The present disclosure relates to a sorbent polymer composite article, methods of forming a sorbent polymer composite article, and methods of using a sorbent polymer composite article for the purpose of adsorption, including adsorption for direct air capture (DAC) of carbon dioxide.
Increasing carbon dioxide (CO2) levels associated with greenhouse gas emission are shown to be harmful to the environment. As reported by the Climate.gov article “Climate Change: Atmospheric Carbon Dioxide,” the 2019 average CO2 level in the atmosphere was 409.8 ppm, the highest level that has been noted in the past 800,000 years. The rate of increase of CO2 in the atmosphere is also much higher than the rates in previous decades.
In order to limit climate change to acceptable levels, it is not only necessary to reduce CO2 emissions in the near future to zero but also to achieve negative CO2 emissions. Several possibilities exist in order to achieve negative emissions, e.g. combustion of biomaterials for the generation of electricity combined with CO2 capture from the combustion flue gas and subsequent CO2 sequestration (“BECCS”) or direct air capture of CO2 (“DAC”).
Gas separation by adsorption has many different applications in industry, for example removing a specific component from a gas stream, where the desired product can either be the component removed from the stream, the remaining depleted stream, or both. Thereby, both trace components as well as major components of the gas stream can be targeted by the adsorption process. One important gas separation application is in capturing CO2 from gas streams, e.g., from flue gases, exhaust gases, industrial waste gases, biogas or atmospheric air. Atmospheric air is considered a dilute feed stream of CO2.
Capturing CO2 directly from the atmosphere, referred to as DAC, is one of several means of mitigating anthropogenic greenhouse gas emissions and has attractive economic perspectives as a non-fossil, location-independent CO2 source for the commodity market and for the production of synthetic fuels. The specific advantages of CO2 capture from the atmosphere include: a) DAC can address the emissions of distributed sources (e.g. vehicles . . . land, sea and air), which account for a large portion of the worldwide greenhouse gas emissions and can currently not be captured at the site of emission in an economically feasible way; b) DAC can address legacy emissions and can therefore create truly negative emissions, and c) DAC systems do not need to be attached to the source of emission but may be location independent and can be located at the site of further CO2 processing or usage.
There is increasing motivation to develop and improve upon these processes to make them more efficient, maximizing the amount of CO2 removed from the atmosphere while minimizing the energy required in the process.
There are established articles and techniques for DAC. An example is using an article including a substrate such as a monolith that can support or be coated with a sorbent material. Variations are established by changing the type of substrate and the sorbent that is used. However, these previously established articles and methods present limitations in the ability to efficiently cycle between adsorbing and desorbing states. They also have limitations with respect to the durability of the article. The articles may also degrade when exposed to high temperatures or high moisture level environments, or combinations thereof, which can result in a shorter lifetime.
A sorbent polymer composite article is disclosed for adsorption. The sorbent polymer composite article includes a sorbent and a flexible porous polymer, the sorbent polymer composite article having an adsorptive configuration in which the sorbent polymer composite article is configured to adsorb one or more components from an input, and a desorptive configuration in which the sorbent polymer composite article is configured to remove the one or more components from the sorbent polymer composite article.
According to one example (“Example A”), a sorbent polymer composite article includes a composite of a sorbent and a flexible porous polymer having a flexibility and the sorbent polymer composite article has an adsorptive configuration in which the sorbent polymer composite article is configured to adsorb one or more components of a feed stream and a desorptive configuration in which the sorbent polymer composite article is configured to remove the one or more components from the sorbent polymer composite article. The flexibility of the flexible porous polymer facilitates a transfiguration between the adsorptive configuration and the desorptive configuration.
According to a second example (“Example B”), a method of using a sorbent polymer composite article includes the steps of providing the sorbent polymer composite article having a porous composite portion including a sorbent and a flexible porous polymer, exposing the sorbent polymer composite article in a first configuration to a feed stream containing carbon dioxide, adsorbing at least a portion of the carbon dioxide onto the sorbent while the sorbent polymer composite article is in the first configuration, positioning the sorbent polymer composite article into a second configuration after the adsorbing step, and desorbing the carbon dioxide from the sorbent polymer composite article while the sorbent polymer composite article is in the second configuration.
This disclosure is not meant to be read in a restrictive manner. For example, the terminology used in the application should be read broadly in the context of the meaning those in the field would attribute such terminology.
With respect to terminology of inexactitude, the terms “about” and “approximately” may be used, interchangeably, to refer to a measurement that includes the stated measurement and that also includes any measurements that are reasonably close to the stated measurement. Measurements that are reasonably close to the stated measurement deviate from the stated measurement by a reasonably small amount as understood and readily ascertained by individuals having ordinary skill in the relevant arts. Such deviations may be attributable to measurement error, differences in measurement and/or manufacturing equipment calibration, human error in reading and/or setting measurements, minor adjustments made to optimize performance and/or structural parameters in view of differences in measurements associated with other components, particular implementation scenarios, imprecise adjustment and/or manipulation of objects by a person or machine, and/or the like, for example. In the event it is determined that individuals having ordinary skill in the relevant arts would not readily ascertain values for such reasonably small differences, the terms “about” and “approximately” can be understood to mean plus or minus 10% of the stated value.
The term “fibril” as used herein describes an elongated piece of material such as a polymer, where the length and width are substantially different from each other. For example, a fibril may resemble a piece of string or fiber, where the width (or thickness) is much shorter or smaller than the length.
The term “node” as used herein describes a connection point of at least two fibrils, where the connection may be defined as a location where the two fibrils come into contact with each other, permanently or temporarily. In some examples, a node may also be used to describe a larger volume of polymer than a fibril and where a fibril originates or terminates with no clear continuation of the same fibril through the node. In some examples, a node has a greater width but a smaller length than the fibril.
As used herein, “nodes” and “fibrils” may be used to describe objects that are usually, but not necessarily, connected or interconnected, and have a microscopic size, for example. A “microscopic” object may be defined as an object with at least one dimension (width, length, or height) that is substantially small such that the object or the detail of the object is not visible to the naked eye or difficult, if not impossible, to observe without the aid of a microscope (including but not limited to a scanning electron microscope or SEM, for example) or any suitable type of magnification device.
The present disclosure relates to a sorbent polymer composite article, methods of forming a sorbent polymer composite article, and methods of using a sorbent polymer composite article to adsorb and separate one or more desired substances from a source stream. While the sorbent polymer composite article is described below for use in DAC of CO2 from a dilute feed stream, such as air, it may also be used in other adsorbent methods and applications. These methods include, but are not limited to, adsorption of substances from various inputs, including other gas feed streams (e.g., combustion exhaust) and liquid feed streams (e.g., ocean water). The adsorbed substance is not limited to CO2. Other adsorbed substances may include, but are not limited to, other gas molecules (e.g., N2, CH4, and CO), liquid molecules, and solutes. In certain embodiments, the input may be dilute, containing on the order of parts per million (ppm) of the adsorbed substance.
The first porous polymer 22 of the first composite region 28 may be one of expanded polytetrafluoroethylene (ePTFE), expanded polyethylene (ePE), polytetrafluoroethylene (PTFE), or another suitable porous polymer. It will be appreciated that non-woven materials such as nanospun, meltblown, spunbond and porous cast films could be among the various other suitable porous polymer forms. The first porous polymer 22 may be expanded by stretching the polymer at a controlled temperature and a controlled stretch rate, causing the polymer to fibrillate. Following expansion, the first porous polymer 22 may comprise a microstructure of a plurality of nodes 30 and a plurality of fibrils 34 that connect adjacent nodes 30. In these instances, the first porous polymer 22 includes pores 32 bordered by the fibrils 34 and the nodes 30. An exemplary node and fibril microstructure is described in U.S. Pat. No. 3,953,566 to Gore, incorporated herein by reference in its entirety. The pores 32 of the first porous polymer 22 may be considered micropores. Such micropores may have a single pore size or a distribution of pore sizes. The average pores size may range from 0.1 microns to 100 microns in certain embodiments.
The sorbent material 24, 24′ of the first composite region 28 is a substrate having a surface configured to hold the desired substance from the input on the solid surface via adsorption. The sorbent material 24, 24′ varies based on which substances are targeted for adsorption. In various embodiments, the sorbent material 24, 24′ is a carbon dioxide adsorbing material which may include, but is not limited to, an ion exchange resin (e.g., a strongly basic anion exchange resin such as Dowex™ Marathon™ A resin available from Dow Chemical Company), zeolite, activated carbon, alumina, metal-organic frameworks, polyethyleneimine (PEI), or another suitable carbon dioxide adsorbing material, such as desiccant, carbon molecular sieve, carbon adsorbent, graphite, activated alumina, molecular sieve, aluminophosphate, silicoaluminophosphate, zeolite adsorbent, ion exchanged zeolite, hydrophilic zeolite, hydrophobic zeolite, modified zeolite, natural zeolites, faujasite, clinoptilolite, mordenite, metal-exchanged silico-aluminophosphate, uni-polar resin, bi-polar resin, aromatic cross-linked polystyrenic matrix, brominated aromatic matrix, methacrylic ester copolymer, graphitic adsorbent, carbon fiber, carbon nanotube, nano-materials, metal salt adsorbent, perchlorate, oxalate, alkaline earth metal particle, ETS, CTS, metal oxide, chemisorbent, amine, organo-metallic reactant, hydrotalcite, silicalite, zeolitic imadazolate framework and metal organic framework (MOF) adsorbent compounds, and combinations thereof.
The sorbent material 24, 24′ may be present in the first porous polymer 22 as a coating, a filling, entrained particles, and/or in another suitable form, as described further below. In the illustrated embodiment of
The optional carrier 26 of the first composite region 28 is a material that is configured to increase the surface area of the region it occupies which may allow for an increased surface area that is available for adsorption of the desired substance. The carrier 26 may include a mesoporous silica, polystyrene beads, porous polymeric bed or sphere, oxide supports, another suitable carrier material. The carrier 26 may further include porous film comprising porous inorganic materials within it such as calcium sulfate, alumina, activated charcoal and fumed silica. As noted above, the carrier 26 may be present in the pores 32 of the first composite region 28 as high surface area particles that are coated or functionalized with the sorbent material 24′. The combination of the carrier 26 coated with the sorbent material 24′ increases the surface area available for adsorption. In these embodiments, the nodes 30 and fibrils 34 may or may not be coated with sorbent material 24. When the nodes 30 and fibrils 34 are not coated, the original hydrophobicity of the first porous polymer 22 may be retained.
The first composite region 28 of the sorbent polymer composite article 20 includes a first side 72 (e.g., an upper side in
The first composite region 28, the second region 36, and the third region 38 of the sorbent polymer composite article 20 may be formed using different processes. In certain embodiments, the first composite region 28, the second region 36, and/or the third region 38 may be formed as discrete layers and then coupled together. In this case, the first porous polymer 22 of the first composite region 28, the second porous polymer 40 of the second region 36, and/or the third porous polymer 48 of the third region 38 may be distinct structures. In other embodiments, the first composite region 28, the second region 36, and/or the third region 38 may be formed together and then subjected to different coating processes or surface treatments, as described further below, to differentiate certain regions. In this case, the first porous polymer 22 of the first composite region 28, the second porous polymer 40 of the second region 36, and/or the third porous polymer 48 of the third region 38 may be continuous or integrated structures.
The first composite region 28, the second region 36, and the third region 38 of the sorbent polymer composite article 20 may have differing degrees of hydrophobicity. The hydrophobicity may be altered through various methods, such as through applying coatings or surface treatments which can include, but are not limited to, plasma etching and applying micro-topographical features. The first composite region 28 has a first hydrophobicity, the second region 36 may have a second hydrophobicity, and the third region 38 may have a third hydrophobicity. The first hydrophobicity is less than that of each the second hydrophobicity and the third hydrophobicity. The second hydrophobicity may be less than, greater than, or equal to the third hydrophobicity. The greater hydrophobicity of the second region 36 and the third region 38 may reduce the permeation of liquid water through the respective regions 36, 38, thus forming a barrier between any liquid water in the surroundings and the components of the first composite region 28. This reduces degradation of the sorbent material 24, 24′ within the first composite region 28 that liquid water could cause, increasing the lifetime and durability of the sorbent polymer composite article 20. The greater hydrophobicity of the second region 36 and the greater hydrophobicity of the third region 38 relative to the first hydrophobicity of the first composite region 28 may result from the lack of sorbent material 24, 24′ within the second and third regions 36, 38.
In some embodiments, the first composite region 28 is sealed with a coating (not shown). In certain instances, the coating is configured to be a carbon adsorbing material similar to the above-described sorbent materials 24, 24′.
The second porous polymer 40 of the second region 36 and the third porous polymer 48 of the third region 38 may be at least one of polytetrafluoroethylene (PTFE), expanded polytetrafluoroethylene (ePTFE), expanded polyethylene (ePE), or other suitable porous polymers. The second porous polymer 40 of the second region 36 may be identical to or different from the third porous polymer 48 of the third region 38. Further, the first porous polymer 22 of the first composite region 28, the second porous polymer 40 of the second region 36, and the third porous polymer 48 of the third region 38 may be identical to or different from each other.
In various embodiments, the thickness of the second region 36 is less than that of the first composite region 28, and the thickness of the third region 38 is less than that of the first composite region 28. The overall thickness of the sorbent polymer composite article 20 may be about 0.1 mm to about 5.0 mm. In certain embodiments, the thickness of the first composite region 28 may account for a majority of the overall thickness, such as about 70%, about 80%, about 90%, or more of the overall thickness.
The pore characteristics of the porous polymers 22, 40, 48 of each of the respective first composite region 28, the second region 36, and the third region 38 are variable. In certain embodiments, the second and third regions 36, 38 may have fewer and/or smaller pores 44, 54, than the first composite region 28 to selectively limit permeation of undesired contaminants (e.g., water) into the first composite region 28 while permitting permeation of desired molecules (e.g., CO2) into the first composite region 28. By contrast, the first composite region 28 may have more and/or larger pores 32 than the second and third regions 36, 38 to encourage movement of CO2 through the first composite region 28 for adsorption and desorption.
Further, the pore characteristics can be varied among different embodiments. This variation of the pore characteristics can be dependent on the entire thickness of the sorbent polymer composite article 20, as well as of the individual thicknesses of the first composite region 28, second region 36 and third region 38.
Referring back to
Further, the ability to vary the hydrophobicity, thickness, pore characteristics, and other properties of the first composite region 28, the second region 36, and the third region 38 may increase durability and conformability of the sorbent polymer composite article 20. Further, the use of a relatively thin and flexible sorbent polymer composite article 20 may allow the sorbent polymer composite article 20 to conform to different configurations for adsorption and desorption of the CO2.
In the illustrated embodiment of
At block 102, the method 100 first includes providing the sorbent polymer composite article 20 having a porous composite portion 62. In certain embodiments, the porous composite portion 62 includes the first composite layer 28 having the sorbent material 24, 24′ and the first porous polymer 22, the second layer 36, and the third layer 38 as shown and described above with respect to
At block 104, the method 100 includes exposing the sorbent polymer composite article 20 in a first, adsorptive configuration to a feed stream 60. The sorbent polymer composite article 20 may have a substantially laminar form in the first configuration, examples of which are shown in
At block 106, the method 100 includes adsorbing the CO2 onto the sorbent material 24, 24′ (
At block 108, the method 100 includes positioning the sorbent polymer composite article 20 in a second, desorptive configuration after adsorbing CO2 onto the sorbent polymer composite article 20 in the prior block 106. In certain instances, this positioning step of block 108 occurs after or before the adsorption capacity has been reached. The sorbent polymer composite article 20 may have a substantially rolled or spooled cylindrical form in the second configuration, with the porous portion 62 being rolled onto a porous drum 72 and the non-porous portion 64 being rolled onto the porous portion 62. As such, the inner, porous portion 62 may be concealed by the outer, non-porous portion 64 according to some examples. The non-porous portion allows vacuum to be applied within the porous drum 72. Applying a vacuum or negative pressure is a standard way of drawing off desorbed CO2. In some examples, the porous portion 62 may be temporarily covered by the outer, non-porous portion 64, which may comprise one or more layers of non-porous material. In some examples, the porous portion 62 may be physically isolated, insulated, or protected from an external environment by the outer, non-porous portion 64.
At block 110, the method 100 includes desorbing the CO2 while the sorbent polymer composite article 20 is in the second configuration by exposing the sorbent polymer composite article 20 to a desorption source 80 (e.g., water, water vapor, and/or heat). In the illustrated embodiments of
The formation of water droplets may inhibit both adsorption from the feed stream 60 during the adsorbing step of block 106 and desorption of the CO2 that occurs during the desorbing step of block 110. The feed stream 60 may contain sufficient water vapor for droplets to form on the sorbent polymer composite article 20 that impedes the adsorption of CO2. Similarly, liquid droplets may condense on the sorbent polymer composite article 20 during desorption. In these circumstances, shaking, vibrating, oscillating, or otherwise moving the sorbent polymer composite article 20 may remove the liquid droplets from the sorbent polymer composite article 20. These techniques may improve the adsorption and desorption efficiency, respectively. This movability demonstrates a further benefit of the sorbent polymer composite article 20 in its flexibility. Various means of imparting motion to remove droplets will be known by those of skill in the art and may include physically vibrating the sorbent polymer composite article 20, shaking the structure 70, applying pulsed air, and/or oscillating the structure 70 through sound or magnetic variations, for example. This step of shaking or vibrating the sorbent polymer composite article 20 may occur simultaneously, before, and/or after, the exposing step of block 104, the adsorbing step of block 106, the positioning step of block 108, and the desorbing step of block 110.
In certain instances, the method 100 further includes collecting the CO2 that was extracted. This collection process may be performed using a vacuum to collect the released CO2.
Another embodiment of the method 100 of
In the illustrated embodiment of
As shown in
Another embodiment of the method 100 of
In this embodiment, the first configuration corresponding to the exposing step of block 104 (
In certain embodiments, the sorbent polymer composite article 20″ may comprise regions that contain the sorbent material 24 (e.g., filled regions) and regions that lack the sorbent material 24 (e.g., un-filled regions). The regions that lack the sorbent material 24 may be more conformable than those that contain the sorbent material 24. This ability to control the conformability of the sorbent polymer composite article 20″ may also allow for controlled positioning of the hinge points 91. Substances, such as silicone, may be entrained in the regions of the sorbent polymer composite article 20 that lack the sorbent material 24 to increase durability. The flexibility of the sorbent composite article 20 facilitates the translation between first and second configurations without the need for mechanical hinges and additional components, which would increase cost and decrease life span and durability.
Further, the desorbing step of block 110 (
Further benefits of a flexible sorbent polymer composite result from the capabilities of volume reduction (folding, rolling, spooling, etc). Minimizing the volume of an air contactor or module will allow reductions in storage space at the CO2 capture site, inventory space at the manufacturing site and shipping and packaging costs. These benefits although listed, are not intended to be limiting. To explain further, the volume reducing benefits may be broad, such as in reduction of workers needed to replace the sorbent polymer composite of the present invention. For instance, in the deployed or adsorbtion configuration, the sorbent polymer composite may be bulky and require a team of technicians to handle and replace it whereas the folded or spooled sorbent polymer composite of the present invention may only require one technician to perform the same tasks that once took multiple technicians.
Various modifications and additions can be made to the exemplary embodiments discussed without departing from the scope of the present disclosure. For example, while the embodiments described above refer to particular features, the scope of this disclosure also includes embodiments having different combinations of features and embodiments that do not include all of the described features. Accordingly, the scope of the present disclosure is intended to embrace all such alternatives, modifications, and variations as fall within the scope of the claims, together with all equivalents thereof.
This application is a national phase application of PCT Application No. PCT/US2022/019104, internationally filed on Mar. 7, 2022, which claims priority to U.S. Provisional Application No. 63/157,451, filed on Mar. 5, 2021, and U.S. Provisional Application No. 63/302,852, filed on Jan. 25, 2022, the disclosure of each application being hereby incorporated herein by reference in its entirety.
Filing Document | Filing Date | Country | Kind |
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PCT/US2022/019104 | 3/7/2022 | WO |
Number | Date | Country | |
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63302852 | Jan 2022 | US | |
63157451 | Mar 2021 | US |