro, geothermal, nuclear energy generating stations, or other clean energy sources. Other than powering this method to capture and concentrate CO.sub.2, this method would enable otherwise excess waste energy not needed by the power grid (during times of low power usage) to be utilized in CO.sub.2 capture.
[0089] In alternatively preferred embodiments, the methods described above are carried out in connection with facilities that generate a suitable supply of input air, or are able to utilize the produced concentrated CO.sub.2 or other concentrated gasses obtained during the blowdown step (3 or 7) or evacuation step (4 or 8).
Preferred Materials and Environmental Conditions For Use With the Invention
[0090] Materials that preferentially sorb water over CO.sub.2 have been used air pre-purification processes since the early 1980s. Air pre-purification units would utilize faujasite structured zeolites such as NaX to capture CO.sub.2 from the air to reduce its concentration to less than the ppm level. Such methods work by first pressurizing the ambient air to high pressures (e.g. 50-150 psia) which serves to separate the water, then feeding the pressurized gas into an adsorbent bed for the removal of trace amounts of water and CO.sub.2. This dry air, free of CO.sub.2, is then fed into another unit for the production of N.sub.2 or O.sub.2. However, these materials have not been used for the capture and concentration of CO.sub.2, and had been deemed unsuitable due to their low affinity for CO.sub.2 in comparison to water.
[0091] However a wide variety of adsorbents, including those previous deemed unsuitable for use in the capture and concentration of CO.sub.2, are suitable for use in accordance with this invention. In a preferred embodiment, the adsorbent chosen for the CO.sub.2 adsorbent bed (10) should have at least an adsorption capacity for CO.sub.2 greater than 0.1, greater than 0.2, greater than 0.3, greater than 0.4, greater than 0.5, greater than 0.6, greater than 0.7, greater than 0.8, greater than 0.9, greater than 1.0, greater than 1.1, greater than 1.2, greater than 1.3, greater than 1.4, greater than 1.5, greater than 1.6, greater than 1.7, greater than 1.8, greater than 1.9, greater than 2.0, greater than 2.1, greater than 2.2, greater than 2.3, greater than 2.4, greater than 2.5, greater than 2.6, greater than 2.7, greater than 2.8, greater than 2.9, greater than 3.0, greater than 3.1, greater than 3.2, greater than 3.3, greater than 3.4, greater than 3.5, greater than 3.6, greater than 3.7, greater than 3.8, greater than 3.9, greater than 4.0, greater than 4.1, greater than 4.2, greater than 4.3, greater than 4.4, greater than 4.5, greater than 4.6, greater than 4.7, greater than 4.8, greater than 4.9, greater than 5.0 mmolCO.sub.2/g adsorbent at conditions of 0 C. and partial pressures of 0.0004 atm of CO.sub.2, including ranges, combinations, and averages thereof.
[0092] In another preferred embodiment the preferred CO.sub.2 adsorbent has a surface area greater than 100 m.sup.2/g. In a further preferred embodiment, the CO.sub.2 adsorbent has a pore structure that allows CO.sub.2 to diffuse through its structure at temperatures below 0 C.
[0093] In another preferred embodiment the adsorbent has an average heat of adsorption of CO.sub.2 less than 100 kJ/mol, less than 95 kJ/mol, less than 90 kJ/mol, less than 85 kJ/mol, less than 80 kJ/mol, less than 75 kJ/mol, less than 70 kJ/mol, less than 65 kJ/mol, less than 60 kJ/mol, less than 55 kJ/mol, less than 50 kJ/mol, less than 45 kJ/mol, less than 40 kJ/mol, less than 35 kJ/mol, less than 30 kJ/mol, or less than 25 kJ/mol, including any ranges, combinations, or averages thereof.
[0094] The heat of adsorption is important with regards to the energy required to desorb the CO.sub.2 with larger heats of adsorption requiring more energy for desorption of the CO.sub.2. The profile of the heat of adsorption with respects to loading, which can be seen in a Clausius-Clapeyron relationship, is also important. This relationship shows that the initial CO.sub.2 that is adsorbed releases more energy than subsequent CO.sub.2 adsorbed. Thus, the initial CO.sub.2 adsorbed would require more energy to desorb than subsequently adsorbed CO.sub.2 molecules. In a particularly preferred embodiment, the heat of adsorption of CO.sub.2 on the adsorbent would be as low as possible and constant over a range of loadings.
[0095] One beneficial aspect of the invention is that adsorbents that are commonly considered to be water unstable, or otherwise preferentially adsorb water over CO.sub.2, can be used to capture and concentrate CO.sub.2 due to the water removal prior to the separation of CO.sub.2. This allows many adsorbents, such as aluminas, zeolites, covalent organic frameworks (COF), and MOFs, to be used for DAC, contrary to accepted practices.
[0096] In a preferred embodiment, the CO.sub.2 adsorbent bed (10) is made up of zeolites having oxygen tetrahedral frameworks incorporating Si, Al, P, Ge, B, Mg, Zn, Ga, Co, or Be, (including the presence of two or more differing structures, or mixtures of different structures). In an alternatively preferred embodiment, the CO.sub.2 adsorbent bed (10) is made up of mixtures of CO.sub.2 adsorbent materials having non-framework species, or mixtures of framework and non-framework species.
[0097] In a further preferred embodiment, the zeolite frameworks include, but are not limited to, Linde Type A, faujasite, or chabazite, which all have large CO.sub.2 adsorption capacities at low CO.sub.2 partial pressures but adsorb water competitively over CO.sub.2. Faujasite structured zeolites, and in particular faujasite structured zeolites with a Si/Al ratio of below 2, are particularly preferable adsorbents for this separation.
[0098] Preferred zeolites can have a variety of counterbalancing cations in the metals group within them, such as alkali or alkaline earth metals, which change the strength of interaction with CO.sub.2 and therefore, the heat of adsorption of CO.sub.2. In a preferred embodiment, MOF's including, but not limited to, NbOFFIVE-1-Ni, SGU-29, Mg-MOF-74, SIFSIX-3-Cu, SIFSIX-2-Cu, Mg-dobpdc-mmen are also preferred adsorbents for this separation.
[0099] In a preferred embodiment, the CO.sub.2 adsorbent bed (10) can be composed of one or more types of adsorbents. In a further preferred embodiment, the adsorbents can be arranged to according to the flow of input air to first expose the air to adsorbent with a weaker CO.sub.2 interaction, then an adsorbent with a stronger CO.sub.2 interaction. In a further preferred embodiment, the same adsorbent in two configurations can be layered according to the direction of the flow. These two configurations can be a pellet/structure/packing with a higher pellet/structure/packing diffusion resistance, and a lower pellet/structure/packing diffusion resistance. These would be oriented with regard to the flow of air as to first have the higher pellet/structure/packing diffusion resistance, and then the lower pellet/structure/packing diffusion resistance
[0100] Another benefit of the invention is that it is can be designed to operate at low temperatures that favour separation, due to the amount of work to separate and concentrate CO.sub.2 operating as a function of the temperature at which the separation occurs. Specifically, the lower the system temperature of the invention, the lower the expected energy required to capture CO.sub.2 in accordance with the invention. Though not intended to be limited by any particular scientific principle, this phenomenon is believed to be governed by the second law of thermodynamics, and illustrated in
[0101] In a low temperature embodiment, the synergistic effects between the adsorption step (2 or 6) occurring at ambient temperatures below 0 C., and the adsorbents are highlighted leading to lower overall energy requirements for the method. This is due to the adsorbents' CO.sub.2 adsorption capacity being greater at colder temperatures. This can be seen in
[0102] At colder temperatures, the Henry's Law constant for CO.sub.2 is significantly higher than that of warmer temperatures (LiX, 3.35 mmol/gatm@60 C., 0.012 mmol/gatm@60 C.). This phenomenon is beneficial for the invention because more CO.sub.2 is adsorbed on the adsorbent per cycle thereby reducing sensible energy losses, leading to overall lower energy demands for the method.
[0103] Another benefit of the invention in such an embodiment is that, due to the use of cold (i.e. below 0 C.) input air, less water needs to be separated prior to capturing and concentrating CO.sub.2, thereby lowering the total energy requirements of the method. Since separating water requires a significant amount of energy, a particularly preferred embodiment of the invention utilizes a dry input air source, such as air from drier locations or air dried from an alternative means as a waste product.
[0104]
[0105] In an alternative embodiment, the invention can utilize air with temperatures above 0 C., provided it contains a very low water content and otherwise behave in an equivalent manner. For example, the Atacama Desert, the Tibetan Plateau, and the Gobi Desert are known for being some of the driest places on the planet, and despite having an annual mean temperature between 0 C. and 20 C., and an annual mean absolute humidity between 0 and 5 g H.sub.2O/kg Air, would be particularly preferable input air source for the invention due to the low amount of water that must be separated before capturing CO.sub.2.
[0106] Adsorbents that co-adsorb both water and CO.sub.2 or preferentially adsorb CO.sub.2 also have similar synergisms with cold conditions as mentioned above. Separations are more favorable in cold conditions, the adsorbents perform better in the cold conditions, and they adsorb less water in comparison to CO.sub.2 in cold conditions. These three synergisms increase the performance of these adsorbents except that the air does not need to be dried before entering into the method. If appropriately cold and/or dried air is utilized in the invention, the air does not need to be dried before entering the method for the adsorption step (2 or 6), pressurization step (5 or 9), or waterbed regeneration step (17).
Example of CO.SUB.2 .Capture Using the Invention
[0107] The embodiment exemplified by
[0108] NaX, a low Si/Al ratio faujasite structured zeolite with Na+ as a cation, was used as the adsorbent in the CO.sub.2 adsorbent bed (10). Modelling used the following properties of NaX, obtained either from NaX analysis or otherwise accepted values: C.sub.ps,0 of 800 J/kg K, k.sub.s of 0.147 W/m K, r.sub.pore of 0.0000001 cm, of 5, .sub.S of 1826 kg/m.sup.3, .sub.pellet of 0.38, .sub.P of 1132 kg/m.sup.3, .sub.bed of 0.38, .sub.B of 778 kg/m.sup.3, and average H.sub.ads of 45 kJ/mol.
[0109] Silica gel was selected as the desiccant for use in the water capture bed (13), modelled using the following properties (as measured or taken from accepted values): C.sub.ps,0 of 870 J/kg K, k.sub.s of 0.151 W/m K, .sub.S of 1240 kg/m.sup.3, .sub.sorbent of 0.348, .sub.B of 720 kg/m.sup.3, and H.sub.ads of 2980 kJ/kg.
[0110] This example assumes no solids or other contaminant that would affect the adsorbent are entering the method. Dry air from a parallel method is used in the pressurization step (9) of the TVSA cycle as well as for the waterbed regeneration step (17), and therefore, no water guard (14) is required for the exemplified method.
[0111] To model the interaction between the ambient air and the adsorbent during the adsorption step (6) of the method, the Rosen model and TD-Toth model were used and were validated experimentally. These experiments allowed for the quantification of the capture fractions and adsorption capacities at 95% inlet concentration within the model.
[0112] From the results of the Rosen Model,
[0113] This synergism can be seen from
[0114] This fast uptake rate can be seen in
[0115] The energy required to capture 1 ton of CO.sub.2 using the TVSA cycle from
[0116] The additional energy required to desiccate the air (E_W) to capture 1 ton of CO.sub.2 using the TVSA cycle from
[0117] To show the benefit of cold and dry conditions for
[0118] The map from
[0119] These locations provide examples to highlight the beneficial properties of the invention when operated using a cold input air source. To the extent an air source can be obtained in a cool state as a by-product from another operation (and not cooled specifically for CO.sub.2 capture), these beneficial properties could be similarly achieved.
[0120] Similarly, given the input variables of temperature and humidity are relevant to efficiency, areas such as the Atacama Desert, the Tibetan Plateau, and the Gobi Desert, which are known for being some of the driest places on the planet, would equally allow for beneficial implementation of the invention. Due to very low humidity in these locations, this method would be expected to require less than 6 MWh/ton CO.sub.2 of energy to operate.
[0121] Combining this method along with an inexpensive renewable energy source would allow for this method to be a viable solution for global warming because it would reduce the amount of CO.sub.2, a known greenhouse gas, within the atmosphere. Using wind power from a location such as Antarctica, known to be the windiest location on Earth, would allow for a cheap renewable energy source to run this method, further reducing the cost per ton of CO.sub.2 captured via this method. Assuming that wind energy can be produced at $6/MWh, which is the least expensive wind PPA in 2018 in the USA, operating costs to run this method can be as low as $6/ton CO.sub.2 which is significantly lower than DOE targets for CO.sub.2 capture and sequestration.
[0122] All references and publication referred to herein are hereby incorporated by reference in their entirety.
[0123] While I believe that the theories that I have presented give benefits to this method, I do not wish to be bound by any particular theory relating to how the invention works, nor should any calculation be taken as exactly true in all circumstances.
[0124] Certain currently preferred embodiments have been described by way of example. It will be apparent to persons skilled in the art that a number of variations and modifications can be made without departing from the scope of the claims.