JP2023146805A - Zeolite molding, adsorption device, and method for producing purified gas - Google Patents

Abstract

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

Description

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

Zeolites can be used as adsorbents, desiccants, separation agents, catalysts, catalyst carriers, detergent aids, ion exchange agents, wastewater treatment agents, fertilizers, food additives, cosmetic additives, etc. Among them, they are used for gas separation. It is useful as a.

For example, among zeolites, those with a GIS structure according to the code that defines the structure of zeolites set by IZA (International Zeolite Association) are called GIS type zeolites. GIS type zeolite is a zeolite having pores composed of eight-membered oxygen rings. Regarding such GIS type zeolite, for example, in Patent Document 1, a GIS type zeolite having adsorption ability for carbon dioxide has been synthesized, and when the GIS type zeolite is used as an adsorbent, it is difficult to separate, recover, and purify carbon dioxide. It has been shown that it can be used for

International publication WO2019/202933

When carbon dioxide is separated, recovered, and purified using an adsorbent, a pressure swing adsorption separation method, a temperature swing adsorption separation method, a pressure/temperature swing adsorption separation method, or the like is used. In these methods, zeolite is used by filling a column or the like. In order to prevent fine powdered zeolite from accumulating and clogging the flow path in the device, the zeolite is shaped and used as a pellet-shaped zeolite molded body. The zeolite molded body is required to have sufficient durability under the conditions of use.

We have discovered that when a zeolite molded body containing zeolite capable of adsorbing carbon dioxide adsorbs a larger amount of carbon dioxide, the zeolite molded body becomes brittle, and if it is a pellet-shaped zeolite molded body, it becomes powder. This embrittlement generates fine powder within the adsorption device, making continuous operation of the device difficult due to pressure loss and the like.

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

The present inventors have made extensive studies to solve the above problem, and as a result, have found that the problem can be solved by setting the elastic modulus of the zeolite molded body to 10.0 MPa or more, and have accomplished the present invention.

That is, the present invention includes the following embodiments.
<1>
A zeolite molded body containing zeolite capable of adsorbing carbon dioxide,
A zeolite molded body having an elastic modulus E of 10.0 MPa or more.
<2>
The zeolite molded article according to <1>, wherein the zeolite has a carbon dioxide adsorption amount of 10 cc/g or more.
<3>
The zeolite molded article according to <1> or <2>, wherein the zeolite is a GIS type zeolite.
<4>
The zeolite molded article according to <3>, wherein the GIS-type zeolite has a silica-alumina ratio of 3.40 or more.
<5>
The zeolite molded article according to <3>, wherein the GIS-type zeolite has a silica-alumina ratio of 4.50 or more.
<6>
The zeolite molded article according to any one of <3> to <5>, which contains potassium or lithium as a cationic species in the GIS type zeolite.
<7>
The ratio (Z/T) of the total amount of potassium and lithium (Z) to the total amount of alkali metals (T) in the GIS-type zeolite is 0.05 or more, described in <6> Zeolite molded body.
<8>
^{29 Let} the peak area intensities attributed to Q4 (3Al), Q4 (2Al), Q4 (1Al), and Q4 (0Al) observed in the Si-MAS-NMR spectrum be a, b, c, and d, respectively, and ( The zeolite molded article according to any one of <3> to <7>, comprising a GIS type zeolite that satisfies a+d)/(b+c)≧0.192.
<9>
The zeolite molded article according to any one of <1> to <8>, comprising a carrier.
<10>
The zeolite molded article according to <9>, wherein the carrier contains one or more selected from the group consisting of an inorganic binder and an organic binder.
<11>
The zeolite molded article according to <10>, wherein the inorganic binder contains alumina.
<12>
The zeolite molded article according to any one of <9> to <11>, wherein the mass ratio of the GIS type zeolite to the carrier is 1:99 to 99:1 as GIS type zeolite:carrier.
<13>
The zeolite molded article according to any one of <1> to <12>, which has a cylindrical shape.
<14>
The zeolite molded article according to <13>, which has 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.
<15>
An adsorption device comprising the zeolite molded article according to any one of <1> to <14>.
<16>
Using the adsorption device described in <15>, CO ₂ , H 2 O is extracted from a mixture containing two or more gases selected from _the group consisting _of H 2 , N ₂ , O ₂ , Ar, CO, and hydrocarbons. , He, Ne, Cl ₂ , NH ₃ , and HCl.
<17>
The method for producing purified gas according to <16>, wherein 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.

According to the present invention, it is possible to provide a zeolite molded body having excellent embrittlement resistance against adsorption of carbon dioxide, an adsorption device including the same, and a method for producing purified gas using the same.

FIG. 1 is a diagram illustrating an adsorption device according to an embodiment of the present invention.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. The present invention is not limited to the following description, and can be implemented with various modifications within the scope of the gist. Note that in this specification, for example, the notation of a numerical range of "1 to 100" includes both the lower limit value "1" and the upper limit value "100". The same applies to other numerical ranges.

The zeolite molded body according to this embodiment contains zeolite capable of adsorbing carbon dioxide, and has an elastic modulus E of 10.0 MPa or more. The zeolite molded body according to this embodiment has excellent embrittlement resistance against adsorption of carbon dioxide. According to this embodiment, by molding using zeolite capable of adsorbing carbon dioxide and setting the elastic modulus E of the zeolite molded body to 10.0 MPa or more, stress caused by expansion and contraction of the zeolite due to adsorption of carbon dioxide It is possible to provide a zeolite molded body that has a structure that is difficult to break and has embrittlement resistance against expansion and contraction, an adsorption device containing the same, and a method for producing purified gas using the same.

The elastic modulus E of the zeolite molded body is 10.0 MPa or more, more preferably 11.0 MPa or more, and still more preferably 12.0 MPa or more, from the viewpoint of improving embrittlement resistance against carbon dioxide adsorption. . The upper limit of the elastic modulus E of the zeolite molded body is not particularly limited, but if the elastic modulus is too high, the maximum principal stress caused by expansion and contraction of the zeolite tends to increase, so the elastic modulus E is preferably 70.0 GPa or less, and 65 .0 GPa or less is more preferable, and 60.0 GPa or less is even more preferable. The elastic modulus E is the compressive elastic modulus. More specifically, the elastic modulus E can be measured by the method described in the Examples below. In addition, when the content of a carrier with a high elastic modulus is increased, the elastic modulus E of the zeolite molded body tends to increase, and when the content of a carrier with a low elastic modulus is increased, the elastic modulus E of the molded body also tends to decrease. be. It is possible to adjust the elastic modulus E by adjusting the composition of the carrier. More specifically, this will be explained in the method for manufacturing a molded body described later.

(zeolite)
It is preferable that the zeolite has a carbon dioxide adsorption amount of 10 cc/g or more. The carbon dioxide adsorption amount of zeolite is preferably 20 cc/g or more, more preferably 40 cc/g or more, and even more preferably 50 cc/g or more. The upper limit of the amount of carbon dioxide adsorbed by zeolite is not particularly limited, but is, for example, 100 cc/or less. The carbon dioxide adsorption amount is the carbon dioxide adsorption capacity (cc) per 1 g of zeolite at 25°C. More specifically, it is measured by the method described in Examples.

Examples of zeolites capable of adsorbing carbon dioxide include GIS type zeolite, FAU type zeolite, MWF type zeolite, and the like. Among these, GIS type zeolite is preferred.

The lower the silica-alumina ratio (representing the molar ratio of silica and alumina expressed as SiO ₂ /Al ₂ O ₃ , hereinafter also simply referred to as "SAR") of the zeolite according to the present embodiment, the more hydrophilic it becomes, and the more carbon dioxide it absorbs. The adsorption power of polar molecules such as If the SAR is low, the adsorption force is too strong and the energy required for desorption by heating or vacuuming increases, so a high SAR is preferable. The SAR of the zeolite is preferably 3.40 or more, more preferably 4.40 or more, more preferably 4.50 or more, still more preferably 4.69 or more, and even more preferably 4.90 or more. It is more preferably 5.40 or more, and still more preferably 6.01 or more. Although the upper limit of the SAR is not particularly limited, if the SAR is too high, the interaction with the adsorbate will be reduced, so the SAR of the zeolite is preferably 3000 or less, more preferably 500 or less, and still more preferably 100 or less. The SAR of the zeolite in the zeolite molded body is determined by measuring ²⁹ Si-MAS-NMR. SAR can be measured in more detail by the method described in Examples below. SAR can be adjusted by adjusting the amount ratio of water and OH- in the mixed gel.

From the viewpoint of the energy required for desorption, a higher SAR is preferable, but it has been confirmed that as the SAR increases in zeolite, adsorption/desorption hysteresis in the carbon dioxide adsorption/desorption isotherm becomes apparent. In the zeolite according to this embodiment, by controlling the bonding mode of Si and Al in the zeolite skeleton, adsorption/desorption hysteresis in the carbon dioxide adsorption/desorption isotherm can be eliminated. Specifically, the peak area intensities attributed to Q4(3Al), Q4(2Al), Q4(1Al), and Q4(0Al) observed in the ²⁹ Si-MAS-NMR spectrum are expressed as a, b, and c, respectively. , d, preferably satisfying (a+d)/(b+c)≧0.192, more preferably 0.913≧(a+d)/(b+c)≧0.195, still more preferably 0.519≧( a+d)/(b+c)≧0.199. ²⁹ Peaks such as Q4 (3Al), Q4 (2Al), Q4 (1Al), and Q4 (0Al) observed in the Si-MAS-NMR spectrum represent the bonding mode of Si and Al in the zeolite framework, and are the sum of the area intensities. (a+d) and (b+c) represent the sum of abundances of those binding modes, and (a+d)/(b+c) represents the abundance ratio. The abundance ratio of the bonding modes of Si and Al affects the structural changes of the zeolite skeleton itself during adsorption and desorption, so the abundance ratio of the bonding modes of Si and Al in the zeolite skeleton is (a + d) / (b + c) By setting the value to an appropriate range, adsorption/desorption hysteresis in the adsorption/desorption isotherm can be eliminated. (a+d)/(b+c) can be measured by the method described in the Examples below. In order to set (a+d)/(b+c) within a predetermined range, a salt compound containing an alkali metal and/or an alkaline earth metal is added, and the ratio of the cation brought about by the addition of the salt compound to the aluminum source is adjusted. It is possible to adjust.

From the viewpoint of improving the selective adsorption ability of carbon dioxide, the cation species in the GIS type zeolite preferably contains potassium or lithium, and more preferably contains potassium. In addition, the total content of potassium and lithium in the zeolite is determined by the ratio (Z/T) of the total amount of potassium and lithium (Z) to the total amount of alkali metals (T) in the GIS type zeolite. Calculated as Z/T is preferably 0.05 or more, more preferably 0.10 or more, and still more preferably 0.15 or more. Although the upper limit of Z/T is not particularly limited, Z/T may be 1.00 or less. Z/T can be measured by thermally dissolving zeolite in an aqueous sodium hydroxide solution or aqua regia, and performing ICP-emission spectroscopy using the appropriately diluted solution. Z/T can be measured in more detail by the method described in the Examples below. Z/T can be adjusted by changing the ratio of potassium and lithium of the cation species of the GIS type zeolite.
The ratio (K/T) of the total amount of potassium (K) to the total amount of each alkali metal (T) in the GIS-type zeolite is preferably 0.05 or more, more preferably is 0.10 or more, more preferably 0.15 or more. Although the upper limit of K/T is not particularly limited, K/T may be 1.00 or less.

The content of zeolite may be preferably 50% by mass or more, 60% by mass or more, or 70% by mass or more with respect to the total amount of 100% by mass of the zeolite molded body. , 80% by mass or more. Further, the content of zeolite may be 98% by mass or less, or 95% by mass or less with respect to 100% by mass of the total amount of the zeolite molded body.

(Synthesis method of GIS type zeolite)
The method for producing a GIS type zeolite according to the present embodiment includes, for example, a silica source containing silicon, an aluminum source containing aluminum, an alkali source containing at least one selected from an alkali metal (M1) and an alkaline earth metal (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. can. The mixed gel and each component contained therein will be explained below.

[Mixed gel]
The mixed gel in this embodiment is a mixture containing a silica source, an aluminum source, a salt compound, and water as components, and optionally a phosphorus source, an alkali source, and an organic structure directing agent.

The silica source refers to the component in the mixed gel that is the raw material for the silicon contained in the zeolite produced from the mixed gel, and the aluminum source refers to the raw material for the aluminum contained in the zeolite produced from the mixed gel. The salt compound refers to a component that is a raw material for the alkali metal and/or alkaline earth metal contained in the zeolite produced from the mixed gel, and the alkali source refers to the component in the mixed gel. It refers to a component that adjusts the alkalinity of the gel, and the phosphorus source refers to a component in the mixed gel that is a raw material for the phosphorus contained in the zeolite produced from the mixed gel.

[Silica source]
The silica source is not particularly limited as long as it is commonly used, and examples thereof include crystalline silica, amorphous silica, silicic acid, silicates, organic silicate compounds, and the like. 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. It will be done. These compounds may be used alone or in combination. Here, aluminosilicate serves as both a silica source and an aluminum source.

Among these, fumed silica, colloidal silica, or precipitated silica is preferable because zeolite with a high degree of crystallinity tends to be obtained.

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

Among these, sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum acetate, aluminum hydroxide, aluminum chloride, and aluminum alkoxide are preferred because they tend to yield zeolites with high crystallinity. From the same point of view, sodium aluminate and aluminum hydroxide are more preferred, and sodium aluminate is even more preferred.

[Salt compound]
When producing zeolite, salt compounds are compounds containing alkali metals such as Li, Na, K, Rb, and Cs, and alkaline earth metals such as Ca, Mg, Sr, and Ba, which promote crystallization into a zeolite structure. be. 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 crystal formation of the GIS type skeleton. Further, the salt compounds may be used alone or in combination.

Specifically, salt compounds include, but are not limited to, sodium sulfate, sodium sulfite, sodium thiosulfate, sodium nitrite, sodium nitrate, sodium carbonate, sodium bicarbonate, sodium phosphate, sodium acetate, and formic acid. Sodium, sodium citrate, sodium oxalate, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium thionate, sodium silicate, sodium metasilicate, sodium tetraborate, sodium chlorate, sodium perchlorate, Sodium cyanide, sodium metastannate, sodium hexahydroxide stannate (IV), sodium hexacyanideferrate (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, thiopotassium, potassium silicate, potassium metasilicate, potassium tetraborate, potassium chlorate, potassium perchlorate, potassium cyanide, potassium metastannate, potassium hexahydroxydostan(IV), iron(II) hexacyanide. ) acid potassium, 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, odor Lithium chloride, lithium iodide, thiolithium, lithium silicate, lithium metasilicate, lithium tetraborate, lithium chlorate, lithium perchlorate, lithium cyanide, lithium metastannate, lithium hexahydroxide tin(IV) oxide, Lithium iron(II) hexacyanide, lithium permanganate, lithium chromate, lithium dichromate,
Rubidium sulfate, rubidium sulfite, rubidium thiosulfate, rubidium nitrite, rubidium nitrate, rubidium carbonate, rubidium hydrogen carbonate, rubidium phosphate, rubidium acetate, rubidium formate, rubidium citrate, rubidium oxalate, rubidium fluoride, rubidium chloride, odor Rubidium chloride, rubidium iodide, thiorbidium, rubidium silicate, rubidium metasilicate, rubidium tetraborate, rubidium chlorate, rubidium perchlorate, rubidium cyanide, rubidium metastannate, rubidium hexahydroxide tin(IV) oxide, Rubidium hexacyanidoferrate (II), rubidium permanganate, rubidium chromate, rubidium dichromate,
Cesium sulfate, cesium sulfite, cesium thiosulfate, cesium nitrite, cesium nitrate, cesium carbonate, cesium hydrogen carbonate, cesium phosphate, cesium acetate, cesium formate, cesium citrate, cesium oxalate, cesium fluoride, cesium chloride, odor Cesium chloride, cesium iodide, thiocesium, cesium silicate, cesium metasilicate, cesium tetraborate, cesium chlorate, cesium perchlorate, cesium cyanide, cesium metastannate, cesium hexahydroxide tin(IV) acid, hexacyanide Cesium iron(II) acid, cesium permanganate, cesium chromate, cesium dichromate,
Magnesium sulfate, magnesium sulfite, magnesium thiosulfate, magnesium nitrite, magnesium nitrate, magnesium carbonate, magnesium hydrogen carbonate, magnesium phosphate, magnesium acetate, magnesium formate, magnesium citrate, magnesium oxalate, magnesium fluoride, magnesium chloride, odor Magnesium chloride, magnesium iodide, thiomagnesium, magnesium silicate, magnesium metasilicate, magnesium tetraborate, magnesium chlorate, magnesium perchlorate, magnesium cyanide, magnesium metastannate, magnesium hexahydroxide stannate (IV), Magnesium hexacyanide 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, thiocalcium, calcium silicate, calcium metasilicate, calcium tetraborate, calcium chlorate, calcium perchlorate, calcium cyanide, calcium metastannate, calcium hexahydroxydotin(IV)ate, iron hexacyanide. (II) calcium acid, calcium permanganate, calcium chromate, calcium dichromate,
Strontium sulfate, strontium sulfite, strontium thiosulfate, strontium nitrite, strontium nitrate, strontium carbonate, strontium hydrogen carbonate, strontium phosphate, strontium acetate, strontium formate, strontium citrate, strontium oxalate, strontium fluoride, strontium chloride, odor Strontium oxide, strontium iodide, thiostronium, strontium silicate, strontium metasilicate, strontium tetraborate, strontium chlorate, strontium perchlorate, strontium cyanide, strontium metastannate, strontium hexahydroxide tin (IV), Strontium hexacyanide iron (II), strontium permanganate, strontium chromate, strontium dichromate,
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, odor Barium chloride, barium iodide, thiobarium, barium silicate, barium metasilicate, barium tetraborate, barium chlorate, barium perchlorate, barium cyanide, barium metastannate, barium hexahydroxydotin(IV) acid, hexacyanide Examples include barium iron(II) acid, barium permanganate, barium chromate, barium dichromate, and the like.

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

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

Among these, phosphoric acid aqueous solution, sodium phosphate, and aluminum phosphate are preferred because they tend to yield zeolite with a high degree of crystallinity. From the same viewpoint, phosphoric acid aqueous solution and sodium phosphate are more preferable, and phosphoric acid aqueous solution is even more preferable.

[Organic structure directing agent]
When producing zeolite by hydrothermally synthesizing 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 necessary.

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

Examples of organic structure directing agents include, but are not limited to, amines, quaternary ammonium salts, alcohols, ethers, amides, alkyl ureas, alkylthioureas, cyanoalkanes, and those containing nitrogen as a heteroatom. Alicycloheterocyclic compounds can be used, preferably alkylamines, more preferably isopropylamine.

Some of these salts include anions. Representative examples of such anions include, but are not limited to, halogen ions such as Cl ^- , Br ^- , and I ^- , hydroxide ions, acetate ions, sulfate ions, nitrate ions, carbonate ions, and carbonate ions. Contains hydrogen ions. Among these, halogen ions and hydroxide ions are preferred, and halogen ions are more preferred, from the viewpoint of facilitating crystal formation of a GIS type skeleton.

[Composition ratio of mixed gel]
In this embodiment, it is most important to add a salt compound containing an alkali metal and/or an alkaline earth metal in order to synthesize a GIS type zeolite with an appropriate structure. In the production of zeolite, the silica source and aluminum source dissolved in an aqueous solvent react and crystallize while being dissolved, but the bonding mode of Si and Al in the zeolite skeleton and their abundance ratio are adjusted by adding a salt compound. This makes it possible to synthesize GIS having an ideal crystal structure.

Also, the ratio of cations provided by the addition of salt compounds to the aluminum source is of particular importance. The ratio of the cations provided by the salt compounds in the mixed gel to the aluminum source is expressed as the additive molar ratio of the amount of cations E to Al ₂ O ₃ , ie E/Al ₂ O ₃ . Here, E represents the molar amount of cations produced from the salt compound. For example, when sodium nitrate is added, Na ⁺ is generated as a cation species, and when sodium carbonate is used, 2Na ⁺ is generated, and the addition of the salt compound produces The added molar amount of the resulting cationic species is represented by E. E/Al ₂ O ₃ can change the aggregation state of Al in the mixed gel, leading to controlling the randomness of Al during zeolite crystal formation, and making it possible to create GIS type zeolite with an ideal crystal structure. It becomes possible to synthesize. From the above viewpoint, it is necessary to optimally control E/Al ₂ O ₃ , and E/Al ₂ O ₃ is preferably 0.1 or more and 100.0 or less, more preferably 0.5 or more and 80.0 or less. It is 0 or less, more preferably 0.8 or more and 50.0 or less.

Furthermore, the ratio of water to OH ^- (H ₂ O/OH ^- ) in the mixed gel is important for synthesizing a GIS-type zeolite with an appropriate SAR. OH ^- is derived from inorganic hydroxides such as NaOH and Ca(OH) ₂ used as alkali sources, and organic hydroxides such as tetraethylammonium ^hydroxide . It does not include those expressed as oxides or OH ^- , which is emitted when the hydrate is dissolved in water. The production of zeolite involves a reaction in which the silica source, aluminum source, and alkali source dissolved in an aqueous solvent crystallize, and a portion of the zeolite is eluted into an alkaline solvent, resulting in an equilibrium between crystallization and redissolution. Adding OH ^- derived from inorganic hydroxides such as NaOH and Ca(OH) ₂ and organic hydroxides such as tetraethylammonium hydroxide to the mixed gel changes the equilibrium between crystallization and redissolution. It means to move it to the side. Re-dissolution proceeds from amorphous or low-crystalline parts. Therefore, by appropriately increasing OH ^-, incomplete crystalline portions can be redissolved and crystallized again, which can be repeated to increase the formation of an ideal crystal structure. On the other hand, if OH ^- increases too much, excessive dissolution progresses, resulting in failure to obtain crystals or the formation of other crystal phases, such as ANA type zeolite, which has a more stable structure. Also, dissolved alumina is more reactive than silica, and alumina is more easily incorporated into crystals. Therefore, by appropriately adjusting OH ^- , we can adjust the speed of crystallization and redissolution, optimize the ratio of silica and alumina incorporated into the crystals, and optimize the SAR of the synthesized GIS type zeolite. I can do it.

If the ratio of water to alumina (H ₂ O/Al ₂ O ₃ ) is high, the components in the mixed gel will be more easily dispersed evenly, but if it is too high, the crystallization rate will be significantly reduced. Therefore, in order to synthesize a GIS- _type zeolite with an optimal SAR and an optimal crystal structure, it is necessary to control H ₂ O/OH ^- and to /Al ₂ O ₃ must be optimally controlled.

From the above viewpoint, H ₂ O/Al ₂ O ₃ and H ₂ O/OH ⁻ are preferably 100≦H ₂ O/Al ₂ O ₃ ≦780 and 50≦H ₂ O/OH ⁻ ≦1000, More preferably 120≦H ₂ O/Al ₂ O ₃ ≦778 and 60≦H ₂ O/OH ^- ≦800, and even more preferably 150≦H ₂ O/Al ₂ O ₃ ≦775 and 70≦H ₂ O. /OH ^- ≦700.

The ratio of silica source to aluminum source in the mixed gel is expressed as the molar ratio of the oxides of the respective elements, ie, SiO ₂ /Al ₂ O ₃ . (Note that the ratio of the synthesized zeolite and the silica-alumina ratio of the mixed gel do not match.The silica-alumina ratio of the synthesized zeolite is determined by other compositions and synthesis conditions.)

The SiO ₂ /Al ₂ O ₃ in this mixed gel is not particularly limited as long as it is in a ratio that allows the formation of zeolite, but since it tends to suppress the formation of zeolite having a skeleton different from the GIS type skeleton, 3. It is preferably 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.

The ratio of the aluminum source to the alkali metal and alkaline earth metal in the mixed gel is expressed as the additive molar ratio of M1 ₂ O and M2O to Al ₂ O ₃ , i.e. (M1 ₂ O + M2O)/Al ₂ O ₃ (where: M1 represents an alkali metal, and M2 represents an alkaline earth metal. These are calculated as oxides.) Note that this (M1 ₂ O + M2O)/Al ₂ O ₃ is preferably 1.5 or more, more preferably 1.6 or more, from the viewpoint of easier crystal formation of the GIS type skeleton. More preferably, it is 1.65. (M1 ₂ O + M2O)/Al ₂ O ₃ is preferably 15.0 or less, more preferably 12.0 or less, from the viewpoint of suppressing the formation of zeolite having a skeleton different from the GIS type skeleton, and more preferably 12.0 or less. .0 or less is more preferable.

The ratio of phosphorus source to aluminum source in the mixed gel is expressed as the molar ratio of the oxides of the respective elements, ie, P ₂ O ₅ /Al ₂ O ₃ . This P ₂ O ₅ /Al ₂ O ₃ ratio is not particularly limited as long as zeolite can be formed, but it is less than 1.0 because it tends to suppress the formation of zeolite having a skeleton different from the GIS type skeleton. is preferable, 0.6 or less is more preferable, 0.4 or less is still more preferable, and 0 is especially preferable.

When an organic structure directing agent is included 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 Al ₂ O ₃ , that is, R/Al ₂ O ₃ (R represents an organic structure directing agent here). The value is preferably less than 7.0, and more preferably 6.0 or less, because crystal formation of the GIS type skeleton becomes easier and/or the synthesis time is shortened, resulting in excellent economic efficiency when producing zeolite. It is preferably 5.0 or less, and 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. In order to remove the organic structure directing agent, it is necessary to heat it to at least 400° C., but since the crystals of GIS type zeolite collapse and become amorphous at 350° C. or higher, it is preferable to use less organic structure directing agent. From that point of view, R/Al ₂ O ₃ is preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 3.0 or less.

As described above, the method for producing GIS type zeolite according to the present embodiment uses a silica source containing silicon, an aluminum source containing aluminum, and at least one metal selected from an alkali metal (M1) and an alkaline earth metal (M2). , a salt compound containing at least one selected from alkali metals (M1) and alkaline earth metals (M2), a phosphorus source, and water. When calculating the molar ratio of each component in the mixed gel as the oxide of each element for silicon, aluminum, alkali metal (M1) and alkaline earth metal (M2), and the phosphorus source, the following formula (1), ( 2), (3), (4), (5) and (6) molar ratios α, β, γ, δ, ε, ζ are 0.1≦α≦100.0, 3.0 It is preferable to satisfy ≦β≦70.0, 1.5≦γ≦15.0, 0≦δ<1.0, 100≦ε≦780 and 50≦ζ≦1000, and 0.5≦α≦80. More preferably, 0, 3.5≦β≦65.0, 1.6≦γ≦12.0, 0≦δ≦0.6, 120≦ε≦778 and 60≦ζ≦800, It is further satisfied that 8≦α≦50, 4.0≦β≦60.0, 1.65≦γ≦10.0, 0≦δ≦0.4, 150≦ε≦775 and 70≦ζ≦700. preferable. It is particularly preferable that the GIS type zeolite according to the present embodiment is obtained by the method for producing a GIS type zeolite according to the present embodiment described above.
α=E/Al ₂ O ₃ (1)
β=SiO ₂ /Al ₂ O ₃ (2)
γ=(M1 ₂ O+M2O)/Al ₂ O ₃ (3)
δ=P ₂ O ₅ /Al ₂ O ₃ (4)
ε=H ₂ O/Al ₂ O ₃ (5)
ζ=H ₂ O/OH- (6)

Furthermore, in the method for producing a GIS type zeolite according to the present 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 expressed by the following formula (7) satisfies η≦4.
η=R/Al ₂ O ₃ (7)

Although it is not always necessary to have a seed crystal in the mixed gel, the GIS type zeolite according to the present embodiment can also be obtained by adding a previously produced GIS type zeolite to the mixed gel as a seed crystal.

[Mixed gel preparation process]
The preparation process of the mixed gel is not particularly limited, but for example, 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 are mixed at once or in multiple stages. and an aging step of the mixture obtained in this mixing step.

In the mixing step, these components including 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 can be mixed all at once or in multiple stages.

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, it may be performed with or without stirring. The stirring method is not particularly limited as long as it is a commonly used stirring method, but specific examples include methods using blade stirring, vibration stirring, rocking stirring, centrifugal stirring, and the like.

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

The temperature of the mixing step is not particularly limited as long as it is a commonly used temperature, and examples thereof include -20°C or more and less than 80°C.

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

The aging step may be performed either by standing still or by stirring. When stirring in the ripening process, there is no particular limitation as long as it is a generally used stirring method, but specific examples include methods using blade stirring, vibration stirring, rocking stirring, centrifugal stirring, etc. .

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

The temperature of the aging step is not particularly limited as long as it is a commonly used temperature, but for example, it may be -20°C or higher and lower than 80°C.

The time for the aging process is not particularly limited and can be appropriately selected depending on the temperature of the aging process, and for example, may be more than 0 minutes and 1000 hours or less.

Zeolite is considered to undergo dissolution of raw materials and generation and re-dissolution of zeolite precursors during the raw material mixing process and aging process. In order to form a large periodic structure containing an 8-membered ring without causing defects, it is preferable that the formation of the zeolite precursor does not proceed excessively. Furthermore, if the formation of the zeolite precursor progresses excessively, the production of ANA type zeolite, which has a more stable structure, tends to increase, so it is preferable not to ripen it excessively. On the other hand, it is preferable that the raw materials are sufficiently mixed so that the raw material gel is uniform. The combined time of the mixing step and aging step is not particularly limited, and may be adjusted as appropriate based on the composition of the raw materials, etc., in order to obtain a zeolite with an appropriate structure. Typically, the above-mentioned time is preferably 1 minute or more and less than 24 hours, more preferably 3 minutes or more and less than 23 hours, further preferably 10 minutes or more and 18 hours or less, even more preferably 12 minutes or more and 15 hours or less, and even more preferably 12 minutes or more and less than 15 hours. The time period is more preferably 6 hours or more.

[Hydrothermal synthesis process]
The method for producing GIS-type zeolite according to the present embodiment preferably further includes a hydrothermal synthesis step in which the hydrothermal synthesis temperature is 80°C to 200°C, and the hydrothermal synthesis temperature is 100°C to 180°C. is more preferable. That is, hydrothermal synthesis is preferably carried out by holding the mixed gel obtained in the preparation step at a predetermined temperature for a predetermined period of time under stirring or in a stationary state.

The temperature for hydrothermal synthesis is not particularly limited as long as it is a commonly used temperature, but it is preferably 80° C. or higher because it shortens the synthesis time and is economically efficient in producing zeolite. From the viewpoint of suppressing the formation of zeolite having a skeleton different from the GIS type skeleton, the temperature is more preferably 90°C or higher, and even more preferably 100°C or higher. From the viewpoint of suppressing the formation of zeolite having a skeleton different from the GIS type skeleton, the temperature is more preferably 200°C or lower, even more preferably 180°C or lower, and even more preferably 170°C or lower. The temperature for hydrothermal synthesis may be constant or may be changed stepwise.

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 hydrothermal synthesis. The hydrothermal synthesis time 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 highly crystalline GIS type zeolite, the heating time is more preferably 24 hours or more. From the viewpoint of excellent economic efficiency in producing zeolite, the hydrothermal synthesis time is preferably 30 days or less, more preferably 20 days or less, and even more preferably 10 days or less.

In the hydrothermal synthesis process, the container in 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 it is under gas pressure that does not inhibit crystallization. In such cases, it is preferable to place the mixture 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 long shape, and a horizontally long shape can be used, for example.

When stirring the mixed gel in the pressure container, the pressure container is rotated vertically and/or horizontally, preferably in the vertical direction. When rotating the pressure container in the vertical direction, 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.

In order to preferably stir the mixed gel in the hydrothermal synthesis step, there is a method in which a vertically elongated pressure vessel is used and the vessel is rotated in the vertical direction.

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

The separated product may be used as it is or may be washed with water or a prescribed solvent. If necessary, the separated material can 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 for drying is not particularly limited as long as it is a commonly used atmosphere, but usually an air atmosphere or an atmosphere to which oxygen or an inert gas such as nitrogen or argon is added is used.

[Firing process]
If necessary, the GIS type zeolite can be calcined and used. The firing 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 remaining proportion can be reduced, so it is preferably 300°C or higher, and 350°C or higher. It is more preferable that The temperature is more preferably 360° C. or higher because the firing time is short and the zeolite is produced economically. Since the crystallinity of zeolite tends to be maintained, the temperature is preferably lower than 450°C, more preferably 420°C or lower, and even more preferably 400°C or lower.

The firing time is not particularly limited as long as the organic structure directing agent is sufficiently removed, and can be appropriately selected depending on the firing temperature, but it tends to reduce the proportion of the organic structure directing agent remaining. Therefore, the duration 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.

The firing atmosphere is not particularly limited as long as it is a commonly used atmosphere, but usually an air atmosphere or an atmosphere to which oxygen or an inert gas such as nitrogen or argon is added is used.

[Cation exchange]
If necessary, the GIS type zeolite can be cation-exchanged into a desired cation type. Cation exchange includes, but is not limited to, carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, ammonium carbonate, or sodium nitrate. Nitrates such as potassium nitrate, lithium nitrate, rubidium nitrate, cesium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate, and ammonium nitrate, or carbonate ions and nitrate ions contained in the carbonates and nitrates, can be converted into halide ions, sulfate ions, Salts changed to carbonate ions, hydrogen carbonate ions, acetate ions, phosphate ions or hydrogen phosphate ions, and acids such as nitric acid and hydrochloric acid can be used.

The temperature of cation exchange is not particularly limited as long as it is a general cation exchange temperature, but is usually from room temperature to 100°C or less.

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

The separated product may be used as it is or may be washed with water or a prescribed solvent. If necessary, the separated material can 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 for drying is not particularly limited as long as it is a commonly used atmosphere, but usually an air atmosphere or an atmosphere to which oxygen or an inert gas such as nitrogen or argon is added is used.

Furthermore, ammonium type zeolite can also be converted into proton type zeolite by calcining the zeolite.

(carrier)
The zeolite molded article according to this embodiment preferably includes a carrier. Examples of the carrier include inorganic binders and organic binders. In addition, when the content of a carrier with a high elastic modulus is increased, the elastic modulus E of the zeolite molded body tends to increase, and when the content of a carrier with a low elastic modulus is increased, the elastic modulus E of the molded body also tends to decrease. be. Therefore, it is preferable to adjust the content of the carrier so that the modulus of elasticity falls within a predetermined range, taking into consideration the strength and performance required depending on the application.

Examples of the inorganic binder 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, and silica and alumina are 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% by mass, more preferably 5 to 90% by mass, and even more preferably 8 to 80% by mass, based on the total amount (100% by mass) of the zeolite molded body.

Examples of the organic binder include cellulose, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, latex, polyvinyl alcohol, vinyl acetate, polyvinyl acetal, vinyl chloride, acrylic, polyamide, urea, melamine, phenolic resin, polyester, polyurethane, polyamide, and polyester. Examples include benzimidazole, 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, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and polyvinyl alcohol are preferred, and cellulose, methylcellulose, and polyvinyl alcohol are more preferred, from the viewpoint of surface bonding with GIS type zeolite.
The content of the organic binder is preferably 1 to 99% by mass, more preferably 5 to 90% by mass, and even more preferably 8 to 80% by mass, based on the total amount (100% by mass) of the zeolite molded body.

In addition, it is preferable to contain one or more types of each of the above-mentioned inorganic binder and organic binder.

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, based on the total amount (100% by mass) of the zeolite molded body. When the content of the carrier is increased, the strength of the molded body tends to increase, but the content of the zeolite itself tends to decrease. Therefore, the content of the carrier may be adjusted in consideration of the strength and performance required depending on the application.

The shape of the zeolite molded body is not particularly limited, and examples thereof include spherical, cylindrical, elliptical, bag-shaped, trefoil-shaped, ring-shaped, and powder-shaped. Among these, spherical and cylindrical shapes are more preferable. The size of the molded body is not particularly limited, but it changes depending on the conditions in which the molded body is used. For example, when using a process that uses a molded body in a state other than a fluidized state, such as a fixed bed or a moving bed, it is preferably cylindrical with 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. The length of the cylinder is more preferably 3 mm or more and 10 mm or less, and even more preferably 3 mm or more and 8 mm or less. The diameter of the cylinder is more preferably 2 mm or more and 4 mm or less.
The above length and diameter are determined by measuring the pellet length and diameter on three samples using a caliper with a minimum reading of 0.1 mm or less, and using the average value as the length and diameter. It can be measured and adjusted to the above-mentioned range by, for example, operations such as classification.
When used in a process in which a molded body is fluidized such as a fluidized bed, it is preferable that the powder has a particle diameter of 20 μm or more and 300 μm or less. The particle diameter is more preferably 20 μm or more and 200 μm or less, and even more preferably 30 μm or more and 100 μm or less. The particle size can be measured as a median diameter (D50) using a laser diffraction/scattering particle size analyzer (MT3000 manufactured by Microtrac) according to the attached manual.

The compressive strength of the zeolite molded body according to the present embodiment is preferably 1.0 MPa or more, more preferably 2.2 MPa or more, and still more preferably 3.4 MPa or more. In particular, when the zeolite molded article according to the present embodiment is in powder form, it is preferable that the above-mentioned range is satisfied.
The above compressive strength can be measured as the average value of the values obtained by measuring 20 times using a micro compression tester (MCT-W500 manufactured by Shimadzu Corporation, compressive strength measurement). can be adjusted within the above-mentioned range.

The breaking strength of the zeolite molded body according to this embodiment is preferably 5N or more, more preferably 10N or more, and still more preferably 20N or more. In particular, when the zeolite molded body according to the present embodiment is a pellet, it is preferable that the above-mentioned range is satisfied.
The above breaking strength can be measured as the average value of the values obtained by measuring each 20 times using a digital hardness meter (KHT-40N manufactured by Fujiwara Seisakusho Co., Ltd., indenter 3 mm, breaking strength measurement). It can be adjusted within the above range by changing the firing temperature and firing time.

[Method for producing zeolite molded body]
The method for producing the zeolite molded body according to the present embodiment is not particularly limited, but includes a raw material mixing step (X) of mixing and preparing the zeolite according to the present embodiment and other optional components (for example, a carrier); The method may include a shaping treatment step (Y) in which the prepared raw material is subjected to a shaping treatment to obtain a precursor, and a firing step (Z) in which the precursor is fired to obtain a zeolite molded body.
Other methods for producing zeolite molded bodies include extrusion processing, injection treatment, injection/casting treatment, rolling granulation treatment, compression molding treatment, and spray drying, if the desired zeolite molded body can be obtained. The molding may be performed by processing or by a combination of two or more of these methods.

[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, for example, 10°C to 80°C, more preferably 15°C to 60°C. For example, when the raw materials are mixed in a slurry state, as in the case of spray drying, the evaporation of water in the raw materials tends to be suppressed when the temperature of the raw materials is 80°C or lower; In the above cases, freezing in the slurry tends to be suppressed. In addition, for example, in extrusion molding process, if the clay-like region from the funicular to the capillary is formed after mixing the raw materials, if the temperature of the raw materials is below 80°C, the evaporation of water from the clay will be suppressed, and the moisture in the clay will be reduced. It tends to be easy to keep the amount constant, and when the temperature of the raw material is 10°C or higher, it tends to suppress the freezing of water in the clay. Any means can be used as the stirring means when preparing the raw materials. For example, when the state after mixing the raw materials is in the form of a slurry, as in the case of spray drying, a stirring blade is preferably used. Specific examples of the blades used for stirring include propeller shapes, paddle shapes, flat paddle shapes, turbine shapes, and cone shapes. Further, in order to perform efficient stirring, a baffle plate or the like may be installed in the tank. The optimum number of stirrers may be selected depending on the size of the catalyst raw material liquid tank, the shape of the stirring blades, etc. In this embodiment, the total stirring time of the raw materials is preferably 1 minute to 24 hours, more preferably 10 minutes to 5 hours, and even more preferably 15 minutes to 3 hours. When the stirring time of the mixed liquid is 1 minute or more, the composition in the raw material tends to become uniform, and when it is 24 hours or less, the influence of water evaporation in the raw material tends to be reduced. Further, when the mixture becomes clay-like in the funicular to capillary region after mixing the raw materials, as in extrusion molding, for example, it is preferable to select a mixer, kneader, etc. according to the condition of the raw materials. In this embodiment, the total time for mixing and kneading the raw materials is preferably 1 minute to 24 hours, more preferably 2 minutes to 5 hours, and still more preferably 3 minutes to 3 hours. When the stirring time of the mixed liquid is 1 minute or more, the composition in the raw material tends to become uniform, and when it is 24 hours or less, the influence of water evaporation in the raw material tends to be reduced. In addition, when an organic binder such as methyl cellulose that is easily gelled by heat is blended, the internal temperature of the mixer or kneader is maintained at a value lower than the thermal gelation temperature of the organic binder. It is possible to suppress gelation of the binder, and it tends to be easier to obtain raw materials with a uniform composition.
Furthermore, the clay-like raw material can be allowed to stand and mature. As it ages, water tends to spread more easily between the raw zeolites, improving moldability, and replaces air and other gases that exist between the zeolites, resulting in a more dense molded product. It is in.

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

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

When using an extrusion molding process as the molding process (Y), the extrusion molding machine is not particularly limited, but examples include a screw type, roll type, blade type, self-molding type, ram type, disk pelleter type, etc. Can be mentioned. Among these, it is particularly preferable to carry out the extrusion molding process using a roll type, screw type, or disk pelleter type extrusion molding machine.

When compression molding is used as the molding process (Y), examples of the compression molding machine include, but are not limited to, uniaxial press molding, hot press molding, and the like.

In the spray drying process, for example, atomization of the slurry can be performed by a rotating disk method, a two-fluid nozzle method, a high-pressure nozzle method, etc., which are usually carried out industrially, but it is especially preferable to use the rotating disk method. is preferred. As the 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.

[Firing process (Z)]
The firing temperature in the firing step (Z) is not particularly limited as long as it is a commonly used temperature, but it is preferably less than 550°C because it tends to ensure strength while maintaining the crystallinity of the zeolite. , more preferably 530°C or lower, and even more preferably 500°C or lower. Further, the firing temperature is preferably 110°C or higher, more preferably 120°C or higher.
The firing time in the firing step (Z) is not particularly limited as long as the carrier is sufficiently dried and sintered, and can be appropriately selected depending on the firing temperature. It is preferable that the period of time is 20 days or less, more preferably 10 days or less, and even more preferably 7 days or less.
The firing atmosphere in the firing step (Y) is not particularly limited as long as it is a commonly used atmosphere, but usually an air atmosphere or an atmosphere to which oxygen or an inert gas such as nitrogen or argon is added is used.
Firing in the firing step (Z) can be performed using a firing furnace such as a rotary furnace, a tunnel furnace, a muffle furnace, or the like.

The applications of the zeolite molded body according to this embodiment are not particularly limited, and include, for example, separation agents or separation membranes for various gases and liquids, electrolyte membranes for fuel cells, fillers for various resin molded bodies, and membrane reactors. or catalysts for hydrocracking, alkylation, etc., catalyst carriers for supporting metals, metal oxides, etc., adsorbents, desiccants, detergent aids, ion exchange agents, wastewater treatment agents, fertilizers, food additives, cosmetic additives. It can be used as, etc.
Among those described above, the zeolite molded body according to this embodiment can be suitably used as a carbon dioxide adsorbent.

[Adsorption device]
The adsorption device according to this embodiment includes the zeolite molded body according to this embodiment. Since the adsorption device according to the present embodiment is configured as described above, it can sufficiently adsorb carbon dioxide and has high selectivity of carbon dioxide adsorption with respect 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.

The adsorption device according to this embodiment includes a zeolite molded body containing the zeolite according to this embodiment, and may have the configuration example shown in FIG. 2. The adsorption device 1 according to the present embodiment illustrated in FIG. The zeolite molded body 4 is provided. As the filter 3, for example, a filter made of quartz can be used. For example, when using the adsorption device 1 to separate carbon dioxide from natural gas, natural gas is introduced from the upper line, impurities are removed by the filter 3, and then the zeolite molded body 4 selectively removes carbon dioxide. can be adsorbed and removed, and methane-rich gas can be taken out from the lower line. However, the target to be supplied 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.

[Production method of purified gas]
The method for producing purified gas according to the present embodiment uses an adsorption device including the zeolite molded body according to the present embodiment, and uses two types selected from the group consisting of H ₂ , N ₂ , O ₂ , CO, and hydrocarbons. One or more selected from the group consisting of CO ₂ , H ₂ O, He, Ne, Cl ₂ , NH ₃ , and HCl is separated from the mixture containing the above gases. In this embodiment, one or more gases selected from the group consisting of CO 2 and H ₂ O are separated from one or more gases selected from the group consisting of N _{2 ,} O ₂ , CO, and hydrocarbons. It is preferable. Note that hydrocarbons include, but are not particularly limited to, methane, ethane, ethylene, propane, propylene, 1-butene, 2-butene, 2-methylpropene, dimethyl ether, acetylene, and the like.

The GIS type zeolite according to the present embodiment has a particularly large adsorption capacity for CO ₂ , and physical adsorption that does not involve chemical bonds is observed. The separation method using the zeolite molded body according to the present embodiment is not particularly limited, but a method that requires low energy during regeneration of the adsorbent and is excellent in economic efficiency is preferred. Specific examples of such methods are not particularly limited, but it is preferable to use any one of a pressure swing adsorption separation method, a temperature swing adsorption separation method, or a pressure/temperature swing adsorption separation method. Pressure swing adsorption separation method (PSA) is a method that lowers the pressure during desorption than the pressure during gas adsorption, and utilizes the difference between the amount of adsorption at high pressure and the amount of adsorption at low pressure. This is a method of separating gases. In addition, the thermal swing adsorption separation method (TSA) is a method in which the temperature during desorption is higher than the temperature during gas adsorption, and the difference between the amount of adsorption at low temperatures and the amount of adsorption at high temperatures is utilized. This is a method of separating gases. Furthermore, a method that combines these methods is a pressure and temperature swing adsorption and desorption method (PTSA). These methods can be carried out under various known conditions.

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

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

[X-ray diffraction; crystal structure analysis]
X-ray diffraction was performed according to the following procedure.
(1) The zeolite molded bodies (dried products) obtained in each of the Examples and Comparative Examples were used as samples and ground in an agate mortar. Further, 10% by mass of crystalline silicon (manufactured by Rare Metallic Co., Ltd.) was added and mixed in an agate mortar until uniform, which was used as a sample for structural analysis.
(2) The sample of (1) above was uniformly fixed on a non-reflective sample plate for powder, and crystal structure analysis was performed by X-ray diffraction under the following conditions.
X-ray diffraction device (XRD): Rigaku powder X-ray diffraction device “RINT2500 model” (product name)
X-ray source: Cu tube (40kV, 200mA)
Measurement temperature: 25℃
Measurement range: 5~60° (0.02°/step)
Measurement speed: 0.2°/min Slit width (scattering, divergence, light reception): 1°, 1°, 0.15mm

[ ²⁹ Si-MAS-NMR spectrum, SAR measurement]
The SAR of zeolite in a zeolite molded body can be determined by measuring ²⁹ Si-MAS-NMR. First, to adjust the humidity of the zeolite, water was filled at the bottom of a desiccator, and the zeolite placed in a sample tube was held on top of the desiccator for 48 hours. After performing humidity conditioning treatment, ²⁹ Si-MAS-NMR measurements were performed under the following conditions.
Equipment: JEOL RESONANCE ECA700
Magnetic field strength: 16.44 T ( ^1H resonance frequency 700MHz)
Measurement nucleus: ²⁹ Si
Resonance frequency: 139.08MHz
NMR tube: 4mmφ (zirconia rotor)
Measurement method: DD/MAS (dipolar decoupling magic angle spinning)
Pulse width: 45°
Waiting time: 50sec
Total number of times: 800 times (measurement time: approximately 22 hours)
MAS: 10,000Hz
Chemical shift standard: silicone rubber (-22.34 ppm) external standard A molded article containing zeolite shows the following five peaks in the ²⁹ Si-MAS-NMR spectrum.
(1) Q4 (0Al): A peak of Si that is not bonded to Al through oxygen (2) Q4 (1Al): A peak of Si that is bonded to one Al through oxygen (3) Q4 (2Al): Peak of Si bonded to 2 Al via oxygen (4) Q4(3Al): Peak of Si bonded to 3 Al via oxygen (5) Q4(4Al ): peak of Si bonded to four Al atoms via oxygen In addition, in the ²⁹ Si-MAS-NMR spectrum, these peak positions generally exist from -112 ppm to -80 ppm, and in a high magnetic field From the side, it can be assigned to Q4 (0Al), Q4 (1Al), Q4 (2Al), Q4 (3Al), and Q4 (4Al). The peak position may vary depending on the cation species present in the zeolite skeleton, but generally the peak position exists within the following range.
(1) Q4 (0Al): -105ppm to -112ppm
(2) Q4 (1Al): -100ppm to -105ppm
(3) Q4 (2Al): -95ppm to -100ppm
(4) Q4 (3Al): -87ppm to -95ppm
(5) Q4 (4Al): -80ppm to -87ppm
²⁹ The peak area intensity of the Si-MAS-NMR spectrum was analyzed using Gaussian and Lorentz functions using the analysis program dmfit (#202000113 version), and the amplitude (height of the maximum value of the spectrum), position (spectral position) , ppm), width (full width at half maximum of the spectrum, ppm), and Gauss/Lorentz ratio (xG/(1-x)L), which are obtained by optimizing and calculating the four parameters using a least squares algorithm. The peak areas of Q4(0Al), Q4(1Al), Q4(2Al), Q4(3Al), Q4(4Al) obtained in this way are A_Q4(0Al), A_Q4(1Al), A_Q4(2Al), A_Q4( 3Al), A_Q4(4Al), and the total value of A_Q4(0Al), A_Q4(1Al), A_Q4(2Al), A_Q4(3Al), A_Q4(4Al) is A_total, and 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

[Evaluation of embrittlement resistance of zeolite molded body in _CO2 atmosphere]
The embrittlement resistance of the zeolite molded bodies obtained in Examples and Comparative Examples in a CO ₂ atmosphere was evaluated using the following procedure.
(1) 100 g of the zeolite molded body was weighed, the short axis of the zeolite molded body was measured, and the average value of the short axis of the zeolite molded body was defined as ds. A sieve with the largest opening size smaller than ds was selected and prepared from the published openings of JIS Z8801-1, and the zeolite molded body remaining on the sieve was evaluated for embrittlement resistance in a CO ₂ atmosphere. used for This was used as a test sample.
(2) The test sample was dried under _N2 atmosphere at 200°C for 3 hours. After cooling to room temperature under a _N2 atmosphere, it was exposed to room temperature _CO2 for 30 minutes.
(3) After measuring the mass W1 of the test sample after exposure to CO ₂ , it was passed through a sieve with the above-mentioned openings, and the mass W2 of the zeolite molded body that passed through the sieve was measured. The value calculated using formula (1) is defined as the powdering rate [mass%] of the zeolite molded body, and the lower the powdery rate of the zeolite molded body, the more embrittlement resistance it has in a CO ₂ atmosphere. And so.

[Alkali metal content]
Zeolite is thermally dissolved in an aqueous sodium hydroxide solution or aqua regia, and the appropriately diluted solution is used for ICP-emission spectrometry analysis (hereinafter also referred to as "ICP-AES", SPS3520UV-DD manufactured by Hitachi High-Tech Science Co., Ltd.: device name). The concentration of alkali metals in zeolite was measured by The content of potassium and lithium in the zeolite was 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 manner.

[CO ₂ adsorption amount and hysteresis amount; gas adsorption/desorption isotherm measurement]
Gas adsorption/desorption isotherm measurement was performed using the following procedure.
(1) A sample of 0.2 g of the dried product obtained in each Example and Comparative Example was placed in a 12 mm cell (manufactured by Micro Meritics).
(2) The sample placed in the cell of (1) above was placed in a gas adsorption measurement device “3-Flex” (trade name) manufactured by Micro Meritics, and heated and vacuum degassed at 250°C and 0.001 mmHg or less for 12 hours. did.
(3) The sample placed in the cell after the treatment in (2) above is placed in constant temperature circulating water at 25℃, and after the sample temperature reaches 25±0.2℃, liquefied carbon dioxide gas (Sumitomo Seika Co., Ltd. Absolute pressure was measured from 0.25 to 760 mmHg. During the above measurement, the pressure was measured over time, and when the pressure fluctuation became 0.001%/10 seconds or less, it was determined that the saturated adsorption amount had been reached, and the CO ₂ adsorption amount at 25°C (unit: :cc/g).
(4) Following the measurement in (3) above, depressurization treatment was carried out over time to an absolute pressure of 760 to 0.25 mmHg, and the desorption isotherm of carbon dioxide was measured. Note that, as in the case of (3), the equilibrium judgment was performed under the assumption that the pressure fluctuation was 0.001%/10 sec or less.
(5) As an index showing the amount of hysteresis in the adsorption/desorption isotherm of carbon dioxide, the equilibrium adsorption amount at the adsorption isotherm of 75 mmHg measured in (3) and the equilibrium adsorption amount at the desorption isotherm of 75 mmHg measured in (4) When the amounts were respectively q(Ad) and q(De), q(Ad)/q(De) was used as an index indicating the amount of hysteresis. When q(Ad)/q(De)=1.00, it indicates that there is no hysteresis, and the smaller q(Ad)/q(De), the greater the hysteresis.

[CH ₄ adsorption amount; gas adsorption isotherm measurement]
Gas adsorption isotherm measurement was performed using the following procedure.
(1) A sample of 0.2 g of the dried product obtained in each Example and Comparative Example was placed in a 12 mm cell (manufactured by Micro Meritics).
(2) The sample placed in the cell of (1) above was placed in a gas adsorption measurement device “3-Flex” (trade name) manufactured by Micro Meritics, and heated and vacuum degassed at 250°C and 0.001 mmHg or less for 12 hours. did.
(3) The sample placed in the cell after the treatment in (2) above was placed in constant temperature circulating water at 35°C, and after the sample temperature reached 25 ± 0.2°C, methane gas (manufactured by Fujii Shoji Co., Ltd., purity (99.99% by mass or more) was used to measure absolute pressures from 0.25 to 760 mmHg. During the above measurement, the pressure was measured over time, and when the pressure fluctuation became 0.001%/10 seconds or less, it was determined that the saturated adsorption amount had been reached, and the CH ₄ adsorption amount at 25°C (unit: :cc/g).

[Measurement of pellet length and diameter]
When the zeolite molded body was in the form of a pellet, the length and diameter of the pellet were measured using a caliper method. In this measurement, measurements were performed on three samples using a caliper with a minimum reading value of 0.1 mm or less, and the average value was taken as the length and diameter.

[Manufacture example 1]
61.93 g of water, 0.403 g of sodium hydroxide (NaOH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 3.39 g of sodium nitrate (NaNO ₃ , manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and sodium aluminate (NaAlO ₂ , A mixed gel was prepared by mixing 1.64 g of Fuji Film (manufactured by Wako Pure Chemical Industries, Ltd.) and 10.82 g of colloidal silica (Ludox AS-40, solid content concentration 40% by mass, manufactured by Grace) and stirring for 30 minutes. The composition of the mixed gel is α=E/Al ₂ O ₃ =4.53, β=SiO ₂ /Al ₂ O ₃ =8.17, γ=Na ₂ O/Al ₂ O ₃ =3.99, δ= P ₂ O ₅ /Al ₂ O ₃ =0.00, ε=H ₂ O/Al ₂ O ₃ =431.0, ζ=H ₂ O/OH ^- =376.7, η=R/Al ₂ O ₃ =0.00. The mixed gel was placed in a 200 mL stainless steel micro cylinder (manufactured by HIRO COMPANY) containing a fluororesin inner cylinder, and stirred at a stirring speed of 30 rpm at 135°C using a stirring type constant temperature bath (manufactured by HIRO COMPANY) that allowed the micro cylinder to rotate vertically. Hydrothermal synthesis was carried out for 4 days. After filtering the product and drying at 120°C, a powdered zeolite was obtained. It was confirmed from the XRD spectrum that the obtained zeolite was a GIS type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica alumina were observed, it was evaluated that it was a high purity GIS type zeolite.

The silica-alumina ratio of the obtained zeolite was calculated from the ²⁹ Si-MAS-NMR spectrum, and the result was SAR=6.90. The contents of potassium and lithium in the zeolite were Z/T=0.00 (=K/T). From the ²⁹ Si-MAS-NMR spectrum, (a+d)/(b+c)=0.305. When the adsorption isotherm and desorption isotherm of CO ₂ of the obtained GIS type zeolite were measured, the adsorption amount at 760 mmHg was 82.2 cc/g, and q(Ad)/q(De) = 0.984. Ta. Further, when the CH ₄ adsorption isotherm was similarly measured, the adsorption amount at 760 mmHg was 6.2 cc/g.

[Production example 2]
21.05 g of water, 0.33 g of sodium hydroxide aqueous solution (NaOH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 1.37 g of sodium nitrate (NaNO ₃ , manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and sodium aluminate (NaAlO ₂ , manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and 15.5 g of Water Glass No. 3 (manufactured by Kishida Chemical Co., Ltd.) were mixed and stirred for 1 hour to prepare a mixed gel. The composition of the mixed gel is α=E/Al ₂ O ₃ =2.66, β=SiO ₂ /Al ₂ O ₃ =12.39, γ=Na ₂ O/Al ₂ O ₃ =5.89, δ= P ₂ O ₅ /Al ₂ O ₃ =0.00, ε=H ₂ O/Al ₂ O ₃ =197.9, ζ=H ₂ O/OH ^- = 145.2, η=R/Al ₂ O ₃ =0.00. The mixed gel was placed in a 100 mL stainless steel micro cylinder (manufactured by HIRO COMPANY) containing a fluororesin inner cylinder, and stirred at a stirring speed of 30 rpm at 130°C using a stirring-type constant temperature bath (manufactured by HIRO COMPANY) that allowed the micro cylinder to rotate vertically. Hydrothermal synthesis was carried out for 5 days. After filtering the product and drying at 120°C, a powdered zeolite was obtained. It was confirmed from the XRD spectrum that the obtained zeolite was a GIS type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica alumina were observed, it was evaluated that it was a high purity GIS type zeolite.

The silica-alumina ratio of the obtained zeolite was calculated from the ²⁹ Si-MAS-NMR spectrum, and the SAR was 4.50. The contents of potassium and lithium in the zeolite were Z/T=0.00 (=K/T). From the ²⁹ Si-MAS-NMR spectrum, (a+d)/(b+c)=0.192, and no carbon atom was detected. When the adsorption isotherm and desorption isotherm of CO ₂ of the obtained GIS type zeolite were measured, the adsorption amount at 760 mmHg was 53.5 cc/g, and q(Ad)/q(De) = 0.980. Ta. Further, when the CH ₄ adsorption isotherm was similarly measured, the adsorption amount at 760 mmHg was 4.0 cc/g.

[Manufacture example 3]
61.65 g of water, 0.60 g of a 48% by mass aqueous sodium hydroxide solution (NaOH, solid content concentration 48% by mass, manufactured by Tokuyama Soda Company), and 2.27 g of sodium carbonate (Na ₂ CO ₃ , manufactured by Tokuyama Soda Company), 1.64 g of sodium aluminate (NaAlO ₂ , manufactured by Hokuriku Kasei Kogyo Co., Ltd.) and 10.82 g of colloidal silica (Ludox AS-40, solid content concentration 40% by mass, manufactured by Grace) were mixed by stirring for 30 minutes. A gel was prepared. The composition of the mixed gel is α=E/Al ₂ O ₃ =4.86, β=SiO ₂ /Al ₂ O ₃ =8.17, γ=Na ₂ O/Al ₂ O ₃ =3.99, δ= P ₂ O ₅ /Al ₂ O ₃ =0.00, ε=H ₂ O/Al ₂ O ₃ =431.2, ζ=H ₂ O/OH ^- =527.8, η=R/Al ₂ O ₃ =0.00. The mixed gel was placed in a 200 mL stainless steel micro cylinder (manufactured by HIRO COMPANY) containing a fluororesin inner cylinder, and stirred at a stirring speed of 30 rpm at 130°C using a stirring-type constant temperature bath (manufactured by HIRO COMPANY) that allowed the micro cylinder to rotate vertically. Hydrothermal synthesis was carried out for 5 days. After filtering the product and drying at 120°C, a powdered zeolite was obtained. 1 g of the obtained zeolite was placed in 500 mL of a 0.05N aqueous potassium carbonate solution prepared using potassium carbonate (K ₂ CO ₃ , manufactured by 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 were exchanged with potassium. It was confirmed from the XRD spectrum that the obtained zeolite was a GIS type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica alumina were observed, it was evaluated that it was a high purity GIS type zeolite.

The silica-alumina ratio of the obtained zeolite was calculated from the ²⁹ Si-MAS-NMR spectrum, and the SAR was 6.90, and (a+d)/(b+c)=0.220. The content of potassium and lithium in the zeolite was Z/T=0.98 (=K/T). When the adsorption isotherm and desorption isotherm of CO ₂ were measured, the adsorption amount at 760 mmHg was 84.0 cc/g, and q(Ad)/q(De) = 1.000. Further, when the CH ₄ adsorption isotherm was similarly measured, the adsorption amount at 760 mmHg was 0.0 cc/g.

[Manufacture example 4]
141.41 g of water, 2.62 g of sodium hydroxide aqueous solution (NaOH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 8.53 g of sodium nitrate (NaNO ₃ , manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and sodium aluminate (NaAlO ₂ , manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and 17.41 g of amorphous silica (Perkasil SM500, manufactured by Grace) were mixed and stirred for 1 hour to prepare a mixed gel. The composition of the mixed gel is α=E/Al ₂ O ₃ =4.85, β=SiO ₂ /Al ₂ O ₃ =14.00, γ=Na ₂ O/Al ₂ O ₃ =5.16, δ= P ₂ O ₅ /Al ₂ O ₃ =0.00, ε=H ₂ O/Al ₂ O ₃ =379.3, ζ=H ₂ O/OH ^- =120.0, η=R/Al ₂ O ₃ =0.00. The mixed gel was placed in a 300 mL stainless steel micro cylinder (manufactured by HIRO COMPANY) containing a fluororesin inner cylinder, and stirred at a stirring speed of 30 rpm at 130°C using a stirring-type constant temperature bath (manufactured by HIRO COMPANY) that allowed the micro cylinder to rotate vertically. Hydrothermal synthesis was carried out for 4 days. After filtering the product and drying at 120°C, a powdered zeolite was obtained. It was confirmed from the XRD spectrum that the obtained zeolite was a GIS type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica alumina were observed, it was evaluated that it was a high purity GIS type zeolite.

The silica-alumina ratio of the obtained zeolite was calculated from the ²⁹ Si-MAS-NMR spectrum, and the SAR was 10.1, and (a+d)/(b+c)=0.519. The contents of potassium and lithium in the zeolite were Z/T=0.00 (=K/T). When the adsorption isotherm and desorption isotherm of CO ₂ were measured, the adsorption amount at 760 mmHg was 80.0 cc/g, and q(Ad)/q(De) = 1.000. Further, when the CH ₄ adsorption isotherm was similarly measured, the adsorption amount at 760 mmHg was 7.2 cc/g.

[Manufacture example 5]
141.41 g of water, 2.62 g of sodium hydroxide aqueous solution (NaOH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 2.43 g of sodium nitrate (NaNO ₃ , manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and sodium aluminate (NaAlO ₂ , manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and 35.33 g of aluminosilicate (SIPERNAT 820A, manufactured by Evonik) were mixed and stirred for 1 hour to prepare a mixed gel. The composition of the mixed gel is α=E/Al ₂ O ₃ =0.88, β=SiO ₂ /Al ₂ O ₃ =14.00, γ=Na ₂ O/Al ₂ O ₃ =2.62, δ= P ₂ O ₅ /Al ₂ O ₃ =0.00, ε=H ₂ O/Al ₂ O ₃ =242.4, ζ=H ₂ O/OH ^- =120.0, η=R/Al ₂ O ₃ =0.00. The mixed gel was placed in a 300 mL stainless steel micro cylinder (manufactured by HIRO COMPANY) containing a fluororesin inner cylinder, and stirred at a stirring speed of 30 rpm at 130°C using a stirring-type constant temperature bath (manufactured by HIRO COMPANY) that allowed the micro cylinder to rotate vertically. Hydrothermal synthesis was carried out for 5 days. After filtering the product and drying at 120°C, a powdered zeolite was obtained. 1 g of the obtained zeolite was placed in 500 mL of a 0.005N aqueous potassium carbonate solution prepared using potassium carbonate (K ₂ CO ₃ , manufactured by 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 were exchanged with potassium. It was confirmed from the XRD spectrum that the obtained zeolite was a GIS type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica alumina were observed, it was evaluated that it was a high purity GIS type zeolite.

The silica-alumina ratio of the obtained zeolite was calculated from the ²⁹ Si-MAS-NMR spectrum, and the SAR was 8.20, and (a+d)/(b+c)=0.356. The content of potassium and lithium in the zeolite was Z/T=0.16 (=K/T). When the adsorption isotherm and desorption isotherm of CO ₂ were measured, the adsorption amount at 760 mmHg was 72.7 cc/g, and q(Ad)/q(De) = 0.991. Further, when the CH ₄ adsorption isotherm was similarly measured, the adsorption amount at 760 mmHg was 0.5 cc/g.

[Production example 6]
207.30 g of water, 8.78 g of sodium hydroxide (NaOH, manufactured by Wako Pure Chemical Industries, Ltd.), 16.4 g of sodium aluminate (NaAlO ₂ , manufactured by Wako Pure Chemical Industries, Ltd.), and water glass No. 3 (Kishida Chemical Co., Ltd.) A mixed gel was prepared by mixing 248.3 g of (manufactured by) and stirring for 15 minutes. The composition of the mixed gel was SiO ₂ /Al ₂ O ₃ = 12.0, Na ₂ O/Al ₂ O ₃ = 4.0, and H ₂ O/Al ₂ O ₃ = 200. The composition of the mixed gel is α=E/Al ₂ O ₃ =0.00, β=SiO ₂ /Al ₂ O ₃ =13.60, γ=Na ₂ O/Al ₂ O ₃ =9.37, δ= P ₂ O ₅ /Al ₂ O ₃ =0.00, ε=H ₂ O/Al ₂ O ₃ =135.9, ζ=H ₂ O/OH ^- =54.56, η=R/Al ₂ O ₃ =0.00. The mixed gel was placed in a 1000 mL stainless steel autoclave containing a fluororesin inner cylinder, and hydrothermally synthesized at 130 °C for 5 days without stirring. The product was filtered and dried at 120 °C to obtain powdered zeolite. Ta. It was confirmed from the XRD spectrum that the obtained zeolite was a GIS type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica alumina were observed, it was evaluated that it was a high purity GIS type zeolite.

The silica-alumina ratio of the obtained zeolite was calculated from the ²⁹ Si-MAS-NMR spectrum, and as a result, SAR=4.30 and (a+d)/(b+c)=0.151. Further, the potassium concentration was measured, and the contents of potassium and lithium in the zeolite were found to be Z/T=0.00 (=K/T). When the adsorption isotherm and desorption isotherm of CO ₂ of the obtained GIS type zeolite were measured, the adsorption amount at 760 mmHg was 52.4 cc/g, and q(Ad)/q(De) = 0.302. Ta. Further, when the CH ₄ adsorption isotherm was similarly measured, the adsorption amount at 760 mmHg was 0.0 cc/g.

[Manufacture example 7]
Mix 41.0 g of water, 1.8 g of sodium hydroxide (reagent special grade manufactured by Wako Pure Chemical Industries, Ltd.), and 3.4 g of sodium aluminate (Wako 1st grade manufactured by Wako Pure Chemical Industries, Ltd.) and dissolve the solution. Obtained. A mixed gel was prepared by adding and mixing 54 g of Water Glass No. 3 (manufactured by Kishida Chemical Co., Ltd.) to this solution and stirring for 15 minutes. The composition of the mixed gel is α=E/Al ₂ O ₃ =0.00, β=SiO ₂ /Al ₂ O ₃ =14.27, γ=Na ₂ O/Al ₂ O ₃ = 9.57, δ=P ₂ O ₅ /Al ₂ O ₃ =0.00, ε=H ₂ O/Al ₂ O ₃ =130.2, ζ=H ₂ O/OH ⁻ =52.85, η= R/Al ₂ O ₃ =0.00.
The mixed gel was placed in a 1000 mL stainless steel autoclave containing a polytetrafluoroethylene resin inner cylinder, and hydrothermally synthesized at 130° C. for 5 days without stirring. The product was filtered and dried at 120°C to obtain zeolite powder. It was confirmed from the XRD spectrum that the obtained zeolite was a GIS type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica alumina were observed, it was evaluated that it was a high purity GIS type zeolite.

The silica-alumina ratio of the obtained zeolite was calculated from the ²⁹ Si-MAS-NMR spectrum, and as a result, SAR=4.40 and (a+d)/(b+c)=0.156. The contents of potassium and lithium in the zeolite were Z/T=0.00 (=K/T). When the adsorption isotherm and desorption isotherm of CO ₂ of the obtained GIS type zeolite were measured, the adsorption amount at 760 mmHg was 53.0 cc/g, and q(Ad)/q(De) = 0.352. Ta. Further, when the CH ₄ adsorption isotherm was similarly measured, the adsorption amount at 760 mmHg was 3.9 cc/g.

[Production example 8]
141.41 g of water, 2.62 g of sodium hydroxide aqueous solution (NaOH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 2.43 g of sodium nitrate (NaNO ₃ , manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and sodium aluminate (NaAlO ₂ , manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and 35.33 g of aluminosilicate (SIPERNAT 820A, manufactured by Evonik) were mixed and stirred for 1 hour to prepare a mixed gel. The composition of the mixed gel is α=E/Al ₂ O ₃ =0.88, β=SiO ₂ /Al ₂ O ₃ =14.00, γ=Na ₂ O/Al ₂ O ₃ =2.62, δ= P ₂ O ₅ /Al ₂ O ₃ =0.00, ε=H ₂ O/Al ₂ O ₃ =242.4, ζ=H ₂ O/OH ^- =120.0, η=R/Al ₂ O ₃ =0.00. The mixed gel was placed in a 300 mL stainless steel micro cylinder (manufactured by HIRO COMPANY) containing a fluororesin inner cylinder, and stirred at a stirring speed of 30 rpm at 130°C using a stirring-type constant temperature bath (manufactured by HIRO COMPANY) that allowed the micro cylinder to rotate vertically. Hydrothermal synthesis was carried out for 5 days. After filtering the product and drying at 120°C, a powdered zeolite was obtained. 1 g of the obtained zeolite was placed in 500 mL of a 0.010N lithium nitrate aqueous solution prepared using lithium nitrate (LiNO ₃ , manufactured by 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 were exchanged with lithium. It was confirmed from the XRD spectrum that the obtained zeolite was a GIS type zeolite. Furthermore, since no peaks derived from other zeolites or amorphous silica alumina were observed, it was evaluated that it was a high purity GIS type zeolite.

The silica-alumina ratio of the obtained zeolite was calculated from the ²⁹ Si-MAS-NMR spectrum, and the SAR was 8.20, and (a+d)/(b+c)=0.356. The content of potassium and lithium in the zeolite was Z/T=0.16. When the adsorption isotherm and desorption isotherm of CO ₂ were measured, the adsorption amount at 760 mmHg was 72.5 cc/g, and q(Ad)/q(De) = 0.991. Further, when the CH ₄ adsorption isotherm was similarly measured, the adsorption amount at 760 mmHg was 0.5 cc/g.

[Example 1]
60 parts by mass of the GIS type zeolite powder obtained in Production Example 1, 60 parts by mass of alumina sol (manufactured by Nissan Chemical Co., Ltd., alumina content: 10.5% by mass), and 1.8 parts of methylcellulose (Selander YB-167, manufactured by Hichem Corporation) parts by mass and 0.3 parts by mass of polyvinyl alcohol (Gohsenol N-300 manufactured by Mitsubishi Chemical Corporation) were mixed.
The above mixture was extruded into a cylinder with a diameter of 3 mm using a wet extrusion granulator MG-55 (manufactured by Dalton Co., Ltd.), and then baked in an air atmosphere at 400° C. for 5 hours using an electric furnace. The elastic modulus E of the GIS type zeolite molded body thus obtained was 10.5 MPa. The embrittlement resistance of the zeolite molded body in a CO ₂ atmosphere was evaluated and the pulverization rate was determined to be 5% by mass.

When the adsorption isotherms of CO ₂ and CH ₄ of the zeolite molded body of Example 1 were measured, the adsorption amounts at 760 mmHg were 74.4 cm ³ /g for CO ₂ and 5.6 cm ³ /g for CH ₄ , respectively. It was confirmed that the adsorption selectivity (CO ₂ /CH ₄ ) was 13.3, and that it had sufficient performance as an adsorbent.

[Example 2]
Using 30 parts by mass of silica sol (manufactured by Nalco) with a silica content of 34% by mass and 35 parts by mass of ion-exchanged water in place of the alumina sol with an alumina content of 10.5% by mass, the GIS type zeolite powder obtained in Production Example 2 was prepared. A molded article was obtained in the same manner as in Example 1 except that the following was used.
The elastic modulus E of the GIS type zeolite molded body thus obtained was 19.8 MPa. The embrittlement resistance of the zeolite molded body in a CO ₂ atmosphere was evaluated and the powdering rate was measured to be 6% by mass.

[Example 3]
60 parts by mass of the GIS type zeolite powder obtained in Production Example 3, 13.2 parts by mass of methyl cellulose (Selander YB-167 manufactured by Hi-Chem Co., Ltd.), and 50 parts by mass of ion-exchanged water were mixed.
The above mixture was extruded into a cylindrical shape with a diameter of 3 mm using a wet extrusion granulator MG-55 (manufactured by Dalton Co., Ltd.), and then baked in a nitrogen atmosphere at 120° C. for 5 hours using an electric furnace.
The elastic modulus E of the GIS type zeolite molded body thus obtained was 32.0 MPa. The embrittlement resistance of the zeolite molded body in a CO ₂ atmosphere was evaluated and the pulverization rate was determined to be 0% by mass.

[Comparative example 1]
A molded body was obtained in the same manner as in Example 1 except that the firing temperature was 300°C.
The elastic modulus E of the GIS type zeolite molded body thus obtained was 7.0 MPa. The embrittlement resistance of the zeolite molded body in a CO ₂ atmosphere was evaluated and the pulverization rate was determined to be 60% by mass.

[Example 4]
A molded body was obtained in the same manner as in Example 1 except that the GIS type zeolite powder obtained in Production Example 4 was used.
The elastic modulus E of the GIS type zeolite molded body thus obtained was 10.7 MPa. The embrittlement resistance of the zeolite molded body in a CO ₂ atmosphere was evaluated and the pulverization rate was determined to be 8% by mass.

[Example 5]
A molded body was obtained in the same manner as in Example 1 except that the GIS type zeolite powder obtained in Production Example 5 was used.
The elastic modulus E of the GIS type zeolite molded body thus obtained was 10.7 MPa. The embrittlement resistance of the zeolite molded body in a CO ₂ atmosphere was evaluated and the pulverization rate was determined to be 8% by mass.

[Comparative example 2]
After mixing 100 parts by mass of the GIS type zeolite powder obtained in Production Example 6, 250 parts by mass of alumina sol (manufactured by Kawaken Fine Chemical Co., Ltd., alumina content: 10% by mass) and 275 parts by mass of ion-exchanged water, the mixture was heated and concentrated at 70°C. The moisture content was adjusted to 40% by mass.
The above mixture was extruded into a cylindrical shape with a diameter of 3 mm using a wet extrusion granulator MG-55 (manufactured by Dalton Co., Ltd.), and then baked in an air atmosphere at 350° C. for 3 hours using an electric furnace.
The elastic modulus E of the GIS type zeolite molded body thus obtained was 6.0 MPa. The embrittlement resistance of the zeolite molded body in a CO ₂ atmosphere was evaluated and the pulverization rate was determined to be 86% by mass.

[Example 6]
A molded body was obtained in the same manner as in Example 3 except that extrusion molding was performed manually using a clay gun instead of the wet extrusion granulator MG-55.
The elastic modulus E of the GIS type zeolite molded body thus obtained was 30.0 MPa. The embrittlement resistance of the zeolite molded body in a CO ₂ atmosphere was evaluated and the pulverization rate was determined to be 10% by mass.

[Example 7]
After dispersing 10.1 parts by mass of the GIS type zeolite obtained in Production Example 1 in 10.3 parts by mass of ion-exchanged water, 79.6 parts of alumina sol (manufactured by Nissan Chemical Co., Ltd., alumina content: 10.5% by mass) was prepared. It was added to parts by mass to form a raw material slurry. The obtained raw material slurry was stirred at 25° C. for 1 hour. The raw material slurry was in the form of a sol, and the viscosity was 300 cP (measured using a B-type viscometer manufactured by Hideko Seiki Co., Ltd.). The raw material slurry was supplied to a spray dryer (OC-16 type spray dryer manufactured by Okawara Kakoki Co., Ltd.) in which the fluid temperature at the inlet of the spray dryer was set to 230°C and the fluid temperature at the outlet of the spray dryer was set to 120°C. After spray drying was performed to obtain a dry powder, it was fired in an air atmosphere at 350° C. for 24 hours using an electric furnace. The rate of temperature increase and decrease was 1° C./min.
The elastic modulus E of the zeolite molded body thus obtained was 19.7 MPa. When the embrittlement resistance of the zeolite molded body was evaluated in a CO ₂ atmosphere and the powdering rate was measured, the powdering rate was 10% by mass.

[Comparative example 3]
70 parts by mass of the GIS type zeolite powder obtained in Production Example 7 and 30 parts by mass of polyamide resin (Zytel 101L manufactured by DuPont Corporation) were melt-kneaded at 285°C and 400 rpm in a twin screw extruder (TEM48-SS manufactured by Toshiba Machinery Co., Ltd.). , a complex was obtained. The resulting composite was molded using an injection molding machine (EC75NII manufactured by Toshiba Machinery Co., Ltd.) set at a cylinder temperature of 285° C. and a mold temperature of 70° C. to obtain a molded product having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm.
The elastic modulus E of the GIS type zeolite molded body thus obtained was 2.1 MPa. The embrittlement resistance of the zeolite molded body in a CO ₂ atmosphere was evaluated and the powdering rate was measured to be 70% by mass.

[Example 8]
A molded body was obtained in the same manner as in Example 1 except that the GIS type zeolite powder obtained in Production Example 8 was used.
The elastic modulus E of the GIS type zeolite molded body thus obtained was 11.0 MPa. The embrittlement resistance of the zeolite molded body in a CO ₂ atmosphere was evaluated and the pulverization rate was determined to be 7% by mass.

Claims (17)

A zeolite molded body containing zeolite capable of adsorbing carbon dioxide,
A zeolite molded body having an elastic modulus E of 10.0 MPa or more. The zeolite molded article according to claim 1, wherein the zeolite has a carbon dioxide adsorption amount of 10 cc/g or more. The zeolite molded article according to claim 1 or 2, wherein the zeolite is a GIS type zeolite. The zeolite molded article according to claim 3, wherein the GIS type zeolite has a silica alumina ratio of 3.40 or more. The zeolite molded article according to claim 3, wherein the GIS type zeolite has a silica alumina ratio of 4.50 or more. The zeolite molded article according to any one of claims 3 to 5, which contains potassium or lithium as a cationic species in the GIS type zeolite. According to claim 6, the ratio (Z/T) of the total amount of potassium and lithium (Z) to the total amount of alkali metals (T) in the GIS-type zeolite is 0.05 or more. Zeolite molded body. ^{29 Let} the peak area intensities attributed to Q4 (3Al), Q4 (2Al), Q4 (1Al), and Q4 (0Al) observed in the Si-MAS-NMR spectrum be a, b, c, and d, respectively, and ( The zeolite molded article according to any one of claims 3 to 7, comprising a GIS type zeolite satisfying a+d)/(b+c)≧0.192. The zeolite molded article according to any one of claims 1 to 8, comprising a carrier. The zeolite molded article according to claim 9, wherein the carrier contains one or more selected from the group consisting of an inorganic binder and an organic binder. The zeolite molded article according to claim 10, wherein the inorganic binder contains alumina. The zeolite molded article according to any one of claims 9 to 11, wherein the mass ratio of the GIS type zeolite to the carrier is 1:99 to 99:1 as GIS type zeolite:carrier. The zeolite molded article according to any one of claims 1 to 12, having a cylindrical shape. The zeolite molded article according to claim 13, 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. An adsorption device comprising the zeolite molded body according to any one of claims 1 to 14. Using the adsorption device according to claim 15, CO ₂ , H 2 O is extracted from a mixture containing two or more gases selected from _the group consisting _of H 2 , N ₂ , O ₂ , Ar, CO, and hydrocarbons. , He, Ne, Cl ₂ , NH ₃ , and HCl. 17. The method for producing purified gas according to claim 16, wherein 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.