Gis-type zeolites, adsorbent materials and separation methods

Abstract

The present application provides a GIS type zeolite, wherein the silica-alumina ratio is 0.87 or more, and 27 When the full width at half maximum in the peak of the framework Al derived from the zeolite observed in the Al-MAS-NMR spectrum is set as A, A satisfies A≦5.6 ppm.

Description

Technical Field

[0001] This invention relates to GIS-type zeolite, adsorbent materials, and separation methods. Background Technology

[0002] Zeolite can be used as an adsorbent, desiccant, separator, catalyst, catalyst carrier, detergent additive, ion exchanger, wastewater treatment agent, fertilizer, food additive, cosmetic additive, etc., and is especially useful for gas separation.

[0003] Among zeolites, those with a GIS structure, as defined by the IZA (International Zeolite Association) code for specifying zeolite structure, are called GIS-type zeolites. GIS-type zeolites are porous zeolites composed of oxygen 8-membered rings. Examples of GIS-type zeolites are described in Patent Documents 1-4 and Non-Patent Documents 1-7.

[0004] Patent Document 1 describes the synthesis of GIS-type zeolite for the effective utilization of coal combustion ash, while Patent Document 2 describes the formation of a zeolite coating (GIS-type zeolite) on the surface of an aluminum plate to improve thermal conductivity. Non-Patent Documents 1, 2, and 3 show GIS-type zeolites of silica-alumina, in which almost no carbon dioxide adsorption was observed in any of the reports. Non-Patent Document 4 shows a GIS-type zeolite of phosphophosphate containing phosphoric acid, which was observed to adsorb carbon dioxide along with oxygen, nitrogen, and methane. However, the amount of carbon dioxide adsorbed was not considered sufficient. Non-Patent Documents 5 and 6 also show GIS-type zeolites of silica-alumina, but do not mention the adsorption performance of carbon dioxide, etc. Patent Documents 3 and 4 show GIS-type zeolites with adjusted crystal structures. Although they have adsorption capacity for carbon dioxide, the amount of carbon dioxide adsorbed is not considered sufficient, and the adsorption-desorption hysteresis in the carbon dioxide adsorption-desorption isotherm is not mentioned. Non-patent literature 7 shows a GIS formed by replacing the cations in zeolite with Li, Na, K, Rb and Cs, which has the ability to adsorb carbon dioxide, but adsorption-desorption hysteresis was observed in the carbon dioxide adsorption-desorption isotherm.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 06-340417

[0008] Patent Document 2: Japanese Patent Publication No. 2012-519148

[0009] Patent Document 3: International Publication No. WO2018 / 110559

[0010] Patent Document 4: International Publication No. WO2019 / 202933

[0011] Non-patent literature

[0012] Non-patent document 1: Matthew D. Oleksiak, Arian Ghorbanpour, Marlon T. Conato, B. Peter McGrail, Lars C. Grabow, Radha Kishan Motkuri, Jeffrey D. Rimer "SynthesisStrategies for Ultrastable Zeolite GIS Polymorphs as Sorbents for SelectiveSeparations" Chem.Eur.J.2016,22,16078-16088.

[0013] Non-patent document 2: Pankaj Sharma, Jeong-gu Yeo, Moon Hee Han, Churl Hee Cho "Knobby surfaced, mesoporous, single-phase GIS-NaP1 zeolite microsphere synthesis and characterization for H2 gas adsorption" J.Mater.Chem.A, 2013, 1, 2602-2612.

[0014] Non-patent document 3: Pankaj Sharma, Jeong-gu Yeo, Moon Hee Han, Churl Hee Cho "GIS-NaP1 zeolite microspheres as potential water adsorption material: Influence of initial silica concentration on adsorptive and physical / topological properties" Sci.Rep.2016,6,1-26.

[0015] Non-patent document 4: Arturo J.Hernandez-Maldonado, Ralph T.Yang, Daniel Chinn, Curtis L.Munson. "Partially Calcined Gismondine Type SilicoaluminophosphateSAPO-43: Isopropylamine Elimination and Separation of Carbon Dioxide, HydrogenSulfide, and Water" Langmuir 2003, 19, 2193-2200.

[0016] Non-patent literature 5: Johann Kecht, B. Mihailova, K. Karaghiosoff, S. Mintova, and Thomas Bein. “Nanosized Gismondine Grown in Colloidal Precursor Solutions” Langmuir 2004, 20, 5271-5276.

[0017] Non-patent literature 6: Ulf Hakansson, Lars Falth, Staffan Hansen, “Structure of a High-Silica Variety of Zeolite Na-P” Acta Cryst. (1990). C46, ​​1363-1364.

[0018] Non-patent literature 7: Hyun June CHOI, Jung Gi Min, Sang Hyun Ahn, Jiho Shin, SukBong Hong, Sambhu Radhakrishnan, C.Vinod Chandran, Robert G.Bell, Eric Breynaert and Christine EAKirschhock "Framework flexibility-driven CO2 adsorption on azeolite" Mater.Horiz., 2020, 1528-1532. Summary of the Invention

[0019] The problem that the invention aims to solve

[0020] If we focus on the carbon dioxide adsorption capacity of GIS-type zeolites, for example, if they can selectively remove carbon dioxide from natural gas, their industrial usefulness becomes significant. If they can selectively remove carbon dioxide from the exhaust gases of power plants and steel mills, carbon dioxide emissions can also be reduced.

[0021] In the separation, recovery, and purification of carbon dioxide using adsorbent materials, methods such as pressure swing adsorption (PSA), temperature swing adsorption (TSA), or PSA are employed. The performance requirements for adsorbent materials include high adsorption capacity, selective adsorption of carbon dioxide, high selectivity for the separated gas, and the absence of adsorption-desorption hysteresis. Adsorption-desorption hysteresis refers to the phenomenon of lag during adsorption and desorption in the carbon dioxide adsorption-desorption isotherm. In the process of carbon dioxide desorption-regeneration using adsorbent materials, high adsorption capacity during adsorption and high desorption capacity during regeneration are crucial. With adsorption-desorption hysteresis, the adsorption capacity decreases during adsorption, and consequently, the desorption capacity decreases during regeneration; therefore, it is not a desirable characteristic when used as an adsorbent material.

[0022] Patent documents 1 and 2 do not mention the adsorption of carbon dioxide based on zeolite. Based on the structural analysis results shown therein, it is difficult to say that a crystal structure required for selective adsorption of carbon dioxide has been formed. That is, it can be considered that the carbon dioxide adsorption capacity of the zeolite described in patent documents 1 and 2 is insufficient.

[0023] Furthermore, the zeolites shown in Non-Patent Documents 1 and 2 do not adsorb carbon dioxide and cannot separate carbon dioxide from molecules such as oxygen, nitrogen, and methane, which have larger molecular diameters, through adsorption or gas permeation. The main reason for this is believed to be the deformation of the 8-membered ring in GIS-type zeolites, resulting in a long axis that is... minor axis is The shape is elliptical, with an average molecular diameter of Carbon dioxide molecules cannot easily penetrate into the fine pores. Non-Patent Literature 3 discloses a GIS-type zeolite of silica-alumina phosphate. Compared with the case of silica-alumina, the bonding distance and bond angle are different, resulting in slightly larger 8-membered ring pores. Carbon dioxide adsorption was observed, but the adsorption capacity cannot be said to be high enough, and the adsorption of oxygen, nitrogen, and methane cannot be said to be low enough, leading to a reduced selectivity in the separation from carbon dioxide. Regarding Non-Patent Literatures 5 and 6, the inventors analyzed the zeolites synthesized according to the descriptions in Non-Patent Literatures 5 and 6. The results, determined by 29Si-NMR, showed that a suitable structure was not formed, and the carbon dioxide adsorption performance of the GIS-type zeolite could not be fully utilized.

[0024] On the other hand, patent documents 3 and 4 show GIS-type zeolites with maximum carbon dioxide adsorption capacities of 52.4 cc / g and 67.5 cc / g, respectively, obtained by optimizing the crystal structure of GIS-type zeolites. However, this is not sufficient from the perspective of gas separation and recovery, and the adsorption-desorption hysteresis is not mentioned. Non-patent document 7 shows a GIS-type zeolite obtained by replacing the cations in the zeolite with Li, Na, K, Rb, and Cs, resulting in a GIS-type zeolite with a maximum carbon dioxide adsorption capacity of 82.9 cc / g. However, adsorption-desorption hysteresis was observed in the carbon dioxide adsorption-desorption isotherm.

[0025] The present invention was made in view of the above circumstances, and its object is to provide GIS-type zeolite with small adsorption-desorption hysteresis in carbon dioxide adsorption-desorption isotherms, adsorption materials, and separation methods.

[0026] Methods for solving problems

[0027] To solve the aforementioned problems, the inventors conducted repeated and in-depth research, and found that when the silica-alumina ratio of GIS-type zeolite is within a specified range, and when supplied to… 27 When the full width at half maximum (FWHM) of the spectrum obtained by Al-MAS-NMR measurement is within the specified range, this problem can be solved, thus completing the present invention.

[0028] That is, the present invention is as follows. [1]

[0030] A type of GIS zeolite, wherein,

[0031] The silicon dioxide to aluminum oxide ratio is above 0.87.

[0032] In 27 When the full width at half maximum (FWHM) of the peaks originating from Al within the framework of this zeolite observed in the Al-MAS-NMR spectrum is set to A, it satisfies A≦5.6ppm. [2]

[0034] As described in [1], GIS-type zeolite contains potassium as a cation species in the zeolite. [3]

[0036] As described in [2], the GIS-type zeolite has a potassium atom concentration to aluminum atom concentration ratio (K / Al) of 0.05 or higher. [4]

[0038] As described in any one of [1] to [3], the GIS-type zeolite has a ratio (Z / T) of the total amount of potassium and lithium in the zeolite to the total amount of alkali metals (T) of 0.05 or more. [5]

[0040] The GIS-type zeolite as described in any one of [1] to [4], wherein the carbon atom content is less than 4% by mass. [6]

[0042] The GIS-type zeolite as described in any one of [1] to [5] contains silicon dioxide and aluminum oxide. [7]

[0044] An adsorbent material comprising any one of the following: [1] to [6] GIS-type zeolite. [8]

[0046] A separation method wherein, using the adsorbent material described in [7], one or more gases selected from the group consisting of CO2, H2O, He, Ne, Cl2, NH3 and HCl are separated from a mixture of two or more gases selected from the group consisting of H2, N2, O2, Ar, CO and hydrocarbons. [9]

[0048] The separation method described in [8] involves separating the above-mentioned gases by pressure swing adsorption separation, temperature swing adsorption separation, or pressure swing-temperature swing adsorption separation.

[0049] The effects of the invention

[0050] According to the present invention, GIS-type zeolites, adsorbent materials, and separation methods with small adsorption-desorption hysteresis in carbon dioxide adsorption-desorption isotherms can be provided. Attached Figure Description

[0051] Figure 1 The GIS-type zeolite obtained from Example 1 27 Al-MAS-NMR image.

[0052] Figure 2 The graphs show the carbon dioxide adsorption isotherms and desorption isotherms of the GIS-type zeolite obtained from Comparative Example 1.

[0053] Figure 3 This is a diagram illustrating an adsorbent material according to one embodiment of the present invention. Detailed Implementation

[0054] The following provides a detailed description of specific embodiments of the present invention (hereinafter referred to as "this embodiment"). The present invention is not limited to the following description and can be implemented with various modifications within the scope of its key points.

[0055] In this embodiment of the GIS-type zeolite, the silica-alumina ratio is 0.87 or higher, which will... 27When the full width at half maximum (FWHM) of the peaks originating from the Al framework of this zeolite, observed in the Al-MAS-NMR spectrum, is set to A, it satisfies A≦5.6ppm. The aforementioned GIS-type zeolite exhibits small adsorption-desorption hysteresis in the carbon dioxide adsorption-desorption isotherm. Furthermore, the carbon dioxide adsorption capacity of the aforementioned GIS-type zeolite is sufficiently high.

[0056] According to this embodiment, by controlling the bonding mode of Al present in the zeolite framework, a GIS-type zeolite with small adsorption-desorption hysteresis in the carbon dioxide adsorption-desorption isotherm and thus a sufficient amount of carbon dioxide adsorbed can be provided. The bonding mode of Al affects the structural changes of the zeolite framework itself during adsorption-desorption. For example, if a structural change occurs associated with the adsorption of the adsorbate, the structural change itself during adsorption requires energy, and adsorption-desorption hysteresis is observed. On the other hand, if the structural change is excessive or insufficient, the adsorption amount decreases because sufficient space to adsorb the adsorbate cannot be guaranteed in the first place. Furthermore, since the structural change also affects the pore size, it also contributes to the selectivity when separating carbon dioxide from gases such as nitrogen and methane.

[0057] In the GIS-type zeolite of this embodiment, by controlling the bonding mode of Al in the zeolite framework, the adsorption-desorption hysteresis in the carbon dioxide adsorption-desorption isotherm can be reduced. Specifically, by... 27 In the NMR spectrum obtained by Al-MAS-NMR determination, when the full width at half maximum (FWHM) of the peaks originating from Al within the zeolite framework observed in the chemical shift region of 50 ppm to 70 ppm is set as A, it is preferable that A ≤ 5.6 ppm, more preferably 0.8 ppm ≤ A ≤ 5.4 ppm, and even more preferably 1.1 ppm ≤ A ≤ 3.9 ppm. 27 The full width at half maximum (FWHM) A of the peaks observed in Al-MAS-NMR represents the distribution of Al bonding modes. Since the distribution of Al bonding modes within the zeolite framework affects the structural changes of the zeolite framework itself during adsorption and desorption, adjusting the FWHM A to an appropriate range can eliminate the adsorption-desorption hysteresis in the adsorption-desorption isotherm. Regarding... 27 The full width at half maximum (FWHM) A of the peak observed in Al-MAS-NMR is represented by the spectral position X1 on the high magnetic field side and the spectral position X2 on the low magnetic field side, which is half the value of the peak height (maximum) relative to the baseline-corrected Al-NMR spectrum. This full WHM A is expressed as A = |X2 - X1|.

[0058] In this embodiment, from the perspective of further improving the selective adsorption capacity of carbon dioxide, GIS-type zeolite is preferably silica-alumina.

[0059] In this embodiment, the silica-alumina ratio (represented by the molar ratio of silica to alumina expressed as SiO2 / Al2O3, hereinafter also referred to as "SAR") in the GIS-type zeolite is 0.87 or higher. The lower the SAR of the zeolite, the more hydrophilic it is, and the stronger its adsorption force on polar molecules such as carbon dioxide. If the SAR is low, the adsorption force is too strong, thus increasing the energy required for desorption by heating or vacuuming; therefore, a high SAR is preferred. A SAR of 1.50 or higher is more preferred, and 3.40 or higher is even more preferred. There is no particular upper limit to the SAR, but if the SAR is too high, the interaction with the adsorbed substance decreases; therefore, a SAR of 3000 or lower is preferred, 500 or lower is more preferred, and 100 or lower is even more preferred. The SAR can be determined based on the amount of silica passing through the zeolite. 29 The area intensity of the spectrum obtained from Si-MAS-NMR measurement was calculated. More specifically, the SAR measurement method is as shown in the examples.

[0060] From the perspective of carbon dioxide adsorption capacity, a high SAR is preferred. On the other hand, if the SAR in GIS-type zeolite increases, the adsorption-desorption hysteresis in the carbon dioxide adsorption-desorption isotherm becomes apparent. However, by making the full width at half maximum (FWHM) A of this embodiment within a specified range, the amount of carbon dioxide adsorbed can be increased and the adsorption-desorption hysteresis can be reduced.

[0061] In the GIS-type zeolite of this embodiment, an organic structure-directing agent can be used during synthesis. Since the organic structure-directing agent remains within the pores and fills the space where carbon dioxide enters, the amount of carbon dioxide adsorbed is reduced, therefore, it is preferable to use a small amount. The quantification of the organic structure-directing agent or the substance obtained by its modification can be performed by measuring the carbon atom content. Preferably, the carbon atom content is 4% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less.

[0062] From the perspective of improving the selective adsorption capacity of carbon dioxide, potassium or lithium is preferably included as the cation species in GIS-type zeolite, and potassium is more preferably included. Furthermore, the total potassium and lithium content in the zeolite is calculated as the ratio (Z / T) of the total mass of potassium and lithium in the GIS-type zeolite to the total mass of alkali metals (T). Z / T is preferably 0.05 or more, more preferably 0.10 or more, and even more preferably 0.15 or more. There is no particular upper limit to Z / T, and Z / T can be 1.00 or less. Regarding Z / T, the zeolite can be thermally dissolved in an aqueous sodium hydroxide solution or aqua regia, and the Z / T can be determined by ICP-luminescence spectrophotometry using the appropriately diluted liquid. More specifically, Z / T can be determined by the method described in the examples below. Z / T can be adjusted by changing the ratio of potassium and lithium in the GIS-type zeolite cation species.

[0063] The ratio (K / T) of the total amount of potassium (K) in GIS-type zeolite to the total amount of alkali metals (T) is preferably 0.05 or more, more preferably 0.10 or more, and even more preferably 0.15 or more. There is no particular upper limit to K / T, and K / T can be 1.00 or less.

[0064] From the perspective of improving the selective adsorption capacity of carbon dioxide, potassium is preferably included as a cation species in zeolite. Furthermore, the potassium content in zeolite is calculated as the ratio of potassium atomic concentration to aluminum atomic concentration (K / Al). The ratio of potassium atomic concentration to aluminum atomic concentration (K / Al) in zeolite is preferably 0.05 or more, more preferably 0.10 or more, and even more preferably 0.15 or more. There is no particular upper limit to the K / Al ratio; if K / Al is greater than 1.00, there are excess K ions, therefore the ratio of potassium atomic concentration to aluminum atomic concentration (K / Al) in zeolite is preferably 2.00 or less, more preferably 1.50 or less, and even more preferably 1.00 or less.

[0065] The content of carbon atoms, potassium atoms, SAR, and the above-mentioned content. 27 Al-MAS-NMR spectra can be determined using the methods described in the examples below. Furthermore, by adjusting the synthesis conditions of GIS-type zeolites to the preferred ranges described below, these conditions can be adjusted to the aforementioned ranges.

[0066] (Synthesis Method)

[0067] The method for manufacturing GIS-type zeolite according to this embodiment may include, for example, a step of preparing a mixed gel, which contains a silicon oxide source containing silicon, an aluminum source containing aluminum, an alkali metal source / alkaline earth metal source containing at least one selected from alkali metals (M1) and alkaline earth metals (M2), an alkali source, a phosphorus source containing phosphorus, an organic structure directing agent, and water. The mixed gel and its constituent components will be described below.

[0068] [Mixed Gel]

[0069] The hybrid gel in this embodiment is a mixture containing a silicon dioxide source, an aluminum source, an alkali metal source / alkaline earth metal source, and water as components, and may include an alkali source, a phosphorus source, and an organic structure directing agent as needed.

[0070] Silica source refers to the component in the mixed gel that serves as a silicon raw material and constitutes the zeolite manufactured from the mixed gel; aluminum source refers to the component in the mixed gel that serves as an aluminum raw material and constitutes the zeolite manufactured from the mixed gel; alkali metal source / alkaline earth metal source refers to the component in the mixed gel that serves as an alkali metal and / or alkaline earth metal raw material and constitutes the zeolite manufactured from the mixed gel; alkali source refers to the component used for adjusting the alkalinity (pH) of the mixed gel; and phosphorus source refers to the component in the mixed gel that serves as a phosphorus raw material and constitutes the zeolite manufactured from the mixed gel.

[0071] [Silica source]

[0072] As a source of silicon oxide, there are no particular limitations on any commonly used silicon oxide source, such as crystalline silicon oxide, amorphous silicon oxide, silicic acid, silicates, and organosilicon compounds. More specific examples include sodium silicate, potassium silicate, calcium silicate, magnesium silicate, fumed silica, precipitated silica, silica gel, colloidal silica, aluminum silicate, tetraethoxysilane (TEOS), and trimethylethoxysilane. These compounds can be used alone or in combination. Here, aluminum silicate is both a silicon oxide source and an aluminum source.

[0073] Among these, fumed silica, colloidal silica, or precipitated silica are preferred because of the tendency to obtain zeolites with high crystallinity.

[0074] [Aluminum source]

[0075] There are no particular limitations on the aluminum source as long as it is a commonly used aluminum source. Specific examples include sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum acetate, aluminum hydroxide, aluminum oxide, aluminum chloride, aluminum alkoxides, metallic aluminum, and amorphous aluminum silicate gel. These compounds can be used alone or in combination.

[0076] Among these, sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum acetate, aluminum hydroxide, aluminum chloride, and aluminum alkoxides are preferred due to the tendency to obtain zeolites with high crystallinity. For the same reason, sodium aluminate and aluminum hydroxide are more preferred, and sodium aluminate is even more preferred.

[0077] [Alkali metal source / Alkali earth metal source]

[0078] There are no particular restrictions on the types of alkali metals / alkaline earth metals in the alkali metal source / alkaline earth metal source; any alkali metal compound and / or any alkaline earth metal compound can be used.

[0079] Alkali metal / alkaline earth metal sources can be, but are not limited to, hydroxides, bicarbonates, carbonates, acetates, sulfates, nitrates, etc., of alkali metals or alkaline earth metals. These compounds can be used alone or in combination.

[0080] Alkali metals and alkaline earth metals used as alkali sources typically include Li, Na, K, Rb, Cs, Ca, Mg, Sr, and Ba. From the perspective of facilitating the crystallization of the GIS-type framework, Na and K are preferred, with Na being more preferred. Furthermore, alkali metals and alkaline earth metals used as alkali / alkaline metal sources can be used individually or in combination.

[0081] Specifically, examples of alkaline sources include, but are not limited to, the following:

[0082] Sodium sulfate, sodium sulfite, sodium thiosulfate, sodium nitrite, sodium nitrate, sodium carbonate, sodium bicarbonate, sodium phosphate, sodium acetate, sodium formate, sodium citrate, sodium oxalate, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium sulfide, sodium silicate, sodium metasilicate, sodium tetraborate, sodium chlorate, sodium perchlorate, sodium cyanide, sodium metastannate, sodium hexahydroxystan(IV) nitrate, sodium hexacyanoferro(II) nitrate, sodium permanganate, sodium chromate, sodium nickel chromate.

[0083] Potassium sulfate, potassium sulfite, potassium thiosulfate, potassium nitrite, potassium nitrate, potassium carbonate, potassium bicarbonate, potassium phosphate, potassium acetate, potassium formate, potassium citrate, potassium oxalate, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, potassium sulfide, potassium silicate, potassium metasilicate, potassium tetraborate, potassium chlorate, potassium perchlorate, potassium cyanide, potassium metastannate, potassium hexahydroxystan(IV), potassium hexacyanoferrous(II) permanganate, potassium chromate, potassium nickel chromate.

[0084] Lithium sulfate, lithium sulfite, lithium thiosulfate, lithium nitrite, lithium nitrate, lithium carbonate, lithium bicarbonate, lithium phosphate, lithium acetate, lithium formate, lithium citrate, lithium oxalate, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium sulfide, lithium silicate, lithium metasilicate, lithium tetraborate, lithium chlorate, lithium perchlorate, lithium cyanide, lithium metastannate, lithium hexahydroxytin(IV) oxide, lithium hexacyanoferro(II) oxide, lithium permanganate, lithium chromate, lithium nickel chromate.

[0085] Rubidium sulfate, rubidium sulfite, rubidium thiosulfate, rubidium nitrite, rubidium nitrate, rubidium carbonate, rubidium bicarbonate, rubidium phosphate, rubidium acetate, rubidium formate, rubidium citrate, rubidium oxalate, rubidium fluoride, rubidium chloride, rubidium bromide, rubidium iodide, rubidium sulfide, rubidium silicate, rubidium metasilicate, rubidium tetraborate, rubidium chlorate, rubidium perchlorate, rubidium cyanide, rubidium metastannate, rubidium hexahydroxystan(IV) acid, rubidium hexacyanoferrous(II) acid, rubidium permanganate, rubidium chromate, rubidium nickel chromate.

[0086] Cesium sulfate, cesium sulfite, cesium thiosulfate, cesium nitrite, cesium nitrate, cesium carbonate, cesium bicarbonate, cesium phosphate, cesium acetate, cesium formate, cesium citrate, cesium oxalate, cesium fluoride, cesium chloride, cesium bromide, cesium iodide, cesium sulfide, cesium silicate, cesium metasilicate, cesium tetraborate, cesium chlorate, cesium perchlorate, cesium cyanide, cesium metastannate, cesium hexahydroxystan(IV) cesium, cesium hexacyanoferrous(II) cesium permanganate, cesium chromate, cesium nickel chromate,

[0087] Magnesium sulfate, magnesium sulfite, magnesium thiosulfate, magnesium nitrite, magnesium nitrate, magnesium carbonate, magnesium bicarbonate, magnesium phosphate, magnesium acetate, magnesium formate, magnesium citrate, magnesium oxalate, magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, magnesium sulfide, magnesium silicate, magnesium metasilicate, magnesium tetraborate, magnesium chlorate, magnesium perchlorate, magnesium cyanide, magnesium metastannate, magnesium hexahydroxystan(IV) nitrate, magnesium hexacyanoferrous(II) nitrate, magnesium permanganate, magnesium chromate, magnesium nickel chromate.

[0088] Calcium sulfate, calcium sulfite, calcium thiosulfate, calcium nitrite, calcium nitrate, calcium carbonate, calcium bicarbonate, calcium phosphate, calcium acetate, calcium formate, calcium citrate, calcium oxalate, calcium fluoride, calcium chloride, calcium bromide, calcium iodide, calcium sulfide, calcium silicate, calcium metasilicate, calcium tetraborate, calcium chlorate, calcium perchlorate, calcium cyanide, calcium metastannate, calcium hexahydroxystan(IV) phosphate, calcium hexacyanoferro(II) phosphate, calcium permanganate, calcium chromate, calcium nickel chromate.

[0089] Strontium sulfate, strontium sulfite, strontium thiosulfate, strontium nitrite, strontium nitrate, strontium carbonate, strontium bicarbonate, strontium phosphate, strontium acetate, strontium formate, strontium citrate, strontium oxalate, strontium fluoride, strontium chloride, strontium bromide, strontium iodide, strontium sulfide, strontium silicate, strontium metasilicate, strontium tetraborate, strontium chlorate, strontium perchlorate, strontium cyanide, strontium metastannate, strontium hexahydroxystan(IV) sulfide, strontium hexacyanoferro(II) sulfide, strontium permanganate, strontium chromate, strontium nickel chromate.

[0090] Barium sulfate, barium sulfite, barium thiosulfate, barium nitrite, barium nitrate, barium carbonate, barium bicarbonate, barium phosphate, barium acetate, barium formate, barium citrate, barium oxalate, barium fluoride, barium chloride, barium bromide, barium iodide, barium sulfide, barium silicate, barium metasilicate, barium tetraborate, barium chlorate, barium perchlorate, barium cyanide, barium metastannate, barium hexahydroxystan(IV) nitrate, barium hexacyanoferro(II) nitrate, barium permanganate, barium chromate, barium nickel chromate, etc.

[0091] [Alkali source]

[0092] The alkali source is used in the manufacture of zeolites to adjust the alkalinity (pH) of the mixed gel in order to promote crystallization into a zeolite structure. Any compound exhibiting alkalinity can be used; both inorganic and organic compounds are acceptable. From a cost perspective, inorganic compounds are preferred, and alkali metal hydroxides are more preferred. Examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide; sodium hydroxide and potassium hydroxide are preferred, and sodium hydroxide is more preferred. These compounds can be used alone or in combination.

[0093] There are no particular limitations on the phosphorus source as long as it is a commonly used phosphorus source. Specific examples include aqueous phosphoric acid solution, sodium phosphate, aluminum phosphate, potassium phosphate, lithium phosphate, calcium phosphate, and barium phosphate. These compounds can be used alone or in combination.

[0094] Among these, aqueous phosphoric acid solution, sodium phosphate, and aluminum phosphate are preferred because of the tendency to obtain zeolites with high crystallinity. Similarly, aqueous phosphoric acid solution and sodium phosphate are more preferred, and aqueous phosphoric acid solution is even more preferred.

[0095] [Organic Structure Directing Agent]

[0096] In the case of zeolite production via hydrothermal synthesis of mixed gels, organic structure-directing agents are compounds that promote crystallization into a zeolite structure. Organic structure-directing agents can be used as needed during zeolite crystallization.

[0097] Organic structure-directing agents can be of any type as long as they can form the desired GIS-type zeolite. Furthermore, organic structure-directing agents can be used alone or in combination.

[0098] As an organic structure directing agent, the following can be used, but are not limited to: amines, quaternary ammonium salts, alcohols, ethers, amides, alkyl ureas, alkyl thioureas, cyanoalkanes, and alicyclic heterocyclic compounds containing nitrogen as a heteroatom. Alkylamines are preferred, and isopropylamine is more preferred.

[0099] Such salts may be accompanied by anions. Examples of such anions include, but are not limited to, Cl-. - ,Br - I - The ions include halide ions, hydroxide ions, acetate ions, sulfate ions, nitrate ions, carbonate ions, and bicarbonate ions. Among these, halide ions and hydroxide ions are preferred, and halide ions are more preferred, from the perspective of making the crystallization formation of the GIS-type framework easier.

[0100] [Composition ratio of the mixed gel]

[0101] In this embodiment, the selection of the silica source is crucial for synthesizing GIS-type zeolites with appropriate structures. The dissolution behavior of the silica source in the initial stage of the reaction significantly influences the bonding mode of Al in the zeolite framework; therefore, an appropriate silica source needs to be selected based on the mixed gel composition. Furthermore, the dissolution behavior of the silica source in the initial stage of the reaction depends on the amount of alkali metal / alkaline earth metal contained in the silica source itself. The ratio of the amount of alkali metal / alkaline earth metal contained in the silica source to SiO2 is expressed as the molar ratio of the sum of L12O and L2O relative to SiO2, i.e., (L12O + L2O) / SiO2. (Here, L1 and L2 represent the alkali metal and alkaline earth metal contained in the silica source, respectively, calculated in the form of oxides.)

[0102] It should be noted that even when using multiple silica sources, the ratio of the total molar amount of alkali metal / alkaline earth metal contained in the multiple silica sources to the total molar amount of SiO2 can be considered. From the perspective of selecting an appropriate silica source and controlling the dissolution behavior of the silica source in the initial stage of the reaction, the ratio of the amount of alkali metal / alkaline earth metal contained in the silica source to SiO2 (L12O+L2O) / SiO2 is preferably 0.30 or less, more preferably 0.25 or less, and even more preferably 0.08 or less.

[0103] To synthesize GIS-type zeolites with appropriate structures, the amount of alkali metal / alkaline earth metal in the mixed gel is related to the OH content. - The ratio is the most important. The amount of alkali metal / alkaline earth metal in the mixed gel is related to the OH group. - The ratio of OH - The molar ratio relative to the total molar ratio of M12O and M2O, i.e., OH - It is expressed in the form of / (M12O+M2O). (Here, M1 represents alkali metals, and M2 represents alkaline earth metals. They are calculated as oxides.) Additionally, OH... - It originates from inorganic hydroxides such as NaOH and Ca(OH)2, and organic hydroxides such as tetraethylammonium hydroxide. - This excludes the OH- ions released when substances such as sodium aluminate and sodium silicate, which are oxides, or their hydrates, are dissolved in water. - .

[0104] In the formation of zeolites, the silica and aluminum sources dissolved in the aqueous solvent react simultaneously with dissolution, resulting in crystallization. This is achieved by adjusting the amount of alkali metal / alkaline earth metal in the mixed gel with OH groups. -When the ratio is within an appropriate range, the bonding mode of Al in the zeolite framework can be controlled, enabling the synthesis of GIS-type zeolites with ideal crystal structures. From the perspective of crystallization to form an ideal GIS-type framework, the ratio of alkali metal to alkaline earth metal and OH... - The ratio of OH - The concentration of (M12O+M2O) is preferably 0.20 or less, more preferably 0.16 or less, and even more preferably 0.10 or less.

[0105] The ratio of silica source to aluminum source in the mixed gel is expressed as the molar ratio of the oxides of each element, i.e., SiO2 / Al2O3. (It should be noted that the silica-alumina ratio of the synthesized zeolite is not the same as that of the mixed gel. The silica-alumina ratio of the synthesized zeolite is determined by other components and synthesis conditions.) The SiO2 / Al2O3 ratio in the mixed gel is not particularly limited as long as it can form zeolite. However, for the purpose of suppressing the formation of zeolites with a framework different from the GIS type framework, it is preferably 3.0 to 70.0 or less, more preferably 3.5 to 65.0 or less, and even more preferably 4.0 to 60.0 or less.

[0106] Furthermore, a high water-to-alumina ratio (H2O / Al2O3) facilitates more uniform dispersion of components in the mixed gel, but excessively high ratios significantly reduce the crystallization rate. Therefore, to synthesize GIS-type zeolites with optimal crystal structure, it is necessary to maintain an optimal H2O / Al2O3 ratio, which influences the balance between crystallization and resolution.

[0107] Based on the above, H2O / Al2O3 is preferably 210≦H2O / Al2O3≦780, more preferably 220≦H2O / Al2O3≦778, and even more preferably 230≦H2O / Al2O3≦775.

[0108] The ratio of phosphorus source to aluminum source in the mixed gel is expressed as the molar ratio of the oxides of each element, i.e., P2O5 / Al2O3. This P2O5 / Al2O3 ratio is not particularly limited as long as it is a ratio capable of forming zeolite. However, for the purpose of suppressing the formation of zeolites with a framework different from the GIS type framework, it is preferably less than 1.0, more preferably 0.6 or less, even more preferably 0.4 or less, and particularly preferably 0.

[0109] When the mixed gel contains an organic structure-directing agent, the ratio of aluminum source to organic structure-directing agent in the mixed gel is expressed as the molar ratio of organic structure-directing agent to Al2O3, i.e., R / Al2O3 (where R represents the organic structure-directing agent). From the perspective of easier crystallization of the GIS-type framework, and / or shorter synthesis time, and better economic efficiency in zeolite production, a ratio of less than 7.0 is preferred, more preferably 6.0 or less, and even more preferably 5.0 or less. When using an organic structure-directing agent, the organic structure-directing agent remains within the zeolite pores, preventing carbon dioxide from entering the pores and reducing adsorption. To remove the organic structure-directing agent, heating to at least 400°C is required, but GIS-type zeolites crystallize and break down at temperatures above 350°C, becoming amorphous; therefore, a lower organic structure-directing agent ratio is preferred. From this perspective, an R / Al2O3 ratio of 4.0 or less is preferred, more preferably 3.5 or less, and even more preferably 3.0 or less.

[0110] As described above, the method for manufacturing GIS-type zeolite in this embodiment includes a mixed gel preparation step. This mixed gel contains a silicon dioxide source containing silicon, an aluminum source containing aluminum, an alkali metal / alkaline earth metal source, an alkali source, a phosphorus source, and water. When calculating the molar ratio of each component in the mixed gel in the form of oxides for the silicon, aluminum, alkali metal (M1), alkaline earth metal (M2), alkali metal (L1), alkaline earth metal (L2) contained in the silicon dioxide source, and phosphorus source, the following formulas (1), (2), and (3) are used. The molar ratios α, β, γ, δ, and ε represented by 3), (4), (5), and (6) preferably satisfy α≦0.30, β≦0.20, 3.0≦γ≦70.0, 210≦δ≦780, and 0≦ε<1.0; more preferably, they satisfy α≦0.25, β≦0.16, 3.5≦γ≦65.0, 220≦δ≦778, and 0≦ε≦0.6; and even more preferably, they satisfy α≦0.08, β≦0.10, 4.0≦γ≦60.0, 230≦δ≦775, and 0≦ε≦0.4. The GIS-type zeolite of this embodiment is particularly preferably obtained by the above-described manufacturing method of the GIS-type zeolite of this embodiment.

[0111] α=(L12O+L2O) / SiO2 (1)

[0112] β=OH - / (M12O+M2O) (2)

[0113] γ=SiO2 / Al2O3 (3)

[0114] δ=H2O / Al2O3 (4)

[0115] ε=P2O5 / Al2O3 (5)

[0116] Furthermore, in the method for manufacturing GIS-type zeolite in this embodiment, when the molar ratios α, β, γ, δ, and ε satisfy the above-mentioned ranges, and the mixed gel further contains an organic structure directing agent R, the molar ratio ζ represented by the following formula (6) preferably satisfies ζ≦4.

[0117] ζ=R / Al2O3 (6)

[0118] It is not necessary to have seed crystals in the mixed gel. Pre-made GIS-type zeolite can also be added to the mixed gel as seed crystals to obtain the GIS-type zeolite of this embodiment.

[0119] [Preparation process of mixed gel]

[0120] The preparation process of the mixed gel is not particularly limited, but may include, for example, a mixing process in which a silica source, an aluminum source, an alkali metal source / alkaline earth metal source, water, and, if necessary, an alkali source, a phosphorus source, and an organic structure directing agent are mixed in one step or in multiple stages; and a maturation process of the mixture obtained in the mixing process.

[0121] In the mixing process, these components, including silicon oxide source, aluminum source, alkali metal source / alkaline earth metal source, water, and if necessary, alkali source, phosphorus source, and organic structure directing agent, can be mixed in one step or in multiple stages.

[0122] There is no fixed order for multi-stage mixing; the appropriate order can be chosen based on the conditions used. Multi-stage mixing can be carried out with or without stirring. When stirring, there are no particular restrictions on the commonly used stirring method; specific examples include paddle stirring, vibratory stirring, oscillating stirring, and centrifugal stirring.

[0123] There is no particular limitation on the rotation speed of the stirring as long as it is a commonly used stirring speed. For example, it can be above 1 rpm and less than 2000 rpm.

[0124] There are no particular restrictions on the temperature of the mixing process, as long as it is a commonly used temperature, such as above -20°C and below 80°C.

[0125] There is no particular time limit for the mixing process; it can be appropriately selected based on the temperature of the mixing process. For example, a time greater than 0 minutes and less than 1000 hours can be used.

[0126] The maturation process can be carried out under either static or stirring conditions. When stirring during the maturation process, there are no particular restrictions on the commonly used stirring method. Specific examples include using paddle stirring, vibration stirring, oscillating stirring, centrifugal stirring, etc.

[0127] There is no particular limitation on the rotation speed of the stirring as long as it is a commonly used stirring speed. For example, it can be above 1 rpm and less than 2000 rpm.

[0128] There are no special restrictions on the temperature of the curing process as long as it is a commonly used temperature, such as -20°C or higher and less than 80°C.

[0129] There is no particular time limit for the curing process; it can be selected appropriately based on the temperature of the curing process. For example, a curing time greater than 0 minutes and less than 1000 hours can be given.

[0130] It is believed that the zeolite undergoes dissolution of raw materials and formation and redissolution of zeolite precursors during the mixing and curing processes. To avoid defects in forming a large-periodic structure containing 8-membered rings, it is preferable not to excessively form the zeolite precursors. Furthermore, excessive formation of the zeolite precursors tends to increase the formation of ANA-type zeolites with more stable structures; therefore, excessive curing is also preferable. On the other hand, it is preferable to thoroughly mix the raw materials until the gel is homogeneous. The time for combining the mixing and curing processes is not particularly limited, as long as it is appropriately adjusted based on the composition of the raw materials to obtain a zeolite with a suitable structure. The aforementioned time is typically preferred to be 1 minute or more and less than 24 hours, more preferably 3 minutes or more and less than 23 hours, further preferably 10 minutes or more and less than 18 hours, even more preferably 12 minutes or more and less than 15 hours, and even more preferably 20 minutes or more and less than 6 hours.

[0131] [Hydrothermal synthesis process]

[0132] In the method for manufacturing GIS-type zeolite according to this embodiment, it is preferable to further include a hydrothermal synthesis step at a hydrothermal synthesis temperature of 80°C to 200°C, more preferably 100°C to 180°C. That is, it is preferable to perform hydrothermal synthesis on the mixed gel obtained by the preparation step at a specified temperature while maintaining it in a stirred or static state for a specified time.

[0133] The hydrothermal synthesis temperature is not particularly limited as long as it is a commonly used temperature. From the perspective of shortening the synthesis time and improving the economy of zeolite production, 80°C or higher is preferred. From the perspective of suppressing the formation of zeolites with a framework different from the GIS type, 90°C or higher is more preferred, and 100°C or higher is even more preferred. From the perspective of suppressing the formation of zeolites with a framework different from the GIS type, 200°C or lower is more preferred, 180°C or lower is even more preferred, and 170°C or lower is even more preferred. The hydrothermal synthesis temperature can be fixed or varied in stages.

[0134] The hydrothermal synthesis time is not particularly limited as long as it is a commonly used time, and can be appropriately selected according to the hydrothermal synthesis temperature. Regarding the hydrothermal synthesis time, from the perspective of forming the GIS framework, 3 hours or more is preferred, and 10 hours or more is more preferred. From the perspective of obtaining highly crystalline GIS-type zeolite, 24 hours or more is even more preferred. From the perspective of excellent economic efficiency in zeolite manufacturing, the hydrothermal synthesis time is preferably 30 days or less, more preferably 20 days or less, and even more preferably 10 days or less.

[0135] In the hydrothermal synthesis process, there are no particular limitations on the container used to hold the mixed gel, as long as it is a commonly used container. However, when the pressure inside the container increases at a specified temperature, or when pressurization is performed using a gas that does not hinder crystallization, it is preferable to use a pressure-resistant container for hydrothermal synthesis. There are no particular limitations on the pressure-resistant container; for example, various shapes such as spherical, elongated, and transversely elongated can be used.

[0136] When stirring the mixed gel in the pressure vessel, the pressure vessel is rotated in the up-down direction and / or left-right direction, preferably in the up-down direction. When rotating the pressure vessel in the up-down direction, the rotation speed is not particularly limited as long as it is within the commonly used range, preferably 1 to 50 rpm, more preferably 10 to 40 rpm.

[0137] In the hydrothermal synthesis process, when stirring the mixed gel, a preferred method is to use a long, vertical container as a pressure vessel and rotate it in the vertical direction.

[0138] [Separation-Drying Process]

[0139] After the hydrothermal synthesis process, the solid product is separated from the liquid containing water. There are no particular limitations on the separation method as long as it is a common method. It can be filtration, decanting, spray drying (rotary spray, nozzle spray and ultrasonic spray, etc.), drying using a rotary evaporator, vacuum drying, freeze drying or natural drying, etc. Separation can usually be achieved by filtration or decanting.

[0140] The separated product can be used directly or washed with water or a specified solvent. If necessary, the separated product can be dried. There are no particular limitations on the drying temperature, as long as it is a commonly used drying temperature, typically from room temperature to below 150°C. There are no particular limitations on the drying atmosphere, as long as it is a commonly used atmosphere, typically using air, an atmosphere containing inert gases such as nitrogen or argon, or an atmosphere containing oxygen.

[0141] [Firing process]

[0142] GIS-type zeolite can be calcined for use as needed. The calcination temperature is not particularly limited as long as it is a commonly used temperature. However, when it is desirable to remove the organic structure-directing agent, a temperature of 300°C or higher, more preferably 350°C or higher, is preferred to reduce its residual proportion. From the perspective of shortening calcination time and improving the economy of zeolite manufacturing, a temperature of 360°C or higher is further preferred. For the purpose of maintaining the crystallinity of the zeolite, a temperature of less than 450°C is preferred, more preferably 420°C or lower, and even more preferably 400°C or lower.

[0143] The firing time is not particularly limited as long as it is sufficient to remove the organic structure-directing agent, and can be appropriately selected according to the firing temperature. For the purpose of reducing the residual proportion of the organic structure-directing agent, 0.5 hours or more is preferred, more preferably 1 hour or more, and even more preferably 3 hours or more is preferred. For the purpose of maintaining the crystallinity of the zeolite, 10 days or less is preferred, more preferably 7 days or less, and even more preferably 5 days or less is preferred.

[0144] There are no special restrictions on the firing atmosphere as long as it is a commonly used atmosphere. Usually, an air atmosphere, an atmosphere containing inactive gases such as nitrogen and argon, or an atmosphere containing oxygen are used.

[0145] [Cation exchange]

[0146] Cation exchange can be performed as needed to transform GIS-type zeolites into the desired cationic form. Cation exchange can use, but is not limited to, carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, and ammonium carbonate; or nitrates such as sodium nitrate, potassium nitrate, lithium nitrate, rubidium nitrate, cesium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate, and ammonium nitrate; or acids such as nitric acid or hydrochloric acid formed by replacing the carbonate and nitrate ions contained in the above carbonates and nitrates with halide ions, sulfate ions, carbonate ions, bicarbonate ions, acetate ions, phosphate ions, or hydrogen phosphate ions.

[0147] There is no particular limitation on the temperature of cation exchange as long as it is the usual temperature for cation exchange, which is usually from room temperature to below 100°C.

[0148] When separating zeolites after cation exchange, there are no particular limitations on the separation method as long as it is a common method. Filtration, decanting, spray drying (rotary spray, nozzle spray and ultrasonic spray, etc.), drying using a rotary evaporator, vacuum drying, freeze drying, or natural drying can be used. Separation can usually be achieved by filtration or decanting.

[0149] The separated product can be used directly or washed with water or a specified solvent. If necessary, the separated product can be dried.

[0150] There is no particular limitation on the temperature at which the separated material is dried, as long as it is the temperature at which drying is usually carried out, typically from room temperature to below 150°C.

[0151] There are no special restrictions on the atmosphere used during drying, as long as it is a commonly used atmosphere. Usually, an air atmosphere, an atmosphere containing inactive gases such as nitrogen or argon, or an atmosphere containing oxygen are used.

[0152] In addition, ammonium-type zeolite can be converted into proton-type zeolite by calcination.

[0153] The applications of the GIS-type zeolite in this embodiment are not particularly limited. For example, it can be used as a separating agent or separation membrane for various gases and liquids, an electrolyte membrane for fuel cells, a packing material for various resin molded bodies, a membrane reactor, a catalyst for hydrogen cracking, alkylation, etc., a catalyst support for supporting metals, metal oxides, etc., an adsorbent, a desiccant, a detergent additive, an ion exchanger, a wastewater treatment agent, a fertilizer, a food additive, a cosmetic additive, etc.

[0154] In the above-described embodiments, the GIS-type zeolite can be suitably used as an adsorbent. That is, the adsorbent of this embodiment comprises the GIS-type zeolite of this embodiment. Because of this configuration, the adsorbent of this embodiment is a GIS-type zeolite capable of sufficiently adsorbing carbon dioxide and exhibiting no adsorption-desorption hysteresis in the carbon dioxide adsorption-desorption isotherm. Therefore, it can be particularly preferably used for purposes such as removing carbon dioxide from natural gas.

[0155] The adsorbent in this embodiment is not particularly limited in its composition as long as it contains the GIS-type zeolite of this embodiment. Representative compositions include... Figure 3 The example shown. Figure 3 The adsorbent 1 of this embodiment, as illustrated in the illustration, includes filters 3 disposed at both the inlet and outlet sides inside the container 2, and a plurality of zeolite particles 4 (GIS-type zeolite of this embodiment) disposed between the two filters 3. For example, a filter made of quartz can be used as the filter 3. For instance, when using adsorbent 1 to remove carbon dioxide from natural gas, natural gas can be introduced through an upper pipeline, impurities can be removed by the filters 3, carbon dioxide can be selectively adsorbed and removed by the zeolite particles 4, and methane-rich gas can be extracted through a lower pipeline. The substance supplied to the adsorbent is not limited to natural gas, and the internal structure of the adsorbent is not limited to... Figure 3 The example shown.

[0156] (Separation Method)

[0157] In the separation method of this embodiment, an adsorbent material comprising the GIS-type zeolite of this embodiment is used to separate one or more gases selected from the group consisting of CO2, H2O, He, Ne, Cl2, NH3, and HCl from a mixture containing two or more gases selected from the group consisting of H2, N2, O2, CO, and hydrocarbons. In this embodiment, it is preferable to separate one or more gases selected from the group consisting of CO2 and H2O from a mixture containing one or more gases selected from the group consisting of N2, O2, CO, and hydrocarbons. It should be noted that hydrocarbons are not particularly limited, and examples include methane, ethane, ethylene, propane, propylene, 1-butene, 2-butene, 2-methylpropene, dimethyl ether, and acetylene.

[0158] In the GIS-type zeolite of this embodiment, CO2 adsorption capacity is high, and physical adsorption without chemical bonding has been observed. The separation method using the GIS-type zeolite of this embodiment is not particularly limited, but a method with low energy consumption and excellent economic efficiency during adsorption material regeneration is preferred. Specific examples of this method are not particularly limited, but pressure swing adsorption (PSA), temperature swing adsorption (TSA), or pressure swing-temperature swing adsorption (PTSA) is preferred. Pressure swing adsorption (PSA) separates gases by using the difference between the adsorption capacity at high and low pressures when the gas desorption pressure is lower than the adsorption pressure. Temperature swing adsorption (TSA) separates gases by using the difference between the adsorption capacity at low and high temperatures when the gas desorption temperature is higher than the adsorption temperature. Furthermore, a combination of these methods is pressure swing-temperature swing adsorption (PTSA). These methods can be implemented under various known conditions.

[0159] Example

[0160] The following examples illustrate this embodiment in more detail, but these examples are illustrative and the embodiment is not limited to these examples. Those skilled in the art can make various modifications to the examples shown below and implement them as this embodiment, and such modifications are included within the scope of the invention as long as they satisfy the specific conditions of this embodiment.

[0161] [Atomic concentrations of aluminum, phosphorus, and potassium]

[0162] Zeolite was thermally dissolved in an aqueous sodium hydroxide solution or aqua regia. The appropriately diluted solution was then analyzed using ICP-AES (Hereinafter referred to as "ICP-AES," device name: SPS3520UV-DD, Hitachi High-Tech Science Co., Ltd.). The concentrations of various elements, including silicon, aluminum, phosphorus, potassium, and lithium, in the zeolite were determined. The potassium and lithium content in the zeolite was calculated as the ratio (Z / T) of the total mass of potassium and lithium in the zeolite to the total mass of each alkali metal (T). The K / T ratio was calculated similarly. Furthermore, the potassium content in the zeolite was calculated as the ratio of potassium atomic concentration to aluminum atomic concentration (K / Al).

[0163] [Determination of carbon atom content]

[0164] Approximately 2 mg of the GIS-type zeolite powder sample was weighed, and the carbon content in the zeolite was determined by CHN elemental analysis (using an MT-6 instrument manufactured by Yanaco Analytical Industry Co., Ltd.). For the zeolite sample after CO2 adsorption, in order to detect only the carbon atoms contained in the zeolite, the zeolite powder sample was placed in a sealed container, heated at 200°C while being evacuated using a vacuum pump for more than 3 hours, and then removed and placed in the atmosphere for more than 24 hours before measurement and elemental analysis.

[0165] [X-ray diffraction; crystal structure analysis]

[0166] X-ray diffraction is performed according to the following steps.

[0167] (1) The dried material obtained in each example and comparative example was used as a sample and pulverized with an agate mortar. 10% by mass of crystalline silicon (manufactured by Rare Metallic Co., Ltd.) was added and mixed with an agate mortar until homogeneous, and this was used as a sample for structural analysis.

[0168] (2) The sample from (1) above is uniformly fixed on a non-reflective powder sample plate, and the crystal structure is analyzed by X-ray diffraction under the following conditions.

[0169] X-ray diffraction (XRD) apparatus: Rigaku Corporation's "RINT2500" powder X-ray diffraction apparatus (trade name).

[0170] X-ray source: Cu tube (40kV, 200mA)

[0171] Measurement temperature: 25℃

[0172] Measurement range: 5–60° (0.02° / step)

[0173] Measurement speed: 0.2° / minute

[0174] Slit width (scattering, divergence, light reception): 1°, 1°, 0.15mm

[0175] [ 27 [Al-MAS-NMR determination]

[0176] As a humidification treatment for zeolite, water was poured into the bottom of the desiccator, and the zeolite in the sample tube was placed on top of it for 48 hours. After the humidification treatment, the following conditions were followed. 27 Determination by Al-MAS-NMR.

[0177] Device: JEOL RESONANCE ECA700

[0178] Magnetic field strength: 16.44T 1 H resonant frequency 700MHz)

[0179] Measurement nucleus: 27 Al

[0180] Resonant frequency: 182.43MHz

[0181] NMR tube: (Zirconium oxide rotor)

[0182] Measurement method: DD / MAS (dipolar decoupling magic anglespinning)

[0183] Pulse width: 15°

[0184] Waiting time: 0.5 seconds

[0185] Number of integrations: 6,400 (Measurement time: approximately 1 hour)

[0186] MAS: 18,000Hz

[0187] Chemical shift standard: AlK(SO4)2 12H2O (0ppm) external standard

[0188] For what was obtained 27 The full width at half maximum (FWHM) of the Al-MAS-NMR spectrum was obtained using the analysis program dmfit (version #202000113) with Gaussian and Lorentz functions. The least squares algorithm was used to optimize the calculation of four parameters: amplitude (height of the maximum value of the spectrum), position (spectral position, ppm), width (full width at half maximum, ppm), and Gaussian / Lorentz ratio (xG / (1-x)L).

[0189] [ 29 Si-MAS-NMR determination, SAR]

[0190] zeolite 29 The Si-MAS-NMR determination was performed using the method described below. Additionally, the SAR of zeolites can be determined by measuring... 29 The value is determined by Si-MAS-NMR.

[0191] First, as a humidification process for the zeolite, water was poured into the bottom of the desiccator, and the zeolite in the sample tube was placed on top of it for 48 hours. After the humidification treatment, the following conditions were followed. 29 Determination by Si-MAS-NMR.

[0192] Device: JEOL RESONANCE ECA700

[0193] Magnetic field strength: 16.44 T (H resonant frequency 700 MHz)

[0194] Measurement nucleus: 29 Si

[0195] Resonant frequency: 139.08MHz

[0196] NMR tube: (Zirconium oxide rotor)

[0197] Measurement method: DD / MAS (dipolar decoupling magic anglespinning)

[0198] Pulse width: 45°

[0199] Waiting time: 50 seconds

[0200] Number of integration attempts: 800 (measurement time: approximately 22 hours)

[0201] MAS: 10,000Hz

[0202] Chemical displacement reference: Silicone rubber (-22.34ppm) external reference

[0203] Molded bodies containing GIS-type zeolites in 29 The following five peaks were observed in the Si-MAS-NMR spectrum.

[0204] (1)Q4(0Al): The peak of Si that is not bonded to Al by oxygen at all.

[0205] (2)Q4(1Al): The peak of Si bonded to one Al by oxygen.

[0206] (3)Q4(2Al): The peak of Si bonded to two Al atoms by oxygen.

[0207] (4)Q4(3Al): The peak of Si bonded to 3 Al atoms by oxygen.

[0208] (5)Q4(4Al): The peak of Si bonded to 4 Al atoms by oxygen.

[0209] In addition, 29 In Si-MAS-NMR spectra, these peak positions are typically found between -112 ppm and -80 ppm, and can be assigned to Q4(0Al), Q4(1Al), Q4(2Al), Q4(3Al), and Q4(4Al) from the high magnetic field side. The peak positions can vary depending on the cation species present in the zeolite framework, but they are generally within the following range.

[0210] (1) Q4(0Al): -105ppm to -112ppm

[0211] (2) Q4(1Al): -100ppm to -105ppm

[0212] (3) Q4(2Al): -95ppm to -100ppm

[0213] (4) Q4(3Al): -87ppm to -95ppm

[0214] (5) Q4(4Al): -80ppm to -87ppm

[0215] about 29 The peak area and intensity of the Si-MAS-NMR spectrum were analyzed using the analysis program dmfit (version #202000113) with Gaussian and Lorentz functions. The four parameters, amplitude (height of the maximum value of the spectrum), position (spectral position, ppm), width (full width at half maximum of the spectrum, ppm), and Gaussian / Lorentz ratio (xG / (1-x)L), were optimized and calculated using the least squares algorithm. The peak areas of Q4(0Al), Q4(1Al), Q4(2Al), Q4(3Al), and Q4(4Al) obtained in this way are denoted as A_Q4(0Al), A_Q4(1Al), A_Q4(2Al), A_Q4(3Al), and A_Q4(4Al). When the sum of A_Q4(0Al), A_Q4(1Al), A_Q4(2Al), A_Q4(3Al), and A_Q4(4Al) is taken as A_total, it can be used as SAR and can be calculated as follows.

[0216] SAR=100 / [A_Q4(1Al) / 4+2×A_Q4(2Al) / 4+3×A_Q4(3Al) / 4+4×A_Q4(4Al) / 4]×2

[0217] [CO2 adsorption capacity and hysteresis; determination of gas adsorption-desorption isotherms]

[0218] The determination of the gas adsorption-desorption isotherm is performed according to the following steps.

[0219] (1) The dried material obtained in each example and comparative example was used as a sample and 0.2g was added to a 12mm sample cell (manufactured by MicroMeritics).

[0220] (2) The sample added to the sample cell in (1) above is placed in the gas adsorption measuring device “3-Flex” (trade name) manufactured by Micro Meritics and subjected to heating and vacuum degassing treatment at 250°C and below 0.001 mmHg for 12 hours.

[0221] (3) The sample treated in (2) above is placed in a constant-temperature circulating water at 25°C. After the sample temperature reaches 25±0.2°C, liquefied carbon dioxide (manufactured by Sumitomo Seika Co., Ltd., with a purity of 99.9% by mass or higher) is used for measurement at an absolute pressure of 0.25 to a maximum of 760 mmHg. It should be noted that in the above measurement, the pressure is measured over time, and the saturation adsorption capacity is determined when the pressure change is less than 0.001% / 10 seconds. This is taken as the CO2 adsorption capacity at 25°C (unit: cc / g). The CO2 adsorption capacity is preferably 70 cc / g or more, and more preferably 80 cc / g or more.

[0222] (4) Following the measurement in (3) above, the pressure was reduced over time until the absolute pressure reached 760–0.25 mmHg, and the carbon dioxide desorption isotherm was measured. It should be noted that, as a criterion for equilibrium, the pressure variation was reduced to less than 0.001% / 10 seconds, as in (3), and the measurement was performed.

[0223] (5) As an indicator of the hysteresis in the carbon dioxide adsorption-desorption isotherm, the equilibrium adsorption amount at 75 mmHg of the adsorption isotherm measured in (3) and the equilibrium adsorption amount at 75 mmHg of the desorption isotherm measured in (4) are set as q(Ad) and q(De), respectively. Then, q(Ad) / q(De) is used as an indicator of the hysteresis. When q(Ad) / q(De) = 1.00, it indicates no hysteresis. The smaller q(Ad) / q(De) is, the greater the hysteresis.

[0224] [Example 1]

[0225] A mixed gel was prepared by mixing 61.93 g of water, 0.202 g of sodium hydroxide (NaOH, manufactured by Fujifilm-Wako Pure Chemicals Co., Ltd.), 3.39 g of sodium nitrate (NaNO3, manufactured by Fujifilm-Wako Pure Chemicals Co., Ltd.), 1.64 g of sodium aluminate (NaAlO2, manufactured by Fujifilm-Wako Pure Chemicals Co., Ltd.), and 10.82 g of colloidal silica (Ludox AS-40, 40% by mass, manufactured by Grace Co., Ltd.) and stirring for 30 minutes. The composition of the mixed gel was α=(L12O+L2O) / SiO2=0.00, β=OH - The coefficients of molecular weight (M12O+M2O) were 0.14, γ = SiO2 / Al2O3 = 8.17, δ = H2O / Al2O3 = 431.0, ε = P2O5 / Al2O3 = 0.00, and ζ = R / Al2O3 = 0.00. The mixed gel was placed in a 200 mL stainless steel miniature storage bottle (manufactured by HIRO COMPANY) with a fluoropolymer inner cylinder. Hydrothermal synthesis was carried out for 4 days at 135°C and a stirring speed of 30 rpm using a stirring-type thermostat (manufactured by HIRO COMPANY) that could rotate vertically along the miniature storage bottle. The product was filtered out and dried at 120°C to obtain powdered zeolite. XRD spectroscopy confirmed that the obtained zeolite was a GIS-type zeolite. Furthermore, no peaks originating from other zeolites or amorphous silica-alumina were observed, therefore it was evaluated as a high-purity GIS-type zeolite.

[0226] The obtained zeolite was subjected to 29 Si-MAS-NMR measurements yielded a silica-alumina ratio of SAR = 7.20. Additionally, ICP-NMR analysis determined the concentrations of various elements, with Z / T = 0.00 (K / T), and the potassium concentration in the zeolite was K / Al = 0.00. CHN analysis was performed to determine the carbon atom concentration, but no carbon atoms were detected.

[0227] The obtained zeolite 27 Al-MAS-NMR spectra are shown in Figure 1 .according to 27 Al-MAS-NMR spectrum, full width at half maximum (FWHM) A = 3.5.

[0228] When the adsorption and desorption isotherms of CO2 obtained from the GIS-type zeolite were measured, the adsorption capacity at 760 mmHg was 82.7 cc / g, and q(Ad) / q(De) = 1.000.

[0229] [Example 2]

[0230] A mixed gel was prepared by mixing 61.65 g of water, 0.30 g of 48% sodium hydroxide aqueous solution (NaOH, solid content concentration 48% by mass, manufactured by Tokuyama Soda), 2.27 g of sodium carbonate (Na2CO3, manufactured by Tokuyama Soda), 1.64 g of sodium aluminate (NaAlO2, manufactured by Hokuriku Chemical Industry), and 10.82 g of colloidal silica (Ludox AS-40, solid content concentration 40% by mass, manufactured by Grace), and stirring for 30 minutes. The composition of the mixed gel was α=(L12O+L2O) / SiO2=0.00, β=OH - / (M12O+M2O)=0.10, γ=SiO2 / Al2O3=8.17, δ=H2O / Al2O3=431.2, ε=P2O5 / Al2O3=0.00, ζ=R / Al2O3=0.00. The mixed gel was placed into a 200mL stainless steel miniature storage bottle (manufactured by HIRO COMPANY) with a fluororesin inner cylinder, and hydrothermal synthesis was carried out for 5 days at 130℃ and a stirring-type thermostat (manufactured by HIRO COMPANY) that could rotate up and down along the miniature storage bottle. The product was filtered out and dried at 120℃ to obtain powdered zeolite. 1g of the obtained zeolite was added to 500mL of a 0.05N potassium carbonate aqueous solution prepared using potassium carbonate (K2CO3, manufactured by Nippon Soda Co., Ltd.), and stirred at 500rpm for 3 hours at room temperature. The product was filtered out and dried at 120°C to obtain a powdery zeolite in which some of the cations were exchanged for potassium. XRD spectroscopy confirmed that the obtained zeolite was a GIS-type zeolite. Furthermore, no peaks originating from other zeolites or amorphous silica-alumina were observed, therefore it was evaluated as a high-purity GIS-type zeolite.

[0231] The values ​​were measured using the same method as in Example 1, and the SAR was 7.20. 27 The Al-MAS-NMR spectrum showed a full width at half maximum (FWHM) of 4.2 (A), with no detected carbon atoms. Furthermore, ICP-luminescence spectrophotometry determined the concentrations of various elements, with Z / T = 0.98 (K / T), and the potassium concentration in the zeolite was K / Al = 0.98. When measuring the adsorption and desorption isotherms of CO2, the adsorption capacity at 760 mmHg was 84.5 cc / g, and q(Ad) / q(De) = 1.000.

[0232] [Example 3]

[0233] A mixed gel was prepared by mixing 141.41 g of water, 8.53 g of sodium nitrate (NaNO3, manufactured by Fujifilm-Wako Pure Chemicals Co., Ltd.), 3.85 g of sodium aluminate (NaAlO2, manufactured by Fujifilm-Wako Pure Chemicals Co., Ltd.), and 17.41 g of amorphous silica (Perkasil SM500, manufactured by Grace Co., Ltd.) and stirring for 1 hour. The composition of the mixed gel was α=(L12O+L2O) / SiO2=0.00, β=OH - / (M12O+M2O)=0.00, γ=SiO2 / Al2O3=14.00, δ=H2O / Al2O3=379.3, ε=P2O5 / Al2O3=0.00, ζ=R / Al2O3=0.00. The mixed gel was placed in a 300mL stainless steel miniature storage bottle (manufactured by HIRO COMPANY) with a fluoropolymer inner cylinder, and hydrothermal synthesis was carried out for 4 days at 130℃ and a stirring speed of 30rpm using a stirring-type thermostat (manufactured by HIRO COMPANY) that could rotate up and down along the miniature storage bottle. The product was filtered out and dried at 120℃ to obtain powdered zeolite. XRD spectroscopy confirmed that the obtained zeolite was GIS-type zeolite. Furthermore, no peaks originating from other zeolites or amorphous silica-alumina were observed, therefore it was evaluated as high-purity GIS-type zeolite.

[0234] The values ​​were measured using the same method as in Example 1, and the SAR was 10.4. 27 The Al-MAS-NMR spectrum showed a full width at half maximum (FWHM) of 2.2 (A), with no carbon atoms detected. Furthermore, ICP-luminescence spectrophotometry determined the concentrations of various elements, with Z / T = 0.00 (K / T), and the potassium concentration in the zeolite was K / Al = 0.00. When measuring the adsorption and desorption isotherms of CO2, the adsorption capacity at 760 mmHg was 80.5 cc / g, and q(Ad) / q(De) = 1.000.

[0235] [Example 4]

[0236] A mixed gel was prepared by mixing 141.41 g of water, 0.66 g of sodium hydroxide aqueous solution (NaOH, manufactured by Fujifilm-Wako Pure Chemicals Co., Ltd.), 2.43 g of sodium nitrate (NaNO3, manufactured by Fujifilm-Wako Pure Chemicals Co., Ltd.), 0.55 g of sodium aluminate (NaAlO2, manufactured by Fujifilm-Wako Pure Chemicals Co., Ltd.), and 35.33 g of aluminum silicate (SIPERNAT 820A, manufactured by Evonik Co., Ltd.) and stirring for 1 hour. The composition of the mixed gel was α=(L12O+L2O) / SiO2=0.08, β=OH - / (M12O+M2O)=0.07, γ=SiO2 / Al2O3=14.00, δ=H2O / Al2O3=242.4, ε=P2O5 / Al2O3=0.00, ζ=R / Al2O3=0.00. The mixed gel was placed in a 300mL stainless steel miniature storage bottle (manufactured by HIRO COMPANY) with a fluoropolymer inner cylinder, and hydrothermal synthesis was carried out for 5 days at 130℃ and a stirring speed of 30rpm using a stirring-type thermostat (manufactured by HIRO COMPANY) that could rotate up and down along the miniature storage bottle. The product was filtered out and dried at 120℃ to obtain powdered zeolite. XRD spectroscopy confirmed that the obtained zeolite was GIS-type zeolite. Furthermore, no peaks originating from other zeolites or amorphous silica-alumina were observed, therefore it was evaluated as high-purity GIS-type zeolite.

[0237] The values ​​were measured using the same method as in Example 1, and the SAR was found to be 8.50. 27 The Al-MAS-NMR spectrum showed a full width at half maximum (FWHM) of 5.6 (A = 5.6), with no carbon atoms detected. Furthermore, ICP-luminescence spectrophotometry determined the concentrations of various elements, with Z / T = 0.00 (K / T), and the potassium concentration in the zeolite was K / Al = 0.00. When measuring the adsorption and desorption isotherms of CO2, the adsorption capacity at 760 mmHg was 73.2 cc / g, and q(Ad) / q(De) = 0.991.

[0238] [Comparative Example 1]

[0239] Based on the content of non-patent literature 7, 143.10 g of water, 40.00 g of 50% sodium hydroxide aqueous solution (NaOH, solid content concentration 50% by mass, manufactured by Aldrich), 2.70 g of aluminum powder (Al, manufactured by Fujifilm-Wako Pure Chemicals Co., Ltd.), and 75.10 g of colloidal silica (Ludox HS-40, solid content concentration 40% by mass, manufactured by Aldrich) were mixed and stirred for 24 hours to prepare a mixed gel. The composition of the mixed gel was α=(L12O+L2O) / SiO2=0.00, β=OH - / (M12O+M2O)=1.00, γ=SiO2 / Al2O3=10.00, δ=H2O / Al2O3=220.0, ε=P2O5 / Al2O3=0.00, ζ=R / Al2O3=0.00. The mixed gel was placed in a 300mL stainless steel miniature storage bottle (manufactured by HIRO COMPANY) with a fluoropolymer inner cylinder, and hydrothermal synthesis was carried out for 3 days at 150℃ and a stirring speed of 60rpm using a stirring-type thermostat (manufactured by HIRO COMPANY) that could rotate up and down along the miniature storage bottle. The product was filtered out and dried at 120℃ to obtain powdered zeolite. XRD spectroscopy confirmed that the obtained zeolite was GIS-type zeolite. Furthermore, no peaks originating from other zeolites or amorphous silica-alumina were observed, therefore it was evaluated as high-purity GIS-type zeolite.

[0240] The values ​​were measured using the same method as in Example 1, and the SAR was 6.00. 27 The Al-MAS-NMR spectrum showed a full width at half maximum (FWHM) of 5.7 (A = 5.7), with no carbon atoms detected. Furthermore, ICP-luminescence spectrophotometry determined the concentrations of various elements, with Z / T = 0.00 (K / T), and the potassium concentration in the zeolite was K / Al = 0.00. When measuring the adsorption and desorption isotherms of CO2, the adsorption capacity at 760 mmHg was 79.8 cc / g, and q(Ad) / q(De) = 0.365.

[0241] [Comparative Example 2]

[0242] Based on the content of Patent Document 3, 207.30g of water, 8.78g of sodium hydroxide, 16.4g of sodium aluminate, and 248.3g of No. 3 water glass were mixed and stirred for 15 minutes to prepare a mixed gel. The composition of the mixed gel was α=(L12O+L2O) / SiO2=0.32, β=OH - / (M12O+M2O)=0.35, γ=SiO2 / Al2O3=12.40, δ=H2O / Al2O3=197.9, ε=P2O5 / Al2O3=0.00, ζ=R / Al2O3=0.00. The mixed gel was placed in a 1000mL stainless steel autoclave with a fluororesin inner cylinder and hydrothermally synthesized at 130℃ for 5 days without stirring. The product was filtered out and dried at 120℃ to obtain powdered zeolite. No peaks originating from other zeolites or amorphous silica-alumina were observed, therefore it was evaluated as a high-purity GIS-type zeolite.

[0243] The values ​​were measured using the same method as in Example 1, and the SAR was 4.10. 27The Al-MAS-NMR spectrum showed a full width at half maximum (FWHM) of 9.8 (A), with no detected carbon atoms. Furthermore, ICP-luminescence spectrophotometry determined the concentrations of various elements, with Z / T = 0.00 (K / T), and the potassium concentration in the zeolite was K / Al = 0.00. When measuring the adsorption and desorption isotherms of CO2, the adsorption capacity at 760 mmHg was 52.4 cc / g, and q(Ad) / q(De) = 0.519.

[0244] [Comparative Example 3]

[0245] Based on the content of Non-Patent Literature 1, 132.86 g of water, 15.66 g of sodium hydroxide, 7.2 g of sodium aluminate (manufactured by Alfa Aesar), and 25.56 g of colloidal silica (Ludox AS-40, solid content 40% by mass) were mixed and stirred at room temperature for 24 hours to prepare a mixed gel. The composition of the mixed gel was α=(L12O+L2O) / SiO2=0.00, β=OH - / (M12O+M2O)=4.90, γ=SiO2 / Al2O3=7.96, δ=H2O / Al2O3=371.8, ε=P2O5 / Al2O3=0.00, ζ=R / Al2O3=0.00. The mixed gel was placed in a 200mL stainless steel autoclave with a fluororesin inner cylinder and hydrothermally synthesized at 100℃ for 7 days without stirring. The product was filtered off and dried at 120℃ to obtain powdered zeolite. No peaks originating from other zeolites or amorphous silica-alumina were observed, therefore it was evaluated as a high-purity GIS-type zeolite.

[0246] The values ​​were measured using the same method as in Example 1, and the SAR was 2.60. 27 The Al-MAS-NMR spectrum showed a full width at half maximum (FWHM) of 8.3 (A), with no detected carbon atoms. Furthermore, ICP-luminescence spectrophotometry determined the concentrations of various elements, with Z / T = 0.00 (K / T), and the potassium concentration in the zeolite was K / Al = 0.00. When measuring the adsorption and desorption isotherms of CO2, the adsorption capacity at 760 mmHg was 8.1 cc / g, and q(Ad) / q(De) = 0.812.

[0247] [Comparative Example 4]

[0248] Based on the content of non-patent literature 3, 102.57 g of water, 2.45 g of sodium hydroxide (manufactured by Pure Chemical Industries, Inc.), 1.15 g of sodium aluminate (manufactured by Showa Chemical Industries, Inc.), and 24.07 g of water glass (manufactured by Fujifilm-Wako Pure Chemical Industries, Inc.) were mixed and stirred at 1800 rpm for 24 hours under a N2 atmosphere to prepare a mixed gel. The composition of the mixed gel was α=(L12O+L2O) / SiO2=0.32, β=OH - / (M12O+M2O)=0.82, γ=SiO2 / Al2O3=20.0, δ=H2O / Al2O3=840.0, ε=P2O5 / Al2O3=0.00, ζ=R / Al2O3=0.00. The mixed gel was stirred at 1000 rpm while undergoing hydrothermal synthesis at 100℃ for 24 hours. The product was filtered out and dried at 120℃ to obtain powdered GIS-type zeolite.

[0249] The values ​​were measured using the same method as in Example 1, and the SAR was 4.68. 27 The Al-MAS-NMR spectrum showed a full width at half maximum (FWHM) of 14.7 (A), with no detected carbon atoms. Furthermore, ICP-luminescence spectrophotometry determined the concentrations of various elements, with Z / T = 0.00 (K / T), and the potassium concentration in the zeolite was K / Al = 0.00. When measuring the adsorption and desorption isotherms of CO2, the adsorption capacity at 760 mmHg was 9.8 cc / g, and q(Ad) / q(De) = 0.788.

[0250] [Comparative Example 5]

[0251] Based on the content of Patent Document 1, the following components were used: 21.54g of silicon dioxide (SiO2, manufactured by Fujifilm-Wako Pure Chemical Industries), 5.97g of aluminum oxide (Al2O3, manufactured by Fujifilm-Wako Pure Chemical Industries), 1.17g of iron oxide (Fe2O3, manufactured by Fujifilm-Wako Pure Chemical Industries), 0.27g of titanium dioxide (TiO2, manufactured by Fujifilm-Wako Pure Chemical Industries), 0.21g of calcium oxide (CaO, manufactured by Fujifilm-Wako Pure Chemical Industries), 0.06g of magnesium oxide (MgO, manufactured by Fujifilm-Wako Pure Chemical Industries), 0.03g of sodium hydroxide, 0.21g of potassium hydroxide, 0.05g of phosphorus oxide (P2O5, manufactured by Fujifilm-Wako Pure Chemical Industries), and carbon powder (Strem). 0.53g of a chemical compound (manufactured by [Chemicals Name]) was mixed using an automatic mortar and pestle. Then, 17.6g of sodium carbonate (Na₂CO₃, manufactured by Fujifilm-Wako Pure Chemical Industries Co., Ltd.) was added and mixed. The mixture was then melted in an electric furnace at 1000°C for 1 hour. The melt was then cooled and pulverized, and 149.78g of water was added to achieve a H₂O / Na₂O molar ratio of 50, thus preparing a mixed gel. The composition of the mixed gel was α=(L₁₂O+L₂O) / SiO₂=0.02, β=OH - / (M12O+M2O)=0.03, γ=SiO2 / Al2O3=6.12, δ=H2O / Al2O3=142.0, ε=P2O5 / Al2O3=0.00, ζ=R / Al2O3=0.00. The mixed gel was heated at 100℃ for 24 hours in an autoclave, the product was filtered out, and dried at 120℃ to obtain powdered GIS-type zeolite.

[0252] The values ​​were measured using the same method as in Example 1, and the SAR was 3.33. 27 The Al-MAS-NMR spectrum showed a full width at half maximum (FWHM) of 7.5 (A), with no detected carbon atoms. Furthermore, ICP-luminescence spectrophotometry determined the concentrations of various elements, with Z / T = 0.00 (K / T), and the potassium concentration in the zeolite was K / Al = 0.00. When measuring the adsorption and desorption isotherms of CO2, the adsorption capacity at 760 mmHg was 2.4 cc / g, and q(Ad) / q(De) = 0.043.

[0253] [Comparative Example 6]

[0254] Based on the content of Non-Patent Document 6, 0.55g of sodium aluminate and 2.91g of sodium metasilicate (Na2SiO3, manufactured by Fujifilm-Wako Pure Chemical Industries Co., Ltd.) were mixed with 10cc of a 0.1mol / L sodium hydroxide aqueous solution to obtain a mixed gel. The composition of the mixed gel was α=(L12O+L2O) / SiO2=1.00, β=OH -The following parameters were used to synthesize zeolite: / (M12O+M2O)=0.08, γ=SiO2 / Al2O3=8.00, δ=H2O / Al2O3=166.0, ε=P2O5 / Al2O3=0.00, ζ=R / Al2O3=0.00. The mixed gel was placed in a micro-storage bottle made of stainless steel and heated at 200℃ for 7 days.

[0255] The values ​​were measured using the same method as in Example 1, and the SAR was 6.98. 27 The Al-MAS-NMR spectrum showed a full width at half maximum (FWHM) of 13.4 (A), with no detected carbon atoms. Furthermore, ICP-luminescence spectrophotometry determined the concentrations of various elements, with Z / T = 0.00 (K / T), and the potassium concentration in the zeolite was K / Al = 0.00. When measuring the adsorption and desorption isotherms of CO2, the adsorption capacity at 760 mmHg was 3.4 cc / g, and q(Ad) / q(De) = 0.665.

[0256] [Comparative Example 7]

[0257] Based on the content of Patent Document 2, triethanolamine (C6H) was added to a liquid prepared by mixing 18g of sodium metasilicate pentahydrate (Na2O3Si / 5H2O, manufactured by Aldrich) and 210.0g of water. 25 NO3 (manufactured by Carl Roth GmbH) 127.1g was stirred at 600 rpm for 30 minutes. A mixture of 2.34g sodium hydroxide and 148.0g water was added to this liquid, and the mixture was stirred at 600 rpm for 30 minutes at room temperature to obtain an Al-free solution. The composition of the solution was α=(L12O+L2O) / SiO2=1.00, β=OH - / (M12O+M2O)=0.51, γ=SiO2 / Al2O3=∞, δ=H2O / Al2O3=∞, ε=P2O5 / Al2O3=∞, ζ=R / Al2O3=∞. 1.134g of aluminum powder (Al, manufactured by Wako Pure Chemicals) was added to a 1000mL stainless steel autoclave with a fluororesin inner cylinder. A mixture was added, and hydrothermal synthesis was carried out at 95℃ for 5 days without aging time or stirring. The product was filtered out and dried at 120℃ to obtain powdered zeolite.

[0258] The values ​​were measured using the same method as in Example 1, and the SAR was 4.60. 27The Al-MAS-NMR spectrum showed a full width at half maximum (FWHM) of 9.2, with carbon atoms comprising 13.5% by mass. Furthermore, the concentrations of various elements were determined by ICP-luminescence spectrophotometry, with Z / T = 0.00 (K / T), and the potassium concentration in the zeolite was K / Al = 0.00. When measuring the adsorption and desorption isotherms of CO2, the adsorption capacity at 760 mmHg was 1.1 cc / g, and q(Ad) / q(De) = 0.339.

[0259] [Comparative Example 8]

[0260] Based on the content of Non-Patent Literature 5, 189.90 g of water, 8.17 g of aluminum isopropoxide, 17.37 g of tetraethyl orthosilicate (manufactured by Aldrich), and 176.85 g of tetramethylammonium hydroxide pentahydrate (manufactured by Aldrich) as an organic structure directing agent were mixed and stirred for 30 minutes. The liquid was kept at 0°C for 1 hour, stirred with a rotary shaker for 20 hours, heated at 120°C for 33 minutes, and then cooled at 0°C for 15 minutes to prepare a mixed gel. The composition of the mixed gel was α=(L12O+L2O) / SiO2=0.00, β=OH - The following parameters were used: / (M12O+M2O)=2.05, γ=SiO2 / Al2O3=4.78, δ=H2O / Al2O3=253.0, ε=P2O5 / Al2O3=0.00, ζ=R / Al2O3=4.78. The mixed gel was subjected to hydrothermal synthesis at 100℃ for 13 days. The product was filtered out and dried at 120℃ to obtain powdered zeolite.

[0261] The values ​​were measured using the same method as in Example 1, and the SAR was 5.00. 27 The Al-MAS-NMR spectrum showed a full width at half maximum (FWHM) of 6.5 (A = 6.5), with 13.2% by mass of carbon atoms. Furthermore, the concentrations of various elements were determined by ICP-luminescence spectrophotometry, with Z / T = 0.00 (K / T), and the potassium concentration in the zeolite was K / Al = 0.00. When measuring the adsorption and desorption isotherms of CO2, the adsorption capacity at 760 mmHg was 0.3 cc / g, and q(Ad) / q(De) = 0.225.

[0262] [Comparative Example 9]

[0263] Based on the content of Patent Document 4, 259.10 g of water, 0.98 g of sodium hydroxide, 20.50 g of sodium aluminate, and 310.4 g of No. 3 water glass were mixed and stirred for 45 minutes to prepare a mixed gel. The composition of the mixed gel was α=(L12O+L2O) / SiO2=0.32, β=OH -The following parameters were given: / (M12O+M2O)=0.03, γ=SiO2 / Al2O3=12.0, δ=H2O / Al2O3=200.0, ε=P2O5 / Al2O3=0.00, ζ=R / Al2O3=0.00. The mixed gel was placed in a 1000mL stainless steel autoclave with a fluororesin inner cylinder and subjected to hydrothermal synthesis at 110℃ for 2 days without stirring. The product was filtered off and dried at 120℃ to obtain powdered zeolite. 1g of the obtained zeolite was added to 500mL of 0.1N potassium nitrate aqueous solution and stirred at 400rpm for 3 hours at 60℃. The product was filtered off and dried at 120℃ to obtain powdered zeolite with a portion of the cations exchanged for potassium.

[0264] The values ​​were measured using the same method as in Example 1, and the SAR was 4.10. 27 The Al-MAS-NMR spectrum showed a full width at half maximum (FWHM) of 12.1 Å, with no carbon atoms detected. Furthermore, ICP-luminescence spectrophotometry determined the concentrations of various elements, with Z / T = 0.97 (K / T), and the potassium concentration in the zeolite was K / Al = 0.97. When measuring the adsorption and desorption isotherms of CO2, the adsorption capacity at 760 mmHg was 67.5 cc / g, and q(Ad) / q(De) = 0.157.

[0265]

[0266] In Table 1, α to ζ represent the following molar ratios.

[0267] α = (L12O + L2O) / SiO2 (Here, L1 and L2 represent the alkali metal and alkaline earth metal contained in the silicon oxide source, respectively.)

[0268] β=OH - / (M12O+M2O) (Here, M1 represents alkali metals and M2 represents alkaline earth metals.)

[0269] γ=SiO2 / Al2O3

[0270] δ=H2O / Al2O3

[0271] ε=P2O5 / Al2O3

[0272] ζ = R / Al₂O₃ (R represents an organic structure directing agent.)

[0273] Industrial applicability

[0274] The GIS-type zeolite of the present invention has industrial applicability as a separating agent and separating membrane for various gases and liquids, electrolyte membrane for fuel cells, filler for various resin molded bodies, membrane reactor, or catalyst for hydrogen cracking, alkylation, etc., catalyst carrier for supporting metals, metal oxides, etc., adsorbent, desiccant, detergent additive, ion exchanger, wastewater treatment agent, fertilizer, food additive, cosmetic additive, etc.

[0275] Explanation of symbols

[0276] 1. Adsorbent

[0277] 2 containers

[0278] 3 Filters

[0279] 4. Zeolite particles

Claims

1. A screening method for GIS-type zeolites, wherein, GIS-type zeolites were selected based on the following criteria: The silicon dioxide to aluminum oxide ratio is above 0.

87. In 27 When the full width at half maximum (FWHM) of the peaks originating from Al within the framework of this zeolite observed in the Al-MAS-NMR spectrum is set to A, it satisfies A≦5.6ppm.

2. The screening method for GIS-type zeolites as described in claim 1, wherein, It meets the requirement of 0.8ppm≦A≦5.4ppm.

3. The screening method for GIS-type zeolites as described in claim 1, wherein, It meets the requirement of 1.1ppm≦A≦3.9ppm.

4. The screening method for GIS-type zeolites as described in claim 1, wherein, The GIS-type zeolite contains potassium as a cation species in the zeolite.

5. The screening method for GIS-type zeolites as described in claim 4, wherein, The potassium atom concentration to aluminum atom concentration ratio (K / Al) in zeolite is above 0.

05.

6. The screening method for GIS-type zeolites as described in claim 5, wherein, The K / Al ratio is 0.10 or higher.

7. The screening method for GIS-type zeolites as described in claim 5, wherein, The K / Al ratio is 0.15 or higher.

8. The screening method for GIS-type zeolites as described in claim 5, wherein, The K / Al ratio is below 1.

00.

9. The screening method for GIS-type zeolites as described in claim 1, wherein, The ratio of the total amount of potassium and lithium Z in zeolite to the total amount of alkali metal T, Z / T, is greater than 0.

05.

10. The screening method for GIS-type zeolites as described in claim 9, wherein, The Z / T ratio is 0.10 or higher.

11. The screening method for GIS-type zeolites as described in claim 9, wherein, The Z / T ratio is 0.15 or higher.

12. The screening method for GIS-type zeolites as described in claim 9, wherein, The Z / T is below 1.

00.

13. The screening method for GIS-type zeolites as described in claim 1, wherein, The carbon atom content of the GIS-type zeolite is less than 4% by mass.

14. The screening method for GIS-type zeolites as described in claim 13, wherein, The carbon atom content of the GIS-type zeolite is less than 3% by mass.

15. The screening method for GIS-type zeolites as described in claim 13, wherein, The carbon atom content of the GIS-type zeolite is less than 2% by mass.

16. The screening method for GIS-type zeolites as described in claim 1, wherein, The silicon dioxide to aluminum oxide ratio is 1.50 or higher.

17. The screening method for GIS-type zeolites as described in claim 16, wherein, The silicon dioxide to aluminum oxide ratio is above 3.

40.

18. The screening method for GIS-type zeolites as described in claim 16, wherein, The silicon dioxide to aluminum oxide ratio is below 3000.

19. The screening method for GIS-type zeolites as described in claim 16, wherein, The silicon dioxide to aluminum oxide ratio is below 500.

20. The screening method for GIS-type zeolites as described in claim 16, wherein, The silicon dioxide to aluminum oxide ratio is below 100.

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