Extruded structural bodies comprising metal organic frameworks for carbon capture

Abstract

In one aspect, monolithic structural bodies formed of extruded carbon dioxide (CO2) sorbent materials are described herein. Additionally, extrusion batch compositions and associated methods of forming such monolithic bodies are also described herein. In some embodiments, an extrusion batch for a monolithic structural gas treatment body comprises a particulate polymeric phase, and a particulate carbon dioxide (CO2) sorbent comprising at least one metal organic framework (MOF), the particulate polymeric phase and the particulate CO2 sorbent being disposed in an aqueous or aqueous-based continuous phase, wherein the extrusion batch has a plasticity of 0.06 to 1.3 kgf.

Description

[0001] EXTRUDED STRUCTURAL BODIES COMPRISING METAL ORGANIC FRAMEWORKS FOR CARBON CAPTURE

[0002] RELATED APPLICATION DATA

[0003] The present application claims priority pursuant to Article 8 of the Patent Cooperation Treaty to United States Patent Application Serial Number 63 / 681,333 filed August 9, 2024 which is incorporated herein by reference.

[0004] FIELD

[0005] The present application relates to monolithic structural bodies for gas treatment applications and, in particular, to extruded structural bodies employing metal organic framework sorbent materials for carbon dioxide capture.

[0006] BACKGROUND

[0007] Global warming and associated climate change induced by human activities presents an existential threat to numerous ecosystems and the way of human life as it is currently understood. The mining and burning of fossil fuels are chief contributors global warming via the massive release of heat trapping gases, including methane and carbon dioxide. Carbon dioxide accounts for the bulk of greenhouse gas emissions, as the concentration of carbon dioxide has eclipsed the 400 ppm mark in recent years. Current carbon dioxide levels exceed any concentration in the last 800,000 years.

[0008] In view of this alarming trend in atmospheric carbon dioxide concentration, countries and industry have initiated various mitigation strategies to reduce carbon dioxide emissions, as well as methane emissions. Electrification of vehicles and transportation systems has drawn considerable attention. Moreover, the transition to green / renewable sources of energy, including wind and solar, has received significant private and public investment. While promising, these mitigation strategies fail to address carbon dioxide that is currently in the atmosphere and the ongoing need for fossil fuel consumption as a source of energy as the global economy transitions to a carbon neutral state. Accordingly, current carbon dioxide levels are left to slow, natural degradation processes. Carbon capture from fossil fuel combustion and from the air is essential to achieve a carbon neutral state. SUMMARY

[0009] In one aspect, monolithic structural bodies formed of extruded carbon dioxide (CO2) sorbent materials are described herein. Additionally, extrusion batch compositions and associated methods of forming such monolithic bodies are also described herein. In some embodiments, an extrusion batch for a monolithic structural gas treatment body comprises a particulate polymeric phase, and a particulate carbon dioxide (CO2) sorbent comprising at least one metal organic framework (MOF), the particulate polymeric phase and the particulate CO2 sorbent being disposed in an aqueous or aqueous-based continuous phase, wherein the extrusion batch has a plasticity of 0.06 to 1.3 kgf.

[0010] Extruded monolithic structural gas treatment bodies are also provided herein. In some embodiments, an extruded monolithic structural gas treatment body comprises a plurality of inner partition walls formed of an extruded batch composition, the batch composition including a polymeric binder phase, and a particulate carbon dioxide (CO2) sorbent associated with the polymeric binder phase, the particulate carbon dioxide CO2 sorbent comprising at least one metal organic framework, wherein the inner partition walls define flow channels through the extruded monolithic structural gas treatment body, and the extruded monolithic structural gas treatment body has a hierarchical pore structure including macroporosity and microporosity. Microporosity of the monolithic structural gas treatment body, in some embodiments, has a volume of 0.01-0.5 cm3 / g in pores of diameter ranging from 0.1-2 nm. Moreover, macroporosity of the monolithic structural gas treatment body can have a volume of 0.05-1.5 cm3 / g in pores of diameter ranging from 100 nm to 10pm.

[0011] In another aspect, methods of making monolithic structural bodies for CO2 adsorption are described herein. A method, in some embodiments, comprises providing an extrusion batch including a particulate polymeric phase, and a particulate CO2 sorbent comprising at least one metal organic framework, the particulate polymer phase and the particulate CO2 sorbent being disposed in an aqueous or aqueous-based continuous phase, wherein the extrusion batch has a plasticity of 0.06 to 1.3 kgf. The extrusion batch is extruded into a monolithic structural gas treatment body comprising a plurality of inner partition walls formed from the extrusion batch wherein the particulate CO2 sorbent is associated with the polymeric binder, and the inner partition walls defining flow channels through the monolithic structural body. The resultant extruded monolithic structural body can have any composition and / or properties described herein.

[0012] In another aspect, methods of capturing CO2 from a gas stream are provided. A method, in some embodiments, comprises providing an extruded monolithic structural gas treatment body including a plurality of inner partition walls formed of an extruded batch composition, the batch composition including a polymeric binder phase, and a particulate CO2 sorbent associated with a polymeric binder phase, the particulate carbon dioxide CO2 sorbent comprising at least one metal organic framework, wherein the inner partition walls define flow channels through the extruded monolithic structural gas treatment body, and the extruded monolithic structural gas treatment body has a hierarchical pore structure including macroporosity and microporosity. A gas stream is flowed through the flow channels, and CO2 is captured from the gas stream with the particulate metal organic framework sorbent. The captured CO2 can be subsequently desorbed from the monolithic structural gas treatment body for downstream processing, including storage or sequestration. The extruded monolithic structural body can have any composition and / or properties described herein.

[0013] These and other embodiments are further described in the following detailed description.

[0014] BRIEF DESCRIPTION OF THE DRAWINGS

[0015] FIG. 1 illustrates a honeycomb-like monolithic structural gas treatment body according to some embodiments herein.

[0016] FIG. 2 illustrates flow channels defined by the inner partition walls in a honeycomb -like monolithic structural gas treatment body according to some embodiments herein.

[0017] FIG. 3 illustrates a method of determining the average thickness of the outer peripheral wall and inner partition wails of a monolithic structural gas treatment body.

[0018] DETAILED DESCRIPTION

[0019] Embodiments described herein can be understood more readily by reference to the following detailed description and examples and their previous and following descriptions. Elements, apparatus and methods described herein, however, are not limited to the specific embodiments presented in the detailed description and examples. It should be recognized that these embodiments are merely illustrative of the principles of the present invention. Numerous modifications and adaptations will be readily apparent to those of skill in the art without departing from the spirit and scope of the invention.

[0020] I. Extrusion Batch Compositions

[0021] Extrusion batch compositions are described herein for the production of monolithic structural gas treatment bodies (adsorbers) formed of extruded particulate metal organic framework CO2 sorbent. In some embodiments, an extrusion batch for a monolithic adsorber comprises a particulate polymeric phase, and a particulate carbon dioxide (CO2) sorbent comprising at least one metal organic framework (MOF), the particulate polymeric phase and the particulate CO2 sorbent being disposed in an aqueous or aqueous-based continuous phase, wherein the extrusion batch has a plasticity of 0.06 to 1.3 kgf. In some embodiments, the particulate metal organic framework sorbent has a DIO particle size of 0.5 pm to 2 pm, and a D90 particle size of 7 pm to 10 pm. The particulate metal organic framework sorbent can be milled to achieve the foregoing particle sizes, in some embodiments.

[0022] Moreover, the particulate metal organic framework sorbent can be present in the extrusion batch in any amount consistent with the technical objectives described herein. For example, the metal organic framework sorbent is present in an amount of 15-70 weight percent or 30-50 weight percent of the extrusion batch. The particulate CO2 sorbent can comprise any metal organic framework species consistent with the technical objectives described herein. In some embodiments, the metal organic framework employed as the particulate CO2 sorbent comprises layers of aryl-bridged metal atoms or heterocyclic-bridged metal atoms. The metal atoms can comprise one or more transition metals. Suitable transition metals, in some embodiments, are selected from Groups 8-12 of the Periodic Table. For example, the metal organic framework can comprise zinc or copper, in some embodiments. Additionally, layers of heterocyclic-bridged metal atoms can comprise one or more azole species as the heterocycle.

[0023] The layers of aryl-bridged metal atoms or heterocycle-bridged metal atoms of the metal organic framework can be pillared by ionic ligands. In some embodiments, the ionic ligands are dianionic. For example, the pillared ionic ligands can be terminated in COO' functionalities. In some embodiments, the dianionic ligands are oxalate or oxalate derivatives. Oxalate derivatives, in some embodiments, include squarate (Squ), fumarate (Fum), benzenedicarboxylate (Bsc), thieno[3,2- / >]thiophene-2,5-dicarboxylate (Ttdc), and cub aedi carb oxy late (Cub). In some embodiments, the metal organic framework employed as the particulate CO2 sorbent comprises CALF -20 and / or derivatives thereof.

[0024] As described herein, extrusion batch compositions also comprise a particulate polymeric phase disposed in the aqueous or aqueous-based continuous phase with the metal organic framework sorbent. In some embodiments, the particulate polymeric phase has a DIO particle size of 0.01 pm to 5 pm, and a D90 particle size of 0.1 pm to 20 pm or 10-60 pm. In some embodiments, the particulate polymeric phase of the extrusion batch composition has a D10 particle size selected from Table 1 and / or a D90 particle size selected from Table 2.

[0025] Table 1 - D10 particle size (pm)

[0026] Depending specific identity, the particulate polymeric phase of the aqueous-based extrusion batch composition can be provided as a powder or as an aqueous dispersion or emulsion.

[0027] The particulate polymeric phase can comprise any polymeric species consistent with the technical objectives described herein. In some embodiments, the particulate polymeric phase comprises one or more of olefin-acetate copolymer, aryl-acrylate copolymer, alkyl-acrylate copolymer, polyalkyl-siloxane, polybutadiene, or aryl-diene copolymer.

[0028] The particulate polymeric phase can comprise a single species of polymer or at least two differing particulate polymeric species. The two differing polymeric species can be thermoplastics. In some embodiments, the particulate polymeric phase comprises a first particulate polymeric species of olefin-acetate copolymer or aryl-acrylate copolymer and a second particulate polymeric species comprising heterocyclic monomeric units. The heterocycle monomeric units can include acetal monomeric units. In some embodiments, the first or second polymeric phase can comprise an elastomeric species. For example, the first polymeric phase can be a thermoplastic recited herein, and the second polymeric phase can comprise and elastomer recited herein. The first and second polymeric species can be present in any desired ratio. In some embodiments, the ratio of the first particulate polymeric species to the second particulate polymeric species ranges from 2:1 to 1 :2. Additionally, the particulate polymeric phase can be present in an amount of 2-20 weight percent of the extrusion batch composition, in some embodiments.

[0029] Additionally, in some embodiments, the extrusion batch composition can comprise an extrusion aid component. The extrusion aid component can comprise one or more species facilitating or aiding the extrusion process. In some embodiments, the extrusion aid component comprises one or more polyalkylene-glycols, fatty acids, or mixtures thereof. The extrusion aid component can be present in an amount of 1-15 weight percent or 5-10 weight percent of the extrusion batch composition. In some embodiments, the extrusion aid component is soluble in water or aqueous-based solvent and can be washed from the extruded monolith. Washing the extrusion aid component can assist in developing pore structure of the extruded monolith, in some embodiments.

[0030] Extrusion batch compositions described herein can optionally include one or more reinforcement agents. Reinforcement agents can include reinforcing fibers, including glass (SiCh) fibers, carbide fibers, ceramic fibers, polymeric fibers, and mixtures thereof. In some embodiments, reinforcing fibers have a diameter of 0.1 pm to 30 pm and / or length up to 10 mm. Reinforcement agent can be present in an amount of 0.5-10 weight percent of the extrusion batch composition, in some embodiments.

[0031] As described herein, the extrusion batch composition has a plasticity of 0.06 to 1.3 kgf. To measure plasticity of an extrusion batch composition described herein, a representative sample of the extrusion batch composition is removed from the mixer and pressed into a steel cup. A piston is inserted into the top of the cup and pressed with a hydraulic press to a pressure of 300 psi + / -10 psi for 3 minutes. When compaction is complete, the piston is removed and the pressed sample of the extrusion batch is aligned under the test unit. The compression test unit (MTS Criterion C42) is setup with a needle that is 47mm in length with a round tip that is 2.01mm +.01 -0.03. The needle is pressed into the extrusion batch at a fixed rate and forced through the material at a fixed rate of 0.635 mm / s. The resultant force (kgf) is recorded and the test software determines the stable pressure required for the needle to pass through the sample. Once complete, the needle is extracted, cleaned and the cup is rotated to a position at least 4 mm away from the original insertion point and the test is repeated. This process occurs for a total of 5 tests - a successful test is accepted if the relative standard deviation of the tests is less than 0.5 kgf.

[0032] II. Extruded Monolithic Structural Gas Treatment Bodies (Adsorbers)

[0033] Extruded monolithic structural gas treatment bodies operable for the capture of CO2 from gas streams are also described herein. In some embodiments, an extruded monolithic structural gas treatment body comprises a plurality of inner partition walls formed of an extruded batch composition, the batch composition including a polymeric binder phase, and a particulate carbon dioxide (CO2) sorbent associated with the polymeric binder phase, the particulate carbon dioxide CO2 sorbent comprising at least one metal organic framework, wherein the inner partition walls define flow channels through the extruded monolithic structural gas treatment body, and the extruded monolithic structural gas treatment body has a hierarchical pore structure including macroporosity and microporosity.

[0034] Microporosity of the monolithic structural gas treatment body, in some embodiments, has a volume of 0.01-0.5 cm3 / g in pores of diameter ranging from 0.1-2 nm. Moreover, macroporosity of the monolithic structural gas treatment body can have a volume of 0.05-1.5 cm3 / g in pores of diameter ranging from 100 nm to 10pm. Further, in some embodiments, the hierarchical pore structure of the gas treatment body also comprises mesoporosity. In some embodiments, the monolithic structural gas treatment body exhibits a mesoporosity having a volume of 0.01-0.5 cm3 / g in pores of diameter ranging from great than 2 nm to 99.9 nm. Mesoporosity, in some embodiments, has a volume of 0.01-0.15 cm3 / g in pores of diameter ranging from great than 2 nm to 99.9 nm. Mesoporosity is in addition to the microporosity and macroporosity. In some embodiments, the sum of microporosity and mesoporosity of the hierarchical pore structure has a volume of 0.01-0.6 cm3 / g in pores of diameter ranging from 0.1 nm to 99.9 nm. In such embodiments, microporosity and mesoporosity are both present, each contributing to the summation. The hierarchical pore structure described herein can be dispersed throughout the outer peripheral wall and inner partition walls of the monolithic structural gas treatment body. Macroporosity is measured by mercury (Hg) porosimetry, while microporosity and mesoporosity are measured by nitrogen (N2) physisorption.

[0035] The inner partition walls are arranged inside the dimensions defined by the outer peripheral wall, and plurality of flow channels are defined by the inner partition walls, the flow channels extending longitudinally through the monolithic structural gas treatment body. FIG. 1 illustrates a honeycomb-like monolithic structural gas treatment body according to some embodiments herein. The extruded honeycomb-like structural gas treatment body in the embodiment of FIG. 1 comprises an outer peripheral wall 10 and a plurality of inner partition walls 11. The inner partition walls 11 define a plurality of flow channels 12 extending longitudinally through the honeycomb-like monolithic structural gas treatment body.

[0036] FIG. 2 illustrates flow channels 12 defined by the inner partition walls 11 in a honeycomb-like monolithic structural body according to some embodiments herein. The inner partition walls 11 and their junctures with the outer peripheral wall serve as boundaries for adjacent flow channels 12. When a portion of the outer peripheral wall 10 serves as a boundary for a flow channel 12, that portion may be referred to as an outer peripheral wall segment 13. As illustrated in FIGS. 1 and 2, the flow channels 12 establish a flow channel density or cell density over the inlet and outlet faces of the monolithic structural gas treatment body. An extruded monolithic structural gas treatment body described herein can have any desired cell density or flow channel density. As described above, the monolithic structural gas treatment body has a cell density of at least 50 cpsi. In some embodiments, the monolithic structural gas treatment body has a cell density of 75 cpsi to 900 cpsi. For example, the monolithic structural gas treatment body can have a cell density of 100 cpsi to 500 cpsi, 140 cpsi to 450 cpsi, or 170 cpsi to 500 cpsi. Additionally, length of the flow channels or cells, in some embodiments, is at least 100 mm or at least 110 mm. In some embodiments, length of the flow channels of cells of the monolithic structural has treatment body is at least 120 mm or at least 125 mm. The flow channels or cells can have any desired cross-sectional geometry, including various polygonal geometries such as triangular, square, or hexagonal.

[0037] The average inner partition wall thickness of an extruded monolithic structural gas treatment body described herein is 0.1 mm to 1.5 mm. In some embodiments, the average inner partition wall thickness can be 0.3 mm to 0.7 mm, or 0.4 mm to 0.6 mm. The thickness of the outer peripheral wall and inner partition walls are determined with a caliper or micrometer with a resolution of 0.01 mm. FIG. 3 illustrates a method of determining the average thickness of the outer peripheral wall 10 and inner partition walls 11. The thickness of the outer peripheral wall 10 is measured in twelve (12) different locations on the monolithic structural gas treatment body. The twelve measuring locations comprise three points on each side of the square outer peripheral wall as demonstrated in FIG. 3. The average thickness of the outer peripheral wall 10 is calculated by averaging the values obtained from the twelve (12) measurements. Similarly, the average thickness of the inner partition walls 11 is determined by initially measuring the thickness of the inner partition walls 11 at twelve (12) different locations throughout the structural body. The inner partition walls 11 are measured in the horizontal and vertical directions as displayed in FIG. 3. The average thickness of the inner partition walls 11 is calculated by averaging the values obtained in the twelve measurements.

[0038] Thin inner partition walls can assist in achieving high cpsi without sacrificing open frontal area of the monolithic structural gas treatment body and / or inducing undesirable pressure drop sustained by gas flow through the monolithic structural body. The open frontal area (OF A) of an extruded monolithic structural gas treatment body is that portion of the body cross-section available for gas flow on a cross-sectional surface normal to the direction of gas flow. An increased open frontal area can result in more efficient fluid flow characteristics within the monolithic body, which can decrease the pressure drop sustained by fluids passing through the monolithic structural gas treatment body. An extruded monolithic structural gas treatment body described herein, in some embodiments, has an OFA of at least 40 percent or at least 50 percent. In some embodiments, a monolithic structural gas treatment body has an OFA of at least 60 percent or at least 70 percent. OFA of an extruded monolithic structural gas treatment body can range from 40-90 percent, 65-90 percent, 65-85 percent, 70-90 percent, 70-80 percent, 75-85 percent, or 80-90 percent, in some embodiments.

[0039] An extruded monolithic structural gas treatment body described herein, in some embodiments, also has a hydraulic diameter of at least 60 mm or at least 100 mm. The hydraulic diameter of the extruded monolithic structural gas treatment body is defined as being equal to the cross-sectional area perpendicular to the direction of flow of the structural body multiplied by four and divided by the value of the outer perimeter of the outer peripheral wall. When the monolithic structural gas treatment body displays a circular cross-sectional geometry, the hydraulic diameter is equal to the diameter of the circular cross-sectional area. In the case of a square cross-sectional geometry, the hydraulic diameter is equal to the length or width of a side. Accordingly, the hydraulic diameter characterizes the size of the monolithic structural gas treatment body with larger values of hydraulic diameter corresponding to larger monolithic structural gas treatment bodies. In some embodiments, the monolithic structural gas treatment body has a hydraulic diameter of at least 100 mm, at least 120 mm, or at least 130 mm. The hydraulic diameter of the monolithic structural gas treatment body can range from 100 mm to 150 mm, from 120 mm to 150 mm, or from 130 mm to 150 mm. In some embodiments, hydraulic diameter of the monolithic structural gas treatment body can be greater than 150 mm. Hydraulic diameter of the monolithic structure gas treatment body can have an upper limit of 300 mm, in some embodiments.

[0040] Monolithic structural gas treatment bodies described herein, in some embodiments, can swell when exposed to water. In some embodiments, for example, the hydraulic diameter of the monolithic structural gas treatment body increases by 1-7 percent upon exposure to water. Increases in hydraulic diameter upon water exposure are determined according to the following protocol. A monolithic structural gas treatment body described herein is initially dried under vacuum at 65°C for two hours. The dried monolithic structural gas treatment body is subsequently immersed in water having a temperature of 80°C for two hours. Upon completion of the two hours, the monolithic structural gas treatment body is removed from the water, and the hydraulic diameter is measured upon removal from the water.

[0041] An extruded monolithic structural gas treatment body described herein can exhibit a dry crush strength of at least 0.4 kg / cm2. In some embodiments, the dry crush strength of an extruded monolithic structural gas treatment body is in the range of 0.4 to 15 kg / cm2. Moreover, an extruded monolithic structural has treatment body can exhibit a hot boil crush strength of at least 0.1 kg / cm2. In some embodiments, the hot boil crush strength of an extruded monolithic structural gas treatment body is in the range of 0.1 to 5 kg / cm2. Dry crush strength and hot boil crush strength values are determined according to the following protocol. Extruded monolithic structural adsorber is trimmed into a cube approximately 25x25x25mm in dimensions - ridges are removed via sandpaper after trimming. Samples are weighed and height, width and length measurements are collected with a caliper. Testing is conducted using a crush test machine (MTS Criterion C42) setup with a 1000N load cell. Each sample is placed in the center of the crush platens with a Ui” piece of silicone closed cell foam on the top and bottom covering the area of the surface. Samples are crushed with the cell orientation perpendicular to the force at a speed of 0.1 in / min. Once catastrophic failure is observed by the machine by registering 5 N drop in force, the peak load is recorded and converted into a compression force response by dividing the force by the measured area of the sample. For each material, testing is conducted under two different conditions dry and hot post boil. For the dry condition, parts are tested at ambient conditions. For the hot post boil test condition, parts are placed in boiling DI water for 1 hour directly next to the test unit; after one hour the sample is extracted, weighed, and dimensionally measured prior to being placed back into boiling DI water next to the test fixture. After an additional 5 minutes of heating, the part is removed and crushed within 30 seconds of removal. Reported values are the average of four crush samples from the same monolith.

[0042] An extruded monolithic structural gas treatment body described herein, in some embodiments, has a CO2 adsorption capacity of at least 0.6 mmol / g, at least 0.7 mmol / g, or at least 0.8 mmol / g of particulate CO2 sorbent in the monolithic structural gas treatment body. Adsorption capacity of the extruded monolithic structural gas treatment body, in some embodiments, can be 0.5 mmol / g of particulate CO2 sorbent to 2 mmol / g of particulate CO2 sorbent in the monolithic structural gas treatment body. CO2 adsorption by monolithic structural gas treatment bodies described herein is measured by thermogravimetric analysis (TA Instruments TGA) under the conditions of 35°C, 2% CO2, 20% O2, and the balance N2. The monolithic structural gas treatment body in desorbed of CO2 at 110°C under N2 for 60 minutes prior to the 120 minute CO2 adsorption cycle. Change in mass of the monolithic structural gas treatment body between post desorption and CO2 adsorption equilibrium is employed to calculate the CO2 adsorption.

[0043] A monolithic structural gas treatment body described herein, in some embodiments, can exhibit a CO2 sorbent utilization efficiency of at least 60 percent or at least 70 percent. In some embodiments, CO2 sorbent utilization efficiency of the monolithic structural gas treatment body can be 60-100 percent, 80-100 percent, 90-100 percent, or 95-100 percent. CO2 sorbent utilization efficiency is the CO2 adsorption capacity of the monolithic structural gas treatment body divided by the CO2 adsorption capacity of the virgin particulate CO2 sorbent, as determined by TGA above.

[0044] As described herein, the extruded monolithic structural gas treatment bodies are formed from an extruded batch composition wherein the particulate metal organic framework CO2 sorbent is associated with the polymeric binder phase. In such a construct, the particulate metal organic framework CO2 sorbent is dispersed throughout the inner partition walls and associated with the hierarchical pore structure described herein. The extruded monolithic structural gas treatment body is formed of an extrusion batch composition described in Section I above. Accordingly, extruded monolithic structural gas treatment bodies can comprise any composition of metal organic framework CO2 sorbent and polymeric binder phase recited in Section I hereinabove. In some embodiments, the metal organic framework CO2 sorbent is present in an amount of 60-95 weight percent or 60-80 weight percent of the monolithic structural gas treatment body. Additionally, the polymeric binder phase can be present in an amount of 5-40 weight percent of the monolithic structural gas treatment body, in some embodiments. Compositional percentages of metal organic framework CO2 sorbent and polymeric binder phase in the monolithic structural gas treatment body will vary from the percentages in the extrusion batch since, the extrusion batch comprises water and the structural gas treatment body is in the dry state. Extruded monolithic structural gas treatment bodies can also include one or more fiber reinforcement agents described in Section I hereinabove. In some embodiments, the one or more fiber reinforcement agents are present in an amount of 0.5-10 weight percent of the monolithic structural gas treatment body.

[0045] III. Methods of Making Extruded Monolithic Structural Gas Treatment Bodies (Adsorbers)

[0046] In another aspect, methods of making monolithic structural bodies for CO2 adsorption are described herein. A method, in some embodiments, comprises providing an extrusion batch including a particulate polymeric phase, and a particulate CO2 sorbent comprising at least one metal organic framework, the particulate polymer phase and the particulate CO2 sorbent being disposed in an aqueous or aqueous-based continuous phase, wherein the extrusion batch has a plasticity of 0.06 to 1.3 kgf. The extrusion batch is extruded into a monolithic structural gas treatment body comprising a plurality of inner partition walls formed from the extrusion batch wherein the particulate CO2 sorbent is associated with the polymeric binder, and the inner partition walls defining flow channels through the monolithic structural body. The resultant extruded monolithic structural body can have any composition and / or properties described herein, including Section II above. Moreover, extrusion batches for the method can be selected from Section I above. The extrusion system may include extruder machines, a filter or screen, and an extrusion die. The filter or screen may be utilized to facilitate passage of the extrusion batch composition through the die while minimizing shear stresses. Particles that can clog the die are removed without removing the CO2 sorbent, binders, pore formers, glass fibers and / or other reinforcement agents that provide advantageous product properties. In some embodiments, for example, a wedge-shaped screen is employed to prevent or mitigate removal of fiber reinforcements from the extrusion batch composition.

[0047] Once extruded, the monolithic structural gas treatment body can be dried at ambient temperature or heated to at least 100°C for drying. Additionally, the extruded monolithic structural gas treatment body can also be washed to remove pore formers, including water soluble extrusion aids.

[0048] IV. Methods of CO2 Capture

[0049] In another aspect, methods of capturing CO2 from a gas stream are provided. A method, in some embodiments, comprises providing an extruded monolithic structural gas treatment body including a plurality of inner partition walls formed of an extruded batch composition, the batch composition including a polymeric binder phase, and a particulate CO2 sorbent associated with a polymeric binder phase, the particulate carbon dioxide CO2 sorbent comprising at least one metal organic framework, wherein the inner partition walls define flow channels through the extruded monolithic structural gas treatment body, and the extruded monolithic structural gas treatment body has a hierarchical pore structure including macroporosity and microporosity. A gas stream is flowed through the flow channels, and CO is captured from the gas stream with the particulate metal organic framework sorbent. The captured CO2 can be subsequently desorbed from the monolithic structural gas treatment body for downstream processing, including storage or sequestration.

[0050] In some embodiments, the monolithic structural gas treatment body is heated with steam or heated nitrogen (N2) to desorb the captured CO2. In some embodiments, the structural gas treatment body is isolated from the gas stream, subjected to vacuum to evacuate the gas, steam is flowed through the adsorber wherein a portion of the steam is condensed on the structural body desorbing the CO2 and carrying away the desorbed CO2 for further processing, and the structural body is subject to vacuum again to evaporate the condensed steam and cool the structural body, prior to removing isolation to start another adsorption cycle to capture the CO2.

[0051] The extruded monolithic structural body can have any composition and / or properties described in Section II herein above. Additionally, the gas stream can be ambient air or a flue gas stream from a combustion source. Such combustions sources include electrical power generation facilities and other industrial emission facilities. In some embodiments, flue gas streams are diluted with ambient air and / or otherwise processed or cooled prior to contact with structural gas treatment bodies described herein.

[0052] These and other embodiments are further illustrated by the following non-limiting examples.

[0053] EXAMPLE 1 - Extrusion Batch Compositions

[0054] Two extrusion batches having the compositions set forth in Table 3 were prepared.

[0055] Table 3 - Extrusion Batch Compositions (wt.%)

[0056] EXAMPLE 2 - Extruded Monolithic Structural Gas Treatment Bodies (CO 2 Adsorbers)

[0057] Each of the extrusion batch compositions in Example 1 were extruded into monolithic structural gas treatment bodies for the capture of CO2 as set forth in Tables 4 and 5. The extruded monolithic bodies were honeycombs with the cell count and hydraulic diameter listed in Table 4. Table 4 - Structural Parameters of Extruded Monolithic Structural Gas Treatment Bodies (Adsorbers)

[0058] Table 5 - Extruded Monolithic Structural Gas Treatment Bodies (Adsorbers)

[0059] *Measured by N2physisorption

[0060] 5 ** Measured by Hg Porosimetry

[0061] The extruded honeycomb monolithic bodies of Samples 1-3 exhibited CO2 adsorption capabilities with efficient CO2 sorbent utilization as provided in Table 5. As set forth herein, CO2 adsorption capacity was determined by TGA.

[0062] 10 Various embodiments of the invention have been described in fulfillment of the various objectives of the invention. It should be recognized that these embodiments are merely illustrative of the principles of the present invention. Numerous modifications and adaptations thereof will be readily apparent to those skilled in the art without departing from the spirit and scope of the invention.

Claims

CLAIMS1. An extrusion batch composition for a monolithic structural gas treatment body comprising: a particulate polymeric phase, and a particulate carbon dioxide (CO2) sorbent comprising at least one metal organic framework, the particulate polymeric phase and the particulate CO2 sorbent being disposed in an aqueous or aqueous-based continuous phase, wherein the extrusion batch has a plasticity of 0.06 to 1.3 kgf.

2. The extrusion batch composition of claim 1, wherein the metal organic framework has a D10 particle size of 0.5 pm to 2 pm.

3. The extrusion batch composition of claim 1, wherein the metal organic framework has a D90 particle size of 7 pm to 10 pm.

4. The extrusion batch composition of claim 1, wherein the particulate CO2 sorbent is present in an amount of 15-70 weight percent of the extrusion batch.

5. The extrusion batch composition of claim 1, wherein the particulate CO2 sorbent is present in an amount of 30-50 weight percent of the extrusion batch.

6. The extrusion batch of claim 1, wherein the metal organic framework comprises layers of aryl-bridged metal atoms or heterocycle-bridged metal atoms.

7. The extrusion batch of claim 6, wherein the metal atoms comprise one or more transition metals.

8. The extrusion batch of claim 7, wherein the one or more transition metal atoms are selected from Groups 8-12 of the Periodic Table.

9. The extrusion batch of claim 7, wherein the metal atoms are zinc or copper.

10. The extrusion batch of claim 6, wherein the metal organic framework comprises layers of heterocycle-bridged metal atoms, the heterocycle comprising one or more azole species.

11. The extrusion batch of claim 6, wherein the layers of aryl-bridged metal atoms or heterocycle-bridged metal atoms are pillared by ionic ligands.

12. The extrusion batch of claim 11, wherein the ionic ligands are dianionic.

13. The extrusion batch of claim 12, wherein the dianionic ligands are terminated in COO" functionalities.

14. The extrusion batch of claim 12, wherein the dianionic ligands are oxalate or oxalate derivatives.

15. The extrusion batch composition of claim 1, wherein the particulate polymeric phase has a particle size of 0.05 pm to 100 pm.

16. The extrusion batch composition of claim 1, wherein the particulate polymeric phase has a D10 particle size of 0.01pm to 5 pm.

17. The extrusion batch composition of claim 1, wherein the particulate polymeric phase has a D90 particle size of 0.1 pm to 20 pm or 10-60 pm.

18. The extrusion batch composition of claim 1, wherein the particulate polymeric phase is present in an amount of 2-20 weight percent of the extrusion batch composition.

19. The extrusion batch composition of claim 1, wherein the particulate polymeric phase comprises an olefin-acetate copolymer, aryl-acrylate copolymer, alkyl-acrylate copolymer, polyalkyl-siloxane, or aryl-diene copolymer.

20. The extrusion batch of claim 1, wherein the particulate polymeric phase comprises at least two differing particulate polymeric species.

21. The extrusion batch of claim 20, wherein the at least two differing particulate polymeric species are thermoplastics.

22. The extrusion batch of claim 1 further comprising a viscosity modifier at least partially solubilized in the aqueous or aqueous-based continuous phase.

23. The extrusion batch composition of claim 20, wherein the viscosity modifier is present in an amount of 1-10 weight percent of the extrusion batch composition.

24. The extrusion batch composition of claim 22, wherein the viscosity modifier comprises one or more alkylene oxides.

25. The extrusion batch composition of claim 1 further comprising one or more fiber reinforcement agents in an amount of 1 to 10 weight percent.

26. An extruded monolithic structural gas treatment body comprising: a plurality of inner partition walls formed of an extruded batch composition, the batch composition including a polymeric binder phase, and a particulate carbon dioxide (CO2) sorbent associated with the polymeric binder phase, the particulate carbon dioxide CO2 sorbent comprising at least one metal organic framework, wherein the inner partition walls define flow channels through the extruded monolithic structural gas treatment body, and the extruded monolithic structural gas treatment body has a hierarchical pore structure including macroporosity and microporosity.

27. The extruded monolithic structural gas treatment body of claim 26, wherein the microporosity has a volume of 0.01-0.5 cm3 / g in pores of diameter ranging from 0.1-2 nm.

28. The extruded monolithic structural gas treatment body of claim 26 or claim 27, wherein the macroporosity has a volume of 0.05-1.5 cm3 / g in pores of diameter ranging from 100 nm to 10pm.

29. The extruded monolithic structural gas treatment body of claim 26, having a combined volume of microporosity and mesoporosity of 0.01-0.6 cm3 / g in pores of diameter ranging from 0.1 nm to 99.9 nm.

30. The extruded monolithic structural gas treatment body of claim 26, having a CCh adsorption capacity of at least 0.6 mmol / g of the particulate CO2 sorbent in the monolithic structural gas treatment body.

31. The extruded monolithic structural gas treatment body of claim 26, having a CO2 adsorption capacity of 0.5 mmol / g to 2 mmol / g of the particulate CO2 sorbent in the monolithic structural gas treatment body.

32. The extruded monolithic structural gas treatment body of claim 26, wherein the polymeric binder phase is present in an amount of 5-40 weight percent of the gas treatment body.

33. The extruded monolithic structural gas treatment body of claim 26, wherein the particulate CO2 sorbent is present in an amount of 60-95 weight percent of the gas treatment body.

34. The extruded monolithic structural has treatment body of claim 26, wherein the particulate CO2 sorbent is present in an amount of 65-80 weight percent of the gas treatment body.

35. The extruded monolithic structural has treatment body of claim 26, wherein the metal organic framework comprises layers of aryl-bridged metal atoms or heterocycle-bridged metal atoms.

36. The extruded monolithic structural has treatment body of claim 35, wherein the metal atoms comprise one or more transition metals.

37. The extruded monolithic structural has treatment body of claim 36, wherein the one or more transition metal atoms are selected from Groups 8-12 of the Periodic Table.

38. The extruded monolithic structural has treatment body of claim 37, wherein the metal atoms are zinc or copper.

39. The extruded monolithic structural has treatment body of claim 35, wherein the metal organic framework comprises layers of heterocycle-bridged metal atoms, the heterocycle comprising one or more azole species.

40. The extruded monolithic structural has treatment body of claim 35, wherein the layers of aryl-bridged metal atoms or heterocycle-bridged metal atoms are pillared by ionic ligands.

41. The extruded monolithic structural has treatment body of claim 40, wherein the ionic ligands are dianionic.

42. The extruded monolithic structural has treatment body of claim 41, wherein the dianionic ligands are terminated in COO' functionalities.

43. The extruded monolithic structural has treatment body of claim 41, wherein the dianionic ligands are oxalate or oxalate derivatives.

44. The extruded monolithic structural has treatment body of claim 26, wherein the polymeric binder comprises an olefin-acetate copolymer, aryl-acrylate copolymer, alkyl-acrylate copolymer, polyalkyl-siloxane, or aryl-diene copolymer.

45. The extruded monolithic structural gas treatment body of claim 26 having a CO2 sorbent utilization efficiency of 60-100 percent.

46. A method of making a monolithic structural body for adsorption of carbon dioxide (CO2) comprising: providing an extrusion batch including a particulate polymeric phase, and a particulate CO2 sorbent comprising at least one metal organic framework, the particulate polymer phase and the particulate CO2 sorbent being disposed in an aqueous or aqueous-based continuous phase, wherein the extrusion batch has a plasticity of 0.06 to 1.3 kgf; and extruding the extrusion batch into the monolithic structural body comprising a plurality of inner partition walls formed from the extrusion batch wherein the particulate CO2 sorbent is associated with the polymeric binder, and the inner partition walls defining flow channels through the monolithic structural body.

47. The method of claim 46, wherein the extruded monolithic structural gas treatment body has a hierarchical pore structure including macroporosity and microporosity.

48. The method of claim 47, wherein the extruded monolithic structural gas treatment body of claim 26, wherein the microporosity has a volume of 0.01-0.5 cm3 / g in pores of diameter ranging from 0.1-2 nm.

49. The method of claim 47, wherein the macroporosity has a volume of 0.05-1.5 cm3 / g in pores of diameter ranging from 100 nm to 10 pm.

50. The method of claim 46, wherein the extruded monolithic structural gas treatment body has a CO2 adsorption capacity of at least 0.6 mmol / g of the particulate CO2 sorbent in the monolithic structural gas treatment body.

51. The method of claim 46, wherein the extruded monolithic structural gas treatment body has a CO2 adsorption capacity of 0.5 mmol / g to 2 mmol / g of the particulate CO2 sorbent in the monolithic structural gas treatment body.

52. The method of claim 46, wherein the polymeric binder phase is present in an amount of 5-40 weight percent of the extruded gas treatment body.

53. The method of claim 46, wherein the particulate CO2 sorbent is present in an amount of 60-95 weight percent of the extruded gas treatment body.

54. The method of claim 46, wherein the particulate CO2 sorbent is present in an amount of 65-80 weight percent of the extruded gas treatment body.

55. The method of claim 46, wherein the particulate CO2 sorbent is present in an amount of 70-80 weight percent of the extruded gas treatment body.

56. The method of claim 46, wherein the metal organic framework comprises layers of aryl- bridged metal atoms or heterocycle-bridged metal atoms.

57. The method of claim 56, wherein the metal atoms comprise one or more transition metals.

58. The method of claim 57, wherein the one or more transition metal atoms are selected from Groups 8-12 of the Periodic Table.

59. The method of claim 58, wherein the metal atoms are zinc or copper.

60. The method of claim 46, wherein the metal organic framework comprises layers of heterocycle-bridged metal atoms, the heterocycle comprising one or more azole species.

61. The method of claim 46, wherein the layers of aryl-bridged metal atoms or heterocycle- bridged metal atoms are pillared by ionic ligands.

62. The method of claim 61, wherein the ionic ligands are dianionic.

63. The method of claim 62, wherein the dianionic ligands are terminated in COO' functionalities.

64. The method of claim 62, wherein the dianionic ligands are oxalate or oxalate derivatives.

65. The method of claim 46, wherein the polymeric binder comprises an olefin-acetate copolymer, aryl-acrylate copolymer, alkyl -acrylate copolymer, polyalkyl-siloxane, or aryl-diene copolymer.

66. The method of claim 46, wherein the extruded monolithic structural gas treatment body has a CO2 sorbent utilization efficiency of 60-99 percent.

67. The method of claim 46, wherein the extruded monolithic structural gas treatment body has a CO2 sorbent utilization efficiency of 85-99 percent.

68. A method of capturing carbon dioxide (CO2) from a gas stream comprising: providing an extruded monolithic structural gas treatment body including a plurality of inner partition walls formed of an extruded batch composition, the batch composition including a polymeric binder phase, and a particulate CO2 sorbent associated with a polymeric binder phase, the particulate carbon dioxide CO2 sorbent comprising at least one metal organic framework, wherein the inner partition walls define flow channels through the extruded monolithic structural gas treatment body, and the extruded monolithic structural gas treatment body has a hierarchical pore structure including macroporosity and microporosity; flowing the gas stream through the flow channels; and capturing CO2 from the gas stream with the particulate CO2 sorbent.

69. The method of claim 68, wherein the microporosity has a volume of 0.01-0.5 cm3 / g in pores of diameter ranging from 0.1-2 nm.

70. The method of claim 68, wherein the macroporosity has a volume of 0.05-1.5 cm3 / g in pores of diameter ranging from 100 nm to 10 pm.

71. The method of claim 68, wherein the extruded monolithic structural gas treatment body has a CO2 adsorption capacity of at least 0.6 mmol / g of the particulate CO2 sorbent in the monolithic structural gas treatment body.

72. The method of claim 68, wherein the extruded monolithic structural gas treatment body has a CO2 adsorption capacity of 0.5 mmol / g to 2 mmol / g of the particulate CO2 sorbent in the monolithic structural gas treatment body.

73. The method of claim 68, wherein the polymeric binder phase is present in an amount of 5-40 weight percent of the extruded gas treatment body.

74. The method of claim 68, wherein the particulate CO2 sorbent is present in an amount of 60-95 weight percent of the gas treatment body.

75. The method of claim 68, wherein the particulate CO2 sorbent is present in an amount of 65-80 weight percent of the gas treatment body.

76. The method of claim 68, wherein the metal organic framework comprises layers of aryl- bridged metal atoms or heterocycle-bridged metal atoms.

77. The method of claim 76, wherein the metal atoms comprise one or more transition metals.

78. The method of claim 77, wherein the one or more transition metal atoms are selected from Groups 8-12 of the Periodic Table.

79. The method of claim 78, wherein the metal atoms are zinc or copper.

80. The method of claim 68, wherein the metal organic framework comprises layers of heterocycle-bridged metal atoms, the heterocycle comprising one or more azole species.

81. The method of claim 80, wherein the layers of aryl -bridged metal atoms or heterocycle- bridged metal atoms are pillared by ionic ligands.

82. The method of claim 81, wherein the ionic ligands are dianionic.

83. The method of claim 82, wherein the dianionic ligands are terminated in COO' functionalities.

84. The method of claim 82, wherein the dianionic ligands are oxalate or oxalate derivatives.

85. The method of claim 68, wherein the polymeric binder comprises an olefin-acetate copolymer, aryl-acrylate copolymer, alkyl -acrylate copolymer, polyalkyl-siloxane, or aryl-diene copolymer.

86. The method of claim 68, wherein the extruded monolithic structural gas treatment body has a CO2 sorbent utilization efficiency of 60-99 percent.

87. The method of claim 68, wherein the extruded monolithic structural gas treatment body has a CO2 sorbent utilization efficiency of 85-99 percent.

88. The method of claim 68, wherein the gas stream is ambient air.

89. The method of claim 68, wherein the gas stream is a flue gas stream.

90. The method of claim 68 further comprising recovering the captured CO2 by exposing the extruded monolithic structural gas treatment body to steam.

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