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 GIS zeolite. In an infrared spectral spectrum, B / A is 5.0 or less where A denotes the sum of peak areas in the range of 1300-800 cm-1 and B denotes the sum of peak areas in the range of 3200-2700 cm-1.SELECTED DRAWING: None

Description

[Technical Field]

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

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

[0003] Among zeolites, those with a GIS structure, a code defining the structure of zeolites established by the International Zeolite Association (IZA), are called GIS-type zeolites. GIS-type zeolites have pores composed of eight-membered oxygen rings. Regarding such GIS-type zeolites, for example, Patent Document 1 discloses that GIS-type zeolites having the ability to adsorb carbon dioxide are synthesized, and that when GIS-type zeolites are used as adsorbents, they can be used for separating, capturing, and purifying carbon dioxide. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. WO2019 / 202933 Summary of the Invention [Problem to be solved by the invention]

[0005] When separating, capturing, and purifying carbon dioxide using an adsorbent, methods such as pressure swing adsorption separation, temperature swing adsorption separation, and pressure-temperature swing adsorption separation are used. In these methods, zeolite is used by packing it into a column or the like. To prevent fine powdered zeolite from accumulating and clogging the flow channels in the device, the zeolite is shaped into pellet-shaped zeolite compacts. As an adsorbent, the zeolite compacts are required to have sufficient durability under the environment.

[0006] We found that when zeolite compacts containing GIS-type zeolite adsorb a large amount of carbon dioxide, they become brittle, and in the case of pellet-shaped zeolite compacts, they turn into powder. This embrittlement generates fine powder inside the adsorption device, which makes continuous operation of the device difficult due to pressure loss and other factors.

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

[0008] The present inventors have conducted extensive research to solve the above problems, and as a result, have discovered that the zeolite formed body exhibits a peak in the IR spectrum of 1300 to 800 cm -1 The peak area in the range of A is defined as 3200 to 2700 cm -1 The inventors have found that when the peak area ratio B / A is 5.0 or less, the above problem can be solved, and have achieved the present invention.

[0009] That is, the present invention includes the following embodiments. <1> A zeolite molded body containing GIS-type zeolite, 1300-800 cm in infrared spectroscopy -1 The sum of the peak areas in the range of 3200 to 2700 cm is A. -1When the sum of the peak areas within the above range is defined as B, the B / A ratio is 5.0 or less. <2> The silica-alumina ratio of the GIS-type zeolite is 3.40 or more. <1> The zeolite molded body according to claim 1. <3> Contains potassium or lithium as a cation species in GIS-type zeolite, <1> or <2> The zeolite molded body according to claim 1. <4> 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. <3> The zeolite molded body according to claim 1. <5> 29 The peak area intensities attributable to Q4(3Al), Q4(2Al), Q4(1Al), and Q4(0Al) observed in the Si-MAS-NMR spectrum are designated as a, b, c, and d, respectively, and the GIS-type zeolite satisfies (a+d) / (b+c)≧0.192. <1> ~ <4> The zeolite molded body according to any one of the preceding claims. <6> including a carrier, <1> ~ <5> The zeolite molded body according to any one of the preceding items. <7> The carrier comprises an inorganic binder. <6> The zeolite molded body according to claim 1. <8> The inorganic binder comprises alumina. <7> The zeolite molded body according to claim 1. <9> the mass ratio of the GIS zeolite to the carrier, GIS zeolite:carrier, is 1:99 to 99:1; <6> ~ <8> The zeolite molded body according to any one of the preceding claims. <10> The weight loss rate at 300°C for 2 hours is 0.20 or less. <1> ~ <9> The zeolite molded body according to any one of the preceding items. <11> having a cylindrical shape, <1> ~ <10> The zeolite molded body according to any one of the preceding claims. <12> 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. <11> The zeolite molded body according to claim 1. <13> <1> ~ <12> An adsorption device comprising the zeolite shaped body according to any one of the preceding items. <14> <13> A method for producing a 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 in the above. <15> In the separation step, the gas is separated by a pressure swing adsorption separation method, a temperature swing adsorption separation method, or a pressure-temperature swing adsorption separation method. <14> A method for producing the purified gas described in claim 1. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a zeolite shaped body that is excellent in resistance to embrittlement due to adsorption of carbon dioxide, an adsorption apparatus including the same, and a method for producing purified gas using the same. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a diagram illustrating an adsorption device according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The present invention is not limited to the following description, and can be practiced with various modifications within the scope of the gist thereof. In this specification, for example, when a numerical range is expressed as "1 to 100," it is intended to include both the lower limit "1" and the upper limit "100." The same applies to other numerical ranges.

[0013] The zeolite molded body according to this embodiment contains GIS-type zeolite and has an infrared spectrum of 1300 to 800 cm -1 The sum of the peak areas in the range of 3200 to 2700 cm is A. -1 When the sum of the peak areas within this range is defined as B, B / A is 5.0 or less. The zeolite shaped body according to this embodiment has excellent resistance to embrittlement due to the adsorption of carbon dioxide. According to this embodiment, by making the above-mentioned B / A 5.0 or less, it is possible to provide a zeolite shaped body having strength capable of withstanding stress generated in accordance with the expansion and contraction of the zeolite itself, and having resistance to embrittlement due to expansion and contraction, an adsorbent containing the zeolite shaped body, and a method for producing purified gas using the zeolite shaped body. Although the detailed mechanism is not necessarily clear, it is believed that the zeolite shaped body has a high resistance to embrittlement due to the adsorption of carbon dioxide within the above range of 3200 to 2700 cm. -1 This is the region where hydroxyl group absorption appears, and it is presumed that by adjusting the amount of hydroxyl groups in the zeolite molded body, it is possible to obtain a molded body strong enough to withstand the maximum stress generated by the expansion and contraction of the zeolite itself.

[0014] From the viewpoint of improving resistance to embrittlement due to carbon dioxide adsorption, the peak area ratio B / A is 5.0 or less, more preferably 4.5 or less, and even more preferably B / A = 4.0 or less. The peak area ratio B / A is determined by powdering a zeolite molded body and measuring the infrared spectrum to determine the B and A areas. More specifically, the peak area ratio B / A can be measured by the method described in the Examples below. In the zeolite production method described below, the dehydration condensation of hydroxyl groups can be controlled to fall within the above range by adjusting the firing temperature and time in the firing step.

[0015] Zeolites capable of adsorbing carbon dioxide include, for example, GIS-type zeolites, FAU-type zeolites, MWF-type zeolites, etc. Among these, GIS-type zeolites are preferred.

[0016] The lower the silica-alumina ratio (representing the molar ratio of silica to alumina expressed as SiO2 / Al2O3, hereinafter also referred to simply as "SAR") of the GIS zeolite according to this embodiment, the more hydrophilic it is, and the stronger its adsorption power for polar molecules such as carbon dioxide. If the SAR is low, the adsorption power will be too strong, and the energy required for desorption by heating or vacuuming will be large, so a higher SAR is preferable. The SAR of the GIS zeolite is preferably 3.40 or more, more preferably 4.40 or more, more preferably 4.50 or more, even more preferably 4.69 or more, even more preferably 4.90 or more, even more preferably 5.40 or more, and even more preferably 6.01 or more. There is no particular upper limit for the SAR, but if the SAR is too high, the interaction with the adsorbate will be reduced, so the SAR of the GIS 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 body is 29 The SAR is determined by measuring Si-MAS-NMR. More specifically, the SAR can be measured by the method described in the Examples below. The SAR can be adjusted by the ratio of water to OH − in the mixed gel, etc.

[0017] From the viewpoint of the energy required for desorption, a high SAR is preferable. However, it has been confirmed that when the SAR of a GIS zeolite increases, adsorption / desorption hysteresis becomes apparent in the carbon dioxide adsorption / desorption isotherm. In the GIS zeolite according to this embodiment, the 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 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 it is preferable that (a+d) / (b+c)≧0.192, more preferably 0.913≧(a+d) / (b+c)≧0.195, and even more preferably 0.519≧(a+d) / (b+c)≧0.199. 29Peaks such as Q4(3Al), Q4(2Al), Q4(1Al), and Q4(0Al) observed in Si-MAS-NMR spectra represent the bonding modes of Si and Al in the zeolite framework. The sum of the area intensities (a + d) and (b + c) represents the sum of the abundances of these bonding modes, and (a + d) / (b + c) represents the abundance ratio. The abundance ratio of Si and Al bonding modes affects the structural changes of the zeolite framework itself during adsorption and desorption. Therefore, by adjusting the abundance ratio of Si and Al bonding modes in the zeolite framework, (a + d) / (b + c), within an appropriate range, adsorption / desorption hysteresis in the adsorption / desorption isotherm can be eliminated. (a + d) / (b + c) can be measured using the method described in the Examples below. To achieve a desired range for (a + d) / (b + c), salt compounds containing alkali metals and / or alkaline earth metals can be added and adjusted by adjusting the amount ratio of the cations and aluminum source provided by the addition of the salt compounds.

[0018] From the viewpoint of improving the selective adsorption capacity of carbon dioxide, the GIS zeolite preferably contains potassium or lithium as a cation species, and more preferably contains potassium. The total content of potassium and lithium in the zeolite is calculated as the ratio (Z / T) of the total amount of potassium and lithium (Z) to the total amount of alkali metals (T) in the GIS zeolite. Z / T is preferably 0.05 or more, more preferably 0.10 or more, and even more preferably 0.15 or more. There is no particular upper limit for Z / T, but Z / T may be 1.00 or less. Z / T can be measured by thermally dissolving the zeolite in a sodium hydroxide aqueous solution or aqua regia and then subjecting the appropriately diluted solution to ICP-emission spectroscopy. 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 zeolite. The ratio (K / T) of the total amount of potassium (K) to the total amount of each alkali metal (T) in the GIS zeolite is preferably 0.05 or more, more preferably 0.10 or more, and even more preferably 0.15 or more. There is no particular upper limit to K / T, but K / T may be 1.00 or less.

[0019] The GIS zeolite preferably has a weight loss rate of 1.0 or less after heating at 300°C for 2 hours. A weight loss rate of 1.0 or less improves high-temperature durability. The weight loss rate is preferably 0.5 or less, and more preferably 0.1 or less. The weight loss rate is measured by the method described in the Examples. The weight loss rate can be adjusted to the above range by, for example, sintering the GIS zeolite molded body at a temperature above 300°C.

[0020] The zeolite content may be preferably 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 shaped body, and 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 shaped body.

[0021] (Method for synthesizing GIS-type zeolite) The method for producing a GIS-type zeolite according to this embodiment can 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-directing agent, and water. The mixed gel and each component contained therein will be described below.

[0022] [Mixed gel] The mixed gel in this embodiment refers to 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-directing agent.

[0023] The silica source refers to a component in the mixed gel that serves as a source of silicon contained in the zeolite produced from the mixed gel, the aluminum source refers to a component in the mixed gel that serves as a source of aluminum contained in the zeolite produced from the mixed gel, the salt compound refers to a component that serves as a source of alkali metals and / or alkaline earth metals contained in the zeolite produced from the mixed gel, the alkali source refers to a component that adjusts the alkalinity of the mixed gel, and the phosphorus source refers to a component in the mixed gel that serves as a source of phosphorus contained in the zeolite produced from the mixed gel.

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

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

[0026] [Aluminum source] The aluminum source is not particularly limited as long as it is a commonly used one, and 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 alone or in combination.

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

[0028] [Salt compounds] The salt compound is a compound containing an alkali metal such as Li, Na, K, Rb, or Cs, or an alkaline earth metal such as Ca, Mg, Sr, or Ba, which promotes crystallization into a zeolite structure when producing zeolite. The alkali metal and alkaline earth metal contained in the salt compound to be added are preferably Na and K, and more preferably Na, from the viewpoint of facilitating the formation of crystals of a GIS-type framework. The salt compounds may be used alone or in combination.

[0029] Specific examples of salt compounds include, but are not limited to, sodium sulfate, sodium sulfite, sodium thiosulfate, sodium nitrite, sodium nitrate, sodium carbonate, sodium hydrogencarbonate, 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 metastannate, sodium hexahydroxide stannate (IV), sodium hexacyanilide ferrate (II), 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 thio, potassium silicate, potassium metasilicate, potassium tetraborate, potassium chlorate, potassium perchlorate, potassium cyanide, potassium metastannate, potassium hexahydroxide stannate(IV), potassium hexacyanilide ferrate(II), 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, lithium thiolithium, lithium silicate, lithium metasilicate, lithium tetraborate, lithium chlorate, lithium perchlorate, lithium cyanide, lithium metastannate, lithium hexahydroxide stannate(IV), lithium hexacyanilide ferrate(II), 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, rubidium thiol, rubidium silicate, rubidium metasilicate, rubidium tetraborate, rubidium chlorate, rubidium perchlorate, rubidium cyanide, rubidium metastannate, rubidium hexahydroxide stannate(IV), rubidium hexacyanidoferrate(II), 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, Cesium thiocesium, Cesium silicate, Cesium metasilicate, Cesium tetraborate, Cesium chlorate, Cesium perchlorate, Cesium cyanide, Cesium metastannate, Cesium hexahydroxide stannate(IV), Cesium hexacyanilide ferrate(II), 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, magnesium thiomagnesium, magnesium silicate, magnesium metasilicate, magnesium tetraborate, magnesium chlorate, magnesium perchlorate, magnesium cyanide, magnesium metastannate, magnesium hexahydroxide stannate(IV), magnesium hexacyanilide ferrate(II), 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 metastannate, calcium hexahydroxide stannate(IV), calcium hexacyanilide ferrate(II), 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, strontium thiostrontium, strontium silicate, strontium metasilicate, strontium tetraborate, strontium chlorate, strontium perchlorate, strontium cyanide, strontium metastannate, strontium hexahydroxide stannate(IV), strontium hexacyanidoferrate(II), strontium permanganate, strontium chromate, strontium dichromate, Examples of suitable cations 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, barium thiosulfate, barium silicate, barium metasilicate, barium tetraborate, barium chlorate, barium perchlorate, barium cyanide, barium metastannate, barium hexahydroxide stannate(IV), barium hexacyanilide ferrate(II), barium permanganate, barium chromate, and barium dichromate.

[0030] [Alkaline source] When producing zeolite, an alkali source is used for the purpose of adjusting the alkalinity (pH) of the mixed gel in order to promote crystallization into a zeolite structure. The alkali used may be any compound that exhibits alkalinity, and may be either an inorganic or organic compound. However, from the standpoint of cost, inorganic compounds are preferred, and alkali metal hydroxides are more preferred. Examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. Sodium hydroxide and potassium hydroxide are preferred, and sodium hydroxide is more preferred. These compounds may be used alone or in combination.

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

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

[0033] [Organic structure directing agent] When producing a zeolite by hydrothermal synthesis of a mixed gel, the organic structure-directing agent is a compound that acts to promote crystallization into a zeolite structure. In the crystallization of zeolite, an organic structure-directing agent can be used as needed.

[0034] The organic structure-directing agent may be of any type as long as it can form the desired GIS-type zeolite. The organic structure-directing agents may be used alone or in combination.

[0035] Examples of organic structure-directing agents that can be used include, but are not limited to, amines, quaternary ammonium salts, alcohols, ethers, amides, alkyl ureas, alkyl thioureas, cyanoalkanes, and alicyclic heterocyclic compounds containing nitrogen as a heteroatom. Preferably, alkyl amines are used, and more preferably isopropylamine is used.

[0036] Such salts may include anions, such as, but not limited to, Cl. - , Br - , I - These include halogen ions such as 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, with halogen ions being more preferred, from the viewpoint of facilitating the formation of GIS-type framework crystals.

[0037] [Composition ratio of mixed gel] In this embodiment, the addition of a salt compound containing an alkali metal and / or alkaline earth metal is the most important factor for synthesizing a GIS-type zeolite with an appropriate structure. Zeolite is produced by reacting and crystallizing a silica source and an aluminum source dissolved in an aqueous solvent while dissolving. The addition of a salt compound makes it possible to adjust the bonding pattern and abundance ratio of Si and Al in the zeolite framework, making it possible to synthesize a GIS with an ideal crystal structure.

[0038] The ratio of the cations provided by the addition of the salt compound to the aluminum source is particularly important. The ratio of the cations provided by the salt compound to the aluminum source in the mixed gel is expressed as the sum molar ratio of the amount of cations E to Al2O3, that is, E / Al2O3. Here, E represents the molar amount of cations provided by the salt compound. For example, when sodium nitrate is added, Na is added as the cationic species. + is produced, and in the case of sodium carbonate, 2Na +is generated, and the sum of the molar amounts of cation species generated by the addition of the salt compound is represented by E. The aggregation state of Al in the mixed gel can be changed by E / Al2O3, which leads to control of the randomness of Al during zeolite crystal formation, making it possible to synthesize GIS-type zeolite with an ideal crystal structure. From the above perspectives, it is necessary to optimally control E / Al2O3, and E / Al2O3 is preferably 0.1 or more and 100.0 or less, more preferably 0.5 or more and 80.0 or less, and even more preferably 0.8 or more and 50.0 or less.

[0039] In addition, water and OH in the mixed gel - The ratio (H2O / OH - ) is important for synthesizing GIS-type zeolites with appropriate SAR. - is the OH derived from inorganic hydroxides such as NaOH and Ca(OH)2, or organic hydroxides such as tetraethylammonium hydroxide, used as an alkali source. - and the OH released when oxides such as sodium aluminate and sodium silicate or their hydrates are dissolved in water. - Zeolite is produced by a reaction in which the silica source, aluminum source, and alkali source dissolved in the aqueous solvent crystallize, and some of them dissolve in the alkaline solvent, creating an equilibrium between crystallization and re-dissolution. OH 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 balance between crystallization and re-dissolution to the re-dissolution side. Re-dissolution proceeds from the amorphous or low-crystalline parts. Therefore, adding OH to the mixed gel moderately - By increasing the amount of OH, the imperfect crystals can be redissolved and recrystallized repeatedly, increasing the formation of the ideal crystal structure. - If the amount of OH increases too much, excessive dissolution will occur, and crystals will not be obtained, or other crystal phases, such as ANA-type zeolite, which has a more stable structure, will be formed. Also, dissolved alumina is more reactive than silica, and alumina is more easily incorporated into crystals. Therefore, -By appropriately adjusting the ratio of silica to alumina incorporated into the crystals, it is possible to adjust the crystallization and redissolution rates and optimize the SAR of the synthesized GIS-type zeolite.

[0040] A high water to alumina ratio (H2O / Al2O3) makes it easier for the components in the mixed gel to be dispersed more uniformly, but if it is too high, it significantly reduces the crystallization rate. Therefore, in order to synthesize GIS-type zeolite with the optimal SAR and optimal crystal structure, it is necessary to select a high H2O / Al2O3 ratio, which affects the equilibrium between crystallization and redissolution. - It is necessary to optimally control H2O / Al2O3 along with the control of

[0041] From the above viewpoints, H2O / Al2O3 and H2O / OH - is preferably 100≦H2O / Al2O3≦780 and 50≦H2O / OH - ≦1000, more preferably 120≦H2O / Al2O3≦778 and 60≦H2O / OH - ≦800, and more preferably 150≦H2O / Al2O3≦775 and 70≦H2O / OH - ≦700.

[0042] The ratio of the silica source to the 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 ratio in the synthesized zeolite and the silica-alumina ratio in the mixed gel do not match. The silica-alumina ratio of the synthesized zeolite is determined by other components and synthesis conditions.)

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

[0044] The ratio of the aluminum source to the alkali metal and alkaline earth metal in the mixed gel is expressed as the sum molar ratio of MO and MO to Al2O3, i.e., (MO + MO) / Al2O3 (where M1 represents an alkali metal and M2 represents an alkaline earth metal. These are calculated as oxides). Note that, from the viewpoint of facilitating the formation of GIS-type framework crystals, this (MO + MO) / Al2O3 is preferably 1.5 or more, more preferably 1.6 or more, and even more preferably 1.65. From the viewpoint of suppressing the formation of zeolites having frameworks different from the GIS-type framework, (MO + MO) / Al2O3 is preferably 15.0 or less, more preferably 12.0 or less, and even more preferably 10.0 or less.

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

[0046] When an organic structure-directing agent is contained in the mixed gel, the ratio of the aluminum source to the organic structure-directing agent in the mixed gel is expressed as the molar ratio of the organic structure-directing agent to Al2O3, i.e., R / Al2O3 (where R represents the organic structure-directing agent). From the viewpoint of easier crystal formation of the GIS framework and / or shorter synthesis time, resulting in superior economics when producing zeolite, the ratio is preferably less than 7.0, more preferably 6.0 or less, and even more preferably 5.0 or less. When an organic structure-directing agent is used, the organic structure-directing agent remains in the zeolite pores, preventing carbon dioxide from entering the pores and reducing the amount of adsorption. Heating to at least 400°C or higher is necessary to remove the organic structure-directing agent. However, since GIS zeolite crystals collapse and become amorphous at temperatures above 350°C, it is preferable to use less organic structure-directing agent. From this viewpoint, the 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 the present embodiment includes a step of preparing a mixed gel that contains: a silica source that contains silicon; an aluminum source that contains aluminum; an alkali source that contains at least one selected from alkali metals (M1) and alkaline earth metals (M2); a salt compound that contains at least one selected from alkali metals (M1) and alkaline earth metals (M2); a phosphorus source; and water; and the molar ratio of each component in the mixed gel, when calculated as an oxide of each element for the silicon, aluminum, alkali metal (M1), alkaline earth metal (M2), and phosphorus source, is expressed by the following formula (1): The molar ratios α, β, γ, δ, ε, and ζ represented by (2), (3), (4), (5), and (6) preferably 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 satisfy 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 satisfy 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. The GIS zeolite according to this embodiment is particularly preferably obtained by the above-described method for producing GIS zeolite according to this embodiment. α = E / Al2O3(1) β = SiO2 / Al2O3(2) γ = (MO + MO) / AlO(3) δ = P2O5 / Al2O3(4) ε = H2O / Al2O3(5) ζ=H2O / OH- (6)

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

[0049] It is not necessarily required that seed crystals be present in the mixed gel, but the GIS zeolite according to this embodiment can also be obtained by adding pre-produced GIS zeolite as seed crystals to the mixed gel.

[0050] [Mixed gel preparation process] The process for preparing the mixed gel is not particularly limited, and may include, for example, a mixing step of mixing a silica source, an aluminum source, a salt compound, water, and, if necessary, a phosphorus source, an alkali source, and an organic structure-directing agent all at once or in multiple stages, and an aging step of the mixture obtained in this mixing step.

[0051] In the mixing step, the silica source, aluminum source, salt compound, water, and, if necessary, the components including the phosphorus source, alkali source and organic structure directing agent can be mixed all at once or in multiple stages.

[0052] The order of mixing in multiple stages is not limited and may be appropriately selected depending on the conditions used. When mixing in multiple stages, the mixture may be mixed with or without stirring. When mixing, any commonly used stirring method may be used without any particular limitation, and specific examples include impeller stirring, vibration stirring, rocking stirring, centrifugal stirring, etc.

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

[0054] The temperature in the mixing step is not particularly limited as long as it is a commonly used temperature, and examples thereof include temperatures of -20°C or higher and lower than 80°C.

[0055] The time for the mixing step is not particularly limited and can be appropriately selected depending on the temperature of the mixing step, but may be, for example, more than 0 minutes and not more than 1000 hours.

[0056] The aging step may be carried out by standing or stirring. The stirring method used in the aging step is not particularly limited as long as it is a commonly used stirring method, and specific examples include methods using blade stirring, vibration stirring, swing stirring, centrifugal stirring, etc.

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

[0058] The temperature in the aging step is not particularly limited as long as it is a commonly used temperature, and examples thereof include a temperature of -20°C or higher and lower than 80°C.

[0059] The time for the aging step is not particularly limited and can be appropriately selected depending on the temperature for the aging step, but may be, for example, more than 0 minutes and not more than 1000 hours.

[0060] It is believed that the dissolution of raw materials, the generation of zeolite precursors, and their re-dissolution occur during the raw material mixing and aging processes. To form a large periodic structure containing eight-membered rings without defects, it is preferable that the formation of the zeolite precursor does not proceed excessively. Furthermore, excessive aging is also preferable because excessive formation of the zeolite precursor tends to increase the formation of ANA zeolite, which has a more stable structure. On the other hand, it is preferable that the raw materials are thoroughly mixed and the raw material gel is in a homogeneous state. The combined time for the mixing and aging processes is not particularly limited and can be adjusted appropriately based on the raw material composition, etc., to obtain a zeolite with the appropriate structure. The above time is typically preferably from 1 minute to less than 24 hours, more preferably from 3 minutes to less than 23 hours, even more preferably from 10 minutes to 18 hours, even more preferably from 12 minutes to 15 hours, and even more preferably from 20 minutes to 6 hours.

[0061] [Hydrothermal synthesis process] The method for producing a GIS-type zeolite according to this embodiment preferably further includes a hydrothermal synthesis step in which the hydrothermal synthesis temperature is 80° C. to 200° C., and more preferably the hydrothermal synthesis temperature is 100° C. to 180° C. That is, preferably, the mixed gel obtained in the preparation step is subjected to hydrothermal synthesis by being stirred or left to stand for a predetermined time at a predetermined temperature.

[0062] The temperature for the hydrothermal synthesis is not particularly limited as long as it is a commonly used temperature, but is preferably 80°C or higher from the viewpoint of shortening the synthesis time and being economical when producing zeolite. From the viewpoint of being able to suppress the formation of zeolite 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 being able to suppress the formation of zeolite 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 the hydrothermal synthesis may be constant or may be changed stepwise.

[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 temperature of the hydrothermal synthesis. The time for hydrothermal synthesis is preferably 3 hours or more, more preferably 10 hours or more, from the viewpoint of forming a GIS skeleton. From the viewpoint of obtaining a highly crystalline GIS-type zeolite, it is even more preferably 24 hours or more. From the viewpoint of excellent economic efficiency in producing zeolite, 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 step, the container into which the mixed gel is placed is not particularly limited as long as it is a commonly used container, but if the pressure inside the container increases at a predetermined temperature or if the mixed gel is placed under gas pressure that does not inhibit crystallization, it is preferable to place the mixed gel in a pressure-resistant container and perform hydrothermal synthesis. The pressure-resistant container is not particularly limited, and various shapes such as a spherical shape, a vertically elongated shape, or a horizontally elongated shape can be used.

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

[0066] In the hydrothermal synthesis step, the mixed gel can be preferably stirred by using a vertically long pressure-resistant vessel and rotating it vertically.

[0067] [Separation / drying process] After the hydrothermal synthesis step, the solid product and the aqueous liquid are separated. The separation method is not particularly limited as long as it is a common method, and examples that can be used include filtration, decantation, spray drying (rotary spraying, nozzle spraying, ultrasonic spraying, etc.), drying using a rotary evaporator, vacuum drying, freeze drying, and natural drying. Separation is usually achieved by filtration or decantation.

[0068] The separated product may be used as is or washed with water or a predetermined solvent. If necessary, the separated product may be dried. The temperature at which the separated product is dried is not particularly limited as long as it is a general drying temperature, but is usually from room temperature to 150°C or lower. The atmosphere during drying is not particularly limited as long as it is a commonly used atmosphere, but usually, an air atmosphere, an inert gas such as nitrogen or argon, or an atmosphere containing oxygen is used.

[0069] [Firing process] If necessary, the GIS zeolite can be calcined before use. The calcination temperature is not particularly limited as long as it is a commonly used temperature, but when it is desired to remove the organic structure-directing agent, the calcination temperature is preferably 300°C or higher, and more preferably 350°C or higher, since the remaining proportion of the organic structure-directing agent can be reduced. From the viewpoint of shortening the calcination time and being economical when producing zeolite, the calcination temperature is even more preferably 360°C or higher. Since the crystallinity of the zeolite tends to be maintained, the calcination temperature is preferably less than 450°C, more preferably 420°C or lower, and even more preferably 400°C or lower.

[0070] The calcination time is not particularly limited as long as it is a time that allows the organic structure-directing agent to be sufficiently removed, and can be appropriately selected depending on the calcination temperature, but since this tends to reduce the proportion of remaining organic structure-directing agent, it is preferably 0.5 hours or more, more preferably 1 hour or more, and even more preferably 3 hours or more.Since the crystallinity of the zeolite tends to be maintained, it is preferably 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 inert gas atmosphere such as nitrogen or argon, or an atmosphere containing oxygen is used.

[0072] [Cation Exchange] If necessary, GIS-type zeolite can be subjected to cation exchange to obtain a desired cation type. For the cation exchange, for example, but not limited to, carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, and ammonium carbonate, 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 in which the carbonate ion or nitrate ion contained in the carbonate or nitrate salt is replaced with a halide ion, sulfate ion, carbonate ion, bicarbonate ion, acetate ion, phosphate ion, or hydrogen phosphate ion, or 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 a general temperature for cation exchange, but is usually from room temperature to 100°C or less.

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

[0075] The separated product may be used as it is or may be washed with water or a predetermined solvent. If necessary, the separated product may be dried.

[0076] The temperature at which the separated product is dried is not particularly limited as long as it is a general drying temperature, but is usually from room temperature to 150°C or less.

[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 inert gas such as nitrogen or argon, or an atmosphere containing oxygen is used.

[0078] Furthermore, the ammonium type zeolite can be converted into a proton type zeolite by calcining the zeolite.

[0079] (Carrier) The zeolite molded body according to this embodiment preferably contains a carrier, such as an inorganic binder or an organic binder.

[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 alone or in combination. Among these inorganic binders, alumina, silica, magnesia, zirconia, and titania are preferred, with silica and alumina being more preferred, from the viewpoint of increasing the strength of the zeolite molded body. The content of the inorganic binder is preferably 1 to 99 mass %, more preferably 5 to 90 mass %, and even more preferably 8 to 80 mass %, relative to the total amount (100 mass %) of the zeolite molded body.

[0081] Examples of organic binders include cellulose, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, 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 alone or in combination. Among these organic binders, cellulose, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, and polyvinyl alcohol are preferred from the viewpoint of surface bonding with GIS-type zeolite, and cellulose, methyl cellulose, and polyvinyl alcohol are more preferred. The content of the organic binder is preferably 1 to 99 mass %, more preferably 5 to 90 mass %, and even more preferably 8 to 80 mass %, relative to the total amount (100 mass %) of the zeolite molded body.

[0082] It is preferable that the binder contains one or more types of inorganic binders and one or more types of organic binders.

[0083] The total content of the carrier 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 shaped body. Increasing the content of the carrier tends to increase the strength of the shaped body, but tends to decrease the content of the zeolite itself. Therefore, the content of the carrier may be adjusted taking into account the strength and performance required depending on the application.

[0084] The shape of the zeolite shaped body is not particularly limited, but examples include spherical, cylindrical, elliptical, bale-shaped, trefoil-shaped, ring-shaped, and powder-shaped. Of these, spherical and cylindrical shapes are more preferred. The size of the shaped body is not particularly limited, but varies depending on the conditions under which the shaped body is used. For example, when using the shaped body in a process that is not in a fluidized state, such as a fixed bed or moving bed, a cylindrical shape with a length of 3 mm to 30 mm and a diameter of 1 mm to 30 mm is preferred. 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 can be determined by measuring the length and diameter of three pellet samples using a vernier caliper with a minimum reading of 0.1 mm or less, and averaging the measurements to determine the length and diameter. The length and diameter can be adjusted to fall within the above-mentioned ranges by, for example, classification or other operations. When used in a process in which the compact is fluidized, such as a fluidized bed, the powder preferably has a particle diameter of 20 μm to 300 μm. The particle diameter is more preferably 20 μm to 200 μm, and even more preferably 30 μm to 100 μm. The particle diameter can be measured as the median diameter (D50) using a laser diffraction / scattering particle size analyzer (MT3000, manufactured by Microtrac) according to the attached manual.

[0085] The compressive strength of the zeolite shaped article according to the present embodiment is preferably 1.0 MPa or more, more preferably 2.2 MPa or more, and even more preferably 3.4 MPa or more. In particular, when the zeolite shaped article according to the present embodiment is in powder form, it is preferable that the compressive strength satisfies the above range. The above-mentioned compressive strength can be measured as the average value of 20 measurements using a micro-compression tester (Shimadzu Corporation MCT-W500, compressive strength measurement), and can be adjusted to the above-mentioned range by, for example, adjusting the firing temperature and firing time.

[0086] The breaking strength of the zeolite shaped article according to this embodiment is preferably 5 N or more, more preferably 10 N or more, and even more preferably 20 N or more. In particular, when the zeolite shaped article according to this embodiment is in the form of pellets, it is preferable that the breaking strength satisfies the above range. The above-mentioned breaking strength can be measured as the average value of the values ​​obtained by measuring 20 times using a digital hardness meter (KHT-40N manufactured by Fujiwara Seisakusho Co., Ltd., indenter 3 mm, breaking strength measurement), and can be adjusted to fall within the above-mentioned range by, for example, adjusting the firing temperature and firing time.

[0087] [Method of manufacturing zeolite molded body] The method for producing the zeolite molded body according to the present embodiment is not particularly limited, but may include a raw material mixing step (X) of mixing the zeolite according to the present embodiment with other optional components (e.g., a carrier) to prepare the zeolite molded body, a molding step (Y) of subjecting the prepared raw material to a molding process to obtain a precursor, and a calcination step (Z) of calcining the precursor to obtain the zeolite molded body. Other methods for producing zeolite shaped bodies include, for example, extrusion molding, injection molding, injection-casting, tumbling granulation, compression molding, spray drying, or a combination of two or more of these methods, as long as the desired zeolite shaped body can be obtained.

[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 is preferably 10°C to 80°C, and more preferably 15°C to 60°C. For example, as in a spray drying process, when the state after raw material mixing is a slurry, evaporation of water from the raw materials tends to be suppressed when the raw material temperature is 80°C or less, and freezing in the slurry tends to be suppressed when the raw material temperature is 10°C or higher. Furthermore, as in an extrusion molding process, when the raw material is in a clay-like state in the funicular to capillary region after mixing, evaporation of water from the clay tends to be suppressed, and the moisture content in the clay tends to be maintained constant when the raw material temperature is 80°C or less, and freezing of water in the clay tends to be suppressed when the raw material temperature is 10°C or higher. Any means can be used as a stirring means when preparing the raw materials. For example, when the state after raw material mixing is a slurry, as in a spray drying process, a stirring blade is preferably used. Specific examples of blades used for stirring include propeller-shaped, paddle-shaped, flat paddle-shaped, turbine-shaped, and cone-shaped blades. In addition, baffles or the like may be installed in the vessel for efficient stirring. The number of stirrers can be optimally selected depending on the size of the catalyst raw material liquid vessel, 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 longer, the composition of the raw materials tends to become uniform, while when it is 24 hours or shorter, the effect of water evaporation in the raw materials tends to be reduced. Furthermore, when the raw materials are mixed in a clay-like state ranging from funicular to capillary, as in extrusion molding, 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 longer, the composition of the raw materials tends to become uniform, while when it is 24 hours or shorter, the effect of water evaporation in the raw materials tends to be reduced.Furthermore, when an organic binder that is prone to gelling due to heat, such as methyl cellulose, is blended, gelling of the organic binder can be suppressed by maintaining the internal temperature of the mixer, kneader, etc. at a value lower than the thermal gelling temperature of the organic binder, which tends to make it easier to obtain raw materials with a uniform composition. Furthermore, the clay-like raw material can be left to stand and mature. By maturing, moisture becomes more easily distributed among the raw zeolite, which tends to improve moldability, and also tends to replace gases such as air present among the zeolite, resulting in a denser molded product.

[0089] [Molding process step (Y)] Examples of the molding process in the molding process step (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 referred to as "raw clay" in the extrusion molding process), the temperature during extrusion molding is preferably 10°C to 80°C, more preferably 15°C to 75°C. The water content in the raw clay is preferably 35% to 50% by mass, more preferably 38% to 45% by mass. When the water content is 50% by mass or less, excessive improvement in the flexibility of the raw clay can be prevented, and moldability tends to be improved, while when the water content is 35% by mass or more, an appropriate decrease in the flexibility of the raw clay can be prevented, and moldability tends to be improved.

[0091] When extrusion molding is used as the molding step (Y), the extruder is not particularly limited, and examples thereof include screw type, roll type, blade type, self-molding type, ram type, disk pelleter type, etc. Among these, it is particularly preferable to carry out extrusion molding using a roll type, screw type, or disk pelleter type extruder.

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

[0093] In the spray drying process, for example, the atomization of the slurry can be carried out by methods such as the rotating disk method, the two-fluid nozzle method, and the high-pressure nozzle method, which are commonly used industrially, but the rotating disk method is particularly preferable. As a drying 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 about 100°C to 400°C, preferably 150°C to 300°C. The temperature at the outlet of the dryer can be about 40°C to 150°C, preferably 50°C to 130°C.

[0094] [Firing process (Z)] 3200 to 2700 cm while maintaining the crystallinity of the zeolite -1 Therefore, the calcination temperature is preferably less than 550° C., more preferably 530° C. or less, and even more preferably 500° C. or less. The calcination temperature is preferably 350° C. or more, more preferably 380° C. or more, and even more preferably 400° C. or more. In addition, the temperature increase and decrease rates during firing are preferably 10°C / min or less, more preferably 8°C / min or less, and even more preferably 5°C / min or less. From the viewpoint of productivity, 0.5°C / min or more is preferable, and 1.0°C / min or more is more preferable. By keeping the temperature increase rate during firing within the above range, productivity can be maintained while reducing the occurrence of structural defects such as cracks in the molded body due to rapid evaporation of water or rapid cooling, and resistance to powdering tends to be improved. In addition, it becomes easier to suppress temperature unevenness in the molded body, and dehydration condensation of hydroxyl groups is easily promoted evenly during firing, and the temperature is increased to 3200 to 2700 cm. -1 There is a tendency to be able to reduce the peak area B within the range. The firing time is preferably 20 days or less, more preferably 10 days or less, and even more preferably 7 days or less.

[0095] The firing temperature is preferably 350°C or higher, more preferably 380°C or higher, and even more preferably 400°C or higher. In addition, the temperature increase and decrease rate during firing is preferably 10°C / min or lower, more preferably 8°C / min or lower, and even more preferably 5°C / min or lower. From the viewpoint of productivity, the rate is preferably 0.5°C / min or higher, and more preferably 1.0°C / min or higher.

[0096] The uses of the zeolite shaped article according to the present embodiment are not particularly limited, and can be used, for example, as a separating agent or separation membrane for various gases and liquids, an electrolyte membrane for fuel cells and the like, a filler for various resin shaped articles, a membrane reactor, a catalyst for hydrocracking, alkylation, etc., a catalyst carrier for supporting metals, metal oxides, etc., an adsorbent, a desiccant, a detergent aid, an ion exchange agent, a wastewater treatment agent, a fertilizer, a food additive, a cosmetic additive, and the like. Among the above, the zeolite molded body according to this embodiment can be suitably used as a carbon dioxide adsorbent.

[0097] [Adsorption device] The adsorption device according to the present embodiment includes the zeolite shaped article according to the present embodiment. Because the adsorption device according to the present embodiment is configured in this manner, it can sufficiently adsorb carbon dioxide and has high selectivity for carbon dioxide adsorption relative to the amount of methane adsorbed. Therefore, it can be particularly preferably used for the purpose of selectively removing carbon dioxide from natural gas, for example.

[0098] The adsorption device according to the present embodiment includes a zeolite shaped body containing the zeolite according to the present embodiment, and may have the configuration shown in FIG. 2. The adsorption device 1 according to the present embodiment illustrated in FIG. 2 includes filters 3 arranged at two locations, one on the inlet side and one on the outlet side, inside a container 2, and a plurality of zeolite shaped bodies 4 packed between the two filters 3. The filters 3 may be made of, for example, quartz. For example, when the adsorption device 1 is used to separate carbon dioxide from natural gas, natural gas is introduced through an upper line, impurities are removed by the filters 3, and carbon dioxide is selectively adsorbed and removed by the zeolite shaped bodies 4, and methane-rich gas is extracted through a lower line. However, the target to be fed to 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 FIG. 3.

[0099] [Method of producing purified gas] The method for producing a purified gas according to this embodiment uses an adsorption apparatus including the zeolite shaped body according to this embodiment to separate one or more gases selected from the group consisting of CO, HO, He, Ne, Cl, NH, and HCl from a mixture containing two or more gases selected from the group consisting of H, N, O, CO, and hydrocarbons. In this embodiment, it is preferable to separate one or more gases selected from the group consisting of CO and HO from one or more gases selected from the group consisting of N, O, CO, and hydrocarbons. Examples of hydrocarbons include, but are not limited to, methane, ethane, ethylene, propane, propylene, 1-butene, 2-butene, 2-methylpropene, dimethyl ether, and acetylene.

[0100] The GIS-type zeolite according to this embodiment has a particularly high CO2 adsorption capacity, and physical adsorption without chemical bonding is observed. Separation methods using the zeolite molded body according to this embodiment are not particularly limited, but a method that requires low energy consumption during adsorption and is economical is preferred. Specific examples of such methods are not particularly limited, but it is preferable to use one of pressure swing adsorption, temperature swing adsorption, and pressure-temperature swing adsorption. Pressure swing adsorption (PSA) is a method in which the pressure during desorption is lower than the pressure during gas adsorption, and gas is separated by utilizing the difference in the amount of adsorption at high pressure and the amount of adsorption at low pressure. Thermal swing adsorption (TSA) is a method in which the temperature during desorption is higher than the temperature during gas adsorption, and gas is separated by utilizing the difference in the amount of adsorption at low pressure and the amount of adsorption at high temperature. Furthermore, a combination of these methods is called pressure-temperature swing adsorption / desorption (PTSA). These methods can be carried out under various known conditions. [Example]

[0101] The present embodiment will be described in more detail below with reference to examples, but these are merely illustrative and the present embodiment is not limited to the following examples. Those skilled in the art can implement the present embodiment by making various modifications to the examples shown below, and such modifications are within the scope of the present invention as long as they satisfy the specified requirements of the present embodiment.

[0102] [Measurement of peak area ratio of infrared spectrum] The infrared spectroscopy spectrum (hereinafter also referred to as "IR spectrum") of the zeolite molded body was measured under the following conditions after the zeolite molded body was left to stand in a dryer at 100°C for 3 hours and then crushed in a mortar to obtain a powder sample. Equipment: PerkinElmer SpectrumOne Measurement method: ATR (reflection method) Base unit: Pike Technology GladiATR Base Unit (PN026-18xx) Wavelength range: 4000-450cm -1 Number of scans: 32 Resolution: 4cm -1 The peak areas of the IR spectrum were analyzed using the analysis software Spectrum. Before analyzing the peak areas, normalization processing was performed. Peak / Abscissa was Ordinate Limit = 1.5A, Start = 4000cm -1 , End=450cm -1 The zero point was set to Auto Zero. Peak determination and area calculation were performed as follows. First, based on the results of the first and second derivative calculations of the IR spectrum, the wave number positions on the IR spectrum where the first derivative coefficient changes from negative to positive were determined as peak candidate points. Next, of the peak candidate points, those with a transmittance of less than 0.5% were excluded. Furthermore, the slope (% / cm) of the peak candidate points and those before and after them was calculated. -1 ) were excluded. After that, points before and after the remaining peak candidate points where the first derivative coefficient changed from positive to negative and the second derivative coefficient at that point was positive were connected as baselines, and the corrected peak area was calculated as 10%T × cm -1 The peak areas were the corrected peak areas described above, and the peaks between 1300 and 800 cm -1 The total area of ​​the peaks in the range of 3200 to 2700 cm is defined as A. -1 The total area of ​​the peaks within this range was defined as B.

[0103] [X-ray diffraction; crystal structure analysis] X-ray diffraction was carried out according to the following procedure. (1) The zeolite molded body (dried product) obtained in each Example and Comparative Example was used as a sample and crushed in an agate mortar. 10% by mass of crystalline silicon (manufactured by Rare Metallic Co., Ltd.) was further added, and the mixture was mixed in the agate mortar until homogeneous, and the resulting mixture was used as a sample for structural analysis. (2) The sample (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 powder X-ray diffractometer "RINT2500" (product name) X-ray source: Cu tube (40kV, 200mA) Measurement temperature: 25℃ Measurement range: 5 to 60° (0.02° / step) Measurement speed: 0.2° / min Slit width (scattering, diverging, receiving): 1°, 1°, 0.15mm

[0104] [ 29 Si-MAS-NMR spectrum, SAR measurement The SAR of zeolite in the zeolite molded body is 29 This can be determined by measuring Si-MAS-NMR. First, to condition the moisture of the zeolite, water was placed at the bottom of a desiccator, and the zeolite placed in a sample tube was kept above it for 48 hours. After the moisture conditioning process, the following conditions were met: 29 Si-MAS-NMR measurements were carried out. Equipment: JEOL RESONANCE ECA700 Magnetic field strength: 16.44 T( 1 H resonance frequency 700MHz) Measurement nuclei: 29 Si Resonance frequency: 139.08MHz NMR tube: 4mmφ (zirconia rotor) Measurement method: DD / MAS (dipolar decoupling angle magic spinning) Pulse width: 45° Waiting time: 50 seconds Accumulation count: 800 times (measurement time: approx. 22 hours) MAS: 10,000Hz Chemical shift reference: Silicone rubber (-22.34 ppm) external reference In the molded body containing GIS-type zeolite, 29 The Si-MAS-NMR spectrum shows the following five peaks: (1) Q4(0Al): Si peak that is not bonded to Al at all via oxygen (2) Q4(1Al): Peak of Si bonded to one Al atom via oxygen. (3) Q4(2Al): Peak of Si bonded to two Al atoms via oxygen atoms (4) Q4(3Al): Peak of Si bonded to three Al atoms via oxygen atoms (5) Q4(4Al): Peak of Si bonded to four Al atoms via oxygen atoms Also, 29 In the Si-MAS-NMR spectrum, these peak positions generally exist between -112 ppm and -80 ppm, and can be assigned to Q4(0Al), Q4(1Al), Q4(2Al), Q4(3Al), and Q4(4Al) from the upfield side. The peak positions may vary depending on the cation species present in the zeolite framework, but generally exist in 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 29The peak area intensity of the Si-MAS-NMR spectrum was analyzed using the analysis program dmfit (Version #202000113) with Gaussian and Lorentzian functions, and the four parameters of amplitude (height of the maximum value of the spectrum), position (spectral position, ppm), width (full width at half maximum of the spectrum, ppm), and Gaussian / Lorentzian ratio (xG / (1-x)L) were calculated by optimizing them using a least-squares algorithm. The peak areas of Q4(0Al), Q4(1Al), Q4(2Al), Q4(3Al), and Q4(4Al) thus determined are designated as A_Q4(0Al), A_Q4(1Al), A_Q4(2Al), A_Q4(3Al), and A_Q4(4Al), and the total of A_Q4(0Al), A_Q4(1Al), A_Q4(2Al), A_Q4(3Al), and A_Q4(4Al) is designated as A_total. 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

[0105] [Evaluation of embrittlement resistance of zeolite molded body in a CO2 atmosphere] The embrittlement resistance of the zeolite molded bodies obtained in the Examples and Comparative Examples in a CO2 atmosphere was evaluated according to the following procedure. (1) 100 g of zeolite compacts were weighed, and the minor axes of the zeolite compacts were measured. The average minor axis value of the zeolite compacts was designated as ds. A sieve with the largest mesh size smaller than ds was selected from the published mesh sizes specified in JIS Z8801-1. The zeolite compacts remaining on the sieve were used as test samples for evaluating embrittlement resistance in a CO2 atmosphere. (2) The test sample was dried in a N2 atmosphere at 200°C for 3 hours, cooled to room temperature in a N2 atmosphere, and then exposed to CO2 at room temperature for 30 minutes. (3) After the CO2 exposure, the mass W1 of the test sample was measured, and then the sample was passed through a sieve with the same opening 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 powdering rate [mass%] of the zeolite molded body, and the lower the powdering rate, the more resistant the zeolite molded body was to embrittlement in a CO2 atmosphere.

number

[0106] [Alkali metal content] Zeolite was thermally dissolved in aqueous sodium hydroxide or aqua regia, and the solution was diluted appropriately to measure the alkali metal concentrations in the zeolite using ICP-AES (hereinafter also referred to as "ICP-AES", Hitachi High-Tech Science Corporation, SPS3520UV-DD: instrument name). The potassium and lithium contents in the zeolite were calculated as the ratio (Z / T) of the total amount of potassium and lithium (Z) to the total amount of each alkali metal (T) in the zeolite. K / T was calculated in the same way.

[0107] [CO2 adsorption amount and hysteresis amount; gas adsorption / desorption isotherm measurement] Gas adsorption / desorption isotherm measurements were carried out in the following manner. (1) The dried product obtained in each example and comparative example was used as a sample, and 0.2 g of the sample was placed in a 12 mm cell (manufactured by Micro Meritics). (2) The sample placed in the cell (1) above was placed in a gas adsorption measuring device "3-Flex" (trade name) manufactured by Micro Meritics, and subjected to a 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 in (2) above was placed in constant-temperature circulating water at 25°C, and after the sample temperature reached 25±0.2°C, liquefied carbon dioxide gas (manufactured by Sumitomo Seika Chemicals Co., Ltd., purity 99.9% by mass or higher) was used to measure absolute pressures from 0.25 to 760 mmHg. Note that during the measurement, the pressure was measured over time, and when the pressure fluctuation became 0.001% / 10 sec or less, it was determined that the saturated adsorption amount had been reached, and this was recorded as the CO2 adsorption amount at 25°C (unit: cc / g). (4) Following the measurement in (3) above, the pressure was gradually reduced from 760 to 0.25 mmHg absolute, and the carbon dioxide desorption isotherm was measured. Note that, as in (3), the equilibrium was determined by measuring the pressure fluctuation of 0.001% / 10 sec or less. (5) As an index showing the amount of hysteresis in the carbon dioxide adsorption / desorption isotherm, q(Ad) / q(De) was used as an index showing the amount of hysteresis, where q(Ad) and q(De) are the equilibrium adsorption amount at 75 mmHg of the adsorption isotherm measured in (3) and the equilibrium adsorption amount at 75 mmHg of the desorption isotherm measured in (4). q(Ad) / q(De) = 1.00 indicates no hysteresis, and the smaller q(Ad) / q(De) indicates a state with greater hysteresis.

[0108] [CH4 adsorption amount; gas adsorption isotherm measurement] Gas adsorption isotherm measurements were carried out according to the following procedure. (1) The dried product obtained in each example and comparative example was used as a sample, and 0.2 g of the sample was placed in a 12 mm cell (manufactured by Micro Meritics). (2) The sample placed in the cell (1) above was placed in a gas adsorption measuring device "3-Flex" (trade name) manufactured by Micro Meritics, and subjected to a 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 in (2) above was placed in circulating water at a constant temperature of 35°C, and after the temperature of the sample reached 25±0.2°C, absolute pressures of 0.25 to 760 mmHg were measured using methane gas (manufactured by Fujii Shoji Co., Ltd., purity 99.99% by mass or higher). During the measurement, the pressure was measured over time, and when the pressure fluctuation became 0.001% / 10 sec or less, it was determined that the saturated adsorption amount had been reached, and this was recorded as the CH4 adsorption amount at 25°C (unit: cc / g).

[0109] [Particle size measurement] When the zeolite molded body was in powder form, the particle size was measured using a laser diffraction / scattering particle size analyzer (MT3000 manufactured by Microtrac) according to the attached manual.

[0110] [Measurement of pellet length and diameter] When the GIS-type zeolite shaped body was in the form of pellets, the length and diameter of the pellets were measured by the vernier caliper method. In this measurement, a vernier caliper with a minimum readable value of 0.1 mm or less was used, and measurements were taken for three samples, and the average values ​​were used as the length and diameter.

[0111] [Weight loss measurement] The weight loss of the zeolite molded bodies obtained in the Examples and Comparative Examples under a high temperature atmosphere was measured by the following procedure. (1) 1.2 g of the zeolite molded body was weighed and dried at 180°C in a N2 atmosphere for 3 hours. (2) The dried zeolite molded body was weighed in a glove box. (3) The weighed zeolite molded body was heated in an air atmosphere at 300°C for 2 hours. (4) The container was sealed to prevent moisture absorption and cooled to room temperature, and then the zeolite molded body was weighed in the glove box. The difference between the weight of the zeolite molded body measured in step (2) and the weight of the zeolite molded body measured in step (4) was defined as the weight loss degree, and the closer this value was to 0, the better the durability was considered to be.

[0112] [Measurement of powdering rate after high temperature exposure] The powdering rate of the zeolite molded body after the weight loss measurement was measured using the same procedure as in the "Evaluation of durability of zeolite molded body under CO2 atmosphere" described above. The powdering rate measured in this way was defined as the powdering rate [mass%] after high-temperature exposure, and the closer this value was to 0, the better the durability.

[0113] [Production Example 1] A mixed gel was prepared by mixing 61.93 g of water, 0.403 g of sodium hydroxide (NaOH, Fujifilm Wako Pure Chemical Industries, Ltd.), 3.39 g of sodium nitrate (NaNO3, Fujifilm Wako Pure Chemical Industries, Ltd.), 1.64 g of sodium aluminate (NaAlO2, Fujifilm Wako Pure Chemical Industries, Ltd.), and 10.82 g of colloidal silica (Ludox AS-40, solids concentration 40 wt%, Grace Chemical Industries, Ltd.) and stirring for 30 minutes. The composition of the mixed gel was: 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. - = 376.7, and η = R / Al2O3 = 0.00. The mixed gel was placed in a 200 mL stainless steel microbomb (manufactured by HIRO COMPANY) with a fluororesin inner cylinder, and hydrothermal synthesis was carried out for 4 days at 135°C and a stirring speed of 30 rpm in a thermostatically controlled stirring bath (manufactured by HIRO COMPANY) that could rotate the microbomb up and down. The product was filtered and dried at 120°C to obtain powdered zeolite. The XRD spectrum confirmed that the obtained zeolite was GIS-type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica-alumina were observed, it was evaluated as high-purity GIS-type zeolite.

[0114] About the obtained zeolite 29 The silica-alumina ratio was calculated from the Si-MAS-NMR spectrum, resulting in SAR = 6.90 and (a + d) / (b + c) = 0.305. The potassium and lithium contents in the zeolite were Z / T = 0.00 (= K / T). Measurements of the CO2 adsorption and desorption isotherms of the obtained GIS-type zeolite revealed that the adsorption capacity at 760 mmHg was 82.2 cc / g, with q(Ad) / q(De) = 0.984. Similarly, measurements of the CH4 adsorption isotherm revealed that the adsorption capacity at 760 mmHg was 6.2 cc / g.

[0115] [Production Example 2] A mixed gel was prepared by mixing 61.65 g of water with 0.60 g of 48% sodium hydroxide solution (NaOH, 48% solids, Tokuyama Soda Co.), 2.27 g of sodium carbonate (NaCO3, Tokuyama Soda Co.), 1.64 g of sodium aluminate (NaAlO2, Hokuriku Chemical Industry Co.), and 10.82 g of colloidal silica (Ludox AS-40, 40% solids, Grace Chemicals Co.) and stirring for 30 minutes. The composition of the mixed gel was: α = E / AlO3 = 4.86, β = SiO2 / AlO3 = 8.17, γ = NaO / AlO3 = 3.99, δ = P2O5 / AlO3 = 0.00, ε = H2O / AlO3 = 431.2, ζ = H2O / OH. - = 527.8, and η = R / Al2O3 = 0.00. The mixed gel was placed in a 200 mL stainless steel microbomb (HIRO COMPANY) with a fluororesin inner cylinder and subjected to hydrothermal synthesis at 130 °C for 5 days at a stirring speed of 30 rpm using a thermostatically controlled stirring bath (HIRO COMPANY) that could rotate the microbomb vertically. The product was filtered and dried at 120 °C to obtain powdered zeolite. 1 g of the obtained zeolite was added to 500 mL of 0.05 N potassium carbonate aqueous solution prepared using potassium carbonate (K2CO3, Nippon Soda Co., Ltd.) and stirred at 500 rpm for 3 hours at room temperature. The product was filtered and dried at 120 °C to obtain powdered zeolite in which some of the cations had been exchanged with potassium. XRD spectrum confirmed that the obtained zeolite was GIS-type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica alumina were observed, it was evaluated as a high-purity GIS-type zeolite.

[0116] About the obtained zeolite 29The 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 contents in the zeolite were Z / T = 0.98 (= K / T). Measurement of the CO2 adsorption and desorption isotherms revealed that the adsorption capacity at 760 mmHg was 84.0 cc / g, with q(Ad) / q(De) = 1.000. Similarly, measurement of the CH4 adsorption isotherm revealed that the adsorption capacity at 760 mmHg was 0.0 cc / g.

[0117] [Production Example 3] A mixed gel was prepared by mixing 141.41 g of water, 2.62 g of sodium hydroxide solution (NaOH, Fujifilm Wako Pure Chemical Industries, Ltd.), 8.53 g of sodium nitrate (NaNO3, Fujifilm Wako Pure Chemical Industries, Ltd.), 3.85 g of sodium aluminate (NaAlO2, Fujifilm Wako Pure Chemical Industries, Ltd.), and 17.41 g of amorphous silica (Perkasil SM500, Grace Chemical Industries, Ltd.) and stirring for 1 hour. The composition of the mixed gel was: 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. - = 120.0, and η = R / Al2O3 = 0.00. The mixed gel was placed in a 300 mL stainless steel micro-bomb (manufactured by HIRO COMPANY) with a fluororesin inner cylinder, and hydrothermal synthesis was carried out for 4 days at 130°C and a stirring speed of 30 rpm in a stirring thermostatic bath (manufactured by HIRO COMPANY) that could rotate the micro-bomb up and down. The product was filtered and dried at 120°C to obtain powdered zeolite. XRD spectrum confirmed that the obtained zeolite was GIS-type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica-alumina were observed, it was evaluated as 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 10.1, with (a + d) / (b + c) = 0.519. The potassium and lithium contents in the zeolite were Z / T = 0.00 (= K / T). Measurements of the CO2 adsorption and desorption isotherms revealed that the adsorption capacity at 760 mmHg was 80.0 cc / g, with q(Ad) / q(De) = 1.000. Similarly, measurements of the CH4 adsorption isotherm revealed that the adsorption capacity at 760 mmHg was 7.2 cc / g.

[0119] [Production Example 4] A mixed gel was prepared by mixing 141.41 g of water, 2.62 g of sodium hydroxide solution (NaOH, Fujifilm Wako Pure Chemical Industries, Ltd.), 2.43 g of sodium nitrate (NaNO3, Fujifilm Wako Pure Chemical Industries, Ltd.), 0.55 g of sodium aluminate (NaAlO2, Fujifilm Wako Pure Chemical Industries, Ltd.), and 35.33 g of aluminosilicate (SIPERNAT 820A, Evonik) and stirring for 1 hour. The composition of the mixed gel was: 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. -= 120.0, and η = R / Al2O3 = 0.00. The mixed gel was placed in a 300 mL stainless steel microbomb (HIRO COMPANY) with a fluororesin inner cylinder and hydrothermally synthesized at 130 °C for 5 days using a stirring thermostatic chamber (HIRO COMPANY) that could rotate the microbomb up and down. The product was filtered and dried at 120 °C to obtain powdered zeolite. 1 g of the obtained zeolite was added to 500 mL of 0.005 N potassium carbonate aqueous solution prepared using potassium carbonate (K2CO3, Nippon Soda Co., Ltd.) and stirred at 500 rpm for 3 hours at room temperature. The product was filtered and dried at 120 °C to obtain powdered zeolite in which some of the cations had been exchanged with potassium. XRD spectrum confirmed that the obtained zeolite was GIS-type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica alumina were observed, it was evaluated as a high-purity GIS-type zeolite.

[0120] The obtained zeolite was 29 The silica-alumina ratio calculated from the Si-MAS-NMR spectrum was SAR 8.20, (a+d) / (b+c)=0.356, and the potassium and lithium contents in the zeolite were Z / T=0.16 (=K / T). The adsorption and desorption isotherms of CO2 were measured, and the adsorption amount at 760 mmHg was 72.7 cc / g, with q(Ad) / q(De) = 0.991. Similarly, the adsorption isotherm of CH4 was measured, and the adsorption amount at 760 mmHg was 0.5 cc / g.

[0121] [Production Example 5] A mixed gel was prepared by mixing 21.05 g of water, 0.53 g of sodium hydroxide solution (NaOH, Fujifilm Wako Pure Chemical Industries, Ltd.), 1.37 g of sodium nitrate (NaNO3, Fujifilm Wako Pure Chemical Industries, Ltd.), 1.13 g of sodium aluminate (NaAlO2, Fujifilm Wako Pure Chemical Industries, Ltd.), and 15.5 g of water glass No. 3 (Kishida Chemical Co., Ltd.) and stirring for 1 hour. The composition of the mixed gel was: α = E / Al2O3 = 2.66, β = SiO2 / Al2O3 = 12.39, γ = Na2O / Al2O3 = 6.10, δ = P2O5 / Al2O3 = 0.00, ε = H2O / Al2O3 = 197.9, ζ = H2O / OH - = 90.2, and η = R / Al2O3 = 0.00. The mixed gel was placed in a 100 mL stainless steel micro-bomb (manufactured by HIRO COMPANY) with a fluororesin inner cylinder, and hydrothermal synthesis was carried out at a stirring speed of 30 rpm at 130°C for 5 days in a stirring thermostatic bath (manufactured by HIRO COMPANY) that could rotate the micro-bomb up and down. The product was filtered and dried at 120°C to obtain powdered zeolite. 1 g of the obtained zeolite was added to 500 mL of 0.006 N lithium nitrate aqueous solution prepared using lithium nitrate (LiNO3, Fujifilm Wako Pure Chemical Industries, Ltd.) and stirred at 500 rpm for 3 hours at room temperature. The product was filtered and dried at 120°C to obtain powdered zeolite in which some of the cations had been exchanged with lithium. XRD spectrum confirmed that the obtained zeolite was GIS-type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica-alumina were observed, it was evaluated as high-purity GIS-type zeolite. The XRD spectrum confirmed that the obtained zeolite was GIS-type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica-alumina were observed, it was evaluated as a high-purity GIS-type zeolite.

[0122] About the obtained zeolite 29The silica-alumina ratio was calculated from the Si-MAS-NMR spectrum, and the SAR was 3.40, with (a + d) / (b + c) = 0.192. The potassium and lithium contents in the zeolite were Z / T = 0.11. Measurements of the CO2 adsorption and desorption isotherms revealed that the adsorption capacity at 760 mmHg was 51.2 cc / g, with q(Ad) / q(De) = 0.978. Similarly, measurements of the CH4 adsorption isotherm revealed that the adsorption capacity at 760 mmHg was 0.8 cc / g.

[0123] Example 1 60 parts by mass of the GIS-type zeolite powder obtained in Production Example 1 and 40 parts by mass of alumina sol (manufactured by Nissan Chemical Industries, Ltd., alumina content: 10.5% by mass) were mixed. The mixture was extruded into a cylindrical shape with a diameter of 3 mm using a wet extrusion granulator MG-55 (Dalton Co., Ltd.), and then calcined in an electric furnace at 400°C for 24 hours in an air atmosphere at a temperature increase and decrease rate of 1°C / min. The peak area ratio B / A of the IR spectrum of the zeolite molded body thus obtained was 0. The weight loss was 0.01. The embrittlement resistance of the zeolite molded body was evaluated in a CO2 atmosphere, and the powdering rate was measured, which was 10% by mass. The powdering rate after high-temperature exposure was 9% by mass.

[0124] When the adsorption isotherms of CO and CH of the zeolite molded body of Example 1 were measured, the adsorption amounts at 760 mmHg were CO: 76.8 cm 3 / g, CH4:5.8cm 3 / g, and the adsorption selectivity (CO2 / CH4) was 13.3, confirming that the material has sufficient performance as an adsorbent.

[0125] Example 2 A molded body was obtained in the same manner as in Example 1, except that the GIS-type zeolite powder obtained in Production Example 2 was used. The peak area ratio B / A of the IR spectrum of the thus obtained zeolite molded body was 0. The weight loss rate was 0.01. The embrittlement resistance of the zeolite molded body was evaluated in a CO atmosphere, and the powdering rate was measured, which was 9% by mass. The powdering rate after high-temperature exposure was 8% by mass.

[0126] Example 3 A molded body was obtained in the same manner as in Example 1, except that the GIS-type zeolite powder obtained in Production Example 3 was used. The peak area ratio B / A of the IR spectrum of the thus obtained zeolite molded body was 0. The weight loss rate was 0.02. The embrittlement resistance of the zeolite molded body was evaluated in a CO atmosphere, and the powdering rate was measured, which was 10% by mass. The powdering rate after high-temperature exposure was 8% by mass.

[0127] Comparative Example 1 A molded body was obtained in the same manner as in Example 1, except that 60 parts by mass of alumina sol (manufactured by Taki Chemical Co., Ltd.) having an alumina content of 7.2% by mass was used instead of the alumina sol having an alumina content of 10.5% by mass. The peak area ratio B / A of the IR spectrum of the zeolite molded product thus obtained was 8.5, and the weight loss was 0.02. The zeolite compact was evaluated for its embrittlement resistance in a CO2 atmosphere, and the powdering rate was measured to be 95% by mass. Furthermore, the powdering rate after exposure to high temperatures was 94% by mass.

[0128] Example 4 A molded body was obtained in the same manner as in Comparative Example 1, except that the firing temperature was set to 500°C in the firing conditions using an electric furnace after extrusion. The peak area ratio B / A of the IR spectrum of the zeolite molded product thus obtained was 5.0, and the weight loss was 0.01. The zeolite compact was evaluated for embrittlement resistance in a CO2 atmosphere, and the powdering rate was measured to be 15% by mass. After exposure to high temperatures, the powdering rate was 13% by mass.

[0129] Comparative Example 2 A molded body was obtained in the same manner as in Example 1, except that 20 parts by mass of alumina sol (manufactured by Nissan Chemical Co., Ltd.) having an alumina content of 20.5% by mass and 20 parts by mass of ion-exchanged water were used instead of the alumina sol having an alumina content of 10.5% by mass. The peak area ratio B / A of the IR spectrum of the zeolite molded product thus obtained was 7.5, and the weight loss was 0.02. The zeolite compact was evaluated for embrittlement resistance in a CO2 atmosphere, and the powdering rate was measured to be 85% by mass. After exposure to high temperatures, the powdering rate was 83% by mass.

[0130] Example 5 100 parts by mass of the GIS-type zeolite powder obtained in Production Example 1, 250 parts by mass of alumina sol (manufactured by Kawaken Fine Chemicals Co., Ltd., alumina content: 10% by mass), and 275 parts by mass of ion-exchanged water were mixed, and then the water content was adjusted to 40% by mass by heating and concentrating at 70°C. The mixture was extruded into a cylindrical shape with a diameter of 3 mm using a wet extrusion granulator MG-55 (Dalton Co., Ltd.), and then calcined in an electric furnace at 350°C for 3 hours in an air atmosphere. The temperature increase and decrease rates were 1°C / min. The peak area ratio B / A of the IR spectrum of the zeolite molded product thus obtained was 4.5, and the weight loss was 0.02. The zeolite compact was evaluated for its embrittlement resistance in a CO2 atmosphere, and the powdering rate was measured to be 10% by mass. After exposure to high temperatures, the powdering rate was 9% by mass.

[0131] Example 6 A molded body was obtained in the same manner as in Example 5, except that the GIS-type zeolite powder obtained in Production Example 4 was used. The peak area ratio B / A of the IR spectrum of the thus obtained zeolite molded body was 4.5. The weight loss was 0.02. The embrittlement resistance of the zeolite molded body was evaluated in a CO atmosphere, and the powdering rate was measured, which was 10% by mass. The powdering rate after high-temperature exposure was 8% by mass.

[0132] Example 7 A molded body was obtained in the same manner as in Example 5, except that the GIS-type zeolite powder obtained in Production Example 5 was used. The peak area ratio B / A of the IR spectrum of the thus obtained zeolite molded body was 4.5. The weight loss rate was 0.02. The embrittlement resistance of the zeolite molded body was evaluated in a CO atmosphere, and the powdering rate was measured, which was 9% by mass. The powdering rate after high-temperature exposure was 8% by mass.

[0133] Comparative Example 3 A molded body was obtained in the same manner as in Example 5, except that the temperature increase rate was 20° C. / min and the temperature decrease rate was left to chance. The peak area ratio B / A of the IR spectrum of the zeolite molded product thus obtained was 7.5, and the weight loss was 0.02. The zeolite compact was evaluated for its embrittlement resistance in a CO2 atmosphere, and the powdering rate was measured to be 80% by mass. After exposure to high temperatures, the powdering rate was 78% by mass.

[0134] Example 8 A molded body was obtained in the same manner as in Example 1, except that manual extrusion molding was carried out using a clay gun instead of the wet extrusion granulator MG-55. The peak area ratio B / A of the IR spectrum of the zeolite molded product thus obtained was 0. The weight loss was 0.01. The zeolite compact was evaluated for embrittlement resistance in a CO2 atmosphere, and the powdering rate was measured to be 11% by mass. After exposure to high temperatures, the powdering rate was 10% by mass.

[0135] Example 9 10.1 parts by mass of the GIS 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 Industries, Ltd., alumina content: 10.5% by mass) to prepare a raw material slurry. The resulting raw material slurry was stirred at 25°C for 1 hour. The raw material slurry was in a sol 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 fed into a spray dryer (Okawahara Kakoki OC-16 spray dryer) with the fluid temperature at the inlet set to 230°C and the fluid temperature at the outlet set to 120°C. Spray drying was performed using a rotating disk method to obtain a dried powder, which was then calcined in an electric furnace at 350°C for 24 hours in an air atmosphere. The temperature increase and decrease rates were 1°C / min. The peak area ratio B / A of the IR spectrum of the zeolite compact thus obtained was 0. The embrittlement resistance of the zeolite compact was evaluated in a CO2 atmosphere, and the powdering rate was measured, which was 10% by mass. The weight loss rate was 0.01, and the powdering rate after high-temperature exposure was also 10% by mass.

[0136] Comparative Example 4 A molded body was obtained in the same manner as in Example 5, except that the temperature increase rate was 20° C. / min and the temperature decrease rate was left to chance. The peak area ratio B / A of the IR spectrum of the GIS-type zeolite compact thus obtained was 7.0. The embrittlement resistance of the zeolite compact was evaluated in a CO2 atmosphere, and the powdering rate was measured, which was 75% by mass. The weight loss rate was 0.01, and the powdering rate after high-temperature exposure was 73% by mass.

[0137] Comparative Example 5 A composite was obtained by melt-kneading 70 parts by mass of GIS-type zeolite powder and 30 parts by mass of polyamide resin (Zytel 101L manufactured by DuPont Co., Ltd.) at 285°C and 400 rpm in a twin-screw extruder (TEM48-SS manufactured by Toshiba Machine Co., Ltd.). The composite was then molded in an injection molding machine (EC75NII manufactured by Toshiba Machine Co., Ltd.) with a cylinder temperature of 285°C and a mold temperature of 70°C to obtain a molded body measuring 80 mm in length, 10 mm in width, and 4 mm in thickness. The peak area ratio B / A of the IR spectrum of the zeolite molded product thus obtained was 6.5, and the weight loss was 1.65. The embrittlement resistance of the zeolite compact was evaluated in a CO2 atmosphere, and the powdering rate was measured to be 12% by mass. After exposure to high temperatures, the powdering rate was 100% by mass.

Claims

1. A zeolite molded body containing GIS-type zeolite, 1300 to 800 cm in the infrared spectrum -1 The sum of the peak areas in the range of A, 3200 to 2700 cm -1 When the sum of the peak areas within the range is B, B / A is 5.0 or less.

2. 2. The zeolite molded body according to claim 1, wherein the GIS-type zeolite has a silica-alumina ratio of 3.40 or more.

3. The zeolite formed body according to claim 1 or 2, wherein the GIS zeolite contains potassium or lithium as a cation species.

4. 4. The zeolite molded body according to claim 3, wherein the ratio (Z / T) of the total amount of substance (Z) of potassium and lithium to the total amount of substance (T) of alkali metals in the GIS zeolite is 0.05 or more.

5. 29 The zeolite shaped body according to any one of claims 1 to 4, comprising a GIS zeolite satisfying (a + d) / (b + c) ≧ 0.192, where a, b, c, and d are the peak area intensities assigned to Q4(3Al), Q4(2Al), Q4(1Al), and Q4(0Al) observed in a Si-MAS-NMR spectrum, respectively.

6. The zeolite shaped body according to any one of claims 1 to 5, which contains a carrier.

7. The zeolite formed body according to claim 6, wherein the carrier contains an inorganic binder.

8. The zeolite formed body according to claim 7 , wherein the inorganic binder comprises alumina.

9. The zeolite molded body according to any one of claims 6 to 8, wherein a mass ratio of the GIS zeolite to the carrier, in terms of GIS zeolite:carrier, is 1:99 to 99:

1.

10. The zeolite molded body according to any one of claims 1 to 9, wherein the weight loss rate under conditions of 300°C for 2 hours is 0.20 or less.

11. The zeolite molded body according to any one of claims 1 to 10, which has a cylindrical shape.

12. 12. The zeolite molded body according to claim 11, having a length of 3 mm or more and 30 mm or less and a diameter of 1 mm or more and 30 mm or less.

13. An adsorption device comprising the zeolite shaped body according to any one of claims 1 to 12.

14. The adsorption device according to claim 13 is used to 2 , N 2 , O 2 , Ar, CO, and a hydrocarbon from a mixture containing two or more gases selected from the group consisting of 2 , H 2 O, He, Ne, Cl 2 , N.H. 3 and HCl.

15. 15. The method for producing a purified gas according to claim 14, wherein in the separation step, the gas is separated by pressure swing adsorption separation, temperature swing adsorption separation, or pressure-temperature swing adsorption separation.

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