Zeolite molded body, adsorption device, and method for producing purified gas

Abstract

To provide a zeolite molding that does not easily become brittle even after adsorbing carbon dioxide, an adsorption device comprising the same, and a method for producing purified gas using the same.SOLUTION: A zeolite molding includes a zeolite that can adsorb carbon dioxide. The elastic modulus E is 10.0 MPa or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a zeolite molded body, an adsorption device, and a method for producing purified gas. [Background technology]

[0002] Zeolites can be used as adsorbents, desiccants, separators, catalysts, catalyst carriers, detergent additives, ion exchangers, wastewater treatment agents, fertilizers, food additives, cosmetic additives, and more, and are particularly useful for gas separation applications.

[0003] For example, among zeolites, those with a GIS structure as defined by the IZA (International Zeolite Association) are called GIS-type zeolites. GIS-type zeolites are zeolites having pores composed of 8-membered oxygen rings. Regarding such GIS-type zeolites, for example, Patent Document 1 shows that a GIS-type zeolite with carbon dioxide adsorption capacity has been synthesized, and that when GIS-type zeolite is used as an adsorbent, it can be used for the separation, recovery, and purification of carbon dioxide. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. WO2019 / 202933 [Overview of the project] [Problems that the invention aims to solve]

[0005] When separating, recovering, and purifying carbon dioxide using an adsorbent, a pressure swing adsorption separation method, a temperature swing adsorption separation method, a pressure-temperature swing adsorption separation method, or the like is used. In these methods, zeolite is used by filling it in a column or the like. In order to prevent fine powder of zeolite from accumulating in the flow path and blocking it in the apparatus, the zeolite is shaped and used as a pellet-shaped zeolite molded body. It is required that the zeolite molded body has sufficient durability under the use conditions.

[0006] It has been found that a zeolite molded body containing a zeolite capable of adsorbing carbon dioxide becomes brittle when adsorbing a larger amount of carbon dioxide, and in the case of a pellet-shaped zeolite molded body, it becomes powdered. Due to this embrittlement, fine powder is generated in the adsorption apparatus, making it difficult to continuously operate the apparatus due to pressure loss and the like.

[0007] An object of the present invention is to provide a zeolite molded body excellent in resistance to embrittlement against carbon dioxide adsorption, an adsorption apparatus including the same, and a method for producing a purified gas using the same.

Means for Solving the Problems

[0008] As a result of intensive studies to solve the above problems, the present inventors have found that the problem can be solved when the elastic modulus of the zeolite molded body is 10.0 MPa or more, and thus the present invention has been completed.

[0009] That is, the present invention includes the following embodiments. <1> A zeolite molded body containing a zeolite capable of adsorbing carbon dioxide, where the elastic modulus E is 10.0 MPa or more. <2> The zeolite molded body according to <1>, wherein the zeolite has a carbon dioxide adsorption amount of 10 cc / g or more. <3> The zeolite molded body according to <1> or <2>, wherein the zeolite is a GIS-type zeolite. <4> The silica-alumina ratio of the aforementioned GIS-type zeolite is 3.40 or higher. <3> Zeolite molded body as described above. <5> The silica-alumina ratio of the aforementioned GIS-type zeolite is 4.50 or higher. <3> Zeolite molded body as described above. <6> GIS-type zeolite containing potassium or lithium as a cation species, <3> ~ <5> A zeolite molded body as described in any of the following. <7> The ratio (Z / T) of the total amount of potassium and lithium to the total amount of alkali metals (T) in the GIS-type zeolite is 0.05 or greater. <6> Zeolite molded body as described above. <8> 29 Let a, b, c, and d be the peak area intensities assigned to Q4(3Al), Q4(2Al), Q4(1Al), and Q4(0Al) as observed in the Si-MAS-NMR spectrum, respectively. The GIS-type zeolite contains such zeolites that satisfy (a+d) / (b+c)≧0.192. <3> ~ <7> A zeolite molded body as described in any of the following. <9> Includes a carrier, <1> ~ <8> A zeolite molded body as described in any of the following. <10> The support comprises one or more selected from the group consisting of inorganic binders and organic binders. <9> Zeolite molded body as described above. <11> The inorganic binder includes alumina, <10> Zeolite molded body as described above. <12> The mass ratio of the GIS-type zeolite to the support is 1:99 to 99:1 as GIS-type zeolite:support. <9> ~ <11> A zeolite molded body as described in any of the following. <13> Having a cylindrical shape, <1> ~ <12> A zeolite molded body as described in any of the following. <14> The length is between 3 mm and 30 mm, and the diameter is between 1 mm and 30 mm. <13> Zeolite molded body as described above. <15> <1> ~ <14> An adsorption device comprising a zeolite molded body as described in any of the following. <16> <15> A method for producing purified gas, comprising a separation step of separating one or more gases selected from the group consisting of CO2, H2O, He, Ne, Cl2, NH3, and HCl from a mixture containing two or more gases selected from the group consisting of H2, N2, O2, Ar, CO, and hydrocarbons, using the adsorption apparatus described above. <17> In the separation step, the gas is separated by a pressure swing type adsorption separation method, a temperature swing type adsorption separation method, or a pressure and temperature swing type adsorption separation method. <16> A method for producing purified gas as described above. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a zeolite molded body with excellent resistance to embrittlement against carbon dioxide adsorption, an adsorption device containing the same, and a method for producing purified gas using the same. [Brief explanation of the drawing]

[0011] [Figure 1] Figure 1 is a diagram illustrating an adsorption device according to one embodiment of the present invention. [Modes for carrying out the invention]

[0012] The following describes in detail embodiments for carrying out the present invention (hereinafter referred to as "this embodiment"). The present invention is not limited to the following description and can be implemented in various modifications within the scope of its gist. In this specification, for example, the notation of a numerical range "1 to 100" includes both the lower limit "1" and the upper limit "100". The same applies to other numerical range notations.

[0013] The zeolite molded article according to this embodiment contains zeolite capable of adsorbing carbon dioxide and has an elastic modulus E of 10.0 MPa or higher. The zeolite molded article according to this embodiment exhibits excellent resistance to embrittlement due to carbon dioxide adsorption. According to this embodiment, by molding using zeolite capable of adsorbing carbon dioxide and setting the elastic modulus E of the zeolite molded article to 10.0 MPa or higher, it is possible to obtain a structure that is less susceptible to fracture due to stress caused by the expansion and contraction of the zeolite due to carbon dioxide adsorption, thereby providing a zeolite molded article with resistance to embrittlement due to expansion and contraction, an adsorption device containing the same, and a method for producing purified gas using the same.

[0014] The elastic modulus E of the zeolite molded article is preferably 10.0 MPa or higher, more preferably 11.0 MPa or higher, and even more preferably 12.0 MPa or higher, from the viewpoint of improving resistance to embrittlement against carbon dioxide adsorption. There is no particular upper limit to the elastic modulus E of the zeolite molded article, but if the elastic modulus is too high, the maximum principal stress caused by the expansion and contraction of the zeolite tends to increase, so the elastic modulus E is preferably 70.0 GPa or less, more preferably 65.0 GPa or less, and even more preferably 60.0 GPa or less. The elastic modulus E is the compressive modulus. The elastic modulus E can be measured in more detail by the method described in the examples below. Furthermore, increasing the content of a carrier with a high elastic modulus tends to increase the elastic modulus E of the zeolite molded article, and increasing the content of a carrier with a low elastic modulus tends to decrease the elastic modulus E of the molded article. It is possible to adjust the elastic modulus E by adjusting the composition of the carrier. More specifically, this will be explained in the method for manufacturing the molded article described later.

[0015] (Zeolite) The zeolite preferably has a carbon dioxide adsorption capacity of 10 cc / g or more. The carbon dioxide adsorption capacity of the zeolite is preferably 20 cc / g or more, more preferably 40 cc / g or more, and even more preferably 50 cc / g or more. The upper limit of the carbon dioxide adsorption capacity of the zeolite is not particularly limited, but for example, it is 100 cc / g or less. The carbon dioxide adsorption capacity is the carbon dioxide adsorption capacity (cc) per gram of zeolite at 25°C. More specifically, it is measured by the method described in the examples.

[0016] Examples of zeolites capable of adsorbing carbon dioxide include GIS-type zeolite, FAU-type zeolite, and MWF-type zeolite. Among these, GIS-type zeolite is preferred.

[0017] In this embodiment, the lower the silica-alumina ratio (represented as the molar ratio of silica to alumina expressed as SiO2 / Al2O3, hereinafter simply referred to as "SAR") of the zeolite, the more hydrophilic it becomes, and the stronger its adsorption capacity for polar molecules such as carbon dioxide. If the SAR is low, the adsorption capacity is too strong, requiring more energy to desorb by heating or vacuum, so a higher SAR is preferable. The SAR of the zeolite is preferably 3.40 or higher, more preferably 4.40 or higher, more preferably 4.50 or higher, even more preferably 4.69 or higher, even more preferably 4.90 or higher, even more preferably 5.40 or higher, and even more preferably 6.01 or higher. There is no particular upper limit to the SAR, but if the SAR is too high, the interaction with the adsorbate decreases, so the SAR of the zeolite is preferably 3000 or less, more preferably 500 or less, and even more preferably 100 or less. The SAR of the zeolite in the zeolite molded article is 29 SAR is determined by measuring Si-MAS-NMR. More specifically, SAR can be measured by the method described in the examples below. SAR can be adjusted by the ratio of water and OH- in the mixed gel, etc.

[0018] From the viewpoint of the energy required for desorption, a higher SAR is preferable. However, it has been confirmed that when the SAR is high in zeolites, adsorption-desorption hysteresis becomes apparent in the carbon dioxide adsorption-desorption isotherm. In the zeolite according to this embodiment, adsorption-desorption hysteresis in the carbon dioxide adsorption-desorption isotherm can be eliminated by controlling the bonding mode of Si and Al in the zeolite framework. Specifically, 29 Let a, b, c, and d be the peak area intensities assigned to Q4(3Al), Q4(2Al), Q4(1Al), and Q4(0Al) as observed in the Si-MAS-NMR spectrum, respectively. Preferably, (a+d) / (b+c)≧0.192 is satisfied, more preferably 0.913≧(a+d) / (b+c)≧0.195, and even more preferably 0.519≧(a+d) / (b+c)≧0.199. 29 The peaks Q4(3Al), Q4(2Al), Q4(1Al), and Q4(0Al) observed in the Si-MAS-NMR spectrum represent the bonding modes of Si and Al within the zeolite framework. The sum of the area intensities, (a+d) and (b+c), represent the sum of the abundances of these bonding modes, and (a+d) / (b+c) represents the relative abundance. Since the relative abundance of Si and Al bonding modes affects the structural changes of the zeolite framework itself during adsorption and desorption, setting the relative abundance of Si and Al bonding modes in the zeolite framework, (a+d) / (b+c), within an appropriate range can eliminate adsorption / desorption hysteresis in the adsorption / desorption isotherm. (a+d) / (b+c) can be measured by the method described in the examples below. To set (a+d) / (b+c) within a predetermined range, it is possible to add a salt compound containing alkali metals and / or alkaline earth metals and adjust the ratio of the cations brought about by the addition of the salt compound to the aluminum source.

[0019] From the viewpoint of improving the selective adsorption capacity of carbon dioxide, it is preferable that the GIS-type zeolite contains potassium or lithium as a cation species, and more preferably potassium. The total content of potassium and lithium in the zeolite is calculated as the ratio (Z / T) of the total amount of substance of potassium and lithium to the total amount of substance of alkali metals (T) in the GIS-type zeolite. Z / T is preferably 0.05 or higher, more preferably 0.10 or higher, and even more preferably 0.15 or higher. There is no particular upper limit to Z / T, but Z / T may be 1.00 or lower. Z / T can be measured by thermally dissolving the zeolite in an aqueous sodium hydroxide solution or aqua regia and performing ICP-emission spectroscopy analysis using a solution that has been appropriately diluted. More specifically, Z / T can be measured by the method described in the examples below. Z / T can be adjusted by changing the ratio of potassium and lithium as cation species in the GIS-type zeolite. The ratio (K / T) of the total amount of potassium to the total amount of each alkali metal (T) in the GIS-type zeolite is preferably 0.05 or higher, more preferably 0.10 or higher, and even more preferably 0.15 or higher. There is no particular upper limit to K / T, but K / T may be 1.00 or lower.

[0020] The zeolite content may preferably be 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more, based on 100% by mass of the total amount of the zeolite molded body. Alternatively, the zeolite content may be 98% by mass or less, or 95% by mass or less, based on 100% by mass of the total amount of the zeolite molded body.

[0021] (Method for synthesizing GIS-type zeolite) The method for producing GIS-type zeolite according to this embodiment may include, for example, a step of preparing a mixed gel containing a silica source containing silicon, an aluminum source containing aluminum, an alkali source containing at least one selected from alkali metals (M1) and alkaline earth metals (M2), a salt compound containing at least one selected from alkali metals (M1) and alkaline earth metals (M2), a phosphorus source containing phosphorus, an organic structure-determining agent, and water. The mixed gel and each of its components will be described below.

[0022] [Mixed gel] In this embodiment, the mixed gel is a mixture containing a silica source, an aluminum source, a salt compound, and water as components, and optionally containing a phosphorus source, an alkali source, and an organic structure-correcting agent.

[0023] Silica source refers to the component in the mixed gel that serves as the raw material for silicon contained in the zeolite manufactured from the mixed gel; aluminum source refers to the component in the mixed gel that serves as the raw material for aluminum contained in the zeolite manufactured from the mixed gel; salt compound refers to the component that serves as the raw material for alkali metals and / or alkaline earth metals contained in the zeolite manufactured from the mixed gel; alkali source refers to the component that adjusts the alkalinity of the mixed gel; and phosphorus source refers to the component in the mixed gel that serves as the raw material for phosphorus contained in the zeolite manufactured from the mixed gel.

[0024] [Silica source] The silica source is not particularly limited as long as it is commonly used, and examples include crystalline silica, amorphous silica, silicic acid, silicates, and organic silicate compounds. More specific examples include sodium silicate, potassium silicate, calcium silicate, magnesium silicate, fumed silica, precipitated silica, silica gel, colloidal silica, aluminosilicate, tetraethoxysilane (TEOS), and trimethylethoxysilane. These compounds may be used individually or in combination. Here, aluminosilicate serves as both a silica source and an aluminum source.

[0025] Among these, fumed silica, colloidal silica, or precipitated silica are preferred because they tend to yield zeolites with a high degree of crystallinity.

[0026] [Aluminum source] The aluminum source is not particularly limited as long as it is commonly used, but specific examples include sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum acetate, aluminum hydroxide, aluminum oxide, aluminum chloride, aluminum alkoxide, metallic aluminum, amorphous aluminosilicate gel, etc. These compounds may be used individually or in combination.

[0027] Among these, sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum acetate, aluminum hydroxide, aluminum chloride, and aluminum alkoxide are preferred because they tend to yield zeolites with a high degree of crystallinity. From a similar viewpoint, sodium aluminate and aluminum hydroxide are more preferred, and sodium aluminate is even more preferred.

[0028] [Salt compounds] Salt compounds are compounds containing alkali metals such as Li, Na, K, Rb, and Cs, or alkaline earth metals such as Ca, Mg, Sr, and Ba, which promote crystallization into a zeolite structure when producing zeolites. From the viewpoint of facilitating crystal formation of the GIS-type framework, the alkali metals and alkaline earth metals included in the added salt compound are preferably Na and K, and more preferably Na. Salt compounds may be used individually or in combination.

[0029] Specifically, the salt compounds are not limited to the following, but include, for example, sodium sulfate, sodium sulfite, sodium thiosulfate, sodium nitrite, sodium nitrate, sodium carbonate, sodium bicarbonate, sodium phosphate, sodium acetate, sodium formate, sodium citrate, sodium oxalate, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium thiosodium, sodium silicate, sodium metasilicate, sodium tetraborate, sodium chlorate, sodium perchlorate, sodium cyanide, sodium metastanate, sodium hexahydroxydostan(IV)ate, sodium hexacyanoferrate(II)ate, sodium permanganate, sodium chromate, sodium dichromate, Potassium sulfate, potassium sulfite, potassium thiosulfate, potassium nitrite, potassium nitrate, potassium carbonate, potassium bicarbonate, potassium phosphate, potassium acetate, potassium formate, potassium citrate, potassium oxalate, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, potassium thiopotassium, potassium silicate, potassium metasilicate, potassium tetraborate, potassium chlorate, potassium perchlorate, potassium cyanide, potassium metastanate, potassium hexahydroxydostan(IV)ate, potassium hexacyanoferrate(II)ate, potassium permanganate, potassium chromate, potassium dichromate, Lithium sulfate, lithium sulfite, lithium thiosulfate, lithium nitrite, lithium nitrate, lithium carbonate, lithium bicarbonate, lithium phosphate, lithium acetate, lithium formate, lithium citrate, lithium oxalate, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, thiolithium, lithium silicate, lithium metasilicate, lithium tetraborate, lithium chlorate, lithium perchlorate, lithium cyanide, lithium metastanate, lithium hexahydroxydostan(IV)ate, lithium hexacyanoferrate(II)ate, lithium permanganate, lithium chromate, lithium dichromate, Rubidium sulfate, rubidium sulfite, rubidium thiosulfate, rubidium nitrite, rubidium nitrate, rubidium carbonate, rubidium bicarbonate, rubidium phosphate, rubidium acetate, rubidium formate, rubidium citrate, rubidium oxalate, rubidium fluoride, rubidium chloride, rubidium bromide, rubidium iodide, thiorbidium, rubidium silicate, rubidium metasilicate, rubidium tetraborate, rubidium chlorate, rubidium perchlorate, rubidium cyanide, rubidium metastanate, rubidium hexahydroxydostan(IV)ate, rubidium hexacyanoferrate(II)ate, rubidium permanganate, rubidium chromate, rubidium dichromate, Cesium sulfate, cesium sulfite, cesium thiosulfate, cesium nitrite, cesium nitrate, cesium carbonate, cesium bicarbonate, cesium phosphate, cesium acetate, cesium formate, cesium citrate, cesium oxalate, cesium fluoride, cesium chloride, cesium bromide, cesium iodide, thiocesium, cesium silicate, cesium metasilicate, cesium tetraborate, cesium chlorate, cesium perchlorate, cesium cyanide, cesium metastanate, cesium hexahydroxydostan(IV)ate, cesium hexacyanoferrate(II)ate, cesium permanganate, cesium chromate, cesium dichromate, Magnesium sulfate, magnesium sulfite, magnesium thiosulfate, magnesium nitrite, magnesium nitrate, magnesium carbonate, magnesium bicarbonate, magnesium phosphate, magnesium acetate, magnesium formate, magnesium citrate, magnesium oxalate, magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, thiomagnesium, magnesium silicate, magnesium metasilicate, magnesium tetraborate, magnesium chlorate, magnesium perchlorate, magnesium cyanide, magnesium metastanate, magnesium hexahydroxydostan(IV)ate, magnesium hexacyanoferrate(II)ate, magnesium permanganate, magnesium chromate, magnesium dichromate, Calcium sulfate, calcium sulfite, calcium thiosulfate, calcium nitrite, calcium nitrate, calcium carbonate, calcium bicarbonate, calcium phosphate, calcium acetate, calcium formate, calcium citrate, calcium oxalate, calcium fluoride, calcium chloride, calcium bromide, calcium iodide, calcium thiocalcium, calcium silicate, calcium metasilicate, calcium tetraborate, calcium chlorate, calcium perchlorate, calcium cyanide, calcium metastanate, calcium hexahydroxydostan(IV)ate, calcium hexacyanoferrate(II)ate, calcium permanganate, calcium chromate, calcium dichromate, Strontium sulfate, strontium sulfite, strontium thiosulfate, strontium nitrite, strontium nitrate, strontium carbonate, strontium bicarbonate, strontium phosphate, strontium acetate, strontium formate, strontium citrate, strontium oxalate, strontium fluoride, strontium chloride, strontium bromide, strontium iodide, thiostrontium, strontium silicate, strontium metasilicate, strontium tetraborate, strontium chlorate, strontium perchlorate, strontium cyanide, strontium metastanate, strontium hexahydroxydostan(IV)ate, strontium hexacyanoferrate(II)ate, strontium permanganate, strontium chromate, strontium dichromate, Examples include barium sulfate, barium sulfite, barium thiosulfate, barium nitrite, barium nitrate, barium carbonate, barium bicarbonate, barium phosphate, barium acetate, barium formate, barium citrate, barium oxalate, barium fluoride, barium chloride, barium bromide, barium iodide, thiobarium, barium silicate, barium metasilicate, barium tetraborate, barium chlorate, barium perchlorate, barium cyanide, barium metastanate, barium hexahydroxydostan(IV)ate, barium hexacyanoferrate(II)ate, barium permanganate, barium chromate, barium dichromate, and the like.

[0030] [Alkaline source] The alkali source is used in the production of zeolites to adjust the alkalinity (pH) of the mixed gel in order to promote crystallization into a zeolite structure. The alkali used can be any alkaline compound, and can be either an inorganic or organic compound, but inorganic compounds are preferred from a cost standpoint, and alkali metal hydroxides are more preferred. Examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide, with sodium hydroxide and potassium hydroxide being preferred, and sodium hydroxide being more preferred. These compounds may be used individually or in combination.

[0031] The phosphorus source is not particularly limited as long as it is commonly used, but specific examples include aqueous phosphoric acid solution, sodium phosphate, aluminum phosphate, potassium phosphate, lithium phosphate, calcium phosphate, and barium phosphate. These compounds may be used individually or in combination.

[0032] Among these, aqueous phosphoric acid solution, sodium phosphate, and aluminum phosphate are preferred because they tend to yield zeolites with a high degree of crystallinity. From a similar viewpoint, aqueous phosphoric acid solution and sodium phosphate are more preferred, and aqueous phosphoric acid solution is even more preferred.

[0033] [Organic structure directing agent] In the production of zeolites by hydrothermal synthesis of mixed gels, the organic structure-determining agent is a compound that promotes crystallization into a zeolite structure. In the crystallization of zeolites, the organic structure-determining agent can be used as needed.

[0034] The organic structure modifier can be of any type, as long as it is capable of forming the desired GIS-type zeolite. Furthermore, the organic structure modifier may be used alone or in combination with other organic structures modifiers.

[0035] Examples of the organic structure-directing agent include, but are not limited to, amines, quaternary ammonium salts, alcohols, ethers, amides, alkylureas, alkylthioureas, cyanoalkanes, and alicyclic heterocyclic compounds containing nitrogen as a heteroatom. Alkylamines are preferred, and isopropylamine is more preferred.

[0036] Some of such salts have anions. Representative examples of such anions include, but are not limited to, for example, Cl - , Br - , I - and other halogen ions, hydroxide ions, acetate ions, sulfate ions, nitrate ions, carbonate ions, and hydrogen carbonate ions. Among these, halogen ions and hydroxide ions are preferred from the viewpoint of facilitating the crystal formation of the GIS-type skeleton, and halogen ions are more preferred.

[0037] 〔Composition ratio of the mixed gel〕 In this embodiment, adding a salt compound containing an alkali metal and / or an alkaline earth metal is most important for synthesizing a GIS-type zeolite having an appropriate structure. The zeolite is formed by the reaction of a silica source and an alumina source dissolved in an aqueous solvent while dissolving, and crystallizing. By adding the salt compound, it is possible to adjust the bonding mode and the abundance ratio of Si and Al in the zeolite skeleton, and it is possible to synthesize GIS having an ideal crystal structure.

[0038] In addition, the ratio of the cation provided by the addition of the salt compound to the alumina source is particularly important. The ratio of the cation provided by the salt compound in the mixed gel to the alumina source is expressed as the addition molar ratio of the cation amount E to Al2O3, that is, E / Al2O3. Here, E represents the molar amount of the cation provided by the salt compound. For example, when sodium nitrate is added, Na + is generated as the cation species, and 2Na +Assuming that a reaction occurs, E represents the total molar amount of cation species generated by the addition of the salt compound. E / Al2O3 can change the aggregation state of Al in the mixed gel, which leads to control of the randomness of Al during zeolite crystal formation, making it possible to synthesize GIS-type zeolites with an ideal crystal structure. From the above viewpoint, it is necessary to optimally control E / Al2O3, and E / Al2O3 is preferably 0.1 to 100.0, more preferably 0.5 to 80.0, and even more preferably 0.8 to 50.0.

[0039] Also, water and OH in the mixed gel - The ratio (H2O / OH - ) is important for synthesizing GIS-type zeolites with appropriate SAR. OH - This refers to OH derived from inorganic hydroxides such as NaOH and Ca(OH)2, or organic hydroxides such as tetraethylammonium hydroxide, which are used as alkali sources. - These include substances represented as oxides, such as sodium aluminate and sodium silicate, and the OH released when their hydrates are dissolved in water. - It does not contain [this]. Zeolite formation involves the crystallization of silica, aluminum, and alkali sources dissolved in an aqueous solvent, with some of the material dissolving into the alkaline solvent, creating an equilibrium between crystallization and redissolution. The OH is derived from inorganic hydroxides such as NaOH and Ca(OH)2, and organic hydroxides such as tetraethylammonium hydroxide. - Adding OH to the mixed gel means shifting the equilibrium between crystallization and redissolution towards redissolution. Redissolution proceeds from amorphous or less crystalline areas. Therefore, adding OH appropriately - By increasing the amount of OH, the incomplete crystalline portion can be redissolved and recrystallized repeatedly, thereby increasing the likelihood of forming an ideal crystalline structure. On the other hand, OH - If the amount increases too much, excessive dissolution occurs, resulting in the failure to obtain crystals or the formation of other crystalline phases, such as the more stable ANA-type zeolite. Also, dissolved alumina is more reactive than silica, and alumina is more easily incorporated into crystals. Therefore, OH -By making appropriate adjustments, the rate of crystallization and redissolution can be controlled, and the ratio of silica to alumina incorporated into the crystal can be optimized, thereby optimizing the SAR of the synthesized GIS-type zeolite.

[0040] A higher water-to-alumina ratio (H2O / Al2O3) allows for more uniform dispersion of components in the mixed gel, but if it is too high, it significantly reduces the crystallization rate. Therefore, since it affects the equilibrium between crystallization and redissolution, in order to synthesize a GIS-type zeolite with the optimal SAR and optimal crystal structure, H2O / OH - Along with controlling the other factors, it is necessary to optimally control the H2O / Al2O3 ratio.

[0041] From the above perspective, H2O / Al2O3 and H2O / OH - Preferably, the ratios are 100 ≤ H2O / Al2O3 ≤ 780 and 50 ≤ H2O / OH - ≤1000, more preferably 120 ≤ H2O / Al2O3 ≤ 778 and 60 ≤ H2O / OH - The ratio is ≤800, and more preferably 150 ≤ H2O / Al2O3 ≤ 775 and 70 ≤ H2O / OH - The value is ≤ 700.

[0042] The ratio of silica source to aluminum source in the mixed gel is expressed as the molar ratio of the oxides of each element, i.e., SiO2 / Al2O3. (Note that the silica-alumina ratio of the synthesized zeolite does not match the silica-alumina ratio of the mixed gel. The silica-alumina ratio of the synthesized zeolite is determined by other compositional factors and synthesis conditions.)

[0043] The SiO2 / Al2O3 ratio in this mixed gel is not particularly limited as long as it allows for zeolite formation, but a ratio of 3.0 to 70.0 is preferred, 3.5 to 65.0 is more preferred, and 4.0 to 60.0 is even more preferred, as this ratio tends to suppress the formation of zeolites having a different skeleton from the GIS-type skeleton.

[0044] The ratio of the aluminum source to the alkali metal and alkaline earth metal in the mixed gel is expressed as the added molar ratio of M12O and M2O to Al2O3, i.e., (M12O + M2O) / Al2O3 (where M1 represents an alkali metal and M2 represents an alkaline earth metal. These are calculated as oxides). The (M12O + M2O) / Al2O3 ratio is preferably 1.5 or higher, more preferably 1.6 or higher, and even more preferably 1.65, from the viewpoint of facilitating the formation of GIS-type skeleton crystals. The (M12O + M2O) / Al2O3 ratio is preferably 15.0 or lower, more preferably 12.0 or lower, and even more preferably 10.0 or lower, from the viewpoint of suppressing the formation of zeolites with skeletons different from the GIS-type skeleton.

[0045] The ratio of phosphorus source to aluminum source in the mixed gel is expressed as the molar ratio of oxides of each element, i.e., P2O5 / Al2O3. This P2O5 / Al2O3 is not particularly limited as long as it is a ratio that allows zeolite formation, but it tends to suppress the formation of zeolites having a skeleton different from the GIS type skeleton, so it is preferably less than 1.0, more preferably 0.6 or less, even more preferably 0.4 or less, and especially preferably 0.

[0046] When an organic structural regulator is included in the mixed gel, the ratio of the aluminum source to the organic structural regulator in the mixed gel is expressed as the molar ratio of the organic structural regulator to Al2O3, i.e., R / Al2O3 (where R represents the organic structural regulator). A ratio of less than 7.0 is preferable, more preferably 6.0 or less, and even more preferably 5.0 or less, as this facilitates crystal formation of the GIS-type skeleton and / or shortens the synthesis time, resulting in superior economics when producing zeolites. When an organic structural regulator is used, the organic structural regulator remains in the zeolite pores, preventing carbon dioxide from entering the pores and reducing adsorption. Heating to at least 400°C is necessary to remove the organic structural regulator, but since GIS-type zeolites disintegrate and become amorphous at temperatures above 350°C, it is preferable to use less organic structural regulator. From this perspective, a preferred R / Al2O3 is 4.0 or less, more preferably 3.5 or less, and even more preferably 3.0 or less.

[0047] As described above, the method for producing GIS-type zeolite according to this embodiment includes a step of preparing a mixed gel containing a silica source containing silicon, an aluminum source containing aluminum, an alkali source containing at least one selected from alkali metals (M1) and alkaline earth metals (M2), a salt compound containing at least one selected from alkali metals (M1) and alkaline earth metals (M2), a phosphorus source, and water, and when the molar ratio of each component in the mixed gel is calculated as oxides of each element for silicon, aluminum, alkali metals (M1) and alkaline earth metals (M2), and for the phosphorus source, the following formula (1) It is preferable that the molar ratios α, β, γ, δ, ε, ζ represented by (2), (3), (4), (5), and (6) satisfy 0.1≦α≦100.0, 3.0≦β≦70.0, 1.5≦γ≦15.0, 0≦δ<1.0, 100≦ε≦780, and 50≦ζ≦1000, more preferably that 0.5≦α≦80.0, 3.5≦β≦65.0, 1.6≦γ≦12.0, 0≦δ≦0.6, 120≦ε≦778, and 60≦ζ≦800, and even more preferably that 0.8≦α≦50, 4.0≦β≦60.0, 1.65≦γ≦10.0, 0≦δ≦0.4, 150≦ε≦775, and 70≦ζ≦700. It is particularly preferable that the GIS-type zeolite according to this embodiment is obtained by the method for producing the GIS-type zeolite according to this embodiment described above. α = E / Al2O3 (1) β = SiO2 / Al2O3(2) γ = (M12O + M2O) / Al2O3 (3) δ = P2O5 / Al2O3(4) ε = H2O / Al2O3 (5) ζ=H2O / OH- (6)

[0048] Furthermore, in the method for producing GIS-type zeolite according to this embodiment, if the molar ratios α, β, γ, δ, ε, and ζ satisfy the above range, and the mixed gel further contains an organic structure-determining agent R, it is preferable that the molar ratio η represented by the following formula (7) satisfies η ≤ 4. η = R / Al2O3 (7)

[0049] While it is not always necessary to include seed crystals in the mixed gel, GIS-type zeolite according to this embodiment can also be obtained by adding pre-fabricated GIS-type zeolite as seed crystals to the mixed gel.

[0050] [Preparation process for mixed gel] The preparation steps for the mixed gel are not particularly limited, but may include, for example, a mixing step of mixing a silica source, an aluminum source, a salt compound, water, and optionally a phosphorus source, an alkali source, and an organic structure-defining agent, either all at once or in multiple stages, and a maturation step of the mixture obtained in the mixing step.

[0051] The mixing process can involve mixing a silica source, an aluminum source, a salt compound, water, and optionally a phosphorus source, an alkali source, and an organic structure modifier, either all at once or in multiple stages.

[0052] The order of mixing in multiple stages is not limited and can be selected as appropriate depending on the conditions being used. When mixing in multiple stages, either stirring or non-stirring may be used. When stirring, there is no particular limit to the commonly used stirring method, but specific examples include methods using impeller stirring, vibratory stirring, oscillating stirring, and centrifugal stirring.

[0053] The rotational speed for stirring is not particularly limited as long as it is a commonly used stirring speed, but for example, it may be between 1 rpm and less than 2000 rpm.

[0054] The temperature of the mixing process is not particularly limited as long as it is within the range of commonly used temperatures, but examples include -20°C to less than 80°C.

[0055] The duration of the mixing process is not particularly limited and can be appropriately selected depending on the temperature of the mixing process, but examples include a duration greater than 0 minutes and less than or equal to 1000 hours.

[0056] The maturation process can be carried out either by standing or by stirring. When stirring during the maturation process, there are no particular limitations as long as it is a commonly used stirring method, but specific examples include methods using impeller stirring, vibratory stirring, oscillating stirring, and centrifugal stirring.

[0057] The rotational speed for stirring is not particularly limited as long as it is a commonly used stirring speed, but for example, it may be between 1 rpm and less than 2000 rpm.

[0058] The temperature during the maturation process is not particularly limited as long as it is within the range of commonly used temperatures, but examples include a range of -20°C to less than 80°C.

[0059] The maturation time is not particularly limited and can be selected as appropriate depending on the maturation temperature, but examples include a time between 0 minutes and 1000 hours.

[0060] In the zeolite process, it is believed that the raw materials dissolve and zeolite precursors are formed and redissolved during the mixing and maturation processes. To form a large periodic structure containing eight-membered rings without defects, it is preferable that the formation of zeolite precursors is not excessive. Furthermore, if the formation of zeolite precursors is excessive, the formation of ANA-type zeolite, which has a more stable structure, tends to increase, so it is preferable not to over-maturate. On the other hand, it is preferable that the raw materials are thoroughly mixed and that the raw material gel is uniform. The combined time of the mixing and maturation processes is not particularly limited and can be adjusted as appropriate based on the composition of the raw materials to obtain zeolite with an appropriate structure. Typically, the above time is preferably 1 minute or more and less than 24 hours, more preferably 3 minutes or more and less than 23 hours, even more preferably 10 minutes or more and 18 hours, even more preferably 12 minutes or more and 15 hours, and even more preferably 20 minutes or more and 6 hours.

[0061] [Hydrothermal synthesis process] In the method for producing GIS-type zeolite according to this embodiment, it is preferable to further include a hydrothermal synthesis step in which the hydrothermal synthesis temperature is 80°C to 200°C, and more preferably 100°C to 180°C. That is, preferably, the mixed gel obtained in the preparation step is hydrothermally synthesized by holding it at a predetermined temperature for a predetermined time, either by stirring or by standing.

[0062] The temperature for hydrothermal synthesis is not particularly limited as long as it is a commonly used temperature, but it is preferably 80°C or higher from the viewpoint of shortening the synthesis time and being economically superior in the production of zeolites. From the viewpoint of suppressing the formation of zeolites having a skeleton different from the GIS type skeleton, it is more preferably 90°C or higher, and even more preferably 100°C or higher. From the viewpoint of suppressing the formation of zeolites having a skeleton different from the GIS type skeleton, it is more preferably 200°C or lower, even more preferably 180°C or lower, and even more preferably 170°C or lower. The temperature for hydrothermal synthesis may be constant or may be changed in stages.

[0063] The time for hydrothermal synthesis is not particularly limited as long as it is a commonly used time, and can be appropriately selected depending on the hydrothermal synthesis temperature. The time for hydrothermal synthesis is preferably 3 hours or more, and more preferably 10 hours or more, from the viewpoint of forming the GIS framework. From the viewpoint of obtaining highly crystalline GIS-type zeolite, it is even more preferably 24 hours or more. From the viewpoint of economic efficiency in zeolite production, the time for hydrothermal synthesis is preferably 30 days or less, more preferably 20 days or less, and even more preferably 10 days or less.

[0064] In the hydrothermal synthesis process, the container for the mixed gel is not particularly limited as long as it is a commonly used container. However, if the pressure inside the container increases at a predetermined temperature, or if the process is carried out under gaseous pressure that does not inhibit crystallization, it is preferable to use a pressure-resistant container for hydrothermal synthesis. The pressure-resistant container is not particularly limited, and various shapes such as spherical, elongated, or horizontal can be used.

[0065] When stirring the mixed gel in the pressure vessel, the pressure vessel is rotated vertically and / or horizontally, but preferably vertically. When rotating the pressure vessel vertically, the rotation speed is not particularly limited as long as it is within the generally used range, but 1 to 50 rpm is preferred, and 10 to 40 rpm is more preferred.

[0066] In the hydrothermal synthesis process, a method for effectively stirring the mixed gel is to use a vertically elongated pressure vessel and rotate it in the vertical direction.

[0067] [Separation / drying process] After the hydrothermal synthesis process, the solid product and the liquid containing water are separated. The separation method is not particularly limited as long as it is a general method, and can be used such as filtration, decantation, spray drying (rotary spray, nozzle spray, ultrasonic spray, etc.), drying using a rotary evaporator, vacuum drying, freeze-drying, or natural drying. Usually, separation can be achieved by filtration or decantation.

[0068] The separated material can be used as is, or it may be washed with water or a specified solvent. If necessary, the separated material can be dried. The drying temperature is not particularly limited as long as it is a general drying temperature, but is usually between room temperature and 150°C. The atmosphere used for drying is not particularly limited as long as it is a commonly used atmosphere, but is usually an air atmosphere, an atmosphere with an inert gas such as nitrogen or argon, or an atmosphere with added oxygen.

[0069] [Firing process] If necessary, GIS-type zeolite can be calcined and used. The calcination temperature is not particularly limited as long as it is a commonly used temperature, but if it is desired to remove the organic structural modifier, it is preferable to use a temperature of 300°C or higher, and more preferably 350°C or higher, as this reduces the proportion of the organic structural modifier remaining. It is even preferable to use a temperature of 360°C or higher, as this shortens the calcination time and improves the economic efficiency of zeolite production. It is preferable to use a temperature of less than 450°C, more preferably 420°C or lower, and even more preferably 400°C or lower, as this tends to preserve the crystallinity of the zeolite.

[0070] The firing time is not particularly limited as long as it is long enough to sufficiently remove the organic structural modifier, and can be appropriately selected depending on the firing temperature. However, since this tends to reduce the proportion of remaining organic structural modifier, it is preferable to fire for 0.5 hours or more, more preferably 1 hour or more, and even more preferably 3 hours or more. Since this tends to preserve the crystallinity of the zeolite, it is preferable to fire for 10 days or less, more preferably 7 days or less, and even more preferably 5 days or less.

[0071] The firing atmosphere is not particularly limited as long as it is a commonly used atmosphere, but typically an air atmosphere, an atmosphere with an inert gas such as nitrogen or argon, or an atmosphere with added oxygen is used.

[0072] [Cation exchange] If necessary, GIS-type zeolite can be subjected to cation exchange to a desired cation type. Cation exchange is not limited to the following, but for example, carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, and ammonium carbonate; nitrates such as sodium nitrate, potassium nitrate, lithium nitrate, rubidium nitrate, cesium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate, and ammonium nitrate; salts obtained by changing the carbonate ions and nitrate ions contained in the carbonates and nitrates to halide ions, sulfate ions, carbonate ions, bicarbonate ions, acetate ions, phosphate ions, or hydrogen phosphate ions; and acids such as nitric acid and hydrochloric acid can be used.

[0073] The temperature for cation exchange is not particularly limited as long as it is within the range of typical cation exchange temperatures, but it is usually between room temperature and 100°C or below.

[0074] When separating zeolite after cation exchange, the separation method is not particularly limited as long as it is a general method, and methods such as filtration, decantation, spray drying (rotary spray, nozzle spray, ultrasonic spray, etc.), drying using a rotary evaporator, vacuum drying, freeze-drying, or natural drying can be used, and separation can usually be achieved by filtration or decantation.

[0075] The separated material can be used as is, or it can be washed with water or a specified solvent. If necessary, the separated material can be dried.

[0076] The temperature at which the separated material is dried is not particularly limited as long as it is within the range of typical drying temperatures, but it is usually between room temperature and 150°C.

[0077] The atmosphere used for drying is not particularly limited as long as it is a commonly used atmosphere, but typically, an air atmosphere, an atmosphere with an inert gas such as nitrogen or argon, or an atmosphere with added oxygen are used.

[0078] Furthermore, ammonium-type zeolites can be converted to proton-type zeolites by calcining them.

[0079] (carrier) The zeolite molded article according to this embodiment preferably contains a carrier. Examples of carriers include inorganic binders and organic binders. It should be noted that increasing the content of a carrier with a high elastic modulus tends to increase the elastic modulus E of the zeolite molded article, while increasing the content of a carrier with a low elastic modulus tends to decrease the elastic modulus E of the molded article. Therefore, it is preferable to adjust the content of the carrier so that the elastic modulus is within a predetermined range, taking into account the strength and performance required for the application.

[0080] Examples of inorganic binders include inorganic oxides such as alumina, silica, magnesia, zirconia, and titania, clay minerals such as bentonite and kaolin, calcium silicate, and calcium aluminate. Examples of alumina include α-alumina, γ-alumina, boehmite, pseudoboehmite, bayerite, gibbsite, and diaspore. Examples of silica include colloidal silica, water glass, fumed silica, silica sol, wet-process silica, dry-process silica, and natural silica. These inorganic binders may be used individually or in combination. Among these inorganic binders, alumina, silica, magnesia, zirconia, and titania are preferred from the viewpoint of increasing the strength of the zeolite molded body, and silica and alumina are more preferred. The inorganic binder content is preferably 1 to 99% by mass, more preferably 5 to 90% by mass, and even more preferably 8 to 80% by mass, based on the total amount (100% by mass) of the zeolite molded body.

[0081] Examples of organic binders include cellulose, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, latex, polyvinyl alcohol, vinyl acetate, polyvinyl acetal, vinyl chloride, acrylic, polyamide, urea, melamine, phenolic resin, polyester, polyurethane, polyamide, polybenzimidazole, chloroprene rubber, nitrile rubber, styrene-butadiene rubber, polysulfide, butyl rubber, silicone rubber, acrylic rubber, and urethane rubber. These organic binders may be used individually or in combination. Among these organic binders, cellulose, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and polyvinyl alcohol are preferred from the viewpoint of surface bonding with GIS-type zeolite, and cellulose, methylcellulose, and polyvinyl alcohol are more preferred. The content of the organic binder is preferably 1 to 99% by mass, more preferably 5 to 90% by mass, and even more preferably 8 to 80% by mass, based on the total amount (100% by mass) of the zeolite molded body.

[0082] It is preferable that the mixture contains one or more of the inorganic binders and organic binders mentioned above.

[0083] The total carrier content is preferably 1 to 99% by mass, more preferably 5 to 90% by mass, and even more preferably 8 to 80% by mass, relative to the total amount (100% by mass) of the zeolite molded body. Increasing the carrier content tends to increase the strength of the molded body, but tends to decrease the zeolite content itself. Therefore, the carrier content may be adjusted considering the strength and performance required for the application.

[0084] The shape of the zeolite molded body is not particularly limited, but examples include spherical, cylindrical, elliptical, barrel-shaped, trefoil-shaped, ring-shaped, and powder-shaped. Among these, spherical and cylindrical shapes are more preferred. The size of the molded body is not particularly limited, but varies depending on the situation in which the molded body is used. For example, in processes that use the molded body in non-flowing states, such as fixed beds or moving beds, it is preferable that it be cylindrical with a length of 3 mm to 30 mm and a diameter of 1 mm to 30 mm. The length of the cylinder is more preferably 3 mm to 10 mm, and even more preferably 3 mm to 8 mm. The diameter of the cylinder is more preferably 2 mm to 4 mm. The length and diameter mentioned above can be determined by measuring the length and diameter of three pellet samples using a caliper with a minimum reading of 0.1 mm or less, and then taking the average value of these measurements. These values ​​can then be adjusted to the aforementioned range through operations such as classification. For use in processes that utilize a fluidized bed or other fluidized bed, the powder is preferably composed of particles with a particle size of 20 μm to 300 μm. More preferably, the particle size is 20 μm to 200 μm, and even more preferably 30 μm to 100 μm. The particle size can be measured as the median diameter (D50) using a laser diffraction / scattering particle size analyzer (Microtrac MT3000) according to the included manual.

[0085] The compressive strength of the zeolite molded article according to this embodiment is preferably 1.0 MPa or higher, more preferably 2.2 MPa or higher, and even more preferably 3.4 MPa or higher. In particular, when the zeolite molded article according to this embodiment is in powder form, it is preferable that it satisfies the above range. The above compressive strength can be measured using a micro-compression testing machine (Shimadzu MCT-W500, Compressive Strength Measurement) and the average value obtained from 20 measurements can be adjusted to the range described above by, for example, the firing temperature and firing time.

[0086] The fracture strength of the zeolite molded article according to this embodiment is preferably 5N or higher, more preferably 10N or higher, and even more preferably 20N or higher. In particular, when the zeolite molded article according to this embodiment is a pellet, it is preferable that it satisfies the above range. The above fracture strength can be measured using a digital hardness tester (KHT-40N, manufactured by Fujiwara Seisakusho Co., Ltd., 3mm indenter, fracture strength measurement), and the average value obtained from 20 measurements can be used to adjust the range described above, for example, by changing the firing temperature and firing time.

[0087] [Method for manufacturing zeolite molded bodies] The method for producing the zeolite molded article according to this embodiment is not particularly limited, but may include a raw material mixing step (X) in which the zeolite according to this embodiment is mixed with other optional components (e.g., a carrier) to prepare the article; a molding step (Y) in which the prepared raw materials are subjected to a molding process to obtain a precursor; and a firing step (Z) in which the precursor is fired to obtain a zeolite molded article. In addition, if a desired zeolite molded body can be obtained, the zeolite molded body may be molded by methods such as extrusion molding, injection molding, injection and casting, rolling granulation, compression molding, spray drying, or a combination of two or more of these methods.

[0088] [Raw material mixing process (X)] In the raw material mixing step (X), the temperature at which the raw materials are mixed is not particularly limited, but for example, 10°C to 80°C is preferred, and 15°C to 60°C is more preferred. For example, in a spray drying process, if the state after mixing the raw materials is slurry-like, when the temperature of the raw materials is 80°C or lower, evaporation of water in the raw materials tends to be suppressed, and when the temperature of the raw materials is 10°C or higher, freezing in the slurry tends to be suppressed. Also, for example, in an extrusion molding process, if the state after mixing the raw materials is clay-like from the funicular to capillary region, when the temperature of the raw materials is 80°C or lower, evaporation of water from the clay tends to be suppressed, making it easier to maintain a constant water content in the clay, and when the temperature of the raw materials is 10°C or higher, freezing of water in the clay tends to be suppressed. Any means can be used as the stirring means when preparing the raw materials. For example, in a spray drying process, if the state after mixing the raw materials is slurry-like, a stirring blade is preferred. Specifically, examples of blades used for stirring include propeller type, paddle type, flat paddle type, turbine type, and cone type. Furthermore, baffles or the like may be installed in the tank to ensure efficient stirring. The number of stirrers should be selected to best suit the size of the catalyst raw material liquid tank, the shape of the stirring blades, and other factors. In this embodiment, the total stirring time of the raw materials 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 mixed liquid is 1 minute or more, the composition of the raw materials tends to become uniform, and when it is 24 hours or less, the effect of water evaporation in the raw materials tends to be smaller. Also, for example, in extrusion molding processes, where the mixture becomes clay-like from funicular to capillary after mixing the raw materials, it is preferable to select a mixer or kneader according to the state of the raw materials. In this embodiment, the total mixing and kneading time of the raw materials is preferably 1 minute to 24 hours, more preferably 2 minutes to 5 hours, and even more preferably 3 minutes to 3 hours. When the stirring time of the mixed liquid is 1 minute or more, the composition of the raw materials tends to become uniform, and when it is 24 hours or less, the effect of water evaporation in the raw materials tends to be smaller.Furthermore, when an organic binder that easily gels with heat, such as methylcellulose, is included, maintaining the internal temperature of the mixer or kneader at a value lower than the thermal gelling temperature of the organic binder can suppress the gelation of the organic binder, making it easier to obtain raw materials with a uniform composition. Furthermore, the clay-like raw material can be left to stand and mature. This maturation process tends to improve moldability as moisture is more easily distributed between the zeolite particles, and also replaces air and other gases present between the zeolite particles, resulting in a denser molded product.

[0089] [Molding process (Y)] Examples of molding processes in the molding process (Y) include extrusion molding, compression molding, and spray drying.

[0090] The extrusion molding process is not particularly limited, but for example, depending on the properties of the raw material used (also called "raw clay" in the extrusion molding process), the temperature during extrusion molding is preferably 10°C to 80°C, and more preferably 15°C to 75°C. The moisture content in the raw clay is preferably 35% to 50% by mass, and more preferably 38% to 45% by mass. When the moisture content is 50% by mass or less, excessive improvement in the flexibility of the raw clay can be prevented, and moldability tends to improve. When the moisture content is 35% by mass or more, a moderate decrease in the flexibility of the raw clay can be prevented, and moldability tends to improve.

[0091] When using an extrusion molding process as the molding process (Y), the extrusion molding machine is not particularly limited, but examples include screw type, roll type, blade type, self-forming type, ram type, and disc pelletizer type. Among these, it is particularly preferable to carry out the extrusion molding process using a roll type, screw type, or disc pelletizer type extrusion molding machine.

[0092] When compression molding is used as the molding process (Y), the compression molding machine is not particularly limited, but examples include uniaxial press molding and hot press molding.

[0093] In spray drying, for example, the slurry can be atomized by methods such as the rotary disc method, the two-fluid nozzle method, and the high-pressure nozzle method, which are commonly used in industry, but the rotary disc method is particularly preferred. As the heat source for drying the sprayed droplets, it is preferable to use air heated by steam, an electric heater, or the like. The temperature at the inlet of the dryer can be around 100°C to 400°C, preferably 150°C to 300°C. The temperature at the outlet of the dryer can be around 40°C to 150°C, preferably 50°C to 130°C.

[0094] [Firing process (Z)] The firing temperature in the firing process (Z) is not particularly limited as long as it is a commonly used temperature, but it is preferably less than 550°C, more preferably 530°C or less, and even more preferably 500°C or less, as this tends to ensure strength while maintaining the crystallinity of the zeolite. Furthermore, the firing temperature is preferably 110°C or higher, and more preferably 120°C or higher. The firing time in the firing process (Z) is not particularly limited as long as it is sufficient time for the support to dry and sinter, and can be appropriately selected depending on the firing temperature. However, it is preferable to have a firing time of 20 days or less, more preferably 10 days or less, and even more preferably 7 days or less, as this tends to ensure strength while maintaining the crystallinity of the zeolite. The atmosphere used in the firing process (Y) is not particularly limited as long as it is a commonly used atmosphere, but typically an air atmosphere, an atmosphere with an inert gas such as nitrogen or argon, or an atmosphere with added oxygen is used. The firing process (Z) can be carried out using firing furnaces such as rotary furnaces, tunnel furnaces, and muffle furnaces.

[0095] The applications of the zeolite molded article according to this embodiment are not particularly limited, and can be used, for example, as a separation agent or separation membrane for various gases and liquids, an electrolyte membrane for fuel cells, a filler for various resin molded articles, a membrane reactor, a catalyst for hydrocracking and alkylation, a catalyst carrier for supporting metals and metal oxides, an adsorbent, a desiccant, a detergent aid, an ion exchange agent, a wastewater treatment agent, a fertilizer, a food additive, a cosmetic additive, etc. Among the above, the zeolite molded body according to this embodiment can be suitably used as a carbon dioxide adsorbent.

[0096] [Adsorption device] The adsorption device according to this embodiment comprises a zeolite molded body according to this embodiment. Because the adsorption device according to this embodiment is configured in this way, it can sufficiently adsorb carbon dioxide and has high selectivity for carbon dioxide adsorption relative to the amount of methane adsorbed. For this reason, it can be used particularly preferably for purposes such as the selective removal of carbon dioxide from natural gas.

[0097] The adsorption device according to this embodiment comprises a zeolite molded body containing the zeolite according to this embodiment, and may have the configuration shown in Figure 2. The adsorption device 1 according to this embodiment illustrated in Figure 2 comprises filters 3 arranged at two locations inside the container 2, on the inlet side and the outlet side, and a plurality of zeolite molded bodies 4 filled between the two filters 3. As the filter 3, for example, a filter made of quartz can be used. For example, when using the adsorption device 1 to separate carbon dioxide from natural gas, natural gas can be introduced from the upper line, impurities can be removed by the filter 3, and then carbon dioxide can be selectively adsorbed and removed by the zeolite molded body 4, and methane-rich gas can be extracted from the lower line. However, the target of the adsorption device is not limited to natural gas, and the internal structure of the adsorption device is not limited to the example shown in Figure 3.

[0098] [Method for producing purified gas] The method for producing purified gas according to this embodiment uses an adsorption apparatus containing a zeolite molded body according to 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, O2, CO, and hydrocarbons. In this embodiment, it is preferable to separate one or more gases selected from the group consisting of CO2 and H2O from one or more gases selected from the group consisting of N2, O2, CO, and hydrocarbons. The hydrocarbons are not particularly limited, but examples include methane, ethane, ethylene, propane, propylene, 1-butene, 2-butene, 2-methylpropene, dimethyl ether, and acetylene.

[0099] The GIS-type zeolite according to this embodiment has a particularly large CO2 adsorption capacity, and physical adsorption without chemical bonding is observed. The separation method using the zeolite molded body according to this embodiment is not particularly limited, but a method that is economically efficient and requires less energy for regeneration of the adsorbent is preferred. Specific examples of such methods are not particularly limited, but it is preferable to use one of the following: pressure swing adsorption separation, temperature swing adsorption separation, or pressure and temperature swing adsorption separation. Pressure swing adsorption separation (PSA) is a method in which the desorption pressure is lower than the adsorption pressure of the gas, and gas separation is performed by utilizing the difference between the adsorption amount at high pressure and the adsorption amount at low pressure. Thermal swing adsorption separation (TSA) is a method in which the desorption temperature is higher than the adsorption temperature of the gas, and gas separation is performed by utilizing the difference between the adsorption amount at low temperature and the adsorption amount at high temperature. Furthermore, a method that combines these is pressure and temperature swing adsorption desorption (PTSA). These methods can be carried out under various publicly known conditions. [Examples]

[0100] The embodiment will be described in more detail below with reference to examples, but these are illustrative examples and the embodiment is not limited to the following examples.

[0101] [Measurement of elastic modulus E] The elastic modulus E of the zeolite molded body was measured in accordance with JIS K 7181:2011. Specifically, the zeolite molded body was placed in a sealable vacuum container, dried at 120°C under vacuum for 3 hours, then air-cooled to room temperature, and finally repressurized to atmospheric pressure with room air. After repressurization, the zeolite molded body was left to stand for 7 days at 23°C and 50% relative humidity. 100g of the zeolite molded body was placed in a cylindrical SUS container with a diameter of 50cm and a height of 10cm. After recording the initial filling height, a SUS lid of the same diameter as the container was placed on top. After aligning the center of the pressure plate with the center of the SUS lid, the test force and compression amount were recorded while lowering the pressure plate from above at a speed of 2mm / min. From the obtained values, the SUS lid area, and the initial filling height, stress and strain were calculated as follows, and the elastic modulus E was calculated from the slope of the elastic region, which has a linear relationship on the obtained stress-strain diagram. Measurements were taken five times at a temperature of 23°C and a relative humidity of 50%, and the average value was used as the modulus of elasticity. Stress (MPa) = Test force (N) / SUS lid area (mm²) 2 ) Strain = Compression amount (mm) / Initial filling height (mm)

[0102] [X-ray diffraction; crystal structure analysis] X-ray diffraction was performed using the following procedure. (1) The zeolite molded bodies (dried) obtained in each example and comparative example were used as samples and ground in an agate mortar. Furthermore, 10% by mass of crystalline silicon (manufactured by Rare Metallic Co., Ltd.) was added and mixed in an agate mortar until homogeneous, and this was used as the sample for structural analysis. (2) The sample from (1) above was uniformly fixed on a non-reflective sample plate for powders, and the crystal structure was analyzed by X-ray diffraction under the following conditions. X-ray diffractometer (XRD): Rigaku Corporation powder X-ray diffractometer "RINT2500" (product name) X-ray source: Cu tube (40kV, 200mA) Measurement temperature: 25℃ Measurement range: 5~60° (0.02° / step) Measurement speed: 0.2° / min Slit width (scattering, divergence, receiving): 1°, 1°, 0.15mm

[0103] [ 29 [Si-MAS-NMR spectroscopy, SAR measurement] The SAR of zeolite in zeolite molded products is 29 This can be determined by measuring Si-MAS-NMR. First, to prepare the zeolite for humidity control, water was placed at the bottom of a desiccator, and the zeolite in a sample tube was kept on top of it for 48 hours. After the humidity control treatment, under the following conditions... 29 Si-MAS-NMR measurements were performed. Equipment: JEOL RESONANCE ECA700 Magnetic field strength: 16.44 T( 1 H resonance frequency 700MHz) Nucleus for measurement: 29 Si Resonance frequency: 139.08MHz NMR tube: 4mm diameter (zirconia rotor) Measurement method: DD / MAS (dipolar decoupling angle magic spinning) Pulse width: 45° Waiting time: 50 seconds Total number of measurements: 800 (Measurement time: approximately 22 hours) MAS: 10,000Hz Chemical shift standard: Silicone rubber (-22.34 ppm) external standard In molded articles containing zeolite, 29 The Si-MAS-NMR spectrum shows the following five peaks. (1) Q4(0Al): Peak of Si that is not bonded to Al at all via oxygen. (2) Q4(1Al): Peak of Si bonded to one Al via oxygen. (3) Q4(2Al): Peak of Si bonded to two Al via oxygen. (4) Q4(3Al): Peak of Si bonded to 3 Al via oxygen. (5) Q4(4Al): Peak of Si bonded to 4 Al via oxygen. Also, 29 In Si-MAS-NMR spectra, these peaks are generally located between -112 ppm and -80 ppm and can be attributed to Q4(0Al), Q4(1Al), Q4(2Al), Q4(3Al), and Q4(4Al) from the high-field side. The peak positions may vary depending on the cation species present in the zeolite framework, but generally the peaks are located within the following range. (1) Q4(0Al): -105 ppm to -112 ppm (2) Q4(1Al): -100 ppm to -105 ppm (3) Q4(2Al): -95 ppm to -100 ppm (4) Q4(3Al): -87 ppm to -95 ppm (5) Q4(4Al): -80 ppm to -87 ppm 29 The peak area intensity of the Si-MAS-NMR spectrum is obtained by analyzing it using the analysis program dmfit (version #202000113) with Gaussian and Lorentz functions, and then optimizing four parameters—amplitude (height of the maximum value of the spectrum), position (spectral position, ppm), width (full width at half maximum of the spectrum, ppm), and Gauss / Lorentz ratio (xG / (1-x)L)—using the least squares algorithm. The peak areas of Q4(0Al), Q4(1Al), Q4(2Al), Q4(3Al), and Q4(4Al) obtained in this way are A_Q4(0Al), A_Q4(1Al), A_Q4(2Al), A_Q4(3Al), and A_Q4(4Al). If we add up the sum of A_Q4(0Al), A_Q4(1Al), A_Q4(2Al), A_Q4(3Al), and A_Q4(4Al) to get A_total, then the SAR can be calculated as follows. SAR=100 / 〔A_Q4(1Al) / 4+2×A_Q4(2Al) / 4 +3×A_Q4(3Al) / 4+4×A_Q4(4Al) / 4〕×2

[0104] [Evaluation of the embrittlement resistance of zeolite molded bodies under a CO2 atmosphere] The embrittlement resistance of the zeolite molded bodies obtained in the examples and comparative examples under a CO2 atmosphere was evaluated using the following procedure. (1) 100 g of zeolite molded material was weighed, and the short diameter of the zeolite molded material was measured. The average value of the short diameter of the zeolite molded material was defined as ds. A sieve with a mesh size smaller than ds and the largest mesh size was selected from the publicly available mesh sizes in JIS Z 8801-1 and prepared. The zeolite molded material remaining on the sieve was passed through this sieve and used as a test sample for evaluating its resistance to embrittlement under a CO2 atmosphere. (2) The test samples were dried in an N2 atmosphere at 200°C for 3 hours. After cooling to room temperature in an N2 atmosphere, they were exposed to room temperature CO2 for 30 minutes. (3) After measuring the mass W1 of the test sample after CO2 exposure, it was passed through a sieve of the above mesh size, and the mass W2 of the zeolite molded body that passed through the sieve was measured. The value calculated using formula (1) was defined as the pulverization rate [mass %] of the zeolite molded body, and it was assumed that zeolite molded bodies with a lower pulverization rate were more resistant to embrittlement under a CO2 atmosphere.

number

[0105] [Alkali metal content] Zeolite was thermally dissolved in an aqueous sodium hydroxide solution or aqua regia, and the concentration of alkali metals in the zeolite was measured using ICP-AES (hereinafter also referred to as "ICP-AES," Hitachi High-Tech Science Corporation, SPS3520UV-DD: instrument name) by appropriate dilution of the solution. The potassium and lithium content in the zeolite was calculated as the ratio (Z / T) of the total amount of substance of potassium and lithium to the total amount of substance of each alkali metal in the zeolite (T). K / T was calculated in the same manner.

[0106] [CO2 adsorption amount and hysteresis amount; gas adsorption / desorption isotherm measurement] Gas adsorption / desorption isotherm measurements were performed using the following procedure. (1) The dried products obtained in each example and comparative example were used as samples, and 0.2 g was placed in a 12 mm cell (Micro Meritics). (2) The sample placed in the cell described in (1) above was placed in the Micro Meritics gas adsorption analyzer "3-Flex" (product name) and subjected to heating and vacuum degassing treatment at 250°C and 0.001 mmHg or less for 12 hours. (3) The sample placed in the cell after the processing described in (2) above was placed in constant temperature circulating water at 25°C. After the sample temperature reached 25±0.2°C, the absolute pressure was measured from 0.25 to 760 mmHg using liquefied carbon dioxide (manufactured by Sumitomo Seika Co., Ltd., purity 99.9% by mass or higher). During the above measurement, the pressure was measured over time, and it was determined that the saturation adsorption amount had been reached when the pressure fluctuation became 0.001% / 10 sec or less, and this was recorded as the amount of CO2 adsorbed at 25°C (unit: cc / g). (4) Following the measurements in (3) above, the pressure was gradually reduced from an absolute pressure of 760 to 0.25 mmHg, and the desorption isotherm of carbon dioxide was measured. As with (3), equilibrium was determined when the pressure fluctuation was 0.001% / 10 sec or less. (5) As an index to indicate the amount of hysteresis in the adsorption-desorption isotherm of carbon dioxide, when the equilibrium adsorption amount at the 75 mmHg adsorption isotherm measured in (3) and the equilibrium adsorption amount at the 75 mmHg desorption isotherm measured in (4) are denoted as q(Ad) and q(De), respectively, q(Ad) / q(De) was used as an index to indicate the amount of hysteresis. When q(Ad) / q(De) = 1.00, it indicates that there is no hysteresis, and the smaller q(Ad) / q(De), the greater the hysteresis.

[0107] [CH4 adsorption amount; gas adsorption isotherm measurement] Gas adsorption isotherm measurements were performed using the following procedure. (1) The dried products obtained in each example and comparative example were used as samples, and 0.2 g was placed in a 12 mm cell (Micro Meritics). (2) The sample placed in the cell described in (1) above was placed in the Micro Meritics gas adsorption analyzer "3-Flex" (product name) and subjected to heating and vacuum degassing treatment at 250°C and 0.001 mmHg or less for 12 hours. (3) The sample placed in the cell after the treatment described in (2) above was placed in constant temperature circulating water at 35°C. After the sample temperature reached 25±0.2°C, the absolute pressure was measured from 0.25 to 760 mmHg using methane gas (manufactured by Fujii Shoji Co., Ltd., purity 99.99% by mass or higher). During the above measurement, the pressure was measured over time, and it was determined that the saturation adsorption amount had been reached when the pressure fluctuation became 0.001% / 10 sec or less, and this was recorded as the CH4 adsorption amount at 25°C (unit: cc / g).

[0108] [Measurement of pellet length and diameter] When the zeolite molded material was in pellet form, the length and diameter of the pellets were measured using calipers. For this measurement, calipers with a minimum reading of 0.1 mm or less were used, and measurements were taken for three samples, with the average values ​​being used as the length and diameter.

[0109] [Manufacturing Example 1] A mixed gel was prepared by mixing 61.93g of water, 0.403g of sodium hydroxide (NaOH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 3.39g of sodium nitrate (NaNO3, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 1.64g of sodium aluminate (NaAlO2, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 10.82g of colloidal silica (Ludox AS-40, solid content concentration 40% by mass, manufactured by Grace Co., Ltd.), and stirring for 30 minutes. The composition of the mixed gel was as follows: α=E / Al2O3=4.53, β=SiO2 / Al2O3=8.17, γ=Na2O / Al2O3=3.99, δ=P2O5 / Al2O3=0.00, ε=H2O / Al2O3=431.0, ζ=H2O / OH -The values ​​were 376.7 and η = R / Al2O3 = 0.00. The mixed gel was placed in a 200 mL stainless steel microcylinder (manufactured by HIRO COMPANY) containing a fluororesin inner cylinder, and hydrothermally synthesized for 4 days at a stirring speed of 30 rpm and 135°C in a stirring-type constant temperature bath (manufactured by HIRO COMPANY) that allows the microcylinder to rotate vertically. The product was filtered and dried at 120°C to obtain powdered zeolite. XRD spectroscopy confirmed that the obtained zeolite was a GIS-type zeolite. Furthermore, since no peaks originating from other zeolites or amorphous silica-alumina were observed, it was evaluated as a high-purity GIS-type zeolite.

[0110] About the obtained zeolite 29 The silica-alumina ratio was calculated from the Si-MAS-NMR spectrum, resulting in a SAR of 6.90. The potassium and lithium content in the zeolite was Z / T = 0.00 (= K / T). 29 From the Si-MAS-NMR spectrum, (a+d) / (b+c) = 0.305 was obtained. When the adsorption and desorption isotherms of the obtained GIS-type zeolite were measured, the adsorption amount at 760 mmHg was 82.2 cc / g, and q(Ad) / q(De) = 0.984. Similarly, when the adsorption isotherm of CH4 was measured, the adsorption amount at 760 mmHg was 6.2 cc / g.

[0111] [Manufacturing Example 2] A mixed gel was prepared by mixing 21.05 g of water, 0.33 g of sodium hydroxide solution (NaOH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 1.37 g of sodium nitrate (NaNO3, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 1.13 g of sodium aluminate (NaAlO2, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 15.5 g of water glass No. 3 (manufactured by Kishida Chemical Co., Ltd.), and stirring for 1 hour. The composition of the mixed gel was as follows: α=E / Al2O3=2.66, β=SiO2 / Al2O3=12.39, γ=Na2O / Al2O3=5.89, δ=P2O5 / Al2O3=0.00, ε=H2O / Al2O3=197.9, ζ=H2O / OH -The values ​​were η = 145.2 and η = R / Al2O3 = 0.00. The mixed gel was placed in a 100 mL stainless steel microcylinder (manufactured by HIRO COMPANY) containing a fluororesin inner cylinder, and hydrothermally synthesized for 5 days at a stirring speed of 30 rpm and 130°C in a stirring-type constant temperature bath (manufactured by HIRO COMPANY) that allows the microcylinder to rotate vertically. The product was filtered and dried at 120°C to obtain powdered zeolite. XRD spectroscopy confirmed that the obtained zeolite was a GIS-type zeolite. Furthermore, since no peaks originating from other zeolites or amorphous silica-alumina were observed, it was evaluated as a high-purity GIS-type zeolite.

[0112] About the obtained zeolite 29 The silica-alumina ratio was calculated from the Si-MAS-NMR spectrum, and the SAR was found to be 4.50. The potassium and lithium content in the zeolite was Z / T = 0.00 (= K / T). 29 From the Si-MAS-NMR spectrum, (a+d) / (b+c) = 0.192, indicating that no carbon atoms were detected. When the adsorption and desorption isotherms of the obtained GIS-type zeolite were measured, the adsorption amount at 760 mmHg was 53.5 cc / g, and q(Ad) / q(De) = 0.980. Similarly, when the adsorption isotherm of CH4 was measured, the adsorption amount at 760 mmHg was 4.0 cc / g.

[0113] [Manufacturing Example 3] A mixed gel was prepared by mixing 61.65 g of water, 0.60 g of 48% by mass sodium hydroxide aqueous solution (NaOH, solid content concentration 48% by mass, manufactured by Tokuyama Soda Co., Ltd.), 2.27 g of sodium carbonate (Na2CO3, manufactured by Tokuyama Soda Co., Ltd.), 1.64 g of sodium aluminate (NaAlO2, manufactured by Hokuriku Chemicals, Ltd.), and 10.82 g of colloidal silica (Ludox AS-40, solid content concentration 40% by mass, manufactured by Grace Co., Ltd.), and stirring for 30 minutes. The composition of the mixed gel was as follows: α=E / Al2O3=4.86, β=SiO2 / Al2O3=8.17, γ=Na2O / Al2O3=3.99, δ=P2O5 / Al2O3=0.00, ε=H2O / Al2O3=431.2, ζ=H2O / OH- The values ​​were 527.8 and η = R / Al2O3 = 0.00. The mixed gel was placed in a 200 mL stainless steel microcylinder (manufactured by HIRO COMPANY) containing a fluororesin inner cylinder, and hydrothermally synthesized for 5 days at a stirring speed of 30 rpm and 130 °C in a stirring-type constant temperature bath (manufactured by HIRO COMPANY) that allows the microcylinder to rotate vertically. The product was filtered and dried at 120 °C to obtain powdered zeolite. 1 g of the obtained zeolite was placed in 500 mL of a 0.05 N potassium carbonate aqueous solution prepared using potassium carbonate (K2CO3, manufactured by Nippon Soda Co., Ltd.), and stirred at 500 rpm at room temperature for 3 hours. The product was filtered and dried at 120 °C to obtain powdered zeolite in which some of the cations were replaced with potassium. XRD spectroscopy confirmed that the obtained zeolite was a GIS-type zeolite. Furthermore, since no peaks originating from other zeolites or amorphous silica-alumina were observed, it was evaluated as a high-purity GIS-type zeolite.

[0114] About the obtained zeolite 29 The silica-alumina ratio was calculated from the Si-MAS-NMR spectrum, and the SAR was 6.90, with (a+d) / (b+c) = 0.220. The potassium and lithium content in the zeolite was Z / T = 0.98 (=K / T). When the adsorption and desorption isotherms of CO2 were measured, the adsorption amount at 760 mmHg was 84.0 cc / g, and q(Ad) / q(De) = 1.000. Similarly, when the adsorption isotherm of CH4 was measured, the adsorption amount at 760 mmHg was 0.0 cc / g.

[0115] [Manufacturing Example 4] A mixed gel was prepared by mixing 141.41 g of water, 2.62 g of sodium hydroxide aqueous solution (NaOH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 8.53 g of sodium nitrate (NaNO3, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 3.85 g of sodium aluminate (NaAlO2, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 17.41 g of amorphous silica (Perkasil SM500, manufactured by Grace Corporation), and stirring for 1 hour. The composition of the mixed gel was as follows: α=E / Al2O3=4.85, β=SiO2 / Al2O3=14.00, γ=Na2O / Al2O3=5.16, δ=P2O5 / Al2O3=0.00, ε=H2O / Al2O3=379.3, ζ=H2O / OH - The values ​​were η = 120.0 and η = R / Al2O3 = 0.00. The mixed gel was placed in a 300 mL stainless steel microcylinder (manufactured by HIRO COMPANY) containing a fluororesin inner cylinder, and hydrothermally synthesized for 4 days at a stirring speed of 30 rpm and 130°C in a stirring-type constant temperature bath (manufactured by HIRO COMPANY) that allows the microcylinder to rotate vertically. The product was filtered and dried at 120°C to obtain powdered zeolite. XRD spectroscopy confirmed that the obtained zeolite was a GIS-type zeolite. Furthermore, since no peaks originating from other zeolites or amorphous silica-alumina were observed, it was evaluated as a high-purity GIS-type zeolite.

[0116] About the obtained zeolite 29 The silica-alumina ratio was calculated from the Si-MAS-NMR spectrum, and the SAR was 10.1, resulting in (a+d) / (b+c)=0.519. The potassium and lithium content in the zeolite was Z / T=0.00 (=K / T). When the adsorption and desorption isotherms of CO2 were measured, the adsorption amount at 760 mmHg was 80.0 cc / g, and q(Ad) / q(De)=1.000. Similarly, when the adsorption isotherm of CH4 was measured, the adsorption amount at 760 mmHg was 7.2 cc / g.

[0117] [Manufacturing Example 5] A mixed gel was prepared by mixing 141.41 g of water, 2.62 g of sodium hydroxide aqueous solution (NaOH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 2.43 g of sodium nitrate (NaNO3, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.55 g of sodium aluminate (NaAlO2, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 35.33 g of aluminosilicate (SIPERNAT 820A, manufactured by Evonik), and stirring for 1 hour. The composition of the mixed gel was as follows: α=E / Al2O3=0.88, β=SiO2 / Al2O3=14.00, γ=Na2O / Al2O3=2.62, δ=P2O5 / Al2O3=0.00, ε=H2O / Al2O3=242.4, ζ=H2O / OH - The values ​​were η=R / Al2O3=0.00 and η=R / Al2O3=0.00. The mixed gel was placed in a 300 mL stainless steel microcylinder (manufactured by HIRO COMPANY) with a fluororesin inner cylinder, and hydrothermally synthesized for 5 days at a stirring speed of 30 rpm and 130 °C in a stirring-type constant temperature bath (manufactured by HIRO COMPANY) that allows the microcylinder to rotate vertically. The product was filtered and dried at 120 °C to obtain powdered zeolite. 1 g of the obtained zeolite was placed in 500 mL of a 0.005 N potassium carbonate aqueous solution prepared using potassium carbonate (K2CO3, manufactured by Nippon Soda Co., Ltd.), and stirred at 500 rpm at room temperature for 3 hours. The product was filtered and dried at 120 °C to obtain powdered zeolite in which some of the cations were replaced with potassium. XRD spectroscopy confirmed that the obtained zeolite was a GIS-type zeolite. Furthermore, since no peaks originating from other zeolites or amorphous silica-alumina were observed, it was evaluated as a high-purity GIS-type zeolite.

[0118] About the obtained zeolite 29The silica-alumina ratio was calculated from the Si-MAS-NMR spectrum, and the SAR was 8.20, with (a+d) / (b+c) = 0.356. The potassium and lithium content in the zeolite was Z / T = 0.16 (=K / T). When the adsorption and desorption isotherms of CO2 were measured, the adsorption amount at 760 mmHg was 72.7 cc / g, and q(Ad) / q(De) = 0.991. Similarly, when the adsorption isotherm of CH4 was measured, the adsorption amount at 760 mmHg was 0.5 cc / g.

[0119] [Manufacturing Example 6] 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 water glass No. 3 (manufactured by Kishida Chemical Co., Ltd.), 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 composition of the mixed gel was α=E / Al2O3=0.00, β=SiO2 / Al2O3=13.60, γ=Na2O / Al2O3=9.37, δ=P2O5 / Al2O3=0.00, ε=H2O / Al2O3=135.9, ζ=H2O / OH - The ratio was 54.56, and η = R / Al2O3 = 0.00. The mixed gel was placed in a 1000 mL stainless steel autoclave containing a fluororesin inner cylinder, and hydrothermally synthesized at 130°C for 5 days without stirring. The product was filtered and dried at 120°C to obtain powdered zeolite. XRD spectroscopy confirmed that the obtained zeolite was a GIS-type zeolite. Furthermore, since no peaks originating from other zeolites or amorphous silica-alumina were observed, it was evaluated as a high-purity GIS-type zeolite.

[0120] About the obtained zeolite 29The silica-alumina ratio was calculated from the Si-MAS-NMR spectrum, resulting in a SAR of 4.30 and a (a+d) / (b+c) ratio of 0.151. Potassium concentration was also measured, and the potassium and lithium content in the zeolite was found to be Z / T = 0.00 (=K / T). The adsorption and desorption isotherms of the obtained GIS-type zeolite showed an adsorption amount of 52.4 cc / g at 760 mmHg, with a q(Ad) / q(De) ratio of 0.302. Similarly, the adsorption isotherm for CH4 was measured, showing an adsorption amount of 0.0 cc / g at 760 mmHg.

[0121] [Manufacturing Example 7] 41.0g of water, 1.8g of reagent-grade sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.), and 3.4g of Wako Grade 1 sodium aluminate (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed and dissolved to obtain a solution. 54g of water glass No. 3 (manufactured by Kishida Chemical Co., Ltd.) was added to this solution and mixed, and stirred for 15 minutes to prepare a mixed gel. The composition of the mixed gel was as follows: α=E / Al2O3=0.00, β=SiO2 / Al2O3=14.27, γ=Na2O / Al2O3=9.57, δ=P2O5 / Al2O3=0.00, ε=H2O / Al2O3=130.2, ζ=H2O / OH - The values ​​were 52.85 and η = R / Al2O3 = 0.00. The mixed gel was placed in a 1000 mL stainless steel autoclave containing a polytetrafluoroethylene resin inner cylinder, and hydrothermally synthesized at 130°C for 5 days without stirring. The product was filtered and dried at 120°C to obtain zeolite powder. XRD spectroscopy confirmed that the obtained zeolite was a GIS-type zeolite. Furthermore, the absence of peaks originating from other zeolites or amorphous silica-alumina indicated that it was a high-purity GIS-type zeolite.

[0122] About the obtained zeolite 29The silica-alumina ratio was calculated from the Si-MAS-NMR spectrum, resulting in a SAR of 4.40 and a (a+d) / (b+c) ratio of 0.156. The potassium and lithium content in the zeolite was Z / T = 0.00 (=K / T). The adsorption and desorption isotherms of the obtained GIS-type zeolite were measured, and the adsorption amount at 760 mmHg was 53.0 cc / g, with a q(Ad) / q(De) ratio of 0.352. Similarly, the adsorption isotherm for CH4 was measured, and the adsorption amount at 760 mmHg was 3.9 cc / g.

[0123] [Manufacturing Example 8] A mixed gel was prepared by mixing 141.41 g of water, 2.62 g of sodium hydroxide aqueous solution (NaOH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 2.43 g of sodium nitrate (NaNO3, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.55 g of sodium aluminate (NaAlO2, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 35.33 g of aluminosilicate (SIPERNAT 820A, manufactured by Evonik), and stirring for 1 hour. The composition of the mixed gel was as follows: α=E / Al2O3=0.88, β=SiO2 / Al2O3=14.00, γ=Na2O / Al2O3=2.62, δ=P2O5 / Al2O3=0.00, ε=H2O / Al2O3=242.4, ζ=H2O / OH -The values ​​were η = 120.0 and η = R / Al2O3 = 0.00. The mixed gel was placed in a 300 mL stainless steel microcylinder (manufactured by HIRO COMPANY) containing a fluororesin inner cylinder, and hydrothermally synthesized for 5 days at a stirring speed of 30 rpm and 130 °C in a stirring-type constant temperature bath (manufactured by HIRO COMPANY) that allows the microcylinder to rotate vertically. The product was filtered and dried at 120 °C to obtain powdered zeolite. 1 g of the obtained zeolite was placed in 500 mL of a 0.010 N lithium nitrate aqueous solution prepared using lithium nitrate (LiNO3, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and stirred at 500 rpm at room temperature for 3 hours. The product was filtered and dried at 120 °C to obtain powdered zeolite in which some of the cations were replaced with lithium. XRD spectroscopy confirmed that the obtained zeolite was a GIS-type zeolite. Furthermore, since no peaks originating from other zeolites or amorphous silica-alumina were observed, it was evaluated as a high-purity GIS-type zeolite.

[0124] About the obtained zeolite 29 The silica-alumina ratio was calculated from the Si-MAS-NMR spectrum, and the SAR was 8.20, with (a+d) / (b+c) = 0.356. The potassium and lithium content in the zeolite was Z / T = 0.16. When the adsorption and desorption isotherms of CO2 were measured, the adsorption amount at 760 mmHg was 72.5 cc / g, and q(Ad) / q(De) = 0.991. Similarly, when the adsorption isotherm of CH4 was measured, the adsorption amount at 760 mmHg was 0.5 cc / g.

[0125] [Example 1] 60 parts by mass of GIS-type zeolite powder obtained in Production Example 1, 60 parts by mass of alumina sol (manufactured by Nissan Chemical Corporation, alumina content: 10.5% by mass), 1.8 parts by mass of methylcellulose (Selander YB-167, manufactured by Hi-Chem Co., Ltd.), and 0.3 parts by mass of polyvinyl alcohol (Gosenol N-300, manufactured by Mitsubishi Chemical Corporation) were mixed. The above mixture was extruded into a cylindrical shape with a diameter of 3 mm using a wet extrusion granulator MG-55 (manufactured by Dalton Co., Ltd.), and then fired in an electric furnace at 400°C for 5 hours in an air atmosphere. The elastic modulus E of the resulting GIS-type zeolite molded body was 10.5 MPa. The embrittlement resistance of the zeolite molded body was evaluated in a CO2 atmosphere, and the pulverization rate was measured to be 5% by mass.

[0126] When the adsorption isotherms of CO2 and CH4 in the zeolite molded body of Example 1 were measured, the adsorption amounts at 760 mmHg were CO2: 74.4 cm³. 3 / g, CH4:5.6cm 3 The ratio was / g, and the adsorption selectivity (CO2 / CH4) was 13.3, confirming that it has sufficient performance as an adsorbent.

[0127] [Example 2] A molded article was obtained in the same manner as in Example 1, except that instead of alumina sol with an alumina content of 10.5% by mass, 30 parts by mass of silica sol (manufactured by Nalco) with a silica content of 34% by mass and 35 parts by mass of ion-exchanged water were used, and the GIS-type zeolite powder obtained in Production Example 2 was used. The elastic modulus E of the GIS-type zeolite molded material obtained in this way was 19.8 MPa. The embrittlement resistance of the zeolite molded material was evaluated under a CO2 atmosphere, and the pulverization rate was measured to be 6% by mass.

[0128] [Example 3] 60 parts by mass of GIS-type zeolite powder obtained in Production Example 3, 13.2 parts by mass of methylcellulose (Selander YB-167 manufactured by Hychem Co., Ltd.), and 50 parts by mass of ion-exchanged water were mixed. The above mixture was extruded into cylindrical shapes with a diameter of 3 mm using a wet extrusion granulator MG-55 (manufactured by Dalton Co., Ltd.), and then calcined in an electric furnace at 120°C for 5 hours under a nitrogen atmosphere. The elastic modulus E of the GIS-type zeolite molded material obtained in this way was 32.0 MPa. When the embrittlement resistance of the zeolite molded material was evaluated under a CO2 atmosphere and the pulverization rate was measured, it was 0% by mass.

[0129] [Comparative Example 1] A molded body was obtained in the same manner as in Example 1, except that the firing temperature was set to 300°C. The elastic modulus E of the GIS-type zeolite molded body obtained in this way was 7.0 MPa. The embrittlement resistance of the zeolite molded body was evaluated under a CO2 atmosphere, and the pulverization rate was measured to be 60% by mass.

[0130] [Example 4] A molded article was obtained in the same manner as in Example 1, except that the GIS-type zeolite powder obtained in Manufacturing Example 4 was used. The elastic modulus E of the GIS-type zeolite molded material obtained in this way was 10.7 MPa. The embrittlement resistance of the zeolite molded material was evaluated under a CO2 atmosphere, and the pulverization rate was measured to be 8% by mass.

[0131] [Example 5] A molded article was obtained in the same manner as in Example 1, except that the GIS-type zeolite powder obtained in Manufacturing Example 5 was used. The elastic modulus E of the GIS-type zeolite molded material obtained in this way was 10.7 MPa. The embrittlement resistance of the zeolite molded material was evaluated under a CO2 atmosphere, and the pulverization rate was measured to be 8% by mass.

[0132] [Comparative Example 2] 100 parts by mass of GIS-type zeolite powder obtained in Production Example 6, 250 parts by mass of alumina sol (manufactured by Kawaken Fine Chemical Co., Ltd., alumina content: 10% by mass), and 275 parts by mass of ion-exchanged water were mixed, and the moisture content was adjusted to 40% by mass by heating and concentration at 70°C. The above mixture was extruded into cylindrical shapes with a diameter of 3 mm using a wet extrusion granulator MG-55 (manufactured by Dalton Co., Ltd.), and then calcined in an electric furnace at 350°C for 3 hours under an air atmosphere. The elastic modulus E of the GIS-type zeolite molded material obtained in this way was 6.0 MPa. The embrittlement resistance of the zeolite molded material was evaluated under a CO2 atmosphere, and the pulverization rate was measured to be 86% by mass.

[0133] [Example 6] A molded body was obtained in the same manner as in Example 3, except that the wet extrusion granulator MG-55 was replaced with manual extrusion molding using a clay gun. The elastic modulus E of the GIS-type zeolite molded body obtained in this way was 30.0 MPa. The embrittlement resistance of the zeolite molded body was evaluated under a CO2 atmosphere, and the pulverization rate was measured to be 10% by mass.

[0134] [Example 7] 10.1 parts by mass of GIS-type zeolite obtained in Production Example 1 was dispersed in 10.3 parts by mass of ion-exchanged water, and then added to 79.6 parts by mass of alumina sol (manufactured by Nissan Chemical Corporation, alumina content: 10.5% by mass) to obtain a raw material slurry. The obtained raw material slurry was stirred at 25°C for 1 hour. The raw material slurry was in a sol-like state and had a viscosity of 300 cP (measured with a B-type viscometer manufactured by Eiko Seiki Co., Ltd.). The raw material slurry was supplied to a spray dryer (OC-16 type spray dryer manufactured by Okawara Chemical Machinery Co., Ltd.) with the fluid temperature at the spray dryer inlet set to 230°C and the fluid temperature at the spray dryer outlet set to 120°C, and spray drying was performed using a rotating disc method to obtain a dried powder. After that, it was calcined in an electric furnace at 350°C for 24 hours under an air atmosphere. The heating and cooling rates were 1°C / min. The elastic modulus E of the zeolite molded body obtained in this way was 19.7 MPa. The embrittlement resistance of the zeolite molded body was evaluated under a CO2 atmosphere, and the pulverization rate was measured to be 10% by mass.

[0135] [Comparative Example 3] 70 parts by mass of GIS-type zeolite powder obtained in Production Example 7 and 30 parts by mass of polyamide resin (Zytel 101L, manufactured by DuPont) were melt-kneaded in a twin-screw extruder (TEM48-SS, manufactured by Toshiba Machine Co., Ltd.) at 285°C and 400 rpm to obtain a composite. The obtained composite was then used in an injection molding machine (EC75NII, manufactured by Toshiba Machine Co., Ltd.) with the cylinder temperature set to 285°C and the mold temperature to 70°C to obtain molded bodies with a length of 80 mm, a width of 10 mm, and a thickness of 4 mm. The elastic modulus E of the GIS-type zeolite molded material obtained in this way was 2.1 MPa. The embrittlement resistance of the zeolite molded material was evaluated under a CO2 atmosphere, and the pulverization rate was measured to be 70% by mass.

[0136] [Example 8] A molded article was obtained in the same manner as in Example 1, except that the GIS-type zeolite powder obtained in Production Example 8 was used. The elastic modulus E of the GIS-type zeolite molded material obtained in this way was 11.0 MPa. The embrittlement resistance of the zeolite molded material was evaluated under a CO2 atmosphere, and the pulverization rate was measured to be 7% by mass.

Claims

1. A zeolite molded body containing a zeolite capable of adsorbing carbon dioxide, The aforementioned zeolite is a GIS-type zeolite. A zeolite molded article having an elastic modulus E of 10.0 MPa or higher.

2. The zeolite molded article according to claim 1, wherein the zeolite has a carbon dioxide adsorption capacity of 10 cc / g or more.

3. The zeolite molded article according to claim 1, wherein the silica-alumina ratio of the GIS-type zeolite is 3.40 or more.

4. The zeolite molded article according to claim 1, wherein the silica-alumina ratio of the GIS-type zeolite is 4.50 or more.

5. A zeolite molded article according to any one of claims 1 to 4, comprising potassium or lithium as a cation species in the GIS-type zeolite.

6. The zeolite molded article according to claim 5, wherein the ratio (Z / T) of the total amount of substance of potassium and lithium (Z) to the total amount of substance of alkali metals (T) in the GIS-type zeolite is 0.05 or more.

7. 29 A zeolite molded article according to any one of claims 1 to 6, comprising a GIS-type zeolite, wherein the peak area intensities assigned to Q4(3Al), Q4(2Al), Q4(1Al), and Q4(0Al) observed in the Si-MAS-NMR spectrum are a, b, c, and d, respectively, and (a+d) / (b+c) ≥ 0.

192.

8. A zeolite molded article according to any one of claims 1 to 7, comprising a carrier.

9. The zeolite molded article according to claim 8, wherein the carrier comprises one or more selected from the group consisting of inorganic binders and organic binders.

10. The zeolite molded article according to claim 9, wherein the inorganic binder contains alumina.

11. A zeolite molded article according to any one of claims 8 to 10, wherein the mass ratio of the GIS-type zeolite to the carrier is 1:99 to 99:1 as GIS-type zeolite:carrier.

12. A zeolite molded body according to any one of claims 1 to 11, having a cylindrical shape.

13. The length is 3 mm or more and 30 mm or less, and the diameter is 1 mm or more and 30 mm or less. The zeolite molded article according to claim 12.

14. An adsorption device comprising a zeolite molded body according to any one of claims 1 to 13.

15. Using the adsorption device described in claim 14, H 2 , N 2 , O 2 From a mixture containing two or more gases selected from the group consisting of Ar, CO, and hydrocarbons, 2 H 2 O, He, Ne, Cl 2 NH 3 A method for producing purified gas, comprising a separation step of separating one or more substances selected from the group consisting of , and HCl.

16. The method for producing purified gas according to claim 15, wherein in the separation step, the gas is separated by a pressure swing type adsorption separation method, a temperature swing type adsorption separation method, or a pressure and temperature swing type adsorption separation method.

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