Gis-type zeolite molded body, adsorption device, separation method, and gis-type zeolite

Abstract

The present application aims to provide a GIS-type zeolite molded body having higher strength. One aspect of the present application relates to a GIS-type zeolite molded body comprising a GIS-type zeolite and a carrier, which satisfies C / A ≦ 1.30 when the total value of the amounts of substances of potassium and lithium is set as A, and the total value of the amounts of substances of alkali metals is set as C.

Description

Technical Field

[0001] This invention relates to GIS-type zeolite molded bodies, adsorption devices, separation methods, and GIS-type zeolites. Background Technology

[0002] Zeolites can be used as adsorbents, desiccants, separating agents, catalysts, catalyst carriers, detergents, ion exchangers, wastewater treatment agents, fertilizers, food additives, and cosmetic additives, and are particularly useful for gas separation. They are sometimes used after metal exchange, depending on the application.

[0003] As a zeolite suitable for various applications, Patent Document 1 describes, for example, a GIS-type zeolite where the diffraction angle 2θ of a specific diffraction peak is within a specified range. Here, GIS-type zeolite refers to a zeolite with a GIS structure according to the criteria for zeolite structure established by the International Zeolite Association (IZA). Furthermore, Patent Document 1 also specifies the amount of potassium that may be included in the GIS-type zeolite.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent No. 6714789 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] Considering the use of GIS-type zeolite as described in Patent Document 1, for example, in catalysts, adsorbent materials, etc., and assuming actual transportation, transfer, and use scenarios, there is still room for improvement in terms of further enhancing its strength.

[0009] The present invention was made in view of the above-mentioned problems, and its object is to provide a molded body of GIS-type zeolite with higher strength.

[0010] Methods for solving problems

[0011] The inventors discovered that by keeping the ratio of the total amount of alkali metals to the total amount of potassium and lithium within a specified range in the molded body of GIS-type zeolite, the strength of the obtained molded body can be improved, thus completing the present invention.

[0012] That is, the present invention includes the following methods.

[0013] <1>

[0014] A GIS-type zeolite molded body, comprising:

[0015] GIS-type zeolite; and

[0016] carrier

[0017] When the total amount of potassium and lithium is set as A, and the total amount of alkali metals is set as C, the condition C / A≦1.30 is satisfied.

[0018] <2>

[0019] like <1> In the GIS-type zeolite molded body, when the total mass of potassium and lithium is set as A, and the total mass of alkali metals and alkaline earth metals is multiplied by their respective valences is set as B, B / A≦1.30 is satisfied.

[0020] <3>

[0021] like <1> or <2> In the GIS-type zeolite molded body, when the total amount of potassium is set as D and the total amount of alkali metals is set as C, the condition C / D≦1.30 is met.

[0022] <4>

[0023] like <1> ~ <3> The GIS-type zeolite molded body according to any one of the following methods, wherein 1.00 is satisfied. <C / A。

[0024] <5>

[0025] like <1> ~ <4> The GIS-type zeolite molded body according to any one of the following methods, wherein 1.00 is satisfied.

[0026] <6>

[0027] like <1> ~ <4> The GIS-type zeolite molded body according to any one of the following methods, wherein 1.00 is satisfied. <C / D。

[0028] <7>

[0029] like <1> ~ <6> The GIS-type zeolite molded body according to any one of the following, wherein the carrier comprises one or more selected from the group consisting of silicon dioxide and aluminum oxide.

[0030] <8>

[0031] like <1> ~ <7> The GIS-type zeolite molded body according to any one of the following methods, wherein the particle size of the GIS-type zeolite molded body is more than 20 μm and less than 300 μm.

[0032] <9>

[0033] like <8> The GIS-type zeolite molded body is obtained by spray drying.

[0034] <10>

[0035] ​like <8> or <9> The GIS-type zeolite molded body has a compressive strength of 6.0 MPa or higher.

[0036] <11>

[0037] like <1> ~ <10> The GIS-type zeolite molded body according to any one of the following methods is a granular material with a length of 3 mm to 50 mm and a diameter of 1 mm to 20 mm.

[0038] <12>

[0039] like <11> The GIS-type zeolite molded body is obtained by extrusion molding.

[0040] <13>

[0041] like <11> or <12> The GIS-type zeolite molded body has a breaking strength of 20N or more.

[0042] <14>

[0043] An adsorption device comprising: <1> ~ <13> The GIS-type zeolite molded body as described in any one of the following.

[0044] <15>

[0045] A separation method, wherein, using <14> The adsorption device described herein separates one or more gases selected from the group consisting of CO2, H2O, He, Ne, Cl2, NH3 and HCl from a mixture of two or more gases selected from the group consisting of H2, N2, CO and hydrocarbons.

[0046] <16>

[0047] like <15> The separation method wherein the above-mentioned gas is separated by pressure swing adsorption separation, temperature swing adsorption separation, or pressure swing-temperature swing adsorption separation.

[0048] <17>

[0049] A method for producing a refined gas, wherein, using <14> The adsorption device described herein separates one or more gases selected from the group consisting of CO2, H2O, He, Ne, Cl2, NH3 and HCl from a mixture of two or more gases selected from the group consisting of H2, N2, CO and hydrocarbons.

[0050] <18>

[0051] A GIS-type zeolite, wherein when the total amount of potassium is set as A and the total amount of alkali metals is set as C, C / A≦1.30 is satisfied.

[0052] The effects of the invention

[0053] According to the present invention, it is possible to provide molded articles of GIS-type zeolites with higher strength. Attached Figure Description

[0054] Figure 1 This is a diagram illustrating an adsorption device according to one embodiment of the present invention. Detailed Implementation

[0055] The specific embodiments of the present invention (hereinafter also referred to as "this embodiment") are described in detail below. It should be noted that the present invention is not limited to the following embodiment, and various modifications can be made within the scope of its key points.

[0056] [GIS-type zeolite molded body]

[0057] The GIS-type zeolite molded body of this embodiment comprises GIS-type zeolite and a carrier. When the total amount of potassium and lithium is set as A, and the total amount of alkali metals is set as C, C / A ≦ 1.30 is satisfied. Because of this configuration, the GIS-type zeolite molded body of this embodiment exhibits excellent strength.

[0058] In the GIS-type zeolite molded body of this embodiment, when the total mass of potassium and lithium is set as A, and the total mass of alkali metals and alkaline earth metals multiplied by their valences is set as B, B / A ≤ 1.30. Because of this configuration, the GIS-type zeolite molded body of this embodiment exhibits excellent strength.

[0059] It should be noted that, at the beginning of their research on the composition of GIS-type zeolite molded articles, the inventors repeatedly conducted trial and error based on the following aspects: Alkali metals promote the dehydration and condensation of silica, alumina, etc., which are commonly used as molding carriers, and the resulting strength of the molded article is affected by the arrangement of electronegativity.

[0060] However, the inventors conducted repeated studies and surprisingly confirmed that in GIS-type zeolite molded bodies, the strength of a composition that also has lithium and potassium as cations may be superior compared to a composition that only has sodium as a cation with electronegativity between lithium and potassium.

[0061] The inventors analyzed such cases and found that when the total amount of alkali metals C is below a certain value relative to the amount of potassium and lithium, there is a tendency for the strength of GIS-type zeolite molded bodies to increase.

[0062] Although the detailed mechanism may not be clear, the inventors speculate that by including at least one of potassium and lithium in the cations of GIS-type zeolite and making its mass above a certain level, the wettability, solvent affinity, surface potential, etc. of the zeolite itself change, which affects the strength of the molded body.

[0063] By increasing the strength of the zeolite molding, damage to the molding during transport or transfer can be suppressed. Furthermore, in fluidized bed systems, for example, by increasing the strength of the zeolite molding, the molding is less prone to damage even with increased gas linear velocity, thus allowing for an increase in the gas supply and consequently, a higher processing capacity per unit time, leading to potential improvements in economic efficiency.

[0064] From the perspective of further improving the strength of GIS-type zeolite molded bodies, the C / A ratio in the GIS-type zeolite molded body is preferably 1.25 or less, more preferably 1.20 or less, and even more preferably 1.15 or less. The lower limit value of C / A is not particularly limited, for example, it can be greater than 1.00 (i.e., satisfying 1.00). <C / A)。

[0065] From the perspective of further improving the strength of GIS-type zeolite molded bodies, the B / A ratio in the GIS-type zeolite molded body is preferably 1.25 or less, more preferably 1.20 or less, and even more preferably 1.15 or less. The lower limit value of B / A is not particularly limited, for example, it can be greater than 1.00 (i.e., satisfying 1.00).

[0066] In GIS-type zeolite molded bodies, when the total amount of potassium is set as D and the total amount of alkali metals is set as C, from the perspective of further improving the strength of the GIS-type zeolite molded body, C / D is preferably 1.30 or less, more preferably 1.25 or less, even more preferably 1.20 or less, and even more preferably 1.15 or less. The lower limit of C / D is not particularly limited, for example, it can be greater than 1.00 (i.e., satisfying 1.00). <C / D)。

[0067] In this embodiment, the values ​​of A, B, C, and D can be determined based on the methods described in the embodiments described later. Furthermore, the values ​​of A, B, C, and D can be controlled, for example, by appropriately adjusting conditions such as the selection of the metal species, ion concentration, and number of treatments during the cation exchange process in the synthesis of GIS-type zeolites, or by controlling the selection of the type of support used and the amount of support, to achieve the desired relationships.

[0068] (GIS-type zeolite)

[0069] ​From the perspective of exhibiting the desired functions as a zeolite, the GIS-type zeolite molded body of this embodiment comprises GIS-type zeolite. Regarding the GIS-type zeolite in this embodiment, as described in ICDD (International Center for Diffraction Data) and other publications (e.g., 00-039-0219), in the spectrum obtained by X-ray diffraction, it preferably has diffraction peaks of (1 0 1) and (3 1 2) near 2θ = 12.45° and 33.36°, respectively. Furthermore, the (1 0 1) diffraction peak is typically observed in the range of 2θ = 12.15° to 12.75°, and the (3 1 2) diffraction peak is typically observed in the range of 33.15° to 33.65°. Additionally, the (2 1 1) diffraction peak is typically observed in the range of 2θ = 20.1° to 24.1°.

[0070] Furthermore, for GIS-type zeolites, it is known that high-angle shifts occur in the spectra obtained by X-ray diffraction after cation exchange with potassium and lithium. For example, a diffraction peak of (1 01) may be observed in the range of 2θ = 12.55° to 12.90°, or a diffraction peak of (3 1 2) may be observed in the range of 33.70° to 34.25°. A more preferred 2θ value for the (3 1 2) diffraction peak is 2θ = 33.85° to 34.22°, and even more preferred is 2θ = 34.02° to 34.20°. It should be noted that diffraction peaks of (3 1 2) may also exist outside the aforementioned 2θ values. Other values ​​of 2θ besides those mentioned above include 2θ = 21.22–22.17°, 22.18–22.38°, 28.34–28.74°, 28.86–29.26°, 31.30–31.70°, and 38.40–38.80°.

[0071] When the total amount of potassium and lithium in GIS-type zeolite is defined as A, and the total amount of alkali metals is defined as C, from the perspective of further improving the strength of the GIS-type zeolite molded body, C / A is preferably 1.30 or less, more preferably 1.25 or less, even more preferably 1.20 or less, and even more preferably 1.15 or less. The lower limit of C / A is not particularly limited, for example, it can be greater than 1.00 (i.e., satisfying 1.00). <C / A)。

[0072] When the total amount of potassium and lithium in GIS-type zeolite is defined as A, and the total amount of alkali metals and alkaline earth metals multiplied by their valences is defined as B, from the perspective of further improving the strength of the GIS-type zeolite molded body, B / A is preferably 1.30 or less, more preferably 1.25 or less, even more preferably 1.20 or less, and even more preferably 1.15 or less. The lower limit of B / A is not particularly limited, for example, it may be greater than 1.00 (i.e., satisfying 1.00). <B / A)。

[0073] When the total amount of potassium in GIS-type zeolite is set as D, and the total amount of alkali metals is set as C, from the perspective of further improving the strength of the GIS-type zeolite molded body, C / D is preferably 1.30 or less, more preferably 1.25 or less, even more preferably 1.20 or less, and even more preferably 1.15 or less. The lower limit of C / D is not particularly limited, for example, it can be greater than 1.00 (i.e., satisfying 1.00). <C / D)。

[0074] In particular, from the perspective of further improving the selective adsorption capacity of carbon dioxide, the GIS-type zeolite in this embodiment is preferably silica-alumina.

[0075] It should be noted that in this specification, "silicon oxide-alumina" means that in GIS-type zeolite, silicon oxide and alumina are the main components of GIS-type zeolite (80% by mass or more), while the aluminum content is 1% by mass or more (more preferably 3% by mass or more, and even more preferably 5% by mass or more), the phosphorus content is 4% by mass or less, and the Zr and Ti contents are 8% by mass or less.

[0076] From the same perspective as above, the aluminum content in the GIS-type zeolite of this embodiment is preferably 20% by mass or less, more preferably 19% by mass or less.

[0077] From the same perspective as described above, the phosphorus atom content in the GIS-type zeolite of this embodiment is more preferably 1.5% by mass or less, and particularly preferably 0% by mass.

[0078] Furthermore, the content of aluminum and phosphorus atoms can be determined using the methods described in the examples below. Additionally, the content of aluminum and phosphorus atoms can be adjusted to the aforementioned range, for example, by adjusting the composition ratio of the mixed gel used in the synthesis of GIS-type zeolite to the preferred range described below.

[0079] (cation)

[0080] The GIS-type zeolite in this embodiment contains at least one of Li and K, preferably K. Furthermore, examples of alkali metals and alkaline earth metals that can be included in the GIS-type zeolite of this embodiment include Na, Rb, Cs, Ca, Mg, Sr, Ba, etc. From the perspective of making the crystallization formation of the GIS-type framework easier, Na, Rb, Cs, and Ca are preferred, and Na is more preferred.

[0081] The content of GIS-type zeolite is preferably 10 to 95% by mass, more preferably 20 to 92% by mass, and even more preferably 30 to 90% by mass, relative to 100% by mass of the GIS-type zeolite molded body.

[0082] (Manufacturing method of GIS-type zeolite)

[0083] The method for manufacturing GIS-type zeolite in this embodiment may include, for example, a step of preparing a mixed gel containing a silicon dioxide source, an aluminum source containing aluminum, an alkali metal source containing at least one selected from alkali metals (M1) and alkaline earth metals (M2), a phosphorus source containing phosphorus, and water. The mixed gel and its constituent components will be described below.

[0084] (Mixed Gel)

[0085] The mixed gel in this embodiment is a mixture containing a silicon dioxide source, an aluminum source, an alkali metal source, and water as components, and may contain a phosphorus source and an organic structure directing agent as needed.

[0086] The silica source refers to the component in the mixed gel that constitutes the silicon raw material contained in the zeolite manufactured from the mixed gel; the aluminum source refers to the component in the mixed gel that constitutes the aluminum raw material contained in the zeolite manufactured from the mixed gel; the alkali metal source refers to the component in the mixed gel that constitutes the alkali metal and / or alkaline earth metal raw material contained in the zeolite manufactured from the mixed gel; and the phosphorus source refers to the component in the mixed gel that constitutes the phosphorus raw material contained in the zeolite manufactured from the mixed gel.

[0087] (Silica source)

[0088] There are no particular limitations on the silica source used; any commonly used silica source can be used. Specific examples include sodium silicate, amorphous silica, colloidal silica, wet silica, dry silica, silica gel, amorphous aluminosilicate gel, tetraethoxysilane (TEOS), and trimethylethoxysilane. These compounds can be used alone or in combination. Here, amorphous aluminosilicate gel serves as both a silica source and an aluminum source.

[0089] Among these, sodium silicate is preferred as the silica source due to its tendency to yield zeolites with high crystallinity.

[0090] (Aluminum source)

[0091] There are no particular limitations on the aluminum source used; 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.

[0092] Among these, sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum acetate, aluminum hydroxide, aluminum chloride, and aluminum alkoxides are preferred aluminum sources due to their tendency to produce zeolites with high crystallinity. Similarly, sodium aluminate and aluminum hydroxide are more preferred, and sodium aluminate is even more preferred.

[0093] (Alkali metal source)

[0094] There are no particular restrictions on the type of alkali in the alkali metal source; any alkali metal and / or any alkaline earth metal compound can be used.

[0095] Alkali metal sources can be categorized, 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 of several.

[0096] Alkali metals and alkaline earth metals used as alkali metal 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, Li, Na, K, Rb, Cs, and Ca are preferred alkali metal sources, with Na, Li, and K being more preferred. Furthermore, alkali metals and alkaline earth metals used as alkali metal sources can be used individually or in combination.

[0097] Specifically, examples of alkali metal sources include, but are not limited to, sodium hydroxide, sodium acetate, sodium sulfate, sodium nitrate, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium acetate, potassium sulfate, potassium nitrate, potassium carbonate, potassium bicarbonate, lithium hydroxide, lithium acetate, lithium sulfate, lithium nitrate, lithium carbonate, lithium bicarbonate, rubidium hydroxide, rubidium acetate, rubidium sulfate, rubidium nitrate, rubidium carbonate, rubidium bicarbonate, cesium hydroxide, cesium acetate, cesium sulfate, cesium nitrate, cesium carbonate, cesium bicarbonate, calcium hydroxide, calcium acetate, calcium sulfate, calcium nitrate, calcium carbonate, calcium bicarbonate, magnesium hydroxide, magnesium acetate, magnesium sulfate, magnesium nitrate, magnesium carbonate, magnesium bicarbonate, strontium hydroxide, strontium acetate, strontium sulfate, strontium nitrate, strontium carbonate, strontium bicarbonate, barium hydroxide, barium acetate, barium sulfate, barium nitrate, barium carbonate, barium bicarbonate, etc.

[0098] Among these, sodium hydroxide, potassium hydroxide, potassium carbonate, lithium hydroxide, lithium nitrate, rubidium hydroxide, cesium hydroxide, calcium hydroxide, magnesium hydroxide, strontium hydroxide, and barium hydroxide are preferred; sodium hydroxide, potassium hydroxide, potassium carbonate, lithium hydroxide, lithium nitrate, rubidium hydroxide, and cesium hydroxide are more preferred; and sodium hydroxide, potassium hydroxide, potassium carbonate, and lithium nitrate are even more preferred.

[0099] (Phosphorus source)

[0100] 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.

[0101] Among these, phosphoric acid aqueous solution, sodium phosphate, and aluminum phosphate are preferred phosphoric acid sources because they tend to produce zeolites with high crystallinity. Similarly, phosphoric acid aqueous solution and sodium phosphate are more preferred, and phosphoric acid aqueous solution is even more preferred.

[0102] (Organic structure directing agent)

[0103] In the case of zeolite production via hydrothermal synthesis of a mixed gel, the organic structure-directing agent is a compound that promotes crystallization into a zeolite structure. Organic structure-directing agents can be used as needed during zeolite crystallization.

[0104] 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.

[0105] As organic structure directing agents, but not limited to, amines, quaternary ammonium salts, alcohols, ethers, amides, alkylureas, alkylthioureas, cyanoalkanes, and alicyclic heterocyclic compounds containing nitrogen as a heteroatom can be used, with alkylamines being preferred, and isopropylamine being more preferred.

[0106] Such salts are accompanied by anions. Representative examples of such anions include, but are not limited to, Cl-. - ,Br - I - Halogen ions or hydroxide ions, acetate ions, sulfate ions, nitrate ions, carbonate ions, and bicarbonate ions are preferred, especially from the perspective of facilitating the crystallization formation of the GIS-type framework.

[0107] (Composition ratio of the mixed gel)

[0108] The ratio of silicon dioxide source to aluminum source in the mixed gel is expressed as the molar ratio of the oxides of each element, i.e., SiO2 / Al2O3.

[0109] The SiO2 / Al2O3 ratio is not particularly limited as long as it is a ratio that can form zeolite. However, in order to suppress the formation of zeolite with a framework different from that of GIS, the SiO2 / Al2O3 ratio is preferably 4.0 to 70.0 or less, more preferably 4.4 to 65.0 or less, even more preferably 5.5 to 55.0 or less, even more preferably 5.8 to 52.0 or less, even more preferably 6.0 to 50.0 or less, and even more preferably 6.5 to 40.0 or less.

[0110] The ratio of aluminum source to alkali metal source in the mixed gel is expressed as the molar ratio of the total of M12O and M2O to Al2O3, i.e., (M12O+M2O) / Al2O3 (where M1 represents the alkali metal and M2 represents the alkaline earth metal). It should be noted that, from the perspective of facilitating the crystallization of the GIS-type framework, this (M12O+M2O) / Al2O3 ratio is further preferably 1.6 or more, even more preferably 1.7 or more, still more preferably 1.8 or more, and even more preferably 1.9 or more.

[0111] From the perspective of being able to suppress the formation of zeolites with a framework different from that of the GIS type, (M12O+M2O) / Al2O3 is preferably 2.5 or more and 75.0 or less, more preferably 3.2 or more and 58.0 or less, and even more preferably 3.4 or more and 55.5 or less.

[0112] 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.

[0113] The ratio of P2O5O2 / Al2O3 is not particularly limited as long as it is a ratio that can form zeolite. However, it is preferable to be less than 1.0, more preferably 0.6 or less, even more preferably 0.4 or less, and particularly preferably 0, in order to suppress the formation of zeolite with a framework different from that of GIS.

[0114] When an organic structure-directing agent is included in the mixed gel, 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 organic structure-directing agent). From the perspective of making the crystallization formation of the GIS-type framework easier and / or shortening the synthesis time, and achieving excellent economic efficiency in zeolite production, R / Al2O3 is preferably less than 9.5, more preferably 7.5 or less, and even more preferably 6.0 or less.

[0115] The ratio of aluminum source to water in the mixed gel is expressed as the molar ratio of water to Al2O3, i.e., H2O / Al2O3. For the purpose of promoting more uniform dispersion of the components in the mixed gel, this H2O / Al2O3 ratio is preferably 100 or more, more preferably 200 or more. From the viewpoint of suppressing the formation of zeolites with a framework different from the GIS-type framework, it is further preferably 300 or more.

[0116] Regarding H2O / Al2O3, from the perspective of shortening the synthesis time and improving the economy of zeolite production, a temperature of 2800 or less is preferred, and more preferably 1800 or less. From the perspective of suppressing the formation of zeolites with a framework different from that of the GIS type, a temperature of 1300 or less is even more preferred.

[0117] As described above, the preferred method for manufacturing the GIS-type zeolite of this embodiment includes a step of preparing a mixed gel containing a silicon oxide source containing silicon, an aluminum source containing aluminum, an alkali metal source containing at least one selected from alkali metals (M1) and alkaline earth metals (M2), a phosphorus source, and water. When the molar ratios of the components in the mixed gel are calculated in the form of oxides of the aforementioned silicon, aluminum, alkali metals (M1), alkaline earth metals (M2), and phosphorus source, the molar ratios α, β, γ, and δ represented by the following formulas (1), (2), (3), and (4) satisfy 4.5≦α≦65.0, 2.5≦β≦75.0, 0≦γ<1.0, and 100≦δ≦2800. The GIS-type zeolite of this embodiment is particularly preferably obtained by the above-described method for manufacturing the GIS-type zeolite of this embodiment.

[0118] α=SiO2 / Al2O3 (1)

[0119] β=(M12O+M2O) / Al2O3 (2)

[0120] γ=P2O5 / Al2O3 (3)

[0121] δ=H2O / Al2O3 (4)

[0122] Furthermore, in the method for manufacturing GIS-type zeolite of this embodiment, when the molar ratios α, β, γ, and δ satisfy the above-mentioned ranges and the mixed gel further contains an organic structure directing agent R, the molar ratio ε represented by the following formula (5) preferably satisfies ε < 9.5.

[0123] ε=R / Al2O3 (5)

[0124] Seed crystals are not necessarily required in the mixed gel, but pre-manufactured GIS-type zeolite can be added to the mixed gel as seed crystals to obtain the GIS-type zeolite of this embodiment.

[0125] (Preparation process of mixed gel)

[0126] There are no particular limitations on the preparation process of the mixed gel. For example, it may include a mixing process in which a silicon oxide source, an aluminum source, an alkali metal source, water, and an organic structure directing agent, if necessary, are mixed in one step or in multiple stages; and a maturation process of the mixture obtained in the mixing process.

[0127] In the mixing process, these components, including silicon oxide source, aluminum source, alkali metal source, water, and, if necessary, organic structure directing agent, can be mixed in one step or in multiple stages.

[0128] There is no restriction on the order of 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.

[0129] There are no particular restrictions on the commonly used stirring methods. For specific examples, methods such as paddle stirring, vibration stirring, oscillating stirring, and centrifugal stirring can be cited.

[0130] There is no particular limitation on the stirring speed as long as it is a commonly used stirring speed, for example, above 1 rpm and less than 2000 rpm.

[0131] There are no particular limitations 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.

[0132] There is no particular limitation on the time of the mixing process. It can be appropriately selected according to the temperature of the mixing process. For example, it can be greater than 0 minutes and less than 1000 hours.

[0133] The maturation process can be carried out under either static or stirring conditions.

[0134] When stirring during the maturation process, there are no particular restrictions on the commonly used stirring methods. For specific examples, methods such as paddle stirring, vibration stirring, oscillating stirring, and centrifugal stirring can be cited.

[0135] There is no particular limitation on the stirring speed as long as it is a commonly used stirring speed, for example, above 1 rpm and less than 2000 rpm.

[0136] 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.

[0137] There is no particular limit to the time of the maturation process. It can be appropriately selected according to the temperature of the maturation process. For example, it can be greater than 0 minutes and less than 1000 hours.

[0138] It is believed that during the mixing and curing processes of zeolite raw materials, the raw materials dissolve, and zeolite precursors are formed and redissolved. To form a large-periodic structure containing 8-membered rings without causing defects, it is preferable not to excessively form the zeolite precursors. Furthermore, if the formation of zeolite precursors is excessive, the formation of more stable ANA-type zeolites tends to increase; therefore, it is also preferable not to excessively cure. On the other hand, it is preferable that the raw materials are thoroughly mixed and the gel is homogeneous. To obtain zeolite with a suitable structure, the total time for the mixing and curing processes can be appropriately adjusted based on the composition of the raw materials, etc., and is not particularly limited. 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 15 minutes or more and less than 15 hours, and even more preferably 31 minutes or more and less than 6 hours.

[0139] (Hydrothermal synthesis process)

[0140] 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 145°C, and more preferably, the hydrothermal synthesis temperature is 80°C to 140°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.

[0141] The temperature for hydrothermal synthesis is not particularly limited as long as it is a commonly used temperature. However, 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 that of the GIS type, 90°C or higher is more preferred, and 100°C or higher is even more preferred.

[0142] From the perspective of being able to suppress the formation of zeolites with a framework different from that of the GIS type, the temperature is more preferably below 145°C, more preferably below 140°C, and even more preferably below 135°C.

[0143] The temperature for hydrothermal synthesis can be fixed or varied in stages.

[0144] There is no particular limitation on the hydrothermal synthesis time as long as it is the commonly used time, and it can be appropriately selected according to the hydrothermal synthesis temperature.

[0145] From the perspective of forming the GIS framework, the hydrothermal synthesis time is preferably 3 hours or more, more preferably 10 hours or more. From the perspective of obtaining highly crystalline GIS-type zeolite, the hydrothermal synthesis time is further preferably 24 hours or more.

[0146] From the perspective of excellent economic efficiency in zeolite production, the hydrothermal synthesis time is preferably 30 days or less, more preferably 20 days or less, and even more preferably 10 days or less.

[0147] In the hydrothermal synthesis process, there are no particular restrictions 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 the gas is pressurized to avoid hindering crystallization, it is preferable to put it into a pressure-resistant container for hydrothermal synthesis.

[0148] There are no particular limitations on pressure vessels; for example, they can be spherical, elongated, transverse, or other shapes.

[0149] When stirring the mixed gel in the pressure vessel, the pressure vessel is rotated in the up-down direction and / or left-right direction, but preferably in the up-down direction.

[0150] When the pressure vessel is rotated in the up-down direction, its 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.

[0151] In the hydrothermal synthesis process, in order to better stir the mixed gel, one method is to use a long container as a pressure vessel and rotate it in the vertical direction.

[0152] (Separation and drying process)

[0153] 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. 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. Filtration or decanting can usually be used for separation.

[0154] The separated substance can be used directly or washed with water or a specified solvent. If necessary, the separated substance can be dried.

[0155] There is no particular limitation on the drying temperature of the separated substance, as long as it is the temperature normally used for drying, which is usually room temperature to below 150°C.

[0156] 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 with added inert gases such as nitrogen or argon, or an atmosphere with oxygen are used.

[0157] (Cation exchange)

[0158] For the GIS-type zeolite in this embodiment, in order to satisfy the specified relationship between the values ​​of A and B, it can be subjected to cation exchange. As for cation exchange, there are no particular limitations as long as the method is generally known; examples include ion exchange and impregnation-supported methods. These methods can use, but are not limited to, nitrates such as NH4NO3, LiNO3, NaNO3, KNO3, RbNO3, CsNO3, Be(NO3)2, Ca(NO3)2, Mg(NO3)2, Sr(NO3)2, Ba(NO3)2, or acids such as nitric acid or hydrochloric acid, where the nitrate ions contained in the aforementioned nitrates are replaced with halide ions, sulfate ions, carbonate ions, bicarbonate ions, acetate ions, phosphate ions, or hydrogen phosphate ions.

[0159] The temperature for cation exchange is not particularly limited as long as it is a standard cation exchange temperature, typically ranging from room temperature to below 100°C. When separating the zeolite after cation exchange, the separation method is not particularly limited as long as it is a standard method. Methods include filtration, decanting, spray drying (rotary spray, nozzle spray, and ultrasonic spray, etc.), drying using a rotary evaporator, vacuum drying, freeze drying, or natural drying. Separation is usually achieved through filtration or decanting. The separated substances can be washed with water or a specified solvent if necessary, or they can be dried. The drying temperature for the separated substances is not particularly limited as long as it is a standard drying temperature, typically ranging from room temperature to below 150°C. The drying atmosphere is not particularly limited as long as it is a commonly used atmosphere, typically using air, an atmosphere with added inert gases such as nitrogen or argon, or an atmosphere with oxygen.

[0160] [Firing process]

[0161] Especially when using organic structure-directing agents, the dried body obtained from the separation and drying process can be calcined as needed to obtain GIS-type zeolite. 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 the calcination time and improving the economy of manufacturing GIS-type zeolite, a temperature of 400°C or higher is more preferred.

[0162] Because of the tendency to maintain the crystallinity of GIS-type zeolite, the firing temperature is preferably less than 550°C, more preferably less than 530°C, and even more preferably less than 500°C.

[0163] The firing time is not particularly limited as long as it is sufficient to remove the organic structure directing agent. It can be appropriately selected according to the firing temperature. For the reason that it tends to reduce the residual proportion of organic structure directing agent, it is preferred to be 0.5 hours or more, more preferably 1 hour or more, and even more preferably 3 hours or more.

[0164] Because of the tendency to maintain the crystallinity of GIS-type zeolite, the firing time is preferably 20 days or less, more preferably 10 days or less, and even more preferably 7 days or less.

[0165] There are no special restrictions on the firing atmosphere as long as it is a commonly used atmosphere. Usually, an air atmosphere, an atmosphere with added inert gases such as nitrogen and argon, or an atmosphere with oxygen are used.

[0166] (Carrier)

[0167] From the perspective of ensuring excellent strength, the GIS-type zeolite molded body of this embodiment includes a carrier. Examples of carriers include inorganic oxides such as alumina, silicon dioxide, magnesium oxide, zirconium oxide, and titanium dioxide, as well as clay minerals such as bentonite and kaolin, and cement-like inorganic binders such as calcium silicate and calcium aluminate. Alumina, silicon dioxide, magnesium oxide, zirconium oxide, and titanium dioxide are preferred, and silicon dioxide and alumina are more preferred.

[0168] The carrier content is preferably 5-90% by mass, more preferably 8-80% by mass, and even more preferably 10-70% by mass relative to 100% by mass of the GIS-type zeolite molded body. Increasing the carrier content tends to increase the strength of the molded body, but the zeolite content itself tends to decrease. Therefore, the carrier content is preferably adjusted according to the required strength and performance for the intended application.

[0169] (shape)

[0170] The GIS-type zeolite molded body of this embodiment can be a powder. The particle size of such a GIS-type zeolite molded body is preferably 20 μm or more and 300 μm or less. More preferably, the particle size is 20 μm or more and 200 μm or less, and even more preferably 30 μm or more and 100 μm or less. When the GIS-type zeolite molded body is in powder form, it is suitable for processes using fluidized beds, and with the above-mentioned particle size, it tends to be more ideally applicable to such processes.

[0171] It should be noted that, in the case of the GIS-type zeolite molded body in this embodiment being in powder form, it is preferably obtained by spray drying. The spray drying process is described below.

[0172] The particle size described above can be determined based on the methods described in the examples below, and can be adjusted to the above range, for example, by spray drying conditions.

[0173] The GIS-type zeolite molded body of this embodiment can be granules. Preferably, the granules have a length of 3 mm to 50 mm and a diameter of 1 mm to 20 mm. The length of the granules can be 3 mm to 40 mm, 3 mm to 30 mm, 3 mm to 15 mm, 3 mm to 10 mm, or 3 mm to 8 mm. The diameter of the granules can be 2 mm to 10 mm, 2 mm to 5 mm, or 2 mm to 4 mm. When the GIS-type zeolite molded body is in granule form, it is suitable for use in processes using a fixed bed, and with the aforementioned length and diameter, it tends to be more ideally applicable to this process.

[0174] The shape of the granules preferably meets the above-mentioned length and diameter, but there are no particular limitations; they can be cylindrical, chamfered cylindrical, or spherical. Chamfered cylindrical refers to a cylindrical shape in which the corners of the upper and lower surfaces are rounded.

[0175] It should be noted that, in the case of the GIS-type zeolite molded body in this embodiment being granular material, it is preferably obtained by extrusion molding. The extrusion molding process is described below.

[0176] The length and diameter described above can be measured based on the methods described in the embodiments below, and can be adjusted to the above range, for example, by operations such as grading.

[0177] The compressive strength of the GIS-type zeolite molded body in this embodiment is preferably 6.0 MPa or more, more preferably 6.2 MPa or more, and even more preferably 6.4 MPa or more. In particular, when the GIS-type zeolite molded body in this embodiment is in powder form, it is preferable to satisfy the above range.

[0178] The above-mentioned compressive strength can be measured based on the method described in the following embodiments, and can be adjusted to the above range by adjusting the firing temperature and firing time.

[0179] The breaking strength of the GIS-type zeolite molded body in this embodiment is preferably 20 N or more, more preferably 22 N or more, and even more preferably 24 N or more. In particular, when the GIS-type zeolite molded body in this embodiment is granular, it is preferable to satisfy the above range.

[0180] The aforementioned destructive strength can be measured based on the methods described in the following embodiments, and for example, it can be adjusted to the aforementioned range by adjusting the firing temperature and firing time.

[0181] [Manufacturing Method of GIS-type Zeolite Molded Body]

[0182] The manufacturing method of the GIS-type zeolite molded body in this embodiment is not particularly limited, and may include the following steps: a molding process (X), in which the GIS-type zeolite, carrier and other optional components in this embodiment are mixed and the prepared raw material is fed into the molding process to obtain a precursor; and a firing process (Y), in which the precursor is fired to obtain the GIS-type zeolite molded body.

[0183] As the molding process (X), commonly known methods can be used without particular limitation, such as spray drying, extrusion molding, injection molding, injection casting, rotary granulation, and pressure molding. Among these, spray drying and extrusion molding are preferred.

[0184] The temperature of the slurry (also referred to as "slurry" in spray drying) used as a raw material for spray drying is not particularly limited, but is preferably 10°C to 80°C, more preferably 15°C to 60°C. When the temperature of the slurry is below 80°C, it tends to suppress the evaporation of water in the slurry, and when the temperature of the slurry is above 10°C, it tends to suppress freezing in the slurry.

[0185] As a stirring method during slurry preparation, any method can be used, but a stirring paddle is preferred. Specifically, paddles used for stirring can be propeller-shaped, short-bladed, flat-bladed, turbine-shaped, conical, etc. Furthermore, baffles can be installed inside the tank for effective stirring. The number of stirrers should be selected based on the size of the catalyst feed tank and the shape of the stirring paddles, among other factors.

[0186] In this embodiment, the total stirring time of the slurry is preferably 1 minute to 24 hours, more preferably 10 minutes to 5 hours, and even more preferably 15 minutes to 3 hours. When the stirring time of the mixture is more than 1 minute, the composition of the slurry tends to become uniform; when it is less than 24 hours, the effect of water evaporation in the slurry tends to decrease.

[0187] The spraying of slurry can be carried out by methods commonly implemented in industry, such as rotating disc method, two-fluid nozzle method and high-pressure nozzle method, with rotating disc method being particularly preferred.

[0188] As the heat source for drying the droplets obtained from the spray, air heated by steam, an electric heater, or the like is preferably used. The inlet temperature of the dryer can be approximately 100°C to 400°C, preferably 150°C to 300°C. The outlet temperature of the dryer can be approximately 40°C to 150°C, preferably 50°C to 130°C.

[0189] There are no particular limitations on the extrusion molding process. For example, the preferred temperature for heating and concentrating the raw material (also referred to as "raw material clay" in the extrusion molding process) is 40°C to 80°C, more preferably 50°C to 75°C. At temperatures above 40°C, there is a tendency to prevent a decrease in heating and concentration efficiency, while at temperatures below 80°C, there is a tendency to prevent an excessive increase in water evaporation and to easily control the concentration state.

[0190] The water content in the raw clay is preferably 35% to 50%, more preferably 38% to 45%. When the water content is below 50%, the excessive increase in the softness of the raw clay can be prevented, and the formability tends to improve. When the water content is above 35%, the moderate decrease in the softness of the raw clay can be prevented, and the formability tends to improve.

[0191] There are no particular limitations on the extrusion molding machine used in the extrusion molding process; examples include screw type, roller type, scraper type, self-forming type, and piston type. Among these, screw type extrusion molding machines are particularly preferred for performing the extrusion molding process.

[0192] [Firing process (Y)]

[0193] The firing temperature in the firing process (Y) is not particularly limited as long as it is a commonly used temperature. However, for the purpose of maintaining the crystallinity of the zeolite while ensuring its strength, it is preferable to be less than 550°C, more preferably less than 530°C, and even more preferably less than 500°C. In addition, the firing temperature is preferably 110°C or higher, and more preferably 120°C or higher.

[0194] Regarding the firing time in the firing process (Y), there is no particular limitation as long as the carrier is sufficiently dried or sintered. It can be appropriately selected according to the firing temperature. For the reason that it tends to ensure strength while maintaining the crystallinity of zeolite, it is preferably 20 days or less, more preferably 10 days or less, and even more preferably 7 days or less.

[0195] The firing atmosphere in the firing process (Y) is not particularly limited as long as it is a commonly used atmosphere. It is usually an air atmosphere, an atmosphere with added inert gases such as nitrogen and argon, or an atmosphere with oxygen.

[0196] The firing process (Y) can be carried out using a rotary kiln, tunnel furnace, muffle furnace, or other firing furnaces.

[0197] [use]

[0198] The applications of GIS-type zeolite molded bodies are not particularly limited. For example, they can be used as separators or separation membranes for various gases and liquids, electrolyte membranes for fuel cells, fillers for various resin molded bodies, membrane reactors, catalysts for hydrogen cracking and alkylation, catalyst supports for metals and metal oxides, adsorbents, desiccants, detergents, ion exchangers, wastewater treatment agents, fertilizers, food additives, cosmetic additives, etc.

[0199] As described above, the GIS-type zeolite molded body of this embodiment can be suitably used as an adsorbent material. That is, the adsorbent material of this embodiment includes the GIS-type zeolite molded body of this embodiment.

[0200] The GIS-type zeolite molded body of this embodiment tends to easily improve the selectivity of carbon dioxide adsorption. Therefore, the adsorbent material of this embodiment can be designed, for example, to be able to sufficiently adsorb carbon dioxide and to have high selectivity for carbon dioxide adsorption relative to the amount of methane adsorbed. In this case, it can be particularly preferably used, for example, for the selective removal of carbon dioxide from natural gas.

[0201] The adsorption device of this embodiment is not particularly limited in its composition as long as it has the GIS-type zeolite molded body of this embodiment. As a representative composition, the following can be cited: Figure 1 The example shown. Figure 1 The adsorption apparatus 1 of this embodiment, as illustrated, 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 molded bodies 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 the adsorption apparatus 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. However, the object processed using the adsorption apparatus is not limited to natural gas, nor is the internal structure of the adsorption apparatus limited to... Figure 1 The example shown.

[0202] [Separation Method]

[0203] In the separation method of this embodiment, an adsorption device equipped with the GIS-type zeolite molded body 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, 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 one or more gases selected from the group consisting of N2, 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, acetylene, etc.

[0204] The separation method using the GIS-type zeolite molded body of this embodiment is not particularly limited, but methods with low energy consumption and excellent economic efficiency during the regeneration of adsorbent materials such as the GIS-type zeolite molded body are 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) are preferred. Pressure swing adsorption (PSA) refers to a method in which the pressure during gas desorption is lower than the pressure during adsorption, and gas separation is achieved by utilizing the difference between the adsorption amount at high pressure and the adsorption amount at low pressure. Temperature swing adsorption (TSA) refers to a method in which the temperature during gas desorption is higher than the temperature during adsorption, and gas separation is achieved by utilizing the difference between the adsorption amount at low temperature and the adsorption amount at high temperature. Furthermore, a combination of these methods constitutes pressure swing-temperature swing adsorption (PTSA). These methods can be implemented under various known conditions.

[0205] It should be noted that the above-described separation method can be implemented as a method for producing purified gas. That is, the method for producing purified gas in this embodiment uses an adsorption device equipped with the GIS-type zeolite molded body of this embodiment 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, CO, and hydrocarbons. Here, for example, when separating methane and carbon dioxide from a mixed gas containing methane and carbon dioxide in a form in which carbon dioxide is adsorbed by the adsorption material, the purified gas in this embodiment can be either methane or carbon dioxide. That is, the gas adsorbed as the adsorption material of this embodiment, as well as other gases, can be recovered as the purified gas in this embodiment.

[0206] Example

[0207] The present embodiment is described in detail below through examples and comparative examples, but the present embodiment is not limited to these examples in any way.

[0208] [Crystal Structure Analysis]

[0209] The crystal structure analysis of GIS-type zeolites was performed in the following order.

[0210] (1) The dried material (powdered zeolite) obtained in Synthesis Examples 1 and 2 was used as a sample and pulverized using an agate mortar. 10% by mass of crystalline silicon (manufactured by Rare Metallic Co., Ltd.) was further added and mixed with an agate mortar until homogeneous, which was used as a sample for structural analysis.

[0211] (2) The sample from (1) above is uniformly fixed on a powder non-reflective sample plate, and crystal structure analysis is performed under the following conditions.

[0212] X-ray diffraction (XRD) apparatus: Rigaku Corporation's "RINT2500" powder X-ray diffraction apparatus (trade name).

[0213] X-ray source: Cu tube (40kV, 200mA)

[0214] Measurement temperature: 25℃

[0215] Measurement range: 5–60° (0.02° / step)

[0216] Measurement speed: 0.2° / minute

[0217] Slit width (scattering, divergence, light reception): 1°, 1°, 0.15mm

[0218] (3) For the obtained X-ray diffraction spectrum, after correcting the 2θ shift using the diffraction peak of crystalline silicon, the XRD data analysis software "PDXL2" (software name, manufactured by Rigaku Corporation) was used to analyze the data, and the "αcut value" in the analysis software was set to 3.00 to measure the 2θ value of the peak.

[0219] [Determination of the content of each element (methods for determining A, B, C, and D)]

[0220] The GIS-type zeolites produced in each synthesis example, as well as the GIS-type zeolite molded bodies produced in each example and comparative example, were thermally dissolved using an aqueous sodium hydroxide solution or aqua regia. Compositional analysis based on ICP-luminescence spectrophotometry (SPS3520UV-DD, manufactured by Seiko Instruments Co., Ltd.) was performed using appropriately diluted liquids to calculate the contents of alkali metals and alkaline earth metals, thus determining A, B, C, and D. Similarly, the contents of Si, Al, P, Zr, and Ti were also calculated.

[0221] [Strength Measurement]

[0222] Regarding the strength of the GIS-type zeolite molded body, a micro compression testing machine (MCT-W500 manufactured by Shimadzu Corporation, compressive strength test) was used in Examples 1-10, 21-22 and Comparative Examples 1-6, 13-14, for compressive strength testing; and a digital hardness tester (KHT-40N manufactured by Fujiwara Corporation, indenter 3mm, for breaking strength testing) was used in Examples 11-20, 23-24 and Comparative Examples 7-12, 15-16, for breaking strength testing. Twenty measurements were performed in each case, and the average value obtained was taken as the strength.

[0223] [Particle Size Measurement]

[0224] In the GIS-type zeolite molded bodies, the particle size was measured using a laser diffraction-scattering particle size analyzer (Microtrac MT3000) in Examples 1-10, 21-22 and Comparative Examples 1-6, 13-14, according to the accompanying manual.

[0225] [Measurement of Pellet Length and Diameter]

[0226] In the GIS-type zeolite molded bodies, the length and diameter of the granules were measured using the vernier caliper method in Examples 11-20, 23, 24 and Comparative Examples 7-12, 15, 16. In this measurement, three samples were measured using vernier calipers with a minimum reading of 0.1 mm or less, and their average value was taken as the length and diameter.

[0227] [Gas Adsorption Isotherm Determination]

[0228] The gas adsorption isotherm measurements were performed in the following order.

[0229] (1) Using GIS-1 and the molded body obtained in the examples as samples, 0.2g was added to a 12mm sample cell (manufactured by Micro Meritics).

[0230] (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.

[0231] (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, it is measured using liquefied carbon dioxide (manufactured by Sumitomo Seika Co., Ltd., purity ≥ 99.9% by mass), methane gas (manufactured by Sumitomo Seika Co., Ltd., purity ≥ 99.0% by mass), or nitrogen gas (manufactured by Taiyo Nippon Sanso Co., Ltd., purity ≥ 99.9995% by mass) at an absolute pressure of 0.25–760 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 sec.

[0232] Synthesis of GIS-type zeolites

[0233] (Synthesis example 1)

[0234] A mixed gel was prepared by mixing 207.30 g of water, 8.78 g of sodium hydroxide (NaOH, manufactured by Wako Pure Chemical Industries, Ltd.), 16.4 g of sodium aluminate (NaAlO2, manufactured by Wako Pure Chemical Industries, Ltd.), and 248.3 g of No. 3 water glass (manufactured by Kishida Chemical) and stirring for 15 minutes. The composition of the mixed gel was SiO2 / Al2O3 = 12.0, Na2O / Al2O3 = 4.0, and H2O / Al2O3 = 200. The mixed gel was placed in a 1000 mL stainless steel autoclave with a fluororesin inner cylinder and subjected to hydrothermal synthesis at 130°C for 5 days without stirring. The product was filtered off and dried at 120°C to obtain powdered GIS-type zeolite. The GIS-type zeolite obtained in this way is an untreated ion-exchange zeolite and is used as GIS-0 for the fabrication of molded bodies described later.

[0235] Based on the XRD pattern obtained from the zeolite of Synthesis Example 1, the diffraction peak of (1 0 1) is 12.40°, the diffraction peak of (2 1 1) is 21.62°, and the diffraction peak of (3 1 2) is 33.38°, thus confirming that the obtained zeolite is of the GIS type.

[0236] In addition, the GIS-type zeolite in Synthetic Example 1 contained 9.9% Al by mass, and P, Zr and Ti were not detected.

[0237] (Synthesis example 2)

[0238] The zeolite, equivalent to the substance described in Example 3 of Patent Document 1, was synthesized as follows: 329.50 g of water, 1.76 g of sodium hydroxide, 3.28 g of sodium aluminate, and 49.7 g of No. 3 water glass were mixed and stirred for 6 hours to prepare a mixed gel. The composition of the mixed gel was SiO2 / Al2O3 = 12.0, Na2O / Al2O3 = 4.0, and H2O / Al2O3 = 1000. The mixed gel was placed in a 1000 mL stainless steel autoclave with a fluororesin inner cylinder and subjected to hydrothermal synthesis at 135 °C for 4 days without stirring. The product was filtered off and dried at 120 °C to obtain powdered zeolite. 1 g of the obtained zeolite was added to 500 mL of a 0.1 N potassium hydroxide aqueous solution and stirred at 400 rpm for 3 hours at 40 °C. The product was filtered off and dried at 120 °C to obtain powdered GIS-type zeolite with a portion of the cations exchanged for potassium.

[0239] Based on the XRD patterns obtained from the zeolite of Synthesis Example 2, the diffraction peak of (101) is 12.78°, the diffraction peak of (211) is 22.20°, and the diffraction peak of (312) is 34.18°, thus confirming that the obtained zeolite is of the GIS type.

[0240] In addition, the GIS-type zeolite in Synthetic Example 2 contained 9.7% Al by mass, and P, Zr and Ti were not detected.

[0241] [Cation exchange]

[0242] The GIS-0 obtained in Synthesis Example 1 was subjected to cation exchange using potassium carbonate or lithium nitrate via ion exchange. By adjusting the ion concentration and the number of exchanges, GIS-1 to 7 were obtained.

[0243] The GIS-type zeolite GIS-8 from Synthesis Example 2 was subjected to cation exchange using potassium carbonate via ion exchange. By adjusting the ion concentration and the number of exchanges, GIS-9 was obtained.

[0244] ICP-luminescence spectrophotometry was performed on GIS-0 to GIS-9 samples, and the contents of alkali metals and alkaline earth metals obtained from the results are shown in Table 1. It should be noted that 1.3A and B in Table 1 represent values ​​within 100g of the sample.

[0245] [Table 1]

[0246] GIS-0 GIS-1 GIS-2 GIS-3 GIS-4 GIS-5 GIS-6 GIS-7 GIS-8 GIS-9 Na (mass%) 9.3386 0.4433 2.1084 1.0014 1.9604 0.1342 3.6888 3.9736 2.3192 0.4322 K (mass%) 0 15.4657 11.9875 0 0 12.1481 9.5919 0 12.3793 15.4344 Li (mass%) 0 0 0 2.5885 2.3068 0.6901 0 1.6767 0 0 A 0 0.395 0.307 0.373 0.332 0.410 0.245 0.242 0.317 0.395 B 0.406 0.415 0.398 0.416 0.418 0.416 0.406 0.414 0.417 0.414 C 0.406 0.415 0.398 0.416 0.418 0.416 0.406 0.414 0.417 0.414 D 0 0.395 0.307 0 0 0.311 0.245 0 0.317 0.395 C / A - 1.050 1.297 1.115 1.258 1.015 1.655 1.714 1.316 1.049 B / A - 1.050 1.297 1.115 1.258 1.015 1.655 1.714 1.316 1.049 C / D - 1.050 1.297 - - 1.338 1.657 - 1.315 1.048

[0247] [mark]

[0248] The meanings of the symbols recorded below are as follows.

[0249] A: The total amount of potassium and lithium in the total amount of alkali metals and alkaline earth metals.

[0250] B: The sum of the values ​​obtained by multiplying the physical mass of each alkali metal and alkaline earth metal by its valence.

[0251] C: Total amount of alkali metals

[0252] D: Total amount of potassium

[0253] [Example 1]

[0254] 561.4 g of GIS-1 was dispersed in 571.9 g of ion-exchanged water, and then added to 4423.8 g of alumina sol (manufactured by Nissan Chemical Co., Ltd., alumina content: 10.5% by mass) to prepare a raw material slurry. The obtained raw material slurry was stirred at 25°C for 1 hour. The raw material slurry was in sol form with a viscosity of 300 cP (measured using a Type B viscometer manufactured by Eiko Seiki Co., Ltd.). The raw material slurry was fed into a spray dryer (Okawahara Chemical Machinery OC-16 spray dryer) with the inlet fluid temperature set at 230°C and the outlet fluid temperature set at 120°C, and spray dried using a rotating disc method to obtain a dried powder. The obtained dried powder was then calcined in an electric furnace at 350°C in air atmosphere for 24 hours.

[0255] The strength of the GIS-type zeolite molded body obtained in this way is 8.2 MPa. Furthermore, A, B, C, and D were calculated based on the content of the aforementioned elements and are shown in Table 2. It should be noted that A, B, C, and D in Table 2 represent values ​​per 100 g of sample. In addition, the particle size of the molded body is 55 μm. Furthermore, the carrier content in the molded body is 45% by mass, and the GIS-type zeolite content is 55% by mass.

[0256] [Example 2]

[0257] Except that the GIS-type zeolite was G-2, a GIS-type zeolite molded body was obtained in the same manner as in Example 1. The strength of the GIS-type zeolite molded body obtained in this way was 7.5 MPa. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2. Furthermore, the particle size of the molded body was 55 μm.

[0258] [Example 3]

[0259] Except that the GIS-type zeolite was G-3, a GIS-type zeolite molded body was obtained in the same manner as in Example 1. The strength of the GIS-type zeolite molded body thus obtained was 8.3 MPa. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2. Furthermore, the particle size of the molded body was 56 μm.

[0260] [Example 4]

[0261] Except that the GIS-type zeolite was G-4, a GIS-type zeolite molded body was obtained in the same manner as in Example 1. The strength of the GIS-type zeolite molded body thus obtained was 7.3 MPa. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2. Furthermore, the particle size of the molded body was 55 μm.

[0262] [Example 5]

[0263] Except that the GIS-type zeolite was G-5, a GIS-type zeolite molded body was obtained in the same manner as in Example 1. The strength of the GIS-type zeolite molded body thus obtained was 8.4 MPa. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2. Furthermore, the particle size of the molded body was 56 μm.

[0264] [Comparative Example 1]

[0265] Except that the GIS-type zeolite was G-0, a GIS-type zeolite molded body was obtained in the same manner as in Example 1. The strength of the GIS-type zeolite molded body obtained in this way was 3.2 MPa. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2. Furthermore, the particle size of the molded body was 55 μm.

[0266] [Comparative Example 2]

[0267] Except that the GIS-type zeolite was G-6, a GIS-type zeolite molded body was obtained in the same manner as in Example 1. The strength of the GIS-type zeolite molded body thus obtained was 4.0 MPa. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2. Furthermore, the particle size of the molded body was 56 μm.

[0268] [Comparative Example 3]

[0269] Except that the GIS-type zeolite was G-7, a GIS-type zeolite molded body was obtained in the same manner as in Example 1. The strength of the GIS-type zeolite molded body obtained in this way was 3.8 MPa. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2. Furthermore, the particle size of the molded body was 55 μm.

[0270] [Example 6]

[0271] Except that 4423.8 g of alumina sol was replaced with 1263.9 g of ion-exchanged water and 3159.9 g of silica sol (manufactured by Nalco, silica content: 14.7% by mass), a GIS-type zeolite molded body was obtained in the same manner as in Example 1. The strength of the GIS-type zeolite molded body thus obtained was 8.0 MPa. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2. Furthermore, the particle size of the molded body was 50 μm.

[0272] [Example 7]

[0273] Except that the GIS-type zeolite was G-2, a GIS-type zeolite molded body was obtained in the same manner as in Example 6. The strength of the GIS-type zeolite molded body thus obtained was 6.5 MPa. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2. Furthermore, the particle size of the molded body was 51 μm.

[0274] [Example 8]

[0275] Except that the GIS-type zeolite was G-3, a GIS-type zeolite molded body was obtained in the same manner as in Example 6. The strength of the GIS-type zeolite molded body thus obtained was 7.9 MPa. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2. Furthermore, the particle size of the molded body was 51 μm.

[0276] [Example 9]

[0277] Except that the GIS-type zeolite was G-4, a GIS-type zeolite molded body was obtained in the same manner as in Example 6. The strength of the GIS-type zeolite molded body thus obtained was 6.4 MPa. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2. Furthermore, the particle size of the molded body was 52 μm.

[0278] [Example 10]

[0279] Except that the GIS-type zeolite was G-5, a GIS-type zeolite molded body was obtained in the same manner as in Example 6. The strength of the GIS-type zeolite molded body thus obtained was 8.0 MPa. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2. Furthermore, the particle size of the molded body was 51 μm.

[0280] [Comparative Example 4]

[0281] Except that the GIS-type zeolite was G-0, a GIS-type zeolite molded body was obtained in the same manner as in Example 6. The strength of the GIS-type zeolite molded body obtained in this way was 3.4 MPa. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2. Furthermore, the particle size of the molded body was 51 μm.

[0282] [Comparative Example 5]

[0283] Except that the GIS-type zeolite was G-6, a GIS-type zeolite molded body was obtained in the same manner as in Example 6. The strength of the GIS-type zeolite molded body thus obtained was 4.2 MPa. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2. Furthermore, the particle size of the molded body was 51 μm.

[0284] [Comparative Example 6]

[0285] Except that the GIS-type zeolite was G-7, a GIS-type zeolite molded body was obtained in the same manner as in Example 6. The strength of the GIS-type zeolite molded body obtained in this way was 3.8 MPa. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2. Furthermore, the particle size of the molded body was 51 μm.

[0286] [Example 11]

[0287] 100g of GIS-1, 250g of alumina sol (manufactured by Kawaken Fine Chemicals Co., Ltd., alumina content: 10% by mass), and 275g of deionized water were mixed and then concentrated by heating at 70°C to adjust the water content to 40%, thus producing raw material clay. The raw material clay was then shaped using a wet extrusion granulator (Multigran MG-55 type (dome die 40rpm), orifice diameter Φ3mm) to obtain extruded granules with a length of 5mm and a diameter of 3mm. The resulting extruded granules were then fired in an electric furnace at 350°C in air atmosphere for 3 hours.

[0288] The strength of the GIS-type zeolite molded body obtained in this way is 30.3 N. Furthermore, the contents of A, B, C, and D, etc., were calculated by determining the contents of the aforementioned elements and are shown in Table 2. In addition, the carrier content in the molded body is 20% by mass, and the GIS-type zeolite content is 80% by mass.

[0289] [Example 12]

[0290] Except that the GIS-type zeolite is G-2, a GIS-type zeolite molded body (granules with a length of 5 mm and a diameter of 3 mm) was obtained in the same manner as in Example 11. The strength of the GIS-type zeolite molded body obtained in this way is 24.6 N. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2.

[0291] [Example 13]

[0292] Except that the GIS-type zeolite is G-3, a GIS-type zeolite molded body (granules with a length of 5 mm and a diameter of 3 mm) was obtained in the same manner as in Example 11. The strength of the GIS-type zeolite molded body obtained in this way is 30.6 N. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2.

[0293] [Example 14]

[0294] Except that the GIS-type zeolite is G-4, a GIS-type zeolite molded body (granules with a length of 5 mm and a diameter of 3 mm) was obtained in the same manner as in Example 11. The strength of the GIS-type zeolite molded body obtained in this way is 24.0 N. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2.

[0295] [Example 15]

[0296] Except that the GIS-type zeolite was G-5, a GIS-type zeolite molded body (granules with a length of 5 mm and a diameter of 3 mm) was obtained in the same manner as in Example 11. The strength of the GIS-type zeolite molded body obtained in this way was 29.7 N. In addition, A, B, C, and D were calculated by measuring the content of each of the above elements, and are shown in Table 2.

[0297] [Comparative Example 7]

[0298] Except that the GIS-type zeolite is G-0, a GIS-type zeolite molded body (granules with a length of 5 mm and a diameter of 3 mm) was obtained in the same manner as in Example 11. The strength of the GIS-type zeolite molded body obtained in this way is 6.0 N. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2.

[0299] [Comparative Example 8]

[0300] Except that the GIS-type zeolite is G-6, a GIS-type zeolite molded body (granules with a length of 5 mm and a diameter of 3 mm) was obtained in the same manner as in Example 11. The strength of the GIS-type zeolite molded body obtained in this way is 13.2 N. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2.

[0301] [Comparative Example 9]

[0302] Except that the GIS-type zeolite is G-7, a GIS-type zeolite molded body (granules with a length of 5 mm and a diameter of 3 mm) was obtained in the same manner as in Example 11. The strength of the GIS-type zeolite molded body obtained in this way is 12.6 N. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2.

[0303] [Example 16]

[0304] Except that 250g of alumina sol was replaced with 176.4g of ion-exchanged water and 73.5g of silica sol (manufactured by Nalco, silica content: 34% by mass), GIS-type zeolite molded bodies (granules with a length of 5mm and a diameter of 3mm) were obtained in the same manner as in Example 11. The strength of the GIS-type zeolite molded bodies thus obtained was 30.0N. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2.

[0305] [Example 17]

[0306] Except that the GIS-type zeolite is G-2, a GIS-type zeolite molded body (granules with a length of 5 mm and a diameter of 3 mm) was obtained in the same manner as in Example 16. The strength of the GIS-type zeolite molded body obtained in this way is 24.6 N. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2.

[0307] [Example 18]

[0308] Except that the GIS-type zeolite is G-3, a GIS-type zeolite molded body (granules with a length of 5 mm and a diameter of 3 mm) was obtained in the same manner as in Example 16. The strength of the GIS-type zeolite molded body obtained in this way is 29.4 N. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2.

[0309] [Example 19]

[0310] Except that the GIS-type zeolite is G-4, a GIS-type zeolite molded body (granules with a length of 5 mm and a diameter of 3 mm) was obtained in the same manner as in Example 16. The strength of the GIS-type zeolite molded body obtained in this way is 24.3 N. In addition, A, B, C and D were calculated by measuring the content of each of the above elements, and are shown in Table 2.

[0311] [Example 20]

[0312] Except that the GIS-type zeolite is G-5, a GIS-type zeolite molded body was obtained in the same manner as in Example 16. The strength of the GIS-type zeolite molded body obtained in this way is 28.5 N. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2.

[0313] [Comparative Example 10]

[0314] Except that the GIS-type zeolite is G-0, a GIS-type zeolite molded body (granules with a length of 5 mm and a diameter of 3 mm) was obtained in the same manner as in Example 16. The strength of the GIS-type zeolite molded body obtained in this way is 5.4 N. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2.

[0315] [Comparative Example 11]

[0316] Except that the GIS-type zeolite is G-6, a GIS-type zeolite molded body was obtained in the same manner as in Example 16. The strength of the GIS-type zeolite molded body obtained in this way is 12.6 N. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2.

[0317] [Comparative Example 12]

[0318] Except that the GIS-type zeolite is G-7, a GIS-type zeolite molded body (granules with a length of 5 mm and a diameter of 3 mm) was obtained in the same manner as in Example 16. The strength of the GIS-type zeolite molded body obtained in this way is 12.0 N. In addition, A, B, C, and D were calculated by measuring the content of each of the above elements, and are shown in Table 2.

[0319] [Example 21]

[0320] Except that the GIS-type zeolite was G-9, a GIS-type zeolite molded body was obtained in the same manner as in Example 1. The strength of the GIS-type zeolite molded body thus obtained was 8.0 MPa. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2. Furthermore, the particle size of the molded body was 55 μm.

[0321] [Example 22]

[0322] Except that the GIS-type zeolite was G-9, a GIS-type zeolite molded body was obtained in the same manner as in Example 6. The strength of the GIS-type zeolite molded body thus obtained was 7.8 MPa. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2. Furthermore, the particle size of the molded body was 51 μm.

[0323] [Example 23]

[0324] Except that the GIS-type zeolite was G-9, a GIS-type zeolite molded body (granules with a length of 5 mm and a diameter of 3 mm) was obtained in the same manner as in Example 11. The strength of the GIS-type zeolite molded body obtained in this way was 29.4 N. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2.

[0325] [Example 24]

[0326] Except that the GIS-type zeolite was G-9, a GIS-type zeolite molded body (granules with a length of 5 mm and a diameter of 3 mm) was obtained in the same manner as in Example 16. The strength of the GIS-type zeolite molded body obtained in this way was 28.2 N. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2.

[0327] [Comparative Example 13]

[0328] Except that the GIS-type zeolite was G-8, a GIS-type zeolite molded body was obtained in the same manner as in Example 1. The strength of the GIS-type zeolite molded body obtained in this way was 5.8 MPa. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements, and are shown in Table 2. Furthermore, the particle size of the molded body was 54 μm.

[0329] [Comparative Example 14]

[0330] Except that the GIS-type zeolite was G-8, a GIS-type zeolite molded body was obtained in the same manner as in Example 6. The strength of the GIS-type zeolite molded body obtained in this way was 5.3 MPa. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2. Furthermore, the particle size of the molded body was 50 μm.

[0331] [Comparative Example 15]

[0332] Except that the GIS-type zeolite is G-8, a GIS-type zeolite molded body (granules with a length of 5 mm and a diameter of 3 mm) was obtained in the same manner as in Example 11. The strength of the GIS-type zeolite molded body obtained in this way is 17.4 N. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2.

[0333] [Comparative Example 16]

[0334] Except that the GIS-type zeolite is G-8, a GIS-type zeolite molded body (granules with a length of 5 mm and a diameter of 3 mm) was obtained in the same manner as in Example 16. The strength of the GIS-type zeolite molded body obtained in this way is 16.8 N. In addition, A, B, C, and D were calculated by measuring the content of the above-mentioned elements and are shown in Table 2.

[0335] [Table 2]

[0336] zeolite A B C D B / A C / A C / D Strength (MPa) Strength (N) Example 1 GIS-1 0.216 0.228 0.228 0.216 1.055 1.055 1.055 8.2 - Example 2 GIS-2 、0.169 0.219 0.219 0.169 1.294 1.294 1.294 7.5 - Example 3 GIS-3 0.205 0.229 0.229 0.000 1.117 1.117 - 8.3 - Example 4 GIS-4 0.183 0.230 0.230 0.000 1.258 1.258 - 7.3 - Example 5 GIS-5 0.225 0.229 0.229 0.171 1.016 1.016 1.341 8.4 - Example 6 GIS-1 0.218 0.228 0.228 0.218 1.044 1.044 1.044 8.0 - Example 7 GIS-2 0.169 0.219 0.219 0.169 1.294 1.294 1.294 6.5 - Example 8 GIS-3 0.205 0.229 0.229 0.000 1.115 1.115 - 7.9 - Example 9 GIS-4 0.183 0.231 0.231 0.000 1.262 1.262 - 6.4 - Example 10 GIS-5 0.225 0.229 0.229 0.171 1.016 1.016 1.341 8.0 - Example 11 GIS-1 0.316 0.332 0.332 0.316 1.050 1.050 1.050 - 30.3 Example 12 GIS-2 0.246 0.318 0.318 0.246 1.292 1.292 1.292 - 24.6 Example 13 GIS-3 0.298 0.333 0.333 0.000 1.116 1.116 - - 30.6 Example 14 GIS-4 0.266 0.334 0.334 0.000 1.255 1.255 - - 24.0 Example 15 GIS-5 0.328 0.333 0.333 0.248 1.016 1.016 1.341 - 29.7 Example 16 GIS-1 0.317 0.331 0.331 0.317 1.044 1.044 1.044 - 30.0 Example 17 GIS-2 0.246 0.318 0.318 0.246 1.292 1.292 1.292 - 24.6 Example 18 GIS-3 0.298 0.333 0.333 0.000 1.116 1.116 - - 29.4 Example 19 GIS-4 0.267 0.335 0.335 0.000 1.255 1.255 - - 24.3 Example 20 GIS-5 0.328 0.332 0.332 0.248 1.012 1.012 1.336 - 28.5 Example 21 GIS-9 0.217 0.227 0.227 0.217 1.046 1.046 1.046 8.0 - Example 22 GIS-9 0.218 0.227 0.227 0.218 1.043 1.043 1.043 7.8 - Example 23 GIS-9 0.315 0.331 0.331 0.315 1.050 1.050 1.050 - 29.4 Example 24 GIS-9 0.315 0.330 0.330 0.315 1.046 1.046 1.046 - 28.2 Comparative Example 1 GIS-0 0.000 0.223 0.223 0.000 - - - 3.2 - Comparative Example 2 GIS-6 0.135 0.223 0.223 0.135 1.647 1.647 1.647 4.0 - Comparative Example 3 GIS-7 0.133 0228 0.228 0.000 1.713 1.713 - 3.8 - Comparative Example 4 GIS-0 0.000 0.223 0.223 0.000 - - - 3.4 - Comparative Example 5 GIS-6 0.135 0.223 0.223 0.135 1.647 1.647 1.647 4.2 - Comparative Example 6 GIS-7 0.132 0.228 0.228 0.000 1.723 1.723 - 3.8 - Comparative Example 7 GIS-0 0.000 0.325 0.325 0.000 - - - - 6.0 Comparative Example 8 GIS-6 0.196 0.324 0.324 0.196 1.652 1.652 1.652 - 13.2 Comparative Example 9 GIS-7 0.194 0.331 0.331 0.000 1.708 1.708 - - 12.6 Comparative Example 10 GIS-0 0.000 0.326 0.326 0.000 - - - - 5.4 Comparative Example 11 GIS-6 0.196 0.324 0.324 0.196 1.652 1.652 1.652 - 12.6 Comparative Example 12 GIS-7 0.193 0.331 0.331 0.000 1.714 1.714 - - 12.0 Comparative Example 13 GIS-8 0.174 0.230 0.230 0.174 1.323 1.323 1.323 5.8 - Comparative Example 14 GIS-8 0.175 0.230 0.230 0.175 1.317 1.317 1.317 5.3 - Comparative Example 15 GIS-8 0.254 0.334 0.334 0.254 1.316 1.316 1.316 - 17.4 Comparative Example 16 GIS-8 0.253 0.334 0.334 0.253 1.320 1.320 1.320 - 16.8

[0337] [Example 25]

[0338] When the adsorption isotherms of CO2, CH4, and N2 of the GIS-type zeolite molded body of Example 1 were measured, the adsorption capacities at 25°C and 760 mmHg were CO2: 29.3 cm⁻¹ 3 / g, CH4: 0.1cm 3 / g, N2: 0.2cm 3 / g, with an adsorption selectivity (CO2 / CH4) of 293 and an adsorption selectivity (CO2 / N2) of 147, confirming its sufficient performance as an adsorbent material.

Claims

1. A GIS-type zeolite molded body, comprising: GIS-type zeolite; and carrier In the GIS-type zeolite When the total amount of potassium and lithium is set as A, and the total amount of alkali metals is set as C, the condition 1.00 is satisfied. <C / A≤1.30, When the total amount of potassium is set as D, and the total amount of alkali metals is set as C, the condition C / D ≤ 1.30 is met. The alkali metal contains at least sodium.

2. The GIS-type zeolite molded body as described in claim 1, wherein, When the total amount of potassium and lithium is set as A, and the total amount of alkali metals and alkaline earth metals obtained by multiplying their respective amounts by their valences is set as B, the condition B / A ≤ 1.30 is met.

3. The GIS-type zeolite molded body as described in claim 2, wherein, Satisfies 1.

00. Satisfies 1.

00. <C / D。 4. The GIS-type zeolite molded body according to any one of claims 1 to 3, wherein, The carrier comprises one or more selected from the group consisting of silicon oxide and aluminum oxide.

5. The GIS-type zeolite molded body according to any one of claims 1 to 3, wherein, The particle size of the GIS-type zeolite molded body is between 20 μm and 300 μm.

6. The GIS-type zeolite molded body according to any one of claims 1 to 3, wherein, The GIS-type zeolite molded body is obtained through spray drying.

7. The GIS-type zeolite molded body as described in claim 6, wherein, The compressive strength of the GIS-type zeolite molded body is above 6.0 MPa.

8. The GIS-type zeolite molded body as described in claim 6, wherein, The GIS-type zeolite molding body is a granular material with a length of 3mm to 50mm and a diameter of 1mm to 20mm.

9. The GIS-type zeolite molded body according to any one of claims 1 to 3, wherein, The GIS-type zeolite molded body is obtained through extrusion molding.

10. The GIS-type zeolite molded body as described in claim 9, wherein, The breaking strength of the GIS-type zeolite molded body is above 20N.

11. The GIS-type zeolite molded body as described in claim 9, wherein, The C / A ratio is greater than 1.00 and less than 1.

25.

12. The GIS-type zeolite molded body according to any one of claims 1 to 3, wherein, The C / A ratio is greater than 1.00 and less than 1.

20.

13. The GIS-type zeolite molded body according to any one of claims 1 to 3, wherein, The C / A ratio is greater than 1.00 and less than 1.

15.

14. The GIS-type zeolite molded body according to any one of claims 1 to 3, wherein, The B / A ratio is below 1.

25.

15. The GIS-type zeolite molded body as described in claim 2, wherein, The B / A ratio is below 1.

20.

16. The GIS-type zeolite molded body as described in claim 2, wherein, The B / A ratio is below 1.

15.

17. The GIS-type zeolite molded body as described in claim 2, wherein, The C / D ratio is below 1.

25.

18. The GIS-type zeolite molded body according to any one of claims 1 to 3, wherein, The C / D ratio is below 1.

20.

19. The GIS-type zeolite molded body according to any one of claims 1 to 3, wherein, The C / D ratio is below 1.

15.

20. The GIS-type zeolite molded body according to any one of claims 1 to 3, wherein, Relative to 100% mass of the GIS-type zeolite molded body, the content of the GIS-type zeolite is 30% to 90% by mass, and the content of the carrier is 10% to 70% by mass.

21. The GIS-type zeolite molded body according to any one of claims 1 to 3, wherein, The compressive strength of the GIS-type zeolite molded body is above 6.2 MPa.

22. The GIS-type zeolite molded body as described in claim 8, wherein, The breaking strength of the GIS-type zeolite molded body is above 22N.

23. The GIS-type zeolite molded body as described in claim 11, wherein, 24. An adsorption device comprising the GIS-type zeolite molded body according to any one of claims 1 to 23. Using the adsorption apparatus of claim 24, 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, CO and hydrocarbons.

25. A separation method, wherein, The gas is separated by pressure swing adsorption separation, temperature swing adsorption separation, or pressure swing-temperature swing adsorption separation.

26. The separation method as described in claim 25, wherein, Using the adsorption apparatus of claim 24, 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, CO and hydrocarbons.

27. A method for producing a refined gas, wherein, ​ 28. A GIS-type zeolite, wherein, When the total amount of the substances of potassium and lithium is set as A and the total amount of the substances of alkali metals is set as C, 1.00 < C / A ≤ 1.30 is satisfied; when the total amount of the substances of potassium is set as D and the total amount of the substances of alkali metals is set as C, C / D is 1.30 or less, and the alkali metals include at least sodium.

29. The GIS-type zeolite as described in claim 28, wherein, The C / A is greater than 1.00 and 1.25 or less.

30. The GIS-type zeolite as described in claim 28, wherein, The C / A is greater than 1.00 and 1.20 or less.

31. The GIS-type zeolite as described in claim 28, wherein, The C / A is greater than 1.00 and 1.15 or less.

32. The GIS-type zeolite as described in claim 28, wherein, When the total amount of the substances of potassium and lithium is set as A and the total amount of the values obtained by multiplying the amounts of substances of alkali metals and alkaline earth metals by their valences is set as B, B / A is 1.30 or less.

33. The GIS-type zeolite as described in claim 32, wherein, The B / A is 1.25 or less.

34. The GIS-type zeolite as described in claim 32, wherein, The B / A is 1.20 or less.

35. The GIS-type zeolite as described in claim 32, wherein, The B / A is 1.15 or less.

36. The GIS-type zeolite as described in claim 32, wherein, 1.00 < B / A is satisfied.

37. The GIS-type zeolite as described in claim 28, wherein, The C / D is 1.20 or less.

38. The GIS-type zeolite as described in claim 28, wherein, The C / D is 1.15 or less.

39. The GIS-type zeolite as described in claim 28, wherein, 1.00 < C / D is satisfied.

Images