Metal-containing MOR-type zeolites and methods of use thereof for capturing carbon dioxide from low CO2 content sources

Abstract

The present disclosure relates to metal ion-containing zeolite compositions having MOR topology that are useful for removing CO2 from low CO2-containing feed streams, including air, and methods of making and using the same.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Application No. 63 / 296,396, filed January 4, 2022, U.S. Provisional Application No. 63 / 352,908, filed June 16, 2022, and U.S. Provisional Application No. 63 / 377,586, filed September 29, 2022. Each of the above-mentioned applications is incorporated herein by reference in its entirety.

[0002] This disclosure relates to water (H 2 O) and low CO 2 Carbon dioxide (CO) from a mixture of gaseous sources 2 The present invention relates to metal ion-containing zeolite compositions useful for removing CO2 from water and methods of making and using the same. In some preferred embodiments, the compositions comprise 2 The present invention includes metal ion doped zeolites having MOR topology that are capable of efficiently removing carbon dioxide from contained gaseous source mixtures. [Background technology]

[0003] Carbon Dioxide (CO 2 ) anthropogenic emissions are associated with a continuing rise in the Earth's temperature. Therefore, many CO2 emissions have been reduced in the past few years, with the goal of achieving net-zero emissions by 2050. 2 Mitigation strategies have been explored. Point source capture offers a solution for the sustainable operation of steel industries, cement plants, coal-based power plants, etc. Air-to-CO2 capture is used to address emissions from mobile sources such as cars, airplanes, and cargo ships. 2 Direct air capture (DAC) and bioenergy with carbon capture and storage (BECCS) have been investigated for the direct removal of CO. 2from ambient air. Chem. Rev. 116, 11840-11876 (2016); 2. WJ Sagues et al., Enhanced carbon dioxide removal from coupled direct air capture-bioenergy systems. Sustain. Energy Fuels 3, 3135-3146 (2019); 3. G. Rim et al., Sub-ambient temperature direct air capture of CO 2 using amine-impregnated MIL-101(Cr)enables ambient temperature CO 2 recovery.JACS Au 2, 380-393 (2022) DAC and BECCS offer the opportunity for net negative emissions.

[0004] The challenge for carbon capture technology is the search for sorbents that are affordable, effective, energy-efficient, environmentally friendly, and safe for large-scale use. 2 Low diffusion rate and low CO 2 Physical adsorbents are particularly important for DACs because of their capacity to absorb CO 2 Therefore, chemisorption-based adsorbents are not effective due to their weak affinity for CO. 2 Liquid amine and alkaline sorbents, as well as other types of chemical sorbents, such as ionic liquids and electrochemically based membranes, are the primary options for CO capture from low-concentration environments. 2Amines have been investigated for the capture of amines. However, the intensive energy requirements for desorption (60-120 kJ / mol) and slow kinetics can be problematic for the large volumes of processing required to implement DAC with chemical sorbents. Amines supported on porous materials have also been investigated for DAC to enhance surface exposure and diffusion rates. The toxic and time-dependent oxidative decomposition and evaporation of amines are inherent challenges to the use of these methods. The development of new physical sorbents with high stability, low desorption energy costs, fast sorption rates, high capacity, as well as moderate heats of adsorption of 30-60 kJ / mol and fully reversible physical adsorption properties may make them feasible for large-scale DAC.

[0005] The most widely studied physical adsorbents for DAC are metal-organic frameworks (MOFs). A subgroup of MOFs, hybrid ultramicroporous materials, shows promise for CO adsorption and desorption. 2 The capture performance of these solids has been reported. The high performance of these solids comes from the toxic, strongly electronegative fluorine-based adsorption centers as well as well-controlled pore sizes. However, obtaining MOF adsorbents for DAC with cost-effective scalability, high performance and long-term stability remains a challenging task. Zeolites are another type of microporous materials with a wide range of structural and physicochemical properties as well as high stability. They can be synthesized in large quantities in a cost-effective process and have a long history in industry for catalysis and adsorption. For carbon capture, they often have faster rates than supported amines. These advantages make zeolites ideal for the capture of high concentrations of CO 2 It is an interesting candidate for the capture of low-concentration CO 2 There are known challenges with the trapping capacity of CO2 and the detrimental effects of water. 2To increase the capture capacity, research has focused on maximizing the number or tailoring the type of extraframework adsorption sites. However, there remains a need for zeolite adsorbents with competitive capacity and high stability.

[0006] The latter issue can be addressed by designing a multi-bed system with a desiccant bed in front of the zeolite adsorbent. Currently, the majority of the literature focuses on performance at dry conditions and the H during the DAC process. 2 The problem of O adsorption has been largely unexplored. NASA has been studying the absorption of CO from air for manned spacecraft since the 1960s. 2 [Ind. Eng. Chem. Process Des. Dev. 1969, vol. 8(4), pp. 469-476, https: / / doi.org / 10.1021 / i260032a006]. Their work has 2 A desiccant bed (bulk H) is placed upstream of the adsorbent bed (5A or 13X zeolite). 2 Silica gel for O, trace H 2 For O, use 13X zeolite) [CO 2Removal for the International Space Station-4-Bed Molecular Sieve Material Selection and System Design. 49th Int. Conf. Environ. Syst. 2019, vols. 1-10; Development of Carbon Dioxide Removal Systems for NASA's Deep Space Human Exploration Missions 2016-2017. 48th Int. Conf. Environ. Syst. 2017, pp. 1-17]. Similar combinations of silica gel and zeolite have been studied by GreenCap Solutions AS and used in DAC by Removr Inc. [A System for Climate Control in Closed or Semi Closed Spaces. WO 2018034570; A Method and Arrangement for Capturing Carbon Dioxide from a Gas Stream Using an Adsorption System Comprising a Heat Storage and Recovery Unit. WO 2021206564]. However, traces of H in zeolite after silica gel desiccant 2 The high regeneration temperatures (typically around 300 °C) resulting from O adsorption limit the use of this configuration for large-scale DAC technology [A Method and Arrangement for Capturing Carbon Dioxide from a Gas Stream Using an Adsorption System Comprising a Heat Storage and Recovery Unit. International Publication No. 2021206564; Investigation of Desiccants and CO 2Sorbents for Exploration Systems 2016-2017,47th Int.Conf.Environ.Syst.2017;Investigation of Desiccants and CO 2 Sorbents for Advanced Exploration Systems 2015-2016. 46th Int. Conf. Environ. Syst. 2016, pp. 1-13] In DAC applications, atmospheric water capture is a CO2 capture strategy in areas where fresh water is highly needed. 2 This could be a useful effort to complement the removal of

[0007] The disclosure herein demonstrates that the trapping effect in zeolites is 2 MOR-type zeolites with eight-membered ring (8-MR) side pockets, synthesized with or without organic structure-directing agents (OSDA), have been shown to significantly affect the adsorption of approximately 1.15 mmol / g of CO. 2 This capacity is the highest of any DAC physical adsorbent. This capacity is in turn compared to standard 13X zeolite adsorbents in terms of adsorption efficiency, i.e., CO per adsorption site. 2 The O33 site in the 8-MR side pocket is the major adsorption site in MOR-type zeolites, and the size of the confined space for the adsorption sites in the zeolite results in an improvement of approximately one order of magnitude in the adsorption of 400 ppm CO. 2 Their properties for the adsorption of are determined. Furthermore, this disclosure also shows that in humid air, the use of commercial AQSOA Z02 (SAPO-34 with CHA framework) with MOR can realize a fully regenerative system for DAC at 100 °C, whereas the use of MOR alone requires 200-300 °C. Regeneration of SAPO-34+MOR was realized by purging the system with countercurrent. Summary of the Invention

[0008] In some embodiments, the present disclosure provides a metal ion-doped crystalline microporous aluminosilicate composition comprising a three-dimensional aluminosilicate framework having a mordenite topology with 12-MR channels and 8-MR side pockets, the crystalline microporous aluminosilicate containing 2.5 to 9 metal ions per unit cell, a ratio of metal ions to aluminum in the unit cell being 0.3 to 1.4, and a CO 2 Gaseous mixtures containing, for example, 400 ppm CO 2 The present invention provides a metal ion doped crystalline microporous aluminosilicate composition that adsorbs carbon dioxide when exposed to a gaseous mixture comprising:

[0009] In another aspect, the present disclosure provides a method for capturing carbon dioxide from a gaseous source mixture containing carbon dioxide, comprising contacting the gaseous source mixture with a metal ion doped crystalline microporous aluminosilicate according to any one of the preceding claims, such that carbon dioxide in the gaseous source mixture is adsorbed by the metal ion doped crystalline microporous aluminosilicate.

[0010] In another aspect, the present disclosure provides a method for capturing carbon dioxide from a gaseous source mixture containing carbon dioxide and moisture, comprising contacting the gaseous source mixture with a molecular sieve for moisture adsorption and a metal ion doped crystalline microporous aluminosilicate according to any one of the preceding claims, such that carbon dioxide in the gaseous source mixture is adsorbed by the metal ion doped crystalline microporous aluminosilicate. [Brief description of the drawings]

[0011] [Figure 1]The performance of MOR-type zeolites for the capture of 400 ppm CO2 is shown. a) MOR-type framework with 12-membered ring (12-MR) channels and 8-MR side pockets highlighted in green and pink, respectively. Linear segments represent bridging oxygen atoms, and their intersections represent tetrahedral atoms (Si or Al). Arrows indicate the adsorption of CO2 molecules in the 8-MR side pockets. b) CO2 adsorption capacity in MOR-type (MORa) zeolites in Na+ form (a indicates Si / Al ratio). Sample codes in brackets are listed in Table S1. 13X and Zn-CHA are used as references. Note that Zn2+ is the adsorption site for Zn-CHA2, and Na+ was used for other zeolites. c) CO2 capacity vs. isosteric heat of adsorption for MOR-type zeolites (7#) compared to other types of physical adsorbents for 400 ppm CO2 capture. The data are from ZIF-8 (S. Mukherjee et al., Trace CO2 capture by an ultramicroporous physisorbent with low water affinity. Sci. Adv. vol. 5, eaax9171 (2019)), 13X (ibid.), SIFSIX-18-Ni (ibid.), SIFSIX-18-Ni-β (ibid.), NbOFFIVE-1-Ni (PM Bhatt et al., A fine-tuned fluorinated MOF addresses the needs for trace CO2 removal and air capture Using physisorption. J. Am. Chem. Soc. vol. 138, pp. 9301-9307 (2016)), Mg2(dobpdc) (TM McDonald et al., Capture of carbon dioxide from air and flue gas in the alkylamineappended Metal-Organic Framework mmen-Mg2(dobpdc). J. Am. Chem. Soc. Vol. 134, pp. 7056-7065 (2012)), and Mg-MOF-74 (S. Mukherjee et al.).

[0012] [Diagram 2] Identification of adsorption sites in MOR-type zeolites. a) Bar graphs of breakthrough and saturation capacities from MOR6(4#) at 30 °C before and after pyridine modification, denoted as MOR and py-MOR, respectively. b) Normalized CO2 adsorption isotherms for MOR-type and FAU-type zeolites in log relative pressure. c) CO2 molecules adsorbed per MOR unit cell (CO2 / UC) as a function of Na+ cation loading density (Na+ / UC). d) Visualization of the four T sites (left panel) and the location of Na+ in the MOR framework as a function of Na+ loading (middle and right panels). (A-D) are results for the sample shown in Figure 2c. N from T sites, oxygen, Na+ and NH4+ are highlighted in light green, red, dark green and blue, respectively. Oxy denotes oxygen atoms bonded to Tx and Ty sites. e) Correlation between the number of adsorbed CO2 molecules at the O33 site of the 8-MR side pocket per MOR unit cell and the Na+ cation loading.

[0013] [Diagram 3] Illustration of the influence of zeolite confinement effect on CO2 adsorption. a) 400 ppm CO2 adsorption capacity by Na+ type zeolites with different frameworks. Three-letter framework code followed by the Si / Al ratio of the corresponding material. Sample codes in brackets are listed in Table S1. b) Adsorption sites of zeolite samples for adsorption of 400 ppm CO2 with increasing size of the confinement space, i.e. CO2 per Na+. c) Capacity of zeolite samples for adsorption of 1 bar ppm CO2 with decreasing adsorption site density / aluminum content. d) FTIR spectra of asymmetric linear vibration of CO2 molecules in zeolites as a function of framework topology. Adsorption capacities were obtained from isotherms measured at 25 °C. MOR-, MFI- and MAZ-type zeolites are highlighted in panels (b and d).

[0014] [Figure 4]Figure 1 shows the performance of MOR-type zeolites for capturing CO2 under simulated DAC conditions. a) Real-time breakthrough profile of MOR-type zeolite (4#) with simulated air gas of 400 ppm CO2 / 1 Ar% (internal standard) / 20% O2 / N2 at 30 °C, c) Capacity of MOR-type (14#) zeolite to capture 400 ppm CO2 at ambient and sub-ambient temperatures compared to amine-modified metal-organic frameworks (MOFs). Data for amine-modified MOFs was taken from (3).

[0015] [Diagram 5] Schematic of the deconvolution of the OH stretching region of MOR zeolites. The spectra were deconvoluted using a Voigt function with contributions from Gaussian and Lorentzian functions.

[0016] [Figure 6] Figure 1 shows the X-ray diffraction patterns of the synthesized MOR-type zeolites (5#-13#) using the patterns from a commercial zeolite (4#, CBV10A) as a reference. Sample codes are listed in Table S1.

[0017] [Figure 7] Figure 1 shows SEM images of commercial MOR-type zeolites (1-4#) and samples (5-13#) synthesized with organic directing agents. Sample codes are listed in Table S1.

[0018] [Figure 8] 1 is a bar graph comparing the capacity of 400 ppm CO2 for MOR-type zeolites, including commercial samples, zeolites synthesized with and without organic structure directing agents (OSDAs). Data are taken from 0.0004 bar from isotherms measured at 25°C up to 1 bar. Sample codes are listed in Table S1.

[0019] [Figure 9]Figure 1 shows the CO2 adsorption isotherms at 25 °C and 1 bar for MOR-type zeolites synthesized with different organic structure directing agents (5#-13#) and commercial zeolites, namely HSZ620 (1#) and CBV10A (4#). Sample codes are listed in Table S1.

[0020] [Figure 10] Correlation of Na+ in the 8-MR side pocket of MOR-type zeolites (Si / Al=5-7) synthesized with different OSDAs (5#-13#) and commercial zeolites, namely HSZ620 (1#) and CBV10A (4#). Data details are summarized in Table S2.

[0021] [Figure 11] Figure 1 shows the CO2 isotherms of organic structure directing agent-free MOR zeolites measured at 25 °C. 14*# is MOR zeolite (14#) after Na+ ion exchange. The results show that high CO2 adsorption capacity can be obtained directly from as-prepared MOR zeolites without further ion exchange. Furthermore, the CO2 adsorption capacity can be tuned by varying the Al content via OSDA-free synthesis. The OSDA-free MOR zeolite (14#) shows a capacity of 1.14 mmol / g, which is comparable to that of the OSDA-defined material (7#). This will lead to cost-efficient and environmentally friendly preparation of MOR zeolites with high capacity on a large industrial scale and provide an opportunity to lower the cost of DAC technology.

[0022] [Figure 12] Figure 2 shows the adsorption and desorption kinetics of MOR zeolite (7#) measured by TGA. a) Uptake profile during adsorption at 30 °C with a gas flow of 70 mL / min 400 ppm CO2 / He. b) Desorption profile with a gas flow of 70 mL / min pure He with a ramp rate of 10 °C / min.

[0023] [Figure 13]Figure 1 shows a comparison of the adsorption behavior of 13X and MOR type (4#) zeolites. Column breakthrough profiles of 13X and MOR7 (4#) zeolites for adsorbing dry CO2 at 30°C. The composition of CO2 gas under adsorption is about 400 ppm CO2 / 400 ppm Ar (internal standard) / He.

[0024] [Figure 14] Figure 1 shows the FTIR spectrum of MOR-type (4#) zeolite. CO2 physisorption (a) and chemisorption (b) regions. The results show that CO2 is only adsorbed in the form of physisorption on MOR-type zeolite, and no obvious absorption peak was observed in the chemisorption region.

[0025] [Figure 15] FIG. 1 shows the nonlinear curve fitting for CO2 sorption of MOR-type zeolite (14#) at different temperatures in the low pressure range of 0 to 0.008 bar.

[0026] [Figure 16] FIG. 1 is a graph showing the isosteric adsorption heat of a representative MOR-type zeolite (14#) in the low pressure range of 0 to 0.008 bar.

[0027] [Figure 17] Mass spectral profiles from temperature programmed desorption of a) parent and b) pyridine-modified MOR-type (4#) zeolite after saturation with 400 ppm CO2 at 30 °C. Gas was 400 ppm CO2 / 400 ppm Ar (internal standard) / He. Detected components are CO2 (red), H2O (black) and pyridine (blue). Both materials were activated at 300 °C. The data show that strongly adsorbed pyridine remained in the MOR-type zeolite after activation at 300 °C.

[0028] [Figure 18]Figure 1 is a bar graph of pyridine adsorption and breakthrough and saturation capacities from parent MOR zeolite after activation at 300 °C. The capacities are compared with isotherms at 400 ppm CO2 as well as values ​​obtained from parent MOR-type (4#) zeolite activated at 550 °C. The results show that about 85% of the capacity was maintained by pyridine adsorption in the 12-MR main channel of the MOR framework compared to the parent material. The results suggest that the adsorption sites in the 8-MR side pockets are responsible for the high capacity of MOR-type zeolite. It should be noted that the slight increase in CO2 uptake of MOR-type zeolite after 300 °C compared to after 550 °C can be attributed to trace amounts of water in the former. It has been shown previously that the presence of trace amounts of water can enhance CO2 adsorption. (7)

[0029] [Figure 19] Figure 1 shows the CO2 isotherms of MOR type (14#) up to 1 bar measured at different temperatures. The results show that the inflection pressure is independent of the measured temperature. Moreover, the CO2 capacity increases with decreasing temperature.

[0030] [Figure 20] FIG. 1 shows CO2 adsorption isotherms up to 1 bar at 25° C. on linear scale (left) and logarithmic scale (right) for MOR type (4#, NH4 + form) as a function of Na+ loading.

[0031] [Figure 21] Figure 1 shows FTIR spectra of the OH stretching region of MOR type (4#, NH4 + form) samples with various Na + loadings. The spectra were deconvoluted using a Voigt function with contributions from Gaussian and Lorentzian functions. Note that the spectra were not normalized based on weight, so the area only qualitatively reflects the consumption of BAS by the loading of Na cations.

[0032] [Figure 22]1H NMR spectra of MOR-type (4#, NH4 + form) samples with various Na + loadings. The spectra were deconvoluted using a Voigt function with contributions from Gaussian and Lorentzian functions.

[0033] [Figure 23] Figure 21 shows the 27Al NMR spectra of MOR type (4#, NH4 + form) with various Na+ loadings. The results show that all materials were free of extra-framework Al3+, although small OH stretching bands due to extra-framework Al3+ were observed in some samples from FTIR (Figure 21).

[0034] [Figure 24] Figure 1 shows FTIR spectra of asymmetric stretching of CO2 for MOR type (4#, NH4+ form) samples with various Na+ loadings. The right panel shows a zoomed-in view of the spectrum in the 2380-2440 cm-1 region in the left panel. The bands at 2348, 2359 and between 2400-2430 cm-1 indicate CO stretching and Na-O stretching of gas-phase, linearly adsorbed CO2 molecules, respectively.

[0035] [Diagram 25] This is a scanning electron microscope image of a large crystal for single crystal X-ray diffraction measurement. The crystal size is 30 to 40 μm.

[0036] [Figure 26]Visualization of the location of Na+ cations in Na-MOR type zeolites as a function of Na+ loading. a) Four different sites were found for balancing extra-framework cations in the MOR type framework, namely O33, O31, O44, O42. Oxy represents oxygen atoms bound to Tx and Ty sites. Extra-framework cations balancing O33 and O31 sites are located in the 8-MR side pocket. The balancing O44 site refers to the 8-MR side pocket. The balancing O42 site refers to the 12-MR channel. Na and N represent sites partially exchanged by Na+ and containing both Na+ and NH4+ cations. b-e) Results for samples (A-D) highlighted in Fig. 2c, respectively. Panel b) shows that sample A had a Na+ cation coordinated to an O atom (indicated as O31) from the T1 site in the 8-MR side pocket. Panel c) shows that sample B has the O31 position fully occupied by Na+ cations, while the O33 position was partially occupied by Na+ cations. Panel d) shows that sample C has both the O31 and O33 sites fully occupied by Na+ cations, while the O44 site was partially occupied by Na+ cations. Panel e) shows that the occupancy of sample D is similar to that of sample C, with an additional Na+ cation added to the O42 site. Details of the occupancy of each site are summarized in Tables S7–S10.

[0037] [Figure 27] FIG. 1 shows the X-ray diffraction patterns of zeolites tested with different framework topologies.

[0038] [Figure 28] X-ray diffraction patterns of ZSM-5 (MFI) and ZSM-11 (MEL) zeolites. The MEL and MFI phases were identified by arrows based on the MEL and MFI reference peaks from the International Zeolite Structure Database. (8)

[0039] [Figure 29] Figure 1 shows visualization of the confinement space in zeolites with different frameworks. The size of the side pockets in LEL, MOR, MAZ and FER zeolites was measured by VESTA. The size of the confinement space is the intersection at MFI, MEL, BEA and FAU, and is shown by the largest sphere that can be contained, as shown on the IZA website (www.iza-structure.org / databases / ).

[0040] [Diagram 30] FIG. 1 shows CO2 isotherms of zeolites with different framework topologies measured at 25° C.

[0041] [Diagram 31] Figure 1 shows mass spectral profiles from temperature programmed desorption of a) CO and b) HO from pyridine-loaded (py-MAZ, red) and parent (MAZ, black) MAZ zeolites after saturation with 400 ppm CO at 30° C. Both materials were activated at 280° C.

[0042] [Diagram 32] Figure 1 shows a comparison of CO2 and N2 capacities measured from single component isotherms and simulated air real-time breakthrough experiments. The simulated air is 400 ppm CO2 / 1 Ar% (internal standard) / 20% O2 / N2. The results show that the CO2 and N2 capacities were reduced in the simulated air measurements compared to those from the single component isotherms. This suggests competitive adsorption of CO2 and N2. The higher CO2 / N2 molar selectivity of the breakthrough experiments than that from the isotherms demonstrated preferential adsorption of CO2 compared to N2.

[0043] [Diagram 33]Figure 1 shows the performance of commercial MOR zeolite (4#, CBV10A) obtained from real-time breakthrough experiments under simulated conditions for direct air capture. a) Comparison of breakthrough and saturation capacities at 30 °C for MOR zeolite (4#, CBV10A) with different gas mixtures. CO2 / He indicates 400 ppm CO2 / 400 ppm Ar (internal standard) / He, CO2 / N2 indicates 400 ppm CO2 / 20% Ar (internal standard) / N2, and CO2 / N2 / O2 indicates 400 ppm CO2 / 1% Ar (internal standard) / 20% O2 / N2. b) Adsorption-desorption recyclability on MOR zeolite (4#, CBV10A) with a gas stream of CO2 / N2 / O2. The first cycle was obtained after activating the material at 550 °C for 20 h. The material was then regenerated at 60° C. and 100° C. for 2 h for each cycle, followed by deep regeneration at 550° C. for 2 h for three cycles. The results show that the material exhibits high recyclability even at temperatures as low as 60° C.

[0044] [Diagram 34] Figure 1 shows that zeolites with pore sizes larger than 4.1 Å maintain CO2 capacity above 80% when N2 is introduced into the adsorption gas stream. Meanwhile, the CO2 capacity of zeolites with pore sizes smaller than 4.1 Å drops dramatically to about 50% under CO2 / N2 gas mixture. MOR7 zeolite shows the highest CO2 capacity of 0.74 and 0.66 mmol / g for CO2 / He and CO2 / N2 gas mixtures, respectively. (However, this material has a very high Si / Al=6.5).

[0045] [Diagram 35] FIG. 13 shows that the capacity of MOR7 is negligibly affected by N2, and no further degradation was observed with CO2 / N2 / O2 gas flow.

[0046] [Diagram 36]FIG. 13 shows that typical breakthrough profiles of N2 indicate high N2 capacity for Zn-AEI and Zn-CHA, as suggested by the larger difference between the Ar and N2 breakthrough profiles.

[0047] [Figure 37] FIG. 1 shows that MOR-type zeolite exhibits high CO2 / N2 selectivity of 4365 when adsorbing CO2 from a gas stream of 400 ppm CO2 / 1% Ar (internal standard) / 20% He / N2.

[0048] [Figure 38] FIG. 1 shows that MOR7 exhibits almost double the CO2 capacity compared to 13X. MOR7 can be regenerated at 60° C.

[0049] [Figure 39] 1 shows zeolites with larger pore size (>4.1 Å) and N2 capacity significantly decreased in CO2 / N2 gas and CO2 capacity slightly decreased. Zeolites with smaller pore size (<4.1 Å): N2 capacity was unchanged and CO2 capacity significantly decreased in CO2 / N2 gas.

[0050] [Diagram 40] FIG. 1 is a table of MOR-type zeolites.

[0051] [Diagram 41] 1 shows a rapid increase in the capacity of the physical adsorbent to 2 mmol / g at lower temperatures, while the capacity of the chemical adsorbent decreases as the temperature decreases. MOR5(7#) zeolite shows a higher capacity at lower temperatures (e.g., −11° C.) than the prior art chemical adsorbent at lower temperatures (e.g., −20° C.).

[0052] [Diagram 42] FIG. 13 shows that MOR type shows the highest capacity for 400 ppm CO2 and the smallest difference in capacity between 1 bar and 400 ppm CO2.

[0053] [Diagram 43] Figure 1 shows that exchange of Li+ cations (Li-MOR7) or Sr2+ cations (Sr-MOR7) increases the capacity from 0.77 mmol / g (Na-MOR7) to 1 and 0.9 mmol / g, respectively, for 400 ppm CO2. Alkaline metals: increasing polarity increases CO2 capacity (both 1 bar and 400 ppm CO2). Alkaline earths: increasing basicity (Mg to Sr) does not change capacity at 1 bar, but increases capacity at 400 ppm. This shows the importance of basicity for adsorption of low concentration CO2.

[0054] [Diagram 44] FIG. 1 shows that all cation-exchanged LTLs exhibit very low capacity.

[0055] [Diagram 45] FIG. 2 shows the CO2 isotherm of alkali-MOR7 zeolite.

[0056] [Diagram 46] FIG. 2 shows the CO2 isotherm of alkaline earth-MOR7 zeolite.

[0057] [Figure 47] FIG. 1 shows the CO2 isotherm of cation-exchanged LTL3 (HSZ500, Tosoh Corporation) zeolite.

[0058] [Figure 48] FIG. 2 shows CO2 isotherms of Na-zeolites as a function of framework topology.

[0059] [Figure 49]Figure 1 shows that Li+ exchange improves the capacity for both low and high concentration CO2 adsorption. Sr2+ exchange improves the capacity for low concentration CO2 adsorption but slightly inhibits high concentration CO2 adsorption. Sr-MOR4(14#) shows the highest capacity of 1.36 mmol / g for 400 ppm CO2 adsorption. Native MOR and 13X adsorb similar amounts of CO2 at 400 ppm CO2, but the CO2 capacity of MOR at 1 bar is 26% of that of 13X.

[0060] [Figure 50] FIG. 1 shows the adsorption and desorption characteristics of several desiccants that may be used in the methods of the present disclosure. Adsorption conditions: 5% Ar / Helium 20 mL / min at 30° C., HO at 5° C. Desorption conditions: 5% Ar / Helium purge 7 hours: 20 mL / min, 550° C., ramp rate 10° C. / min.

[0061] [Figure 51] FIG. 1 shows the CO2 capacity of MOR zeolite as a function of humidity and temperature of the source gas. The CO2 capacity of MOR zeolite is maintained under humid conditions in the presence of upstream SAPO-34 for both low temperature and room temperature DACs.

[0062] [Figure 52] Figure 1 shows the CO2 capacity of MOR zeolite in multi-cycle adsorption-desorption with SAPO-34 upstream of MOR as a function of regeneration temperature for DAC from simulated air containing 2500 ppm H2O. MOR with SAPO-34 upstream required 100 °C for regeneration, while MOR alone required 200-300 °C. Adsorption: 2500 ppm H2O, simulated air at 30 °C. 100C-1: Regeneration with He at 100 °C for 300 min, then first cycle of adsorption of simulated air with 2500 ppm H2O. Breakthrough time for 300 mg SAPO-34 is 400 min, while 250 mg MOR requires 300 min.

[0063] [Diagram 53]FIG. 1 shows multi-cycle adsorption-desorption of two parallel adsorption units with a dual-layer bed containing SAPO-34 upstream of the MOR. [Figure 54] Figure 1 shows the multi-cycle adsorption-desorption of two parallel adsorption units with a dual-layer bed containing SAPO-34 upstream of the MOR. For adsorption, the wet air gas mixture flows through SAPO-34 and then through the MOR. Meanwhile, for desorption, the CO2- and H2O-free air gas mixture flows through the MOR and then through SAPO-34. The schematic showing the adsorption unit has gas entering from the bottom, and the schematic showing the desorption unit has gas exiting from the bottom. The direction of gas flow was switched for adsorption by unit B and desorption by unit A.

[0064] [Figure 55] Schematic of the SAPO-34+MOR system, where SAPO-34 is upstream of the MOR layer. To avoid water adsorption in the MOR layer, countercurrent was used to regenerate the system. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0065] In this disclosure, the singular forms "a," "an," and "the" include plural references and reference to a particular numerical value includes at least that particular value unless the context clearly dictates otherwise. Thus, for example, reference to a "material" is a reference to at least one of such materials and equivalents thereof known to those of skill in the art, and so forth.

[0066] When values ​​are expressed as approximations using the statement "about," it will be understood that the particular value forms another embodiment. In general, use of the term "about" indicates approximations that may vary depending on the desired properties sought to be obtained by the disclosed subject matter and should be interpreted in the particular context in which it is used based on its function. Those skilled in the art will be able to interpret this as a matter of routine. In some cases, the number of significant figures used for a particular value may be one non-limiting way of determining the scope of the term "about." In other cases, the gradations used for a series of values ​​can be used to determine the intended range available to the term "about" for each value. When present, all ranges are inclusive and combinable. That is, reference to values ​​recited in a range includes all values ​​within that range. For example, a range defined as 400 to 450 ppm includes 400 ppm and 450 ppm as separate embodiments.

[0067] It should be understood that certain features of the invention that are described herein in the context of separate embodiments for clarity may also be provided in combination in a single embodiment. That is, unless expressly incompatible or specifically excluded, each individual embodiment is considered to be combinable with any other embodiment, and such combination is considered to be another embodiment. Conversely, various features of the invention that are described in the context of a single embodiment for brevity may also be provided separately or in any subcombination. Finally, while an embodiment may be described as part of a series of steps or as part of a more general structure, each said step may also be considered as an independent embodiment that can itself be combined with others.

[0068] The transitional phrases "comprising," "consisting essentially of," and "consisting" are intended to connote their generally accepted meanings in patent terminology, namely: (i) "comprising," which is synonymous with "including," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional unrecited elements or method steps; (ii) "consisting of" excludes any elements, steps, or ingredients not recited in the claim; and (iii) "consisting essentially of" limits the claim to certain materials or steps, and those that do not materially affect the "basic and novel characteristics" of the claimed invention. An embodiment described with the phrase "comprising" (or its equivalent) also provides as an embodiment those described independently with the phrases "consisting of" and "consisting essentially of." For the embodiments provided with respect to "consisting essentially of," the basic and novel feature is the ease of operation of the process or composition / system (or the ability of the system to use only the recited components) to provide the aluminosilicate composition in significant yield. Other components or steps may be included so long as those additional components or steps do not materially affect the basic and novel features of the claimed invention.

[0069] When lists are presented, it is to be understood that each individual element of the list, and every combination of that list, is a separate embodiment, unless otherwise stated. For example, a list of embodiments presented as "A, B, or C" should be interpreted as including the embodiments "A," "B," "C," "A or B," "A or C," "B or C," or "A, B, or C," as separate embodiments, as well as C1-3.

[0070] Throughout this specification, terms should be given their ordinary meaning as understood by those of ordinary skill in the art. However, to avoid any doubt, the meaning of certain terms will be specifically defined or clarified.

[0071] The terms "method" and "process" are considered interchangeable within this disclosure.

[0072] The terms "separate" or "separated" have their ordinary meaning as understood by those of skill in the art, insofar as they refer to the physical partitioning or isolation of one material from another, or the selective capture of one component from a broader mixture. For example, when the terms are used in the context of gas processing, the terms "separate" or "separated" refer to the partitioning of gases by adsorption or permeation based on size or physical or chemical properties, as would be understood by one of skill in the art.

[0073] CO in the gaseous source mixture 2 In the context of content, "low concentration" or "low CO 2 The term "content" refers to CO 2 A concentration in the range of 100 ppm to 1000 ppm, or more preferably atmospheric CO 2 In some particular embodiments, the CO content in the gaseous source mixture is in an amount that approximates the CO content (i.e., about 400 ppm), but is also at a higher level than would be found, for example, in a make-up process stream. 2 The content may be in the range of 300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-600 ppm, 600-700 ppm, 700-800 ppm, 800-900 ppm, 900-1000 ppm, or CO 2 The content may be defined in terms of any of the aforementioned values ​​or two or more of the aforementioned ranges. 2refers to the gas being extracted, typically air, or in the case of testing, helium, optionally in the presence of argon present as an internal standard. The gaseous source mixture is typically at ambient atmospheric pressure (i.e., 101 kPa) or within 10% or 20% of that pressure, although higher pressures (i.e., up to 350 kPa) or lower pressures (i.e., down to 50 kPa) may also be considered in this context.

[0074] The term "microporous" according to IUPAC notation refers to materials with pore diameters less than 2 nm. Similarly, the term "macroporous" refers to materials with pore diameters greater than 50 nm. Also, the term "mesoporous" refers to materials with pore sizes intermediate between microporous and macroporous. Within the context of this disclosure, material properties and applications depend on the properties of the framework, such as pore size and dimensions, cage dimensions and material composition.

[0075] "Optional" or "optionally" means that the subsequently described circumstance may or may not occur, such that the description includes instances where the circumstance occurs and instances where it does not occur. For example, the phrase "optionally heated" refers to both embodiments where the material is heated and where it is not heated. Similarly, the term "optionally present" refers to both embodiments where the component is present and where it is not present. Each of these embodiments (heated and not heated, or present and absent) represents an individual and separate embodiment.

[0076] As used herein, the term "crystalline microporous solids" or "crystalline microporous aluminosilicates" refers to crystalline structures with pore structures with highly regular molecular dimensions, i.e., less than 2 nm. The maximum size of species that can enter the pores of crystalline microporous solids is controlled by the dimensions of the openings. These materials are sometimes called "molecular sieves" that have pore structures with highly regular molecular dimensions, i.e., less than 2 nm. The term "molecular sieve" refers to the ability of a material to selectively sort molecules based primarily on a size exclusion process. The maximum size of species that can enter the pores of crystalline microporous solids is controlled by the dimensions of the openings. These are conventionally defined by the ring size of the openings, for example, the term "8-MR" or "8-membered ring" refers to a closed loop typically constructed from eight tetrahedrally coordinated silicon (or aluminum) atoms and eight oxygen atoms. These rings are not necessarily symmetrical due to various effects, including distortion induced by the bonds between the units required to generate the overall structure, or the coordination of some of the oxygen atoms of the ring to cations within the structure. As used herein, in the context of the present invention, the term "8-MR" or "8-MR zeolite" refers only to aluminosilicate crystalline materials, or optionally substituted derivatives, having a framework containing an 8-membered ring as the largest ring for molecular entry into the intracrystalline void space. Exemplary structures can be identified in Baerlocher et al., Atlas of Zeolite Framework Types, 6th Revised Edition (2007), which reference is incorporated herein by reference for its teachings.

[0077] The term "metal ion doped" is intended to give the same meaning as "metal ion-containing" in the context of metal ions described elsewhere herein.

[0078] The term "silicate" refers to any composition that contains silicate (or silicon oxide) within its framework. It is a general term that encompasses, for example, pure silica (i.e., no other detectable metal oxides within the framework), aluminosilicate, borosilicate, ferrosilicate, germanosilicate, stannosilicate, titanosilicate or zincosilicate structures. The term "aluminosilicate" refers to any composition that contains both silicon and aluminum oxide within its framework. The term "zeolite" refers to an aluminosilicate composition that is a member of this family. Thus, the terms "metal ion doped zeolite composition" and "metal ion doped crystalline microporous aluminosilicate composition" are considered equivalent and are used interchangeably herein. Such aluminosilicates may be "pure aluminosilicates (i.e., no other detectable metal oxides are present within the framework) or may be optionally substituted (i.e., containing other metal oxides within the lattice framework). Where "optionally substituted" is described, each framework may contain boron, gallium, germanium, hafnium, iron, tin, titanium, indium, vanadium, zinc, zirconium, or other atoms substituted with one or more of the atoms not already contained in the parent lattice or framework.

[0079] As used herein, the term "metal ion doped crystalline microporous aluminosilicate composition" may be referred to as "zeolite composition" or "metal doped zeolite composition".

[0080] The present disclosure relates to a feed stream, particularly one containing air, with low levels of CO 2 from a feed stream containing carbon dioxide (CO 2Such novel compositions include metal-containing zeolites, including zeolites having the framework characteristics described herein, preferably compositions in which the metal is an alkali or alkaline earth metal and the zeolite has a MOR topology. The disclosure also relates to methods of making and using these compositions, comprising extracting CO from a gaseous feed stream. 2 The present invention relates to methods, including compositions useful for using these compositions to extract

[0081] The present invention may be more readily understood by reference to the following description, which is made in conjunction with the accompanying drawings and examples, all of which form a part of this disclosure. It is to be understood that the present invention is not limited to the specific products, methods, conditions, or parameters described or shown herein, and that the terms used herein are for the purpose of describing specific embodiments by way of example only, and are not intended to limit the claimed invention. Similarly, unless otherwise stated, descriptions of possible mechanisms or modes of action or reasons for improvements are intended to be illustrative only, and the invention herein should not be constrained by the correctness or incorrectness of such proposed mechanisms or modes of action or reasons for improvements. For example, while some of the present disclosures refer to the placement of metal ions in a zeolite framework, the present invention is not constrained by the correctness or incorrectness of these references to placement. It is recognized that throughout the text, descriptions refer to compositions and methods of using said compositions. That is, when the present disclosure describes or claims features or embodiments related to compositions or methods of making or using compositions, it is understood that such descriptions or claims are intended to extend these features or embodiments to the embodiments in each of these contexts (i.e., compositions, methods of making and methods of using).

[0082] composition In some embodiments, the present disclosure provides a metal ion doped crystalline microporous aluminosilicate composition comprising a three-dimensional aluminosilicate framework having a mordenite (or MOR-type) topology with 12-MR channels and 8-MR side pockets, the crystalline microporous aluminosilicate containing 2.5 to 9 metal ions per unit cell, a ratio of metal ions to aluminum in said unit cell being 0.3 to 1.4, and a CO 2 The present invention relates to a metal ion doped crystalline microporous aluminosilicate composition that adsorbs carbon dioxide when exposed to a gaseous mixture comprising:

[0083] In some embodiments, CO 2 The gaseous mixture further comprises oxygen.

[0084] In some embodiments, CO 2 The gaseous mixture further comprises nitrogen.

[0085] In some embodiments, CO 2 The gaseous mixture further comprises air.

[0086] In some embodiments, CO 2 The gaseous mixture further comprises oxygen and air.

[0087] As used herein, "air" refers to a gaseous mixture comprising carbon dioxide and nitrogen. In some embodiments, "air" further comprises oxygen, i.e., air comprises carbon dioxide, oxygen, and nitrogen. In some embodiments, air refers to atmospheric air. In other embodiments, air refers to the gaseous effluent from a process.

[0088] In some embodiments, the metal ion doped crystalline microporous aluminosilicate compositions of the present disclosure have a molecular weight of 0.01 to 0.1, e.g., ... , 5.7:1, 5.8:1, 5.9:1, 6:1, 6.1:1, 6.2:1, 6.3:1, 6.4:1, 6.5:1, 6.6:1, 6.7:1, 6.8:1, 6.9:1, 7:1, 7.1:1, 7.2:1, 7.3:1, 7.4:1, 7.5:1, 7.6:1, 7.7:1, 7.8:1, 7.9:1, 8:1, 8.1:1, 8.2:1, 8.3:1, 8.4: 1, 8.5:1, 8.6:1, 8.7:1, 8.8:1, 8.9:1, 9:1, 9.1:1, 9.2:1, 9.3:1, 9.4:1, 9.5:1, 9.6:1, 9.7:1, 9.8:1, 9.9:1, 10:1, 10.1:1, 10.2:1, 10.3:1, 10.4:1, 10.5:1, 10.6:1, 10.7:1, 10.8:1, 10.9:1, 11 12.1:1, 12.2:1, 12.3:1, 12.4:1, 12.5:1, 12.6:1, 12.7:1, 12.8:1, 12.9:1, or 13:1.

[0089] In some embodiments, the metal ion doped crystalline microporous aluminosilicate compositions of the present disclosure have a molecular weight of 0.01 to 0.1 in the range of 6:1 to 13:1, e.g., 6:1, 6.1:1, 6.2:1, 6.3:1, 6.4:1, 6.5:1, 6.6:1, 6.7:1, 6.8:1, 6.9:1, 7:1, 7.1:1, 7.2:1, 7.3:1, 7.4:1, 7.5:1, 7.6:1, 7.7:1, 7.8:1, 7.9:1, 8:1, 8.1:1, 8.2:1, 8.3:1, 8.4:1, 8.5:1, 8.6:1, 8.7:1, 8.8:1, 8.9:1, 9:1, 9.1:1, 9.2:1, 9.3:1, 9.4:1, 9.5:1, 9.6:1, 9.7:1, 9.8:1, 9.9:1, 9.1:1, 9.2:1, 9.3:1, 9.4:1, 9.5 ... 4:1, 9.5:1, 9.6:1, 9.7:1, 9.8:1, 9.9:1, 10:1, 10.1:1, 10.2:1, 10.3:1, 10.4:1, 10.5:1, 10.6:1, 10.7:1, 10.8:1, 10.9:1, 11:1, 11.1:1, 11.2:1, 11.3:1, 11.4 12.1:1, 12.2:1, 12.3:1, 12.4:1, 12.5:1, 12.6:1, 12.7:1, 12.8:1, 12.9:1 or 13:1.

[0090] In other embodiments, the metal ion doped crystalline microporous aluminosilicate compositions of the present disclosure have a Si:Al atomic ratio in the range of 4:1 to 6:1, such as one of 4:1, 4.1:1, 4.2:1, 4.3:1, 4.4:1, 4.5:1, 4.6:1, 4.7:1, 4.8:1, 4.9:1, 5:1, 5.1:1, 5.2:1, 5.3:1, 5.4:1, 5.5:1, 5.6:1, 5.7:1, 5.8:1, 5.9:1, or 6:1.

[0091] In yet other embodiments, the metal ion doped crystalline microporous aluminosilicate compositions of the present disclosure have a Si:Al atomic ratio in the range of 4:1 to 5.9:1, such as one of 4:1, 4.1:1, 4.2:1, 4.3:1, 4.4:1, 4.5:1, 4.6:1, 4.7:1, 4.8:1, 4.9:1, 5:1, 5.1:1, 5.2:1, 5.3:1, 5.4:1, 5.5:1, 5.6:1, 5.7:1, 5.8:1, or 5.9:1.

[0092] In some embodiments, the metal ion-doped crystalline microporous aluminosilicate composition of the present disclosure contains metal ions. In this embodiment, the metal ion-doped crystalline microporous aluminosilicate composition of the present disclosure contains 2.5 to 9 metal ions per unit cell, for example, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4:1, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4:1 ... .9, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9 or 9 metal ions.

[0093] In some embodiments, the metal ion doped crystalline microporous aluminosilicate compositions of the present disclosure contain 6 to 9 metal ions per unit cell, for example, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9 or 9 metal ions per unit cell.

[0094] In some embodiments, the metal ion doped crystalline microporous aluminosilicate compositions of the present disclosure contain 3 to 4.5 metal ions per unit cell, such as 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4:1, 4.1, 4.2, 4.3, 4.4 or 4.5 metal ions per unit cell.

[0095] In some embodiments, the ratio of metal ion to aluminum in the unit cell is between 0.3 and 1.4, for example, one of 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, or 1.4.

[0096] In some embodiments, the metal ions are disposed within the voids or channels of a three-dimensional aluminosilicate framework.

[0097] In some embodiments, the metal ion doped crystalline microporous aluminosilicate compositions of the present disclosure contain 2.5 to 5 metal ions per unit cell, e.g., 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4:1, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9 or 5 metal ions in the 8-MR side pockets.

[0098] In some embodiments, the metal ion doped crystalline microporous aluminosilicate compositions of the present disclosure contain 1.2 to 2.5 metal ions per unit cell, e.g., 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4 or 2.5 metal ions in the 8-MR side pockets.

[0099] In some embodiments, the metal ion is an alkali metal cation.

[0100] In some embodiments, the alkali metal cation is Li + , Na + , K+ , Rb + , or Cs + It is.

[0101] In some embodiments, the alkali metal cation is Li + It is.

[0102] In some embodiments, the alkali metal cation is Na + It is.

[0103] In some embodiments, the alkali metal cation is K + It is.

[0104] In some embodiments, the alkali metal cation is Rb + It is.

[0105] In some embodiments, the alkali metal cation is Cs + It is.

[0106] In other embodiments, the metal ion is an alkaline earth metal cation.

[0107] In some embodiments, the alkaline earth metal cation is Mg 2+ , Ca 2+ , Sr 2+ , or Ba 2+ It is.

[0108] In some embodiments, the alkaline earth metal cation is Mg 2+ It is.

[0109] In some embodiments, the alkaline earth metal cation is Ca 2+ It is.

[0110] In some embodiments, the alkaline earth metal cation is Sr 2+ It is.

[0111] In some embodiments, the alkaline earth metal cation is Ba. 2+ It is.

[0112] In some embodiments, the metal ion-doped crystalline microporous aluminosilicate compositions of the present disclosure are characterized by certain performance characteristics. Thus, in some embodiments, the metal ion-doped crystalline microporous aluminosilicate compositions of the present disclosure are characterized by carbon dioxide adsorption capacity. In some embodiments, the carbon dioxide adsorption capacity is measured in mmol of carbon dioxide per gram of the metal ion-doped crystalline microporous aluminosilicate composition under specific conditions of pressure and temperature. Methods for measuring mmol of carbon dioxide adsorbed per gram of the composition under specific conditions of pressure and temperature are known to those skilled in the art and include the methods described herein. Capacity is often measured by volumetric techniques, such as isotherm or fixed-bed column breakthrough experiments, or by weight-based methods, such as thermogravimetric analysis, using an instrument equipped with a microbalance.

[0113] In some embodiments, the metal ion doped crystalline microporous aluminosilicate compositions of the present disclosure can be subjected to CO ion exchange at a pressure of 0.0004 bar and a temperature of 25° C. 2 When exposed to at least 0.1 mmol, or at least 0.2 mmol, or at least 0.3 mmol, or at least 0.4 mmol, or at least 0.5 mmol, or at least 0.6 mmol, or at least 0.7 mmol, or at least 0.8 mmol, or at least 0.9 mmol, or at least 1 mmol, or at least 1.1 mmol, or at least 1.2 mmol, or at least 1.3 mmol, or at least 1.4 mmol of carbon dioxide per gram of the metal ion doped crystalline microporous aluminosilicate composition.

[0114] In another embodiment, the metal ion doped crystalline microporous aluminosilicate composition of the present disclosure is capable of withstanding CO at a pressure of 0.0004 bar and a temperature of -11°C. 2When exposed to at least 2.0 mmol of carbon dioxide per gram of the metal ion doped crystalline microporous aluminosilicate composition.

[0115] In another embodiment, the carbon dioxide adsorption capacity is measured by the number of molecules of carbon dioxide adsorbed per unit cell of the metal ion-doped crystalline microporous aluminosilicate composition under a specific condition of pressure and temperature.Methods for measuring the number of molecules of carbon dioxide adsorbed per unit cell of a composition under a specific condition of pressure and temperature are known to those skilled in the art and include the methods described herein.The number of molecules of carbon dioxide adsorbed per unit cell is calculated using the molar weight of the unit cell based on the composition measured by elemental analysis, e.g., EDX, and the carbon dioxide capacity measured by volumetric or gravimetric methods.

[0116] In some embodiments, the metal ion doped crystalline microporous aluminosilicate compositions of the present disclosure can be subjected to CO ion exchange at a pressure of 0.0004 bar and a temperature of 25° C. 2 0.3 to 4.4 molecules of CO per unit cell when exposed to 2 Adsorbs molecules.

[0117] In some embodiments, the metal ion doped crystalline microporous aluminosilicate compositions of the present disclosure can be subjected to CO ion exchange at a pressure of 0.0004 bar and a temperature of 25° C. 20.3 to 3.5 molecules per unit cell, e.g., 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4 or 3.5 CO 2 Adsorbs molecules.

[0118] In another embodiment, the metal ion doped crystalline microporous aluminosilicate composition of the present disclosure is capable of withstanding CO at a pressure of 0.0004 bar and a temperature of 25° C. 2 0.3 to 2.4 molecules per unit cell, e.g., 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3 or 2.4 CO 2 Adsorbs molecules.

[0119] In another embodiment, the metal ion doped crystalline microporous aluminosilicate composition of the present disclosure is capable of withstanding CO at a pressure of 0.0004 bar and a temperature of 25° C. 2 2.5 to 3.4 molecules per unit cell, e.g., 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4 or 3.5 CO molecules per unit cell when exposed to 2 Adsorbs molecules.

[0120] In another embodiment, the metal ion doped crystalline microporous aluminosilicate composition of the present disclosure is capable of withstanding CO at a pressure of 0.0004 bar and a temperature of 25° C. 2 3.5 to 4.4 molecules per unit cell, e.g., 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3 or 4.4 CO 2 Adsorbs molecules.

[0121] In another embodiment, the metal ion doped crystalline microporous aluminosilicate composition of the present disclosure is capable of withstanding CO at a pressure of 0.0004 bar and a temperature of -11°C. 2 When exposed to 2 Adsorbs molecules.

[0122] In some embodiments, the metal ion doped crystalline microporous aluminosilicate composition is subjected to (a) a total pressure in the range of 50 kPa to 350 kPa, and (b) a CO concentration in the range of 350 to 1000 ppm. 2 The CO concentration was then increased under the same conditions by passing a gaseous mixture having a CO concentration of 100 ppm or more through a tube containing a fixed bed of the metal ion doped crystalline microporous aluminosilicate composition. 2 CO adsorbed by an equal weight of zeolite 13X before complete saturation of 2 1.5 to 2 times more CO than the amount of 2 After adsorption of (mmol / g basis), CO 2 This will result in a complete breakthrough.

[0123] In some embodiments, the metal ion doped crystalline microporous aluminosilicate composition is subjected to (a) a total pressure in the range of 50 kPa to 350 kPa, and (b) a CO concentration in the range of 350 to 1000 ppm. 2 The CO concentration was measured under the same conditions by passing a gaseous mixture having a CO concentration of 100 ppm or more through a tube containing a powder of the metal ion-doped crystalline microporous aluminosilicate composition. 2 CO adsorbed by an equal weight of zeolite 13X before complete equilibrium occurred 2 1.5 to 2 times more CO than the amount of 2 (mmol / g basis) after adsorption of CO 2 is the equilibrium.

[0124] In some embodiments, the gaseous mixture has a total pressure in the range of 50 kPa to 350 kPa, e.g., 50 kPa, 75 kPa, 100 kPa, 125 kPa, 150 kPa, 175 kPa, 200 kPa, 225 kPa, 250 kPa, 275 kPa, 300 kPa, 325 kPa, or 350 kPa.

[0125] In other embodiments, the gaseous mixture contains CO in the range of 350 to 1000 ppm, e.g., 350 ppm, 375 ppm, 400 ppm, 425 ppm, 450 ppm, 475 ppm, 500 ppm, 525 ppm, 550 ppm, 575 ppm, 600 ppm, 625 ppm, 650 ppm, 675 ppm, 700 ppm, 725 ppm, 750 ppm, 775 ppm, 800 ppm, 825 ppm, 850 ppm, 875 ppm, 900 ppm, 925 ppm, 950 ppm, 975 ppm, or 1000 ppm. 2 It has a content.

[0126] In some embodiments, CO is produced under the same conditions by passing the gaseous mixture through a fixed bed of the metal ion doped crystalline microporous aluminosilicate composition. 2 CO adsorbed by an equal weight of zeolite 13X before complete saturation of 2 1.5 to 2 times, e.g., 1.5, 1.6, 1.7, 1.8, 1.9 or 2 times more CO than the amount of 2 (mmol / g basis) after adsorption of CO 2 As used herein, "complete breakthrough" refers to the total CO2 emission from a fixed bed of the metal ion doped crystalline microporous aluminosilicate composition. 2 The amount or concentration of CO entering the fixed bed 2 It means that the amount or concentration is the same as that of the amount or concentration of "complete breakthrough." Methods for measuring "complete breakthrough" are known to those of skill in the art and include the methods described herein.

[0127] In some embodiments, the gaseous mixture is heated to 30° C. for 20 mL min -1 At a flow rate of 400 ppm CO 2 / 1% Ar / He.

[0128] In another embodiment, the gaseous mixture is heated to 30° C. for 20 mL min -1 At a flow rate of 400 ppm CO 2 / 1% Ar / 20% He / Remainder N 2 It is.

[0129] In yet another embodiment, the gaseous mixture is heated to 30° C. for 20 mL min -1 At a flow rate of 400 ppm CO 2 / 1% Ar / 20% O 2 / Remainder N 2 It is.

[0130] In some embodiments, the gaseous mixture is at 20 mL min -1 At a flow rate of 400 ppm CO 2 / 1% Ar / He.

[0131] In another embodiment, the gaseous mixture is at 20 mL min -1 At a flow rate of 400 ppm CO 2 / 1% Ar / 20% He / Remainder N 2 It is.

[0132] In yet another embodiment, the gaseous mixture is at 20 mL min 2 at −11° C. -1 At a flow rate of 400 ppm CO 2 / 1% Ar / 20% O 2 / Remainder N 2 It is.

[0133] In some aspects, the metal ion doped crystalline microporous aluminosilicate compositions of the present disclosure that have adsorbed carbon dioxide have the adsorbed carbon dioxide desorbed at a temperature of less than 150° C. In such embodiments, the carbon dioxide can be desorbed by heating the metal ion doped crystalline microporous aluminosilicate composition while passing a stream of inert gas through the composition.

[0134] In other embodiments of the metal ion doped crystalline microporous aluminosilicate compositions of the present disclosure, the adsorbed carbon dioxide desorbs at temperatures below 125°C.

[0135] In other embodiments of the metal ion doped crystalline microporous aluminosilicate compositions of the present disclosure, the adsorbed carbon dioxide desorbs at temperatures below 100°C.

[0136] In other embodiments of the metal ion doped crystalline microporous aluminosilicate compositions of the present disclosure, the adsorbed carbon dioxide desorbs at a temperature below 75°C.

[0137] In other embodiments of the metal ion doped crystalline microporous aluminosilicate compositions of the present disclosure, the adsorbed carbon dioxide desorbs at a temperature below 60°C.

[0138] In other embodiments of the metal ion doped crystalline microporous aluminosilicate compositions of the present disclosure, the adsorbed carbon dioxide desorbs at a temperature below 50°C.

[0139] In some embodiments, the metal ion doped crystalline microporous aluminosilicate composition of the present disclosure is a crystalline microporous aluminosilicate composition comprising: 2 More than CO 2 As used herein, "selectivity" means that the metal ion doped crystalline microporous aluminosilicate composition preferentially adsorbs one type of molecule over another. Selectivity is expressed as the ratio of one molecule to another, as opposed to the ratio of the mole fractions of the one molecule to another. CO 2 / N 2 The selectivity is

number

[0140] In some embodiments, the metal ion doped crystalline microporous aluminosilicate compositions of the present disclosure include N 2 CO 2 The selectivity is at least 4000:1.

[0141] In other embodiments, the metal ion doped crystalline microporous aluminosilicate composition of the present disclosure comprises N 2 CO 2 The selectivity is at least 3000:1.

[0142] How to use In some aspects, the present disclosure relates to a method for capturing carbon dioxide from a gaseous source mixture containing carbon dioxide, comprising contacting the gaseous source mixture with a metal ion doped crystalline microporous aluminosilicate described herein such that carbon dioxide in the gaseous source mixture is adsorbed by the metal ion doped crystalline microporous aluminosilicate.

[0143] In some embodiments, the gaseous mixture further comprises oxygen.

[0144] In another embodiment, the gaseous mixture further comprises nitrogen.

[0145] In other embodiments, the gaseous mixture further comprises air.

[0146] In some embodiments, the methods of the present disclosure further comprise desorbing the adsorbed carbon dioxide from the metal ion doped crystalline microporous aluminosilicate comprising carbon dioxide.

[0147] In some embodiments of the disclosed method, contacting the metal ion doped crystalline microporous aluminosilicate composition with the gaseous source mixture is carried out in the absence of an added desiccant or without the use of an added desiccant.

[0148] In other embodiments of the method of the present disclosure, contacting the metal ion doped crystalline microporous aluminosilicate with the gaseous source mixture is carried out in the presence of or using an added desiccant.

[0149] In some embodiments of the methods of the present disclosure, contacting the gaseous source mixture with the metal ion-doped crystalline microporous aluminosilicate comprises passing the gaseous source mixture through a fixed bed of an adsorbent comprising the metal ion-doped crystalline microporous aluminosilicate.

[0150] In some embodiments of the method of the present disclosure, contacting the gaseous source mixture with the metal ion doped crystalline microporous aluminosilicate is carried out at a temperature of less than 50°C.

[0151] In some embodiments of the methods of the present disclosure, contacting the gaseous source mixture with the metal ion doped crystalline microporous aluminosilicate is carried out at a temperature of less than 30°C.

[0152] In another embodiment of the method of the present disclosure, contacting the gaseous source mixture with the metal ion doped crystalline microporous aluminosilicate is carried out at a temperature of less than 10°C.

[0153] In some embodiments of the methods of the present disclosure, contacting the gaseous source mixture with the metal ion doped crystalline microporous aluminosilicate is carried out at a temperature below 0°C.

[0154] In another embodiment of the method of the present disclosure, contacting the gaseous source mixture with the metal ion doped crystalline microporous aluminosilicate is carried out at a temperature below -10°C.

[0155] In some embodiments of the method of the present disclosure, desorbing carbon dioxide from the metal ion doped crystalline microporous aluminosilicate containing carbon dioxide is carried out at a temperature of less than 150°C.

[0156] In another embodiment of the method of the present disclosure, desorbing carbon dioxide from the metal ion doped crystalline microporous aluminosilicate containing carbon dioxide is carried out at a temperature of less than 125°C.

[0157] In another embodiment of the method of the present disclosure, desorbing carbon dioxide from the metal ion doped crystalline microporous aluminosilicate containing carbon dioxide is carried out at a temperature below 100°C.

[0158] In another embodiment of the method of the present disclosure, desorbing carbon dioxide from the metal ion doped crystalline microporous aluminosilicate containing carbon dioxide is carried out at a temperature of less than 75°C.

[0159] In another embodiment of the method of the present disclosure, desorbing carbon dioxide from the metal ion doped crystalline microporous aluminosilicate containing carbon dioxide is carried out at a temperature of less than 60°C.

[0160] In some embodiments of the disclosed methods, the gaseous source mixture has (a) a total pressure in the range of 50 kPa to 350 kPa, and (b) a CO concentration in the range of 350 to 1000 ppm. 2 The content is

[0161] In some embodiments of the disclosed methods, the gaseous source mixture has a total pressure in the range of 50 kPa to 350 kPa, e.g., 50 kPa, 75 kPa, 100 kPa, 125 kPa, 150 kPa, 175 kPa, 200 kPa, 225 kPa, 250 kPa, 275 kPa, 300 kPa, 325 kPa, or 350 kPa.

[0162] In some embodiments of the disclosed methods, the gaseous source mixture has a total pressure in the range of 50 kPa to 350 kPa, e.g., 50 kPa, 75 kPa, 100 kPa, 125 kPa, 150 kPa, 175 kPa, 200 kPa, 225 kPa, 250 kPa, 275 kPa, 300 kPa, 325 kPa, or 350 kPa.

[0163] In some embodiments of the disclosed method, the gaseous source mixture has a total pressure in the range of 50 kPa to 300 kPa.

[0164] In some embodiments of the disclosed method, the gaseous source mixture has a total pressure in the range of 50 kPa to 250 kPa.

[0165] In some embodiments of the disclosed method, the gaseous source mixture has a total pressure in the range of 50 kPa to 200 kPa.

[0166] In some embodiments of the disclosed method, the gaseous source mixture has a total pressure in the range of 50 kPa to 150 kPa.

[0167] In some embodiments of the disclosed method, the gaseous source mixture has a total pressure in the range of 50 kPa to 125 kPa.

[0168] 84. The method of any one of claims 74 to 83, wherein the gaseous source mixture has a total pressure in the range of 50 kPa to 100 kPa.

[0169] In some embodiments of the disclosed methods, the gaseous source mixture contains CO in the range of 350 to 1000 ppm, e.g., 350 ppm, 375 ppm, 400 ppm, 425 ppm, 450 ppm, 475 ppm, 500 ppm, 525 ppm, 550 ppm, 575 ppm, 600 ppm, 625 ppm, 650 ppm, 675 ppm, 700 ppm, 725 ppm, 750 ppm, 775 ppm, 800 ppm, 825 ppm, 850 ppm, 875 ppm, 900 ppm, 925 ppm, 950 ppm, 975 ppm, or 1000 ppm. 2 The content is

[0170] In some embodiments of the disclosed method, the gaseous source mixture contains CO in the range of 350-750 ppm. 2 The content is

[0171] In some embodiments of the disclosed method, the gaseous source mixture contains CO in the range of 350-600 ppm. 2 The content is

[0172] In some embodiments of the disclosed method, the gaseous source mixture contains CO in the range of 350-500 ppm. 2 The content is

[0173] In some embodiments of the disclosed method, the gaseous source mixture contains CO in the range of 350-425 ppm. 2 The content is

[0174] In some embodiments of the disclosed methods, the gaseous source mixture is wet, i.e., contains water vapor.

[0175] In some embodiments, the gaseous source mixture contains 30,000 ppm or less of water, e.g., 30,000 ppm or less, 20,000 ppm or less, 17,500 ppm or less, 15,000 ppm or less, 12,500 ppm or less, 10,000 ppm or less, 7500 ppm or less, 5000 ppm or less, or 2500 ppm or less.

[0176] In some embodiments, the gaseous source mixture contains no more than 2500 ppm water.

[0177] In some embodiments of the disclosed method, the moist gaseous source mixture is passed through a desiccant before passing through the metal ion doped crystalline microporous aluminosilicate. Without intending to be bound by theory, it is believed that the desiccant removes water from the gaseous source mixture. The water in the gaseous source mixture is absorbed by the CO2 of the metal ion doped crystalline microporous aluminosilicate. 2 Therefore, removing water in the gaseous source mixture may reduce the CO adsorption capacity of the metal ion doped crystalline microporous aluminosilicates. 2In addition, the temperature required to desorb water from the metal ion doped crystalline microporous aluminosilicates of the present disclosure is reduced by 100% compared to the temperature required to desorb CO from the metal ion doped crystalline microporous aluminosilicates. 2 This is significantly higher than the temperature required to desorb

[0178] In some embodiments, the desiccant is configured to adjust the temperature at which water desorbs from the desiccant by CO 2 The desiccant is selected by matching it to the temperature at which the metal ion doped crystalline microporous aluminosilicate is desorbed. By selecting the desiccant in this manner, both the desiccant and the metal ion doped crystalline microporous aluminosilicate can be regenerated simultaneously at the same temperature.

[0179] In some embodiments, the desiccant desorbs water at a temperature of 150° C. or less, e.g., 150° C. or less, 140° C. or less, 130° C. or less, 120° C. or less, 110° C. or less, 100° C. or less, 90° C. or less, or 80° C. or less.

[0180] In some embodiments, the desiccant desorbs water at a temperature of 120° C. or less.

[0181] In some embodiments, the desiccant desorbs water at a temperature of 110° C. or less.

[0182] In some embodiments, the desiccant desorbs water at a temperature of 100° C. or less.

[0183] In some aspects, the present disclosure relates to a method of capturing carbon dioxide from a wet gaseous source mixture comprising water and carbon dioxide, the method comprising first contacting the gaseous source mixture with a desiccant and a metal ion doped crystalline microporous aluminosilicate as described herein, such that water in the gaseous source mixture is adsorbed by the desiccant and carbon dioxide in the gaseous source mixture is adsorbed by the metal ion doped crystalline microporous aluminosilicate.

[0184] In some embodiments, the desiccant is SAPO-34.

[0185] In another embodiment, the desiccant is ALPO-34.

[0186] In some embodiments, the moist gaseous source mixture is contacted with the desiccant at a temperature of 120° C. or less, 110° C. or less, 100° C. or less, 90° C. or less, or 80° C. or less, 70° C. or less, 60° C. or less, 50° C. or less, 40° C. or less, 30° C. or less, 20° C. or less, 10° C. or less, 0° C. or less, −10° C. or less, or −20° C. or less.

[0187] In some embodiments, the moist gaseous source mixture is contacted with the desiccant at a temperature of 30° C. or less.

[0188] In other embodiments, the moist gaseous source mixture is contacted with the desiccant at a temperature of 10° C. or less.

[0189] In other embodiments, the moist gaseous source mixture is contacted with the desiccant at a temperature of 0° C. or less.

[0190] In other embodiments, the moist gaseous source mixture is contacted with the desiccant at a temperature of -10°C or less.

[0191] In some embodiments, the moist gaseous source mixture is contacted with the desiccant and then contacted with the metal ion doped crystalline microporous aluminosilicate at a temperature of 120°C or less, 110°C or less, 100°C or less, 90°C or less, or 80°C or less, 70°C or less, 60°C or less, 50°C or less, 40°C or less, 30°C or less, 20°C or less, 10°C or less, 0°C or less, -10°C or less, or -20°C or less.

[0192] In some embodiments, the moist gaseous source mixture is contacted with a desiccant and then contacted with a metal ion doped crystalline microporous aluminosilicate at a temperature of 30° C. or less.

[0193] In some embodiments, the moist gaseous source mixture is contacted with a desiccant and then contacted with a metal ion doped crystalline microporous aluminosilicate at a temperature of 10° C. or less.

[0194] In some embodiments, the moist gaseous source mixture is contacted with a desiccant and then contacted with a metal ion doped crystalline microporous aluminosilicate at a temperature of 0° C. or less.

[0195] In some embodiments, the moist gaseous source mixture is contacted with a desiccant and then contacted with a metal ion doped crystalline microporous aluminosilicate at a temperature of -10°C or less.

[0196] In some embodiments, the desiccant and the metal ion-doped crystalline microporous aluminosilicate are arranged in successive layers within a single vessel (e.g., a column). In these embodiments, the moist gaseous source mixture is first passed through the layer of desiccant and then through the layer of the metal ion-doped crystalline microporous aluminosilicate.

[0197] In other embodiments, the desiccant and the metal ion doped crystalline microporous aluminosilicate are contained in separate containers. In these embodiments, the moist gaseous source mixture is first passed through the desiccant in a first container and then through the metal ion doped crystalline microporous aluminosilicate in a second container.

[0198] In some embodiments, the method of capturing carbon dioxide from a wet gaseous source mixture using a desiccant and a metal ion-doped crystalline microporous aluminosilicate further includes regenerating the desiccant and the metal ion-doped crystalline microporous aluminosilicate by passing the gas through the metal ion-doped crystalline microporous aluminosilicate and the desiccant at a temperature of 150° C. or less, such as 150° C. or less, 140° C. or less, 130° C. or less, 120° C. or less, 110° C. or less, 100° C. or less, 90° C. or less, or 80° C. or less.

[0199] In some embodiments, regenerating the desiccant and the metal ion doped crystalline microporous aluminosilicate by passing a gas through the metal ion doped crystalline microporous aluminosilicate and the desiccant is performed at a temperature of 110°C or less, 100°C or less, 90°C or less, or 80°C or less.

[0200] In some embodiments, regenerating the metal ion doped crystalline microporous aluminosilicate and the desiccant by passing a gas through the desiccant and the metal ion doped crystalline microporous aluminosilicate is performed at a temperature of 100°C or less.

[0201] In some embodiments, the metal ion doped crystalline microporous aluminosilicate is regenerated by passing a gas through the metal ion doped crystalline microporous aluminosilicate and the desiccant at a temperature of 150°C or less, such as 150°C or less, 140°C or less, 130°C or less, 120°C or less, 110°C or less, 100°C or less, 90°C or less, or 80°C or less.

[0202] In some embodiments, the metal ion doped crystalline microporous aluminosilicate is regenerated by passing a gas through the metal ion doped crystalline microporous aluminosilicate at a temperature of 110°C or less, 100°C or less, 90°C or less, or 80°C or less.

[0203] In some embodiments, the metal ion doped crystalline microporous aluminosilicate is regenerated by passing a gas through the metal ion doped crystalline microporous aluminosilicate at a temperature of 100° C. or less.

[0204] In some embodiments, the desiccant is regenerated by passing a gas through the desiccant at a temperature of 150° C. or less, e.g., 150° C. or less, 140° C. or less, 130° C. or less, 120° C. or less, 110° C. or less, 100° C. or less, 90° C. or less, or 80° C. or less.

[0205] In some embodiments, the desiccant is regenerated by passing a gas through the desiccant at a temperature of 110°C or less, 100°C or less, 90°C or less, or 80°C or less.

[0206] In some embodiments, the desiccant is regenerated by passing a gas through the desiccant at a temperature of 100° C. or less.

[0207] In some embodiments, regeneration of the desiccant and metal ion doped crystalline microporous aluminosilicate is such that water desorbed from the desiccant during regeneration does not pass through the metal ion doped crystalline microporous aluminosilicate.

[0208] In some embodiments, the regeneration gas is an inert gas such as nitrogen, argon, helium, or mixtures thereof, hi other embodiments, the regeneration gas is air.

[0209] In embodiments where the desiccant and the metal ion doped crystalline microporous aluminosilicate are contained in separate vessels, after regenerating the desiccant, water can be collected from the regeneration gas for beneficial use.

[0210] In some embodiments, the disclosure relates to a multi-unit system including two or more parallel adsorption units, each unit including a desiccant bed and a metal ion-doped crystalline microporous aluminosilicate bed. In these embodiments, the wet gaseous source mixture is passed through a first adsorption unit, first through the desiccant bed and then through the metal ion-doped crystalline microporous aluminosilicate bed. The effluent from the first adsorption unit is then passed in the opposite direction through a second parallel adsorption unit (i.e., the effluent from the first adsorption unit first passes through the metal ion-doped crystalline microporous aluminosilicate bed of the second unit and then through the desiccant bed of the second adsorption unit).

[0211] In some embodiments, the adsorption and desorption processes are carried out at the same temperature.

[0212] In other embodiments, the adsorption and desorption processes are carried out at different temperatures.

[0213] In some embodiments, the adsorption process is carried out at about 30° C. or below.

[0214] In some embodiments, the desorption process is carried out at or below about 150°C.

[0215] In some embodiments, the desorption process is carried out at about 100°C.

[0216] example Material synthesis

[0217] MOR-type zeolites were synthesized from mixtures with or without organic structure directing agents. Large MOR crystals (~40 μm) were synthesized for single crystal X-ray diffraction (XRD) analysis. The synthesis procedures for MOR-type zeolites as well as MAZ-type, *BEA-type, MFI-type, and MEL-type zeolites are shown below.

[0218] MOR Zeolite. MOR zeolite with Si / Al=6.5 (CBV10A, Zeolyst) was used as received. MOR zeolite with Si / Al=5 was synthesized by modifying the method reported in M. Wang et al., Modifying the acidity of H-MOR and its catalytic carbonylation of dimethyl ether. Chin. J. Catal. vol. 37, pp. 1530-1537 (2016) using different OSDAs. Typically, sodium hydroxide (50 wt% aqueous solution, Sigma-Aldrich), silica (Ludox-40, Sigma-Aldrich), sodium aluminate and water were mixed in a Teflon liner. After stirring for 30 min, OSDAs (pyrrolidine, piperidine, azepane, piperazine, DABCO, 4-methylpiperidine) were added and the mixture was stirred for 60 min. Approximately 5 wt. % (silica-based) seeds (CBV10A) were then added before being loaded into a Teflon lined Parr autoclave. The molar composition of the synthesis gel was 1 SiO 2 :0.067 Al 2 O 3 :0.23 OSDA:0.75 Na 2 O:11 H 2 The autoclave was placed in a preheated static convection oven at 170° C. for 3 days.

[0219] The synthesis procedure of OSDA-free Si / Al=4 MOR zeolite was followed by J. Zhu et al., Ultrafast, OSDA-free synthesis of mordenite zeolite. CrystEngComm vol. 19, pp. 632-640 (2017). Silica, sodium aluminate, sodium hydroxide and water were mixed and stirred for 30 min. Then, about 5 wt.% (silica-based) seeds (CBV10A) were added before loading into a Teflon-lined Parr autoclave. The molar composition of the synthesis gel was 1 SiO 2 :0.1 Al 2 O 3: 0.2 Na 2 O:26 H 2 The autoclave was placed in a preheated rotating convection oven at 170° C. for 7 days.

[0220] Large MOR-type zeolite crystals were synthesized according to L. Zhang, AN C van Laak, PE de Jongh, KP de Jong, Synthesis of large mordenite crystals with different aspect ratios. Microporous Mesoporous Mater. Vol. 126, pp. 115-124 (2009). Silica (LuDox-40, Sigma-Aldrich), sodium aluminate, sodium hydroxide (50 wt% aqueous solution, Sigma-Aldrich) and water were mixed and stirred for 30 min. Then, about 5 wt% (silica-based) seeds (CBV10A, Zeolyst) were added before loading into a Teflon-lined Parr autoclave. The molar composition of the synthesis gel was 1 SiO 2 :0.052 Al 2 O 3 :0.23 Na 2 O:3.42 H 2 The autoclave was placed in a preheated rotating convection oven at 170° C. for 7 days.

[0221] Omega-1 (MAZ). Omega-1 zeolite was synthesized according to A.J. Perrotta, C. Kibby, B.R. Itchell, E.R.Tucci, The synthesis, characterization, and catalytic activity of omega and ZSM-4 zeolites. J. Catal. vol. 55, pp. 240-249 (1978). OSDA (TMAOH, Sigma-Aldrich) was first mixed with water. Sodium hydroxide and sodium aluminate were then added. Silica (LuDox-40, Sigma-Aldrich) was added to the solution and stirred for 30 min. The molar composition of the resulting solution was 10 SiO 2 :1.0 Al 2O 3 :1.6 TMAOH:3.2 Na 2 O:160 H 2 The solution was placed in a polypropylene bottle and heated to 95° C. for 10 days.

[0222] *BEA. *BEA type zeolite was described by S.-T.Yang, J.Kim, W.-S.Ahn, CO 2 Adsorption over ion-exchanged zeolite beta with alkali and alkaline earth metal ions.Synthesis was performed according to Microporous Mesoporous Mater. Vol. 135, pp. 90-94 (2010). Sodium aluminate, OSDA (TEAOH, Sigma-Aldrich) and water were mixed. Silica (Carbosil M5) was then added and stirred for 120 min. The molar composition of the resulting gel was 1 SiO 2 :0.1 Al 2 O 3 :1.0 TEAOH:0.1 Na 2 O:6.2 H 2 The thick gel was loaded into a Teflon-lined Parr autoclave and placed in a preheated static convection oven at 170° C. for 3 days.

[0223] MEL (ZSM-11). ZSM-11 zeolite with Si / Al=15 was synthesized according to L. Zhang et al., Differences between ZSM-5 and ZSM-11 zeolite catalysts in 1-hexene aromatization and isomerization. Fuel Process. Technol. 91, 449-455 (2010). Silica (TEOS) and OSDA (TBABr) were mixed. Aluminum sulfate and sodium hydroxide were then added and stirred for 60 min to obtain a solution. The molar composition of the resulting solution was 1 SiO 2 :0.025 Al 2 O 3 :0.18 TBABr:0.14 Na 2O:42.35 H 2 The solution was loaded into a Teflon-lined Parr autoclave and placed in a rotating convection oven at 150° C. for 3 days.

[0224] MFI, FER and LTL. FER type with Si / Al=10 (CP914C, NH 4 type) zeolite and MFI type with Si / Al=12 (CBV2314, NH 4 Zeolite type ZSM-5) was obtained from Zeolyst. LTL type zeolite (HSZ500, K type) with Si / Al=3 was obtained from Tosoh Corporation. The LTL type zeolite was heated at 80 °C for three times (total 72 h) in 1 M NH 4 NO 3 By ion exchange with NH 4 converted to type.

[0225] Calcination of the zeolite. After the synthesis was completed, the resulting solid was washed three times with distilled water. The material synthesized with OSDA was further washed with acetone. To remove the OSDA from the zeolite, the resulting solid was then dried at 80 °C and then calcined in a flowing air furnace at 580 °C for 8 h with a ramp rate of 1.0 °C / min. Laboratory-based X-ray diffraction (XRD) was used to investigate the crystallinity of the material.

[0226] Aqueous phase ion exchange of zeolites. Na-form zeolites were calcined or as-received with 1M NaNO 3 The crystals were prepared by ion-exchange with aqueous solutions. Typically, 600 mg of zeolite was added to 30 mL of salt solution, which was then stirred at 80° C. for 24 hours. The exchanged crystals were dried overnight at 100° C. in a free convection oven in ambient air. A similar ion-exchange procedure was used to prepare various Na + A sample for the preparation of loaded MOR-type zeolite was prepared. MOR6 zeolite (CBV10A, Zeolyst, 4# in Table 1) was dissolved in 1M NH 4 NO 3After two ion exchanges (total 48 h) with aqueous solutions, it was first completely converted to the ammonium form. + Depending on the exchange level, 30 mL of 0.002 M to 5 M NaNO 3 Aqueous solutions were used as precursors. The materials were collected by centrifugation and washed six times with copious amounts of distilled water. The exchanged crystals were dried overnight at 100 °C. Na- and H-densities were determined by energy dispersive X-ray spectroscopy (EDS) and solid state 1 H nuclear magnetic resonance (NMR) spectroscopy was used.

[0227] Pyridine modification of zeolites. For pyridine modification of MOR-type zeolites, denoted as py-MOR, a previously reported method was followed. Briefly, Na-MOR was dehydrated overnight at 170 °C under vacuum (0.1 mbar). After the sample was cooled to room temperature and flushed with ultra-high purity Ar, pyridine was charged to the MOR zeolite in an amount of approximately 0.5 mL pyridine / mg zeolite. The py-MOR zeolite was heated to 300 °C and held for 19 h to remove water and excess pyridine, followed by CO 2 -deposition at 30 °C in a dynamic column fixed bed system. 2 The adsorption was measured.

[0228] Characterization

[0229] The crystallinity, morphology, chemical composition and porosity of the zeolites were characterized by powder XRD, scanning electron microscopy, electron dispersive spectroscopy and N 2 The distribution and density of Brønsted acid sites were analyzed using Fourier transform infrared spectroscopy (FTIR) and 1H solid state magic-angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, respectively. The coordination environment of Al species in MOR-type zeolites was analyzed using 27 The Na content in MOR zeolites was investigated using Al NMR spectroscopy. + The location of the cations was characterized using X-ray crystallography, i.e., single crystal XRD analysis. The detailed method is given below.

[0230] X-ray diffraction. The crystallinity of the materials was investigated using powder X-ray diffraction (XRD). The XRD patterns were collected using a Rigaku Miniflex II desktop instrument equipped with a Cu radiation source, Kα=1.5418A.

[0231] Scanning electron microscopy. The morphology of the materials was measured using a scanning electron microscope (SEM, ZEISS 1550 VP FESEM). The SEM was equipped with an Oxford X-Max SDD. Energy dispersive X-ray spectroscopy (EDS) was used to measure the elemental content of each sample.

[0232] Solid-state magic-angle spinning nuclear magnetic resonance. Solid-state magic-angle spinning nuclear magnetic resonance (MAS NMR) spectra were obtained on a Bruker AVANCE 500 MHz (11.2 T) spectrometer using a 4 mm zirconia rotor with a Kel-F cap. 1 H MAS NMR spectroscopy was used to determine the Na + Residual H density of exchanged MOR zeolite is calculated by + Quantified as a function of loading. 4 A mold material was used to avoid dealumination by ion exchange and dehydration. Samples were loaded into a rotor and dehydrated in a Schlenk manifold at 400 °C for 12 h under vacuum (10-2 Torr). Spectra were acquired at 500.1 MHz with a 90° pulse length of 4 μs and a spinning speed of 12 kHz, then deconvoluted using DMFit software. The number of framework NH4 sites (mmol / g) was calculated by referencing the signal intensity to hexamethylbenzene and normalizing it by the sample mass, followed by NH 4 + The residual NH of the Na-exchanged MOR zeolite was then measured by dividing the number of protons per unit mass by 4. 4 The site density was quantified using the same procedure as a function of Na loading. To investigate the state of aluminum in Na-exchanged MOR zeolites, a 10″ pulse length of 0.5 μs, a cycle delay time of 0.5 s, and a spin speed of 12 kHz was used to measure the site density of the same sample not subjected to dehydration at 130.2 MHz.27 Al MAS NMR spectra were also recorded.

[0233] Fourier transform infrared spectroscopy. Fourier transform infrared (FTIR) spectra of the zeolite samples were collected using a Nexus 470 FTIR spectrometer equipped with a deuterated L-alanine doped triglycine sulfate (DTGS) detector. The catalyst sample (~10-12 mg) was pressed into a self-supporting wafer (~1.2 cm diameter) and placed in a custom-built FTIR cell. The wafer was treated at 723 K for 120 min in flowing dry air, then 500 s in flowing dry air for 30 min in CO. 2 It was cooled to room temperature for adsorption. Spectra were collected at a resolution of 4 cm-1 and averaged over 64 scans.

[0234] Single crystal X-ray diffraction. Single crystal X-ray diffraction was performed at 100K on a Bruker D8Venture CCD diffractometer using CuKα radiation (λ=1.5406 Å). Crystals were mounted on a Mitegen MicroMount. Multiscan absorption corrections were applied to collected reflections. The structure was solved with the ShelXS structure solving program using Direct Methods and refined with the ShelXL refinement package using Least Squares minimization. All non-hydrogen atoms were refined anisotropically. Figures were exported using Olex2.

[0235] Adsorption performance test. CO 2 The adsorption performance of zeolites towards CO was tested using both single-component static adsorption and dynamic column breakthrough techniques. For single-component experiments, UHP grade (99.999% purity) carbon dioxide was used for all adsorption measurements. 2The isotherms were measured on a Quantachrome Autosorb iQ adsorption. For each measurement, approximately 100 mg of adsorbent was placed in a sample holder immersed in a liquid bath connected to a recirculating chiller equipped with a precision temperature controller. Prior to the adsorption measurements, all samples were outgassed at 60 °C for 0.5 h, then held at 120 °C for 0.5 h, and then held at 350 °C for 6 h, all with a ramp rate of 1.0 °C / min. 2 The performance of zeolites for adsorption was also tested using fixed-bed column breakthrough experiments. (30) Typically, about 500 mg of material was placed in a quartz tube (inner diameter 6.74 mm) to form a fixed bed. First, water and CO 2 To completely remove , the adsorbent bed was purged under 5% Ar / He gas flow of 20 mL min −1 at 550 °C for 24 h before the breakthrough experiment.

[0236] Once cooled to 30 °C, the gas flow was increased to the desired gas mixture (approximately 400 ppm CO) at a flow rate of 20 mL / min. 2 / 400ppm Ar (internal standard) / He or 400ppm CO 2 / 1Ar%(internal standard) / 20% O 2 / N 2 ) was switched to CO. The outlet composition was continuously monitored using an Ametek Dymaxion Dycor mass spectrometer until complete breakthrough was achieved. After each breakthrough experiment, the packed column bed was regenerated at 550 °C for 2 h or at 100 °C or 60 °C for 240 min with a constant 5% Ar / He flow (20 mL / min) to test the recyclability of the material. 2 / N 2 The selectivity is

number

[0237] CO 2 Adsorption rate. C.O. 2The adsorption kinetics of MOR-type zeolites for adsorption was investigated using a TGA (Perkin Elmer STA6000). Typically, about 35-50 mg of zeolite was loaded into an alumina sample pan. The loaded sample was activated at 600 °C for 20 h with a He flow of 70 mL / min. After cooling to 30 °C, the gas was passed at 70 mL / min with 400 ppm CO. 2 / He flow was switched to 0.05 mL / min. Desorption was performed with a ramp rate of 10 °C / min to 600 °C using a He flow of 70 mL / min. The weight of the sample was recorded as a function of time on stream.

[0238] Isosteric heat of adsorption. The isotherms measured at different temperatures were first fitted using the Langmuir-Freundlich (LF) isotherm model:

number

[0239] The heat of adsorption was calculated from the Clausius-Clapeyron equation:

number

number

[0240] result low concentration CO 2MOR-type zeolites for the capture of . The MOR-type zeolite framework (Fig. 1a) is composed of unidirectional 12-membered rings (12-MR, 7.0 × 6.5 Å). 2 ) channel. It has an elliptical opening (5.7 × 2.6 Å 2 ) run in parallel and are interconnected to the 12-MR to form an 8-MR window (4.8 × 3.4 Å 2 As shown below, the side pockets of MOR zeolites can trap low concentrations of CO 2 The present invention can provide a site at which the antibody can be captured.

[0241] Na + The cation is CO in the zeolite. 2 are active sites for the adsorption of Na, and their distribution in the two channels of the MOR framework positions can be determined by deconvoluting the OH stretching region of the Fourier transform infrared spectrum (FTIR, Figure 5). F. Jiao et al., Shape-selective zeolites promote ethylene formation from syngas via a ketene intermediate. Angew. Chem. Int. Ed. Vol. 57, pp. 4692-4696 (2018). Total Na + A series of MOR-type zeolites (Table S1), in which 49–67% of the cations are located in the 8-MR side pocket, were prepared from commercial and synthetic samples (Figs. 6 and 7). [Table 1]

[0242] Equilibrium capacity is measured at 25 °C. 2 isotherms (Figures 8 and 9). 2 Capacity: 8-MR side pockets with Na + It increases with the number of cations (Figure 10). The highest CO 2The capacity (Fig. 1b, Table S2 and Fig. 8) is 1.15 mmol / g for MOR (7#) with a Si / Al ratio of 5 and 1.08 mmol / g for 13X zeolite (0.06 CO 2 / Na + ) has improved adsorption efficiency (0.48 CO 2 / Na + ). [Table 2]

[0243] The capacity of MOR (7#) is also about twice that of the recently developed Zn-CHA adsorbent. D. Fu, Y. Park, M.E. Davis, Zinc containing small-pore zeolites for capture of low concentration carbon dioxide. Angew. Chem. Int. Ed. vol. 61, e202112916 (2022). We successfully synthesized an OSDA-free MOR-type zeolite (14#) with a slightly increased Al content (Si / Al=4), resulting in a capacity of 1.14 mmol / g (Fig. 1b and Figs. 8 and 11), comparable to the value obtained from the OSDA-defined material (7#). CO as monitored by gravimetry (Fig. 12) 2 The rate of adsorption indicates that the adsorption and desorption rates for the MOR zeolite are faster than those for 13X. Furthermore, the steeper breakthrough curve observed for the MOR zeolite compared to that of 13X (Figure 13) further confirms the faster rate of the former material. The FTIR results (Figure 14) show that the CO 2 Molecules are 400 ppm CO 2 We demonstrated that CO is exclusively physisorbed on MOR-type zeolites from 400 ppm CO. In agreement with the FTIR results, the calculated isosteric heat of adsorption for MOR-type (14#) zeolites (Figures 15 and 12) is approximately 30 kJ / mol, and therefore, the adsorption rate of 400 ppm CO is approximately 1.5 kJ / mol. 2 It offers a good compromise between capture capacity and the heat required for regeneration (Figure 1c).

[0244] Adsorption sites in MOR zeolites. Low concentration CO in MOR zeolites. 2 Studies were conducted to identify the active sites involved in the adsorption of CO. MOR-type (4#) zeolite was modified with pyridine, designated as py-MOR, to selectively block the adsorption sites in the 12-MR channel as well as the intersection between the 12-MR channel and the 8-MR side pocket (Figure 17). The pyridine molecule is too large to enter the 8-MR (39) and cannot adsorb CO under ambient conditions. 2 Interestingly, about 85% of the capacity was obtained for the py-MOR zeolite compared to the fresh MOR zeolite (Figure 2a, Figure 18). These data indicate that the CO 2 The isotherms (Figure 2b) demonstrate that the CO molecules are mainly adsorbed in the 8-MR side pockets of the MOR framework. 2 The zeolite shows a two-step uptake of CO, with an inflection at 0.0001 bar, whereas no obvious change is observed in 13X zeolite. This behavior is likely due to the switching of the adsorption cages within the MOR framework. Similar results have been reported for argon (Ar) adsorption in zeolites with multiple accessible cages. Although structural changes in structurally flexible zeolites can cause two-step uptake in the isotherm, the inflection pressure is highly temperature dependent. MOR-type zeolites (Figure 19) show a constant inflection pressure at different temperatures. Moreover, the ratio of the capacity at 0.0001 bar to that at 0.0004 bar (equivalent to 400 ppm, Figure 2b) is about 80%, which is comparable to the 85% obtained from the pyridine shielding experiment (Figure 2a). This result is consistent with the interpretation that the inflection is a result of the switching of the adsorption cages. Taken together, the data suggest that the inflection pressure ... 2 When CO is in the low pressure range 2 It is demonstrated that molecules preferentially adsorb into the 8-MR side pocket of the MOR framework.

[0245] To better understand the structural features and active adsorption sites that provide the adsorption performance of MOR-type zeolites, a series of Na-MOR-type samples (Figures 20–23 and Tables S3–S4) were prepared with fixed Al composition and Na ranging from 0 to 5.81. + / UC, where Na + / UC is the number of Na per MOR unit cell + Represents the number of cations. [Table 3] [Table 4] Notes: a Values ​​were obtained from 1H NMR. b Values ​​were calculated based on proton density from 1H NMR. c. Values ​​were calculated based on the proton densities from 1H NMR and deconvolution of the FTIR spectra of the corresponding samples.

[0246] As shown in Figure 2c, three stages are observed: 2 The capacity increases slightly and then becomes approximately 1.0Na. + / UC started with a rapid increase, followed by 4.8Na + / UC is a constant value. Generally, monovalent Na + The species is Na + The distinct phases observed in these samples are therefore due to the microenvironment of the Na+ cations, i.e., dependent on their location in the MOR-type framework. FTIR spectra (Figure 24 and Table S5) were recorded to confirm the presence of Na+ cations in the MOR-type framework. + CO as a function of load 2 The adsorption state of was tracked. For stage I, 2348 cm -1 Gas phase CO with vibrations of 2 Only 10% was seen, consistent with the low volumes observed. [Table 5]

[0247] Na + As the density increases, the gas phase vibration moves to the right at 2359 cm -1 A shoulder of CO occurs. 2 This suggests that the molecules were linearly physisorbed. Importantly, in the second stage, an additional band due to Na-O vibrations appeared at 2400–2430 cm -1 This is observed between the extra-framework Na + Cations and CO 2 B. Bonelli, B. Onida, B. Fubini, COArean, E. Garrone, Vibrational and thermodynamic study of the adsorption of carbon dioxide on the zeolite Na-ZSM-5. Langmuir 16, 4976-4983 (2000). Single crystal XRD analysis was performed to determine the adsorption of carbon dioxide on the Na + Na in MOR-type frameworks as a function of loading + The locations of Na, which correspond to the samples highlighted as A, B, C, and D in Figure 2c, were identified. + Densities 0.88, 2.59, 4.38 and 5.96Na + Representative samples that were / UC were evaluated (Figure 25 and Table S6). [Table 6]

[0248] The structure was solved using the orthorhombic Cmcm space group with cell parameters of a) 18.094 Å, b) 20.516 Å, and c) 7.524 Å, typical of the MOR unit cell. x Si40.6Al7.4O96 (where x is the amount of Na detected per MOR unit cell) + The chemical formula of Na (representing the number of cations) was obtained. The results (Figure 2d, Figure 26, and Tables S7 to S10) show that Na +shows that is preferentially located in the 8-MR side pocket, followed by the 12-MR main channel. [Table 7] [Table 8] [Table 9] [Table 10]

[0249] Specifically, the O atom site in the 8-MR side pocket connecting to T1 is the only position occupied in stage I (sample A), whereas Na + Cations began to localize at the O33 site connected to T4 in stage II, with an occupancy of 61% observed in sample B. CO 2 The capacity increases rapidly, so the O33 site is exposed to low CO 2 It can be concluded that the O33 site is responsible for the adsorption of CO. Similarly, Corma et al. demonstrated that the O33 site is active for the selective carbonylation of DME, since it stabilizes the adsorbed methoxy species. M. Boronat, C. Martinez-Sanchez, D. Law, A. Corma, Enzyme-like Specificity in Zeolites: A unique site position in mordenite for selective carbonylation of methanol and dimethyl ether with CO. J. Am. Chem. Soc. Vol. 130, pp. 16316-16323 (2008). Interestingly, as shown in sample C, the O33 site continues to adsorb CO even after it is fully occupied. 2The capacity continues to increase. The material had partial occupancy of the O44 site, which connects to T4, located at the intersection of the 8-MR side pocket and the 12-MR channel. These data suggest that the O44 site is a potent endothelial cell that responds to low CO 2 This suggests that the adsorption of py-MOR (Fig. 2a) and CO 2 This corroborates the results from the isotherms (Figure 2b). However, as shown by the data for sample D in stage III (Figures 2c and 2d), there is a large amount of Na equilibrating to the O atom sites in the 12-MR channel. + The addition of cations did not result in an apparent increase in capacity. Furthermore, quantitative analysis of the location and number of Na+ in MOR zeolites was performed using IR spectroscopy and 1 H NMR spectroscopy (Figures 22-23, Table S4). + Number and CO 2 The correlation with CO / UC shows a linear relationship in stage II (Fig. 2d). Thus, these results suggest that the presence of a restricted site, O33, in the 8-MR side pocket within the MOR framework may be involved in the prevention of CO from low concentrations. 2 It has been demonstrated that the intersection sites are the major sites for adsorption, contributing approximately 20% of the capacity.

[0250] The trapping effect is low concentration CO 2 The size of the zeolite pore space and low concentration CO 2 Zeolites with different topologies were investigated to determine the relationship between the adsorption behavior for capturing ZnO and ZnO (Figure 3, Tables S11-S12, and Figures 27-26). [Table 11] [Table 12]

[0251] The 8-MR channel window in LTL zeolite is 2 2.3×5.2 Å, too small for molecules to enter 2The LTL zeolite with a Si / Al ratio of 3 has an elliptical structure with a 400 ppm CO 2 The LTL zeolites also showed almost no uptake at 1 bar CO 2 Note that the MAZ zeolite with Si / Al of 3 has a low capacity at 400 ppm CO 2 The pyridine-containing MAZ-type zeolite showed a high adsorption capacity of 0.65 mmol / g for CO. 2 Adsorption results (Figure 31) show that the 8-MR side pockets of the MAZ framework can absorb 400 ppm CO 2 This indicates that the adsorption of 400 ppm CO is responsible for the adsorption of 400 ppm CO (similar to that observed for MOR-type zeolites). MFI-type (39#) zeolite exhibits a capacity of 0.57 mmol / g, which is much higher than the 0.4 mmol / g from 13X zeolite, but its cation content (Si / Al=12) is 8% of that of 13X (34#) (Si / Al=1.1). MEL-type (40#) zeolite, with a similar structure and cation content (Si / Al=15) to MFI-type zeolite, has a larger intersection (7.7 A) and can adsorb 400 ppm CO. 2 The high capacity of MFI zeolite is therefore likely due to the size of the intersections (6.4 Å). These results suggest that the uptake of CO from low concentrations 2 These results suggest that there are certain regions in the microporous zeolite where adsorption is favorable for the capture of CO. Furthermore, in this regard, the total micropore volume (Table S11) and the CO 2 There is no clear correlation with capacity (table S12).

[0252] However, the adsorption efficiency (CO 2 / Na + ) and CO 2 There is a relationship between the size of the confined space (see definition in Figure 29) in the zeolite where molecules are preferentially adsorbed. As shown in Figure 3b, the highest CO 2The adsorption efficiency is from MOR type zeolites with a confinement space of about 6.2 Å. A decrease in the adsorption efficiency is observed with increasing size of the confinement space in MFI and MAZ type zeolites. A further increase in the confinement space is observed for sizes above 0.8 nm, resulting in a decrease in the adsorption efficiency of CO. 2 Adsorption efficiency of about 0.1CO 2 / Al. Interestingly, the adsorption performance of zeolites is 2 and 400 ppm CO 2 These results are clearly different from those for saturated CO at 1 bar. 2 They show that the adsorption capacity is highly dependent on the total number of adsorption sites in the zeolite. As shown in Figure 3c, the capacity gradually decreases with increasing Si / Al ratio in the zeolite. Indeed, Lobo et al. found that the number of energetically favorable sites is significantly increased for low-pressure CO 2 While this is crucial for the adsorption of CO at high pressures, 2 The molecule uses all available sites, i.e. Na + TDPham, R. Xiong, SISandler, RFLobo, Experimental and computational studies on the adsorption of CO 2 and N 2 on pure silica zeolites. Microporous Mesoporous Mater. vol. 185, pp. 157-166 (2014). FTIR spectra (Figure 3d) were obtained to characterize the CO 2 The adsorption state of gas phase CO was identified. LTL-type zeolite shows an adsorption band at 2348 cm-1. 2 The appearance of the molecule CO for MOR, MFI and MAZ zeolites was shown. 2 The asymmetric vibration of is 2357-2360cm -1and suggested strong ion-dipole interactions induced by large electric field gradients in these zeolites with confinement spaces between 6.2 and 6.7 Å. JW Hardt, HW Abgood, The infrared spectra of carbon dioxide adsorbed on zeolite XJPhys.Chem. 70, 1178-1182 (1966). Interestingly, further increasing the size of the confinement space resulted in the formation of a large ion-dipole interaction, which was induced by large electric field gradients in these zeolites with confinement spaces between 6.2 and 6.7 Å. 2 The molecular physisorption bands were red-shifted, indicating a decrease in the electric field of the zeolite. These results suggest that the low-concentration CO 2 We demonstrated the importance of the size of the confinement space (confinement effect) in the adsorption of CO, while the total density of adsorption sites was 2 This determines the adsorption of the

[0253] MOR-type zeolite for DAC. The real-time breakthrough experiment was carried out using a commercially available MOR-type zeolite (4#) at 400 ppm CO 2 / 1% Ar / 20% O 2 / N 2 The analysis was carried out at 30 °C using simulated air containing a gas mixture of 0.72 mmol / g CO with Ar as the internal standard for quantitative analysis. 2 The capacity was obtained with a breakthrough time of 1839 min / g (800 min for 435 mg of dry material) under a flow of 20 mL / min. This value was obtained under the same conditions with 400 ppm CO 2 This is slightly lower than the 0.77 mmol / g obtained from CO 2 and N 2 This may be due to the weak competitive adsorption between CO 2 The preferential adsorption of CO also leads to higher CO concentrations in breakthrough experiments with simulated air compared to values ​​obtained from single-component isotherm measurements. 2 / N 2 This material also yielded comparable CO selectivity from six adsorption-desorption cycles with simulated air (Figure 32). 2It is very stable under DAC conditions as demonstrated by the capacity (Figure 33). Note that the material can be fully regenerated at temperatures as low as 60 °C, which is an advantage of using pure physisorption (Figure 14) with a low isosteric heat of adsorption (Figure 16). 2 The capacity increased sharply to 2.02 mmol / g at -11 °C for MOR(14#) compared to that from 25 °C (Figure 4b and Figure 33), but a decrease in adsorption efficiency / capacity was observed for the chemical adsorbents with increasing adsorption temperature. Therefore, this material may be promising for DAC under sub-ambient conditions, since about 80% of the world's land temperatures are below 25 °C. G. Rim et al., Sub-ambient temperature direct air capture of CO2 using amine-impregnated MIL-101(Cr) enables ambient temperature CO2 recovery. JACS Au vol. 2, pp. 380-393 (2022). As with all zeolites used so far, the presence of water typically reduces their CO2 recovery. 2 As mentioned above, CO 2 There are circumstances in which pre-intake water removal can be accomplished.

[0254] Summary MOR-type zeolites are 2 The Na2+ ion exchange ligand (O33) is a promising physisorbent for capturing Na, for example, DAC. + is 1.15 mmol CO under low concentration conditions. 2 The zeolite is responsible for most of the capture, and this value is the highest obtained for a physical adsorbent with a low isosteric heat of adsorption of about 30 kJ / mol. The size of the trapped space within the zeolite is sufficient to allow for the capture of low concentrations of CO. 2 It is important to achieve high performance for the adsorption of N. MOR-type zeolites show the greatest benefit from the entrapment. They also 2 and O, which can cause time-dependent degradation of amine-based sorbents. 2 The effect of the presence of CO is negligible.2 Furthermore, the capacity of MOR zeolites is 2 mmol CO at subambient temperatures. 2 / g zeolite and is superior to the amine-based adsorbents under these conditions since the latter show a decrease in capacity with decreasing temperature.

[0255] MOR-type zeolites for DAC from wet gaseous source mixtures.

[0256] 2500 ppm H 2 Simulated air containing O was passed through a column of MOR zeolite at 30 °C. MOR zeolite has a CO content of 0.94 mmol / g of zeolite. 2 When the zeolite was regenerated at 200 °C, the zeolite reacted with only 0.73 mmol / g of CO 2 When the zeolite was regenerated at 300 °C, it released only 0.93 mmol / g CO 2 capacity. Therefore, in the absence of a desiccant, CO 2 A regeneration temperature of 300° C. is required to maintain capacity.

[0257] 2500 ppm H 2 Simulated air containing O was passed through a column of SAPO-34 and then a column of MOR zeolite at 30 °C. MOR zeolite has a CO content of 0.94 mmol / g of zeolite. 2 The capacity of the zeolite was shown to be 0.93 mmol / g CO in the first cycle after regeneration at 100 °C. 2 capacity and then back to 0.94 mmol / g in the second cycle. Thus, when SAPO-34 is used as a desiccant to pretreat the source gas mixture, the CO 2 A regeneration temperature of only 100° C. is required to maintain capacity. The results of this study are shown in FIG.

[0258] MOR-type zeolites for DAC from wet gaseous source mixtures at low temperatures.

[0259] For the multi-bed experiments, SAPO-34 (Mitsubishi Plastics, Inc.) was used as a CO 2 The adsorbent bed was packed upstream and the two materials were separated by quartz wool. 2 The ratio of the adsorbent to the duration of water breakthrough by SAPO-34 and the CO 2 The duration of saturation was determined. Typically, 300 mg of SAPO-34 and 250 mg of MOR-type zeolite were saturated with 2500 ppm H 2 350 mg of SAPO-34 and 150 mg of MOR-type zeolite with Si / Al=7 (MOR7, CBV10A) were used in a simulated air containing 20,000 ppm H 2 Simulated air containing O was used. Adsorption measurements were carried out at 30 or -10 °C with a simulated air flow of 60 mL / min. A counterflow of 5% Ar / He gas was used for regeneration at the corresponding temperatures.

[0260] SAPO-34 desiccant reduces CO2 emissions by 7% at low temperatures 2 The effect of temperature on the ability to maintain capacity was also demonstrated. 2 Simulated air containing O was passed through a column of SAPO-34 and then a column of MOR zeolite at -10 °C and 30 °C. 2 The capacity is the CO observed in dry air at the same temperature. 2 The results of this experiment are shown in Figure 51.

[0261] Multi-cycle adsorption-desorption of two parallel adsorption units with dual-layer beds.

[0262] A two-bed system was designed and used for multi-cycle experiments with two parallel SAPO-34+MOR units. Typically, one unit (unit A) was operated at 30 °C with simulated humid air and CO2. 2One unit was operated for adsorption and the other unit (unit B) was operated for regeneration at 100° C. using the exhaust gas from unit A. The adsorption measurements were carried out at about 30° C. and with a simulated air flow of about 64 mL / min. A counterflow of 5% Ar / He gas was used for regeneration at the corresponding temperatures.

[0263] Adsorption-desorption in a DAC system with two parallel adsorption units was demonstrated through 15 adsorption-desorption cycles. Each adsorption unit had a bilayer bed containing a layer of SAPO-34 upstream of a layer of MOR. Adsorption was demonstrated using simulated air containing 2500 ppm water at 30 °C. Desorption was achieved by passing the effluent gas from the adsorption unit to a unit undergoing desorption at 100 °C. These results were obtained by operating two parallel units with moist air (2500 ppm H) while adsorbing and desorbing at 30 °C and 100 °C, respectively. 2 O) to CO 2 It was demonstrated that the method can efficiently capture the ion beam. The results of this experiment are shown in Figures 53 and 54.

Claims

1. A metal ion doped crystalline microporous aluminosilicate composition comprising a three-dimensional aluminosilicate framework with a mordenite topology comprising 12-MR channels and 8-MR side pockets, said crystalline microporous aluminosilicate composition containing 2.5 to 9 metal ions per unit cell, a ratio of metal ions to aluminum within said unit cell being 0.3 to 1.4, and ２ 1. A metal ion doped crystalline microporous aluminosilicate composition that adsorbs carbon dioxide when exposed to a gaseous mixture comprising:

2. 2. The metal ion doped crystalline microporous aluminosilicate composition of claim 1, wherein the gaseous mixture further comprises oxygen and / or oxygen.

3. 3. The metal ion doped crystalline microporous aluminosilicate composition of claim 1 or 2, having a Si:Al atomic ratio in the range of 4:1 to 13:

1.

4. A metal ion-doped crystalline microporous aluminosilicate composition as described in claim 1 or 2, wherein the metal ions are arranged within voids or channels of the three-dimensional aluminosilicate framework.

5. The metal ion-doped crystalline microporous aluminosilicate composition of claim 1, wherein the metal ion is (i) an alkali metal cation or (ii) an alkaline earth metal cation.

6. A metal ion-doped crystalline microporous aluminosilicate composition as described in claim 1 or 2, wherein the crystalline microporous aluminosilicate composition (i) contains 6 to 9 metal ions per unit cell, or (ii) contains 2.5 to 5 metal ions in the 8-MR side pockets per unit cell.

7. A metal ion-doped crystalline microporous aluminosilicate composition as described in claim 1 or 2, wherein the crystalline microporous aluminosilicate composition (i) contains 3 to 4.5 metal ions per unit cell, or (ii) contains 1.2 to 2.5 metal ions in the 8-MR side pockets per unit cell.

8. A metal ion-doped crystalline microporous aluminosilicate composition as described in claim 1 or 2, which adsorbs at least 0.1 mmol of carbon dioxide per gram of metal ion-doped crystalline microporous aluminosilicate composition when exposed to CO 2 at a pressure of 0.0004 bar and a temperature of 25°C.

9. A metal ion-doped crystalline microporous aluminosilicate composition as described in claim 1 or 2, which adsorbs at least 2.0 mmol of carbon dioxide per gram of metal ion-doped crystalline microporous aluminosilicate composition when exposed to CO 2 at a pressure of 0.0004 bar and a temperature of -11°C.

10. A metal ion-doped crystalline microporous aluminosilicate composition as described in claim 1 or 2, wherein exposure of the crystalline microporous aluminosilicate composition to CO2 at a pressure of 0.0004 bar and a temperature of 25°C results in adsorption of carbon dioxide in the range of 0.3 to 4.4 molecules of CO2 adsorbed per unit cell.

11. The metal ion-doped crystalline microporous aluminosilicate composition of claim 1 or 2, wherein passing a gaseous mixture having (a) a total pressure in the range of 50 kPa to 350 kPa and (b) a CO2 content in the range of 350 to 1000 ppm through a tube containing a fixed bed of the metal ion-doped crystalline microporous aluminosilicate composition results in complete breakthrough of CO2 after adsorption of an amount of CO2 (on a mmol / g basis) that is 1.5 to 2 times greater than the amount of CO2 adsorbed by an equal weight of zeolite 13X under the same conditions before complete saturation of CO2 occurs.

12. A metal ion-doped crystalline microporous aluminosilicate composition as described in claim 11, wherein the gaseous mixture is (i) 400 ppm CO2 / 1% Ar / He at a flow rate of 20 mL min-1 at 30°C, (ii) 400 ppm CO2 / 1% Ar / 20% He / balance N2 at a flow rate of 20 mL min-1 at 30°C, or (iii) 400 ppm CO2 / 1% Ar / 20% O2 / balance N2 at a flow rate of 20 mL min-1 at 30°C.

13. A metal ion-doped crystalline microporous aluminosilicate composition as described in claim 1 or 2, wherein the adsorbed carbon dioxide desorbs at a temperature below 150°C.

14. The metal ion doped crystalline microporous aluminosilicate composition of claim 1 or 2, having a selectivity for CO 2 to N 2 of at least 3000:

1.

15. A method for capturing carbon dioxide from a gaseous source mixture containing carbon dioxide, comprising contacting the gaseous source mixture with the metal ion-doped crystalline microporous aluminosilicate composition of claim 1 or 2 such that carbon dioxide in the gaseous source mixture is adsorbed by the metal ion-doped crystalline microporous aluminosilicate composition.

16. The method of claim 15, wherein the gaseous mixture further comprises oxygen and / or air and / or water.

17. The method of claim 15, further comprising desorbing the adsorbed carbon dioxide from the metal ion-doped crystalline microporous aluminosilicate composition containing the carbon dioxide.

18. The method described in claim 15, wherein the contacting of the metal ion-doped crystalline microporous aluminosilicate composition with the gaseous source mixture is carried out in the absence of an added desiccant or without the use of an added desiccant.

19. The method described in claim 15, wherein the contacting of the metal ion-doped crystalline microporous aluminosilicate composition with the gaseous source mixture is carried out in the presence of or using an added desiccant.

20. The method of claim 15, wherein contacting the gaseous source mixture with the metal ion-doped crystalline microporous aluminosilicate composition comprises passing the gaseous source mixture through a fixed bed of adsorbent comprising the metal ion-doped crystalline microporous aluminosilicate composition.

21. The method of claim 15, wherein contacting the gaseous source mixture with the metal ion-doped crystalline microporous aluminosilicate composition is carried out at a temperature of less than 50°C.

22. The method of claim 15, wherein desorbing the carbon dioxide from the metal ion-doped crystalline microporous aluminosilicate composition containing the carbon dioxide is carried out at a temperature of less than 150°C.

23. The method of claim 15, wherein the gaseous source mixture has (a) a total pressure in the range of 50 kPa to 350 kPa, and (b) a CO 2 content in the range of 350 to 1000 ppm.

24. A method for capturing carbon dioxide from a moist gaseous source mixture comprising water and carbon dioxide, comprising contacting the gaseous source mixture first with a desiccant and then with the metal ion-doped crystalline microporous aluminosilicate composition of claim 1 or 2, such that water in the gaseous source mixture is adsorbed by the desiccant and carbon dioxide in the gaseous source mixture is adsorbed by the metal ion-doped crystalline microporous aluminosilicate composition.

Images