JP2015116532A - Raw material composition for producing carbon dioxide separation/recovery composition, and carbon dioxide separation/recovery composition produced from the raw material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a raw material composition for producing a COseparation/recovery composition which reduces an amount of a structure regulating agent to be used, provides inexpensive and high-quality pure silica zeolite, uses the pure silica zeolite, has a small steam adsorption amount, and has excellent COseparation/recovery performance, and to provide a COseparation/recovery composition which is produced from the raw material composition and is industrially advantageous.SOLUTION: There is provided a raw material composition for producing a COseparation/recovery composition containing silica, organic hydroxylated amine, water and hydrofluoric acid which has a content of organic hydroxylated amine of 7-40 pts.mol and a content of water of 50-200 pts.mol with respect to 100 pts.mol of silica. There is also provided a carbon dioxide separation/recovery composition produced by heating the raw material composition.

Description

  The present invention is produced using a raw material composition that enables production of a carbon dioxide gas separation and recovery composition having a low production cost while maintaining excellent water repellency and carbon dioxide separation and recovery ability, and the raw material composition. An industrially advantageous carbon dioxide separation and recovery composition is provided.

Carbon dioxide (hereinafter abbreviated as CO ₂ ) is contained in large amounts in the exhaled gas of living organisms, combustion waste, or exhaust gas generated from thermal power plants, iron and cement plants, natural gas recovery plants, etc. Currently, the global greenhouse effect caused by CO ₂ is regarded as a problem.
Therefore, a method for treating exhaust gas using various CO ₂ adsorbents has been proposed. For example, from a CO ₂ -containing exhaust gas using a zeolite-based adsorbent and utilizing pressure adsorption-desorption under reduced pressure by physical adsorption. An exhaust gas treatment method for adsorbing and removing CO ₂ has been proposed.

Most of zeolites are composed of aluminosilicates of alkali or alkaline earth metals, and the basic framework structure is a three-dimensional network structure in which SiO ₄ and AlO ₄ tetrahedrons share oxygen and share them. There are many types (types) having different crystal structures such as ANA, CHA, ERI, GIS, KFI, and LTA. Each of these zeolites has its own unique pore structure, pore diameter, surface electric field, ion exchange capacity, adsorption characteristics, solid acidity, etc. From these characteristics, desiccants, adsorbents, molecular sieves, Adsorption separation, ion exchange agent, catalyst, fertilizer additive, soil modification improver, filler, etc. are extremely industrially useful and one of industrially useful materials.

Among them, CHA-type zeolite (chabasite-type zeolite) has relatively small light carbonization such as carbon dioxide (CO ₂ ), methane (CH ₄ ), and methanol (CH ₃ OH) because of its small pore size and skeleton density. Since hydrogen molecules can be selectively adsorbed even under high-pressure conditions, they are expected to be used as gas separation membranes or adsorbents that can selectively separate these molecules.

However, zeolite-based adsorbent is often used, because it significantly higher adsorption capacity for water, when water coexists in the exhaust gas containing CO _2, the adsorption capacity for CO ₂ is significantly impaired by adsorption of moisture , CO ₂ adsorption amount is significantly reduced. Therefore, the advent of a zeolitic adsorbent with low moisture adsorption ability and excellent CO ₂ adsorption ability has been desired.

  On the other hand, in order to modify the chemical / physical properties of zeolite, synthesis of pure silica zeolite which is mainly composed of silica and does not contain an aluminum component has been attempted. Pure silica zeolite is obtained, for example, by heating and pressurizing a substance (referred to as a structure-directing agent) serving as a template for forming a crystal structure, a silicon source, and other predetermined components in the presence of water. In addition, since the hydrophilicity of ordinary zeolite made of aluminosilicate is lost, the hydrophobicity becomes strong, and as a result, it has the characteristics of excellent heat resistance and acid resistance. Therefore, pure silica zeolite is expected to expand in applications such as carbon dioxide adsorption separation from gas containing a large amount of water vapor, such as combustion exhaust gas, and addition of a catalyst function, and future industrial usefulness is expected.

For example, Patent Document 1 and Non-Patent Document 1 disclose industrially advantageous methods for producing CHA-type pure silica zeolite. However, in this method, it is essential to use a large amount of the expensive structure-directing agent and the like, and the advent of an industrially advantageous production method capable of further cost reduction has been desired. Further, Patent Document 2 discloses a method for producing a CHA-type zeolite that uses a small amount of the structure-directing agent. However, since aluminum oxide that also acts as a crystallization agent is added as a raw material, Only a CHA-type zeolite as a crystalline alumina silicate incorporating aluminum can be obtained. This is because aluminum ions dissolved under hydrothermal synthesis conditions act as a crystallization agent that promotes zeolite crystal formation. If the amount of aluminum used is large, the amount of organic structure directing agent used can be reduced. The content of aluminum in the minute zeolite framework increases. Therefore, regarding the method for producing pure silica zeolite containing no aluminum, it is necessary to use a large amount of an organic structure-directing agent as a crystallization agent. In Non-Patent Document 1, the water content of the composition before adding hydrofluoric acid to the raw material composition is H ₂ O / SiO ₂ = 3.0, but if the water content is further reduced, the raw material composition Since the product could not maintain a gel state with a uniform composition and became a dry powder, the subsequent heat treatment was not performed well, and pure silica zeolite was not obtained.
Patent Document 3 describes that when a high-pressure gas containing CO ₂ is treated with CHA-type or STT-type pure silica zeolite, the amount of CO ₂ separation is improved as compared with conventional zeolite. However, even in this method, it is necessary to use a large amount of the expensive structure-directing agent.

JP 2009-114007 A International Publication No. 2010/098473 Patent No. 5186410

M.J.Diaz-Cabanas, P.A.Barrett, M.A. Camblor, Chemical Communications, Royal Society of Chemistry, 1881 (1998)

In view of the above-mentioned present situation, the present invention provides a pure silica zeolite with a low cost and a high quality by reducing the amount of a structure directing agent (for example, a hydroxylated organic amine) that is a raw material, and using the pure silica zeolite. A raw material composition for producing a CO ₂ separation and recovery composition having a small amount of water vapor adsorption and having an excellent CO ₂ separation and recovery ability, and an industrially advantageous CO ₂ separation and recovery produced from the raw material composition It is an object to provide a composition.

As a result of intensive research to solve the above problems, the present inventors have surprisingly set the water content in the raw composition of the pure silica zeolite within a specific range different from that of the prior art. Thus, the content of the hydroxylated organic amine in the raw composition of the pure silica zeolite can be remarkably reduced, and the pure silica zeolite has a low water vapor adsorption amount and has an excellent CO ₂ separation and recovery ability. The present invention was completed through further studies.

That is, the present invention relates to the following CO ₂ separation and recovery composition and the like.
[1] In the raw material composition for producing a carbon dioxide gas separation and recovery composition containing silica, a hydroxylated organic amine, water and hydrofluoric acid, the content of the hydroxylated organic amine is 7 with respect to 100 mol parts of silica. A raw material composition for producing a carbon dioxide separation and recovery composition, characterized in that it is -40 mol parts and the water content is 50-200 mol parts.
[2] The raw material composition for producing the carbon dioxide separation and recovery composition according to [1] above, wherein the molar ratio of hydrofluoric acid / hydroxylated organic amine is 0.5 to 1.5 object.
[3] A carbon dioxide separation and recovery composition produced by subjecting the raw material composition according to [1] to a heat treatment step.
[4] The composition according to [3], wherein the water vapor adsorption amount of the carbon dioxide separation and recovery composition is less than 3 mol / kg, and the carbon dioxide separation and recovery amount is 2.5 mol / kg or more.
[5] The composition according to any one of [1] to [4], wherein the carbon dioxide gas separation and recovery composition contains pure silica zeolite.
[6] The composition according to the above [5], wherein the pure silica zeolite is a CHA type.
[7] The composition according to any one of [1] to [6], wherein the hydroxylated organic amine is N, N, N-trimethyl-1-adamantanamine hydroxide.
[8] As described in any one of [1] to [7] above, wherein one or more selected from the group consisting of colloidal silica, fumed silica, tetraethyl orthosilicate, and tetrapropyl orthosilicate is used as a silica source. Composition.
[9] The heat treatment step of heating the raw material composition according to the above [1] at 130 ° C. to 200 ° C. for 12 to 30 hours, according to any one of the above [2] to [8] Composition.
[10] A production method for producing a carbon dioxide separation and recovery composition from a raw material composition containing silica, a hydroxylated organic amine, water and hydrofluoric acid,
A step of preparing a raw material composition in which the content of the hydroxylated organic amine is 7 to 40 mol parts and the water content is 50 to 200 mol parts with respect to 100 mol parts of the silica;
And a step of heat-treating the raw material composition. A method for producing a carbon dioxide separation and recovery composition.
[11] The method for producing a carbon dioxide gas separation and recovery composition as described in [10] above, wherein the molar ratio of hydrofluoric acid / hydroxylated organic amine is 0.5 to 1.5.

According to the present invention, since the amount of the structure directing agent (hydroxylated organic amine) used as a raw material is less than that of a conventional CO ₂ separation and recovery agent, CO ₂ can be separated and recovered at a low cost. Accordingly, the amount of hydrofluoric acid used at the same time can be suppressed, thereby further reducing the cost. In addition, since the CO ₂ separation and recovery composition of the present invention has a small amount of water vapor adsorption, it is hardly affected by moisture when adsorbing CO _2, and the water vapor repellency of conventional excellent CO ₂ separation and recovery agents, CO ₂ adsorption without compromising CO ₂ separation recovery amount, efficiently CO ₂ can be separated and recovered. That is, the water vapor adsorption amount of the CO ₂ separation and recovery composition according to the present invention can reach less than 3 mol / kg, preferably less than 2.5 mol / kg, more preferably less than 2 mol / kg in the case of the CHA type. The CO ₂ separation and recovery amount can reach 2.5 mol / kg or more. (Patent No. 5186410 describes that the CHA-type water vapor adsorption amount is 3.5 mol / kg.)

2 is a scanning electron micrograph showing the structure of the pure silica zeolite crystal of Example 1. FIG. 2 is a powder X-ray diffraction chart of Example 1. FIG. 6 is a scanning electron micrograph showing the structure of the pure silica zeolite crystal of Example 5. FIG. 6 is a powder X-ray diffraction chart of Example 5. FIG. 3 is a scanning electron micrograph showing the structure of a pure silica zeolite crystal of Comparative Example 1. FIG. 2 is a powder X-ray diffraction chart of Comparative Example 1. 3 is a scanning electron micrograph showing the structure of a pure silica zeolite crystal of Comparative Example 2. FIG. 6 is a powder X-ray diffraction chart of Comparative Example 2. 4 is a scanning electron micrograph showing the structure of a pure silica zeolite crystal of Comparative Example 3. 6 is a powder X-ray diffraction chart of Comparative Example 3.

Hereinafter, the present invention will be described in detail.
The CO ₂ -containing gas that is industrially processed by the CO ₂ separation and recovery composition of the present invention is not particularly limited, and examples thereof include gas generated from an IGCC (gasification combined power generation) facility, mined natural gas, and the like. However, it is preferable if it is a gas containing CO ₂ that exceeds atmospheric pressure, including a gas obtained by boosting atmospheric pressure exhaust gas. The CO ₂ -containing gas may contain N ₂ , CH ₄ or the like in addition to water vapor and CO ₂ .

The raw material composition for producing the CO ₂ separation and recovery composition of the present invention contains silica, a hydroxylated organic amine, water and hydrofluoric acid.
Examples of the silica used in the present invention include silicon dioxide or silicon dioxide hydrate.
Although it does not specifically limit as a supply source of the silica contained in the said raw material composition, For example, colloidal silica, fumed silica, tetraethyl orthosilicate, tetramethyl orthosilicate, orthopropyl orthosilicate, etc. are mentioned preferably. These may be used alone or in combination of two or more.

  In particular, when colloidal silica, fumed silica or the like is used as a silica supply source, hydrolysis is not required in the production process, and the water vapor adsorption amount and lattice defect rate of the produced zeolite are greatly reduced. Therefore, it is preferable. The silica contained in the raw material composition is preferably in the form of a fine powder for the preparation of the raw material composition. For this reason, amorphous silica is preferably used from the standpoint of production and availability stability.

Even when the raw material composition of the present invention is prepared using an alkoxide capable of producing silica by hydrolysis, such as tetraethyl orthosilicate, tetramethyl orthosilicate and tetrapropyl orthosilicate, the amount of the hydroxylated organic amine used is greatly reduced. The raw material composition for producing the CO ₂ separation and recovery composition of the present invention can be obtained.

  In the specific preparation of the raw material composition, a colloidal silica sol containing water from the beginning (hereinafter also referred to as colloidal silica) may be used as a silica supply source. As the colloidal silica sol, a commercially available product may be used, or the water content of the commercially available product may be appropriately adjusted and used. In addition, fine powdered silica (for example, fumed silica that is amorphous, particle size of about 2 to 500 nm) is directly mixed with a hydroxylated organic amine powder and hydrofluoric acid and then mixed with water. Alternatively, it may be previously dispersed in water and used as a colloidal silica sol. Here, the colloidal silica sol is one in which silica is dispersed in water to form a sol. A commercial product of colloidal silica sol is preferable because it is inexpensive and convenient in the present invention.

  Further, when using tetraethyl orthosilicate, tetramethyl orthosilicate, tetrapropyl orthosilicate, etc. as a silica source, for example, by stirring at room temperature in the presence of a hydroxylated organic amine, the silica source is It can be used by hydrolyzing and freeing silica. Moreover, the alcohol produced | generated as a by-product of a hydrolysis can be remove | eliminated by a subsequent concentration process process. Therefore, it is possible to apply the silica source to the present invention without performing a particularly complicated treatment.

  The hydroxylated organic amine contained in the raw material composition is a structure-directing agent in the synthesis of pure silica zeolite, that is, if it can constitute a template for forming the crystal structure of pure silica zeolite. It is not limited. Examples of the hydroxylated organic amine include N, N, N-trimethyl-1-adamantanamine hydroxide, hexamethonium dihydroxide, and the like. These may be used alone or in combination of two or more. The hydroxylated organic amine is preferably N, N, N-trimethyl-1-adamantanamine hydroxide, hexamethonium dihydroxide or the like. The hydroxylated organic amine may be used as a powder or as an aqueous solution, but it is preferably used as an aqueous solution from the viewpoint of easy adjustment of the amount used.

The content of the hydroxylated organic amine contained in the raw material composition is about 7 to 40 mole parts, preferably about 10 parts per 100 mole parts of silica (SiO ₂ ) contained in the colloidal silica. ~ 25 mol parts. The content of water contained in the raw material composition is about 50 to 200 mol parts, preferably about 100 to 160 mol, with respect to 100 mol parts of silica (SiO ₂ ) contained in the colloidal silica. The mole part. When the content of the hydroxylated organic amine exceeds about 50 mole parts, pure silica zeolite can be formed, but in terms of performance such as water vapor adsorption amount and CO ₂ separation and recovery amount, it becomes difficult to make a stable one, When the amount is less than 7 parts by mole, the hydroxylated organic amine as a structure-directing agent is insufficient, so that pure silica zeolite cannot be formed, or the yield of pure silica zeolite becomes very low, which is not preferable.

On the other hand, when the amount of water exceeds 200 parts by mole with respect to 100 parts of silica, the silica (SiO ₂ ) concentration in the raw material composition is too thin, so that the rate at which pure silica zeolite is generated becomes slow, and the purity of pure silica zeolite is reduced. Since the rate becomes very low, it is not preferable. Furthermore, when the amount of water increases relative to the amount of silica, crystallization of pure silica zeolite does not occur. On the other hand, when the water is less than 50 parts by mole with respect to 100 parts of silica, the silica concentration in the raw material composition is too high, so that the reaction vessel does not have conditions suitable for the subsequent heat treatment and does not crystallize. A large amount of the silica component of the reaction remains, and the yield of pure silica zeolite becomes very low. Furthermore, if the amount of water is reduced relative to the amount of silica, crystallization of pure silica zeolite will not occur.

  When the colloidal silica sol is used as the raw material, the water contained in the raw material composition may be supplied from the water contained in the silica sol. Moreover, when using low concentration hydrofluoric acid, it is good also considering the water contained in this hydrofluoric acid as a supply source. The water contained in the colloidal silica sol and / or hydrofluoric acid is used as the supply source of the water contained in the raw material composition, and the raw material composition can be prepared without adding additional water. Good. The water content in the raw material composition may be adjusted in the course of mixing the silica source, the hydroxylated organic amine, and hydrofluoric acid, or may be adjusted by evaporation and / or addition after mixing.

As the hydrofluoric acid contained in the raw material composition, a commercially available compound can be used, and it may be further purified by any method. Examples of hydrofluoric acid include those manufactured by Wako Pure Chemical Industries, Ltd.
The amount of hydrofluoric acid used is not particularly limited, but usually the molar ratio of hydrofluoric acid / hydroxylated organic amine is 0.5 to 1.5, most preferably 1 to 1.25. It is.

  The hydroxylated organic amine is strongly alkaline, but in order to form pure silica zeolite, the pH when the raw material composition is subjected to the heat treatment described later is preferably near neutral. Hydrofluoric acid is used to adjust the pH and to improve the properties of the crystal structure formed. For this reason, the molar ratio of hydroxylated organic amine to hydrofluoric acid (HF) is important. Yes, the amount of hydrofluoric acid (HF) is appropriately selected from the above range so that the pH of the raw material mixture is near neutral. Further, if necessary, a pH adjusting agent such as an acid or a base may be added. It is preferable to confirm the introduction amount of hydrofluoric acid (HF) by verifying that it is neutral with a universal test paper (pH test paper) as appropriate. Although the density | concentration of hydrofluoric acid is not specifically limited, Usually, the high concentration goods marketed, for example, 40-55 mass%, are used.

  In the preparation of the raw material composition, the method and order of mixing the silica source, the hydroxylated organic amine and hydrofluoric acid are not particularly limited as long as the effects of the present invention are not hindered, and a known mixing method may be used. In addition, ammonia or the like may be added as a pH buffer, and ammonium fluoride may be used in place of the hydrofluoric acid. By adding ammonia, ammonia evaporates during the stirring of the raw material composition, and hydrolysis progresses mildly, so that a uniform raw material composition can be obtained.

  Although the preparation of the raw material composition has been described above, as another particularly preferable embodiment, water is added after mixing the powdered hydroxylated organic amine, fine powdered silica, and hydrofluoric acid, and then water is added. And a method of preparing the raw material composition having the above-described composition without evaporating.

In addition to pure silica zeolite, the CO ₂ separation and recovery composition of the present invention can be used within the range where the object of the present invention can be achieved, for example, a binder or a sintering aid for granulating silica, alumina, etc. An additive may be contained.

Zeolite is usually made of an aluminosilicate of an alkali (earth) metal, and has a basic skeleton structure of a three-dimensional network structure in which SiO ₄ and AlO ₄ tetrahedrons share oxygen and share them. In the CO ₂ separation and recovery composition, it is an important feature to use pure silica zeolite whose main component is composed only of silica and substantially free of an aluminum component. However, the CO ₂ separation and recovery composition may contain an aluminum component as an impurity in the process of synthesizing pure silica zeolite. Usually, the molar ratio SiO ₂ / _Al 2 _{O 3} of SiO ₄ is 90 or more pure-silica zeolite used for the AlO _4.
Pure silica zeolite has the characteristics that conventional zeolite made of aluminosilicate loses its hydrophilicity and becomes more hydrophobic, resulting in excellent acid resistance and heat resistance.

Pure silica zeolite used in the CO ₂ separation and recovery composition of the present invention includes CHA type, STT type, DDR type, FER, FAU type, IHW type, UFI type, RHO type, BEA type, LTA type, SBS type, Examples include MFI type, SBE type, ISV type, and AFY type, but are not particularly limited as long as they are pure silica zeolite.
Pure silica zeolite is preferably CHA type, STT type, DDR type, FER, FAU type, LTA type, SBS type and IHW type in that the amount of CO ₂ recovered in the high-pressure gas is large even in the presence of water vapor. The CHA type and STT type are more preferably used, and the CHA type is more preferably used in that the amount of CO ₂ adsorption is large due to the large pore volume, and as a result, the amount of CO ₂ recovered is remarkably large.

The production method of the pure silica zeolite is not particularly limited and can be produced by a known method. Preferably, a pure silica zeolite is preferably used as a template for forming a crystal structure (referred to as a structure-directing agent), and a fluorine. In this method, hydrofluoric acid and a silicon source are heated and pressurized (hydrothermal synthesis) in the presence of water.
Pure silica zeolite may be regenerated by heating and firing after deterioration as an adsorbent.

Pure silica zeolite can be suitably manufactured by heat-treating the raw material composition prepared as described above.
Although the heat processing method is not specifically limited, Pure silica zeolite can be synthesize | combined by heat-processing the said raw material composition prepared as mentioned above at about 130-200 degreeC. The heat treatment method is not particularly limited as long as the effect of the present invention is not hindered. For example, crystal growth occurs following nucleation in the solution by the dissolution-precipitation mechanism, and thus the resulting product has high crystallinity. Hydrothermal synthesis is preferred from the viewpoints of high compositional uniformity within one crystal, continuous synthesis, and ability to synthesize powder by a short time reaction at low temperature. Here, the hydrothermal synthesis is a general term for a method of synthesizing substances generally carried out in the presence of water at high temperature and high pressure, and zeolite is often synthesized by this method.

  The heat treatment temperature of the raw material composition is preferably in the range of about 130 to 200 ° C, and more preferably in the range of about 150 to 200 ° C. When the temperature of the heat treatment is less than about 130 ° C., pure silica zeolite is not formed in a short time, or even if pure silica zeolite is produced, the yield is less than about 30%, or non-combined with pure silica zeolite. This is not preferable for reasons such as formation of crystalline silica. On the other hand, the upper limit of the heat treatment temperature is not particularly limited, but a lower temperature than 200 ° C. is preferable because the manufacturing cost increases.

  The heat treatment time of the raw material composition is preferably about 12 to 30 hours, and a pure silica zeolite can be synthesized in a very short time. For reducing the yield and production cost, it is more preferably about 12 to 24 hours. In the present invention, the molar ratio of water and silica, preferably, the raw material composition in which the molar ratio of hydroxylated organic amine and silica and the hydroxylated organic amine and hydrofluoric acid is adjusted is used. Production of pure silica zeolite is promoted. When the heat treatment time is less than about 12 hours, pure silica zeolite is not produced, or even if pure silica zeolite is produced, the yield is less than about 30%, or amorphous silica together with pure silica zeolite. Is not preferable for reasons such as

  The heat treatment is preferably performed in a fluororesin container sealed in a stainless steel autoclave container, and is performed under pressure by an expanding gas such as water vapor generated spontaneously by heating. Although the pressure at the time of pressurization is not specifically limited, Preferably, it is about 0.1-2 MPa, More preferably, it is about 0.4-2 MPa.

The pure silica zeolite used in the CO ₂ separation and recovery agent of the present invention may be one in which a hydroxylated organic amine as a structure-directing agent is incorporated in the crystal structure of the zeolite, and is oxidized and burned. May be.

  The pure silica zeolite produced as described above may further have a step of heat-treating (calcining) and burning out the structure derived from the hydroxylated organic amine. Specifically, after the heat treatment, the powdered solid formed in the autoclave container is taken out from the autoclave container, washed with water, dried, and then in the atmosphere in an electric furnace at about 400 to 800 ° C., preferably about 500 to By raising the temperature to 700 ° C. and holding it for about 1 to 48 hours, preferably about 4 to 12 hours, it is incorporated into the crystal structure of zeolite and is a template for forming a crystal structure of pure silica zeolite. It is preferable to oxidize and burn the amine to produce a porous zeolite crystal having a framework composed entirely of silica components.

It is confirmed by the powder X-ray diffraction etc. of the pure silica zeolite crystal mentioned later that the obtained powder crystal is pure silica zeolite.
The pure silica zeolite production method described above is excellent as an industrial production method for pure silica zeolite because the yield of pure silica zeolite obtained in a heat treatment time of 12 to 30 hours is 92% or more.

The CO ₂ separation and recovery composition of the present invention is capable of adsorbing and desorbing CO _{2 in} high-pressure gas using a conventionally known method.
In general, the amount of CO ₂ adsorbed by the adsorbent for adsorbing CO ₂ varies depending on the pressure and temperature. There are _two methods for adsorbing and desorbing CO ₂ using this property: PSA method for changing pressure (Pressure Swing Adsorption method), TSA method for changing temperature (Thermal Swing Adsorption) Method) and the PTSA method (Pressure and Temperature Swing Adsorption method) that changes temperature in addition to pressure change, and the CO ₂ separation and recovery composition of the present invention is used in any of these methods. It can be done.

In the CO ₂ adsorption step, exhaust gas is supplied to the adsorption tower packed with the pure silica zeolite to adsorb CO ₂ . The temperature in the adsorption is preferably about 0 to 150 ° C., more preferably about 1 to 60 ° C., and the pressure is preferably about 100 to 4000 kPa as CO ₂ partial pressure, more preferably about 500 to 3000 kPa, and further about 800 to 2000 kPa. preferable. Further, the pressure is preferably about 0.6 to 476 kPa, more preferably about 0.6 to 20 kPa, and further preferably about 0.6 to 4 kPa as the partial pressure of water vapor. In the CO ₂ desorption step, usually, the adsorption tower is depressurized at room temperature or under heating, the adsorbed CO ₂ is desorbed, and the pure silica zeolite adsorbed with CO ₂ is regenerated. The temperature for desorption is preferably about 1 to 200 ° C, more preferably about 15 to 140 ° C, the pressure is about 1 to 500 kPa (about 0.01 to 5.0 atm), and more preferably about 10 to 200 kPa (about 0). 0.1 to 2.0 atmospheres). A value obtained by subtracting the CO ₂ desorption amount from the CO ₂ adsorption amount thus measured is referred to as a CO ₂ separation and recovery amount.

In addition to the raw material composition and the CO ₂ separation / recovery composition described above, the present invention also includes a production method for producing a CO ₂ separation / recovery composition from the raw material composition. ₂ Description is omitted as it is explained as a method for obtaining a separated and recovered composition.

  The present invention will be specifically described with reference to the following examples and comparative examples, but the present invention is not limited thereto. Hereinafter, “%” representing yield means “% by mass”.

(Synthesis Example 1: Synthesis of hydroxyl N, N, N, -trimethyl-1-adamantanamine (TMAdaOH))
50 g of chloroform was added to 4.667 g of 1-adamantanamine (manufactured by Aldrich) and completely dissolved at room temperature, and 11.350 g of potassium carbonate was added. The inside of the flask was replaced with N ₂ , and the whole solution was sufficiently cooled for about 30 minutes, and 13.14 g of CH ₃ I was added and sufficiently stirred for 1 day. Furthermore, 6.5 g of CH ₃ I was added and allowed to sufficiently stir for 10 days. This solution was filtered using filter paper 5A to remove K ₂ CO ₃ , and then the chloroform solvent contained in the filtrate was evaporated to dryness using a rotary evaporator. Thereafter, methanol was slowly added to the product, and the product was completely dissolved at reflux temperature. After slowly cooling to room temperature and recrystallization, small white flake crystals (TMAdaI) were precipitated. Filtration was performed with filter paper 5A, the filtrate was placed in an anion exchange resin, stirred with a Teflon rod and allowed to stand overnight, and the aqueous solvent was evaporated to dryness with a rotary evaporator to obtain TMAdaOH. As a result of NMR analysis of the obtained TMAdaOH and Liquid-Mass analysis of TMAdaI, it was confirmed that the purity of the product was 98% or more.

<Synthesis of pure silica zeolite>
Example 1
1.664 g of N, N, N produced in Synthesis Example 1 in a stainless steel autoclave (trade name: Double Reactor RW-20, manufactured by Hiro Co., Ltd., volume 20 ml) in which a fluororesin container is set as an inner cylinder , -Trimethyl-1-adamantanamine 2 molar aqueous solution (structure-directing agent (hereinafter also referred to as SDA)) and 2.5 g of silica sol (trade name: Colloidal Silica TM-40, manufactured by Aldrich, solid content: 40% by mass , Containing Na ⁺ stabilizer and an average particle diameter of 22 nm of silica, and 0.178 g of hydrofluoric acid (manufactured by Wako Pure Chemical Industries, Ltd., HF content of 46.9% by mass) was added to this mixed solution. Aqueous solution) was added with vigorous stirring. At this time, the molar ratio of N, N, N, -trimethyl-1-adamantanamine hydroxide / silica sol in silica (SiO ₂ ) component molar ratio is 0.2, hydrofluoric acid (HF) / hydroxylated N, N, N The molar ratio of, -trimethyl-1-adamantanamine was 1.25.

A fluororesin-coated rotor is placed in a fluororesin container containing the raw material composition, and 350 rpm while keeping the set temperature at 100 ° C. on a hot stirrer (trade name: REXIM RSH-6DR, manufactured by ASONE CORPORATION). And stirred. Water was evaporated until the mass of the composition in the container reached 2.101 g to obtain a powdery raw material composition in the present invention. At this time, the molar ratio of the silica (SiO ₂ ) component in the water / silica sol was 1.25.

  The autoclave container removed from the hot stirrer was set in a stainless steel autoclave, and hydrothermal synthesis was performed at 175 ° C. for 24 hours. The pressure of hydrothermal synthesis was about 1 MPa. After the heat treatment, a powdery solid was formed in the fluororesin container. The powdery solid is taken out from the container, washed with water, dried, then heated to 680 ° C. at a rate of 1.0 ° C./min in the air at a rate of 1.0 ° C./min and held for 12 hours, at a rate of 1 ° C./min. Cooled to room temperature.

  Next, the crystalline phase was evaluated by examining the crystalline phase of the obtained powdery solid by powder X-ray diffraction (RINT2000, manufactured by Rigaku Corporation), and the crystal form was a scanning electron microscope (S-5000, Hitachi, Ltd.). It was observed and evaluated. Further, the elements forming the framework of the zeolite crystal were analyzed by inductively coupled plasma emission spectroscopy (ICP-7000, manufactured by Shimadzu Corporation).

  In the powder X-ray diffraction, the “diffraction peak of CHA-type zeolite” means “M. M.M. J. et al. TreacyJ. B. It is a diffraction peak described in Higgins, Collection of Simulated XRD Powder Patterns for Zeolites, Elsevier, 100 (2001). In addition, the zeolite crystal is amorphous in the case where a clear peak cannot be confirmed only by a broad halo showing amorphous silica in the region of 2θ = 18 to 30 ° (CuKα) in X-ray diffraction. The case where a peak of CHA-type zeolite was observed was in the course of crystallization, the peak indicating CHA-type zeolite was clearly recognized, and the case where there was no halo was defined as complete crystal.

  In addition, elemental analysis of zeolite crystals by inductively coupled plasma emission spectroscopy was determined by measuring the element concentration of a solution prepared by dissolving the prepared zeolite crystal in an alkaline aqueous solution. Specifically, 0.08 g of the prepared zeolite powder was placed in a 20 ml fluororesin autoclave container and stirred in 3.0 normal 2.0 ml aqueous sodium hydroxide solution, followed by heat treatment at 90 ° C. for 24 hours. The zeolite crystals were dissolved in the solution. This concentrated solution was diluted 30 times with a 0.5 N aqueous sodium hydroxide solution to prepare a measurement solution.

  As a result of the powder X-ray diffraction of the CHA type pure silica zeolite crystal, only the diffraction peak of the CHA type zeolite was clearly detected, and no halo was observed over the region of 2θ = 18 to 30 ° (CuKα). Further, by inductively coupled plasma emission spectroscopic analysis, the element forming the framework of the zeolite crystal was only silicon, and introduction of impurities such as aluminum from the production container was not recognized. That is, a complete crystal of CHA type pure silica zeolite was obtained. Further, when the powdered solid was observed with a scanning electron microscope, it was a simple substance and an aggregate of a rhombohedral crystal having a substantially cubic shape with a side length of about 10 μm, and this was a single crystal of CHA type pure silica zeolite crystal and It was confirmed to be an aggregate. FIG. 1 is a scanning electron micrograph of the produced CHA type pure silica zeolite crystal. FIG. 2 is a diffraction chart obtained by powder X-ray diffraction. The yield of the CHA type pure silica zeolite was 95% with respect to the silica in the raw material silica sol.

(Example 2)
In Example 1, as described in Table 1, the same operation as in Example 1 was performed except that the content of each component in the raw material composition was changed. As a result, very good pure silica zeolites were obtained.

(Example 3)
In Example 1, the type of silica sol was changed to “Colloidal silica AS-40 (manufactured by Aldrich, solid content purity 40% by mass, containing NH ₄ ⁺ stabilizer, silica average particle size 22 nm)” and used for the reaction. The autoclave container made of fluororesin is changed to an autoclave container made of fluororesin (trade name: RDV-TM, manufactured by Sanai Kagaku Co., Ltd., volume 100 ml), and as shown in Table 1, in the raw material composition The same operation as in Example 1 was performed except that the content of each component was changed. As a result, a very good pure silica zeolite was obtained.

Example 4
In Example 1, as described in Table 1, the same operation as in Example 1 was performed except that the content of each component in the raw material composition was changed. As a result, very good pure silica zeolites were obtained.

(Example 5)
Fluorine resin autoclave container (trade name: Double Reactor RW-20, manufactured by Hiro Co., Ltd., volume 20 ml) and 1-adamantanamine (manufactured by Aldrich) hydroxide N, N, N, -trimethyl-1 -1.170 g of a 2 mol aqueous solution of adamantaneamine and 8.157 g of water were added and mixed with stirring for 10 minutes, and 2.48 g of tetraethylorthosilicate (manufactured by Aldrich, purity 98 mass%) was added thereto, and this raw material composition was contained. Place a fluororesin-coated magnetic rotor in an autoclave container, set on a hot stirrer (trade name: REXIM RSH-6DR, manufactured by ASONE Co., Ltd.), and first stir at 400 to 500 rpm for 1 hour or more at room temperature. Hydrolysis of orthosilicate (hereinafter also referred to as TEOS) was promoted.

Next, the speed of the magnetic rotor is lowered to 350 rpm, the surface temperature of the hot plate is set to 110 ° C., and the periphery of the autoclave container is double-wound with a glass fiber woven cloth (thickness 1.5 mm, width 50 mm). The water vapor is evaporated while blowing nitrogen gas from a thin stainless steel tube (outer diameter: 1.0 mm, inner diameter: 0.5 mm) into the autoclave container at a speed of about 150 to 200 ml / min from a height of 20 mm from the liquid level. And concentrated to dryness to approximately 1.965 g of the composition. After the autoclave Teflon container was dried to room temperature, the contents were scraped cleanly and crushed into a powder by a small pulverizer (sample mill: SK-M type, Kyoritsu Riko Co., Ltd.). Again, the crushed composition was put in a Teflon container for autoclave, and 0.1254 g of hydrofluoric acid (46.9% by mass, manufactured by Wako Pure Chemical Industries, Ltd.) was added little by little while stirring the inside with a Teflon stirring rod. Hydroxylated N, N, N, -trimethyl-1-adamantanamine was neutralized. Thereafter, the surface temperature of the hot plate is set again to 110 ° C., and dried by heating in the same manner as described above, dried to a mass of the composition of 1.1.470 g or less, cooled to room temperature, Added to a predetermined mass (1.470 g). At this time, the molar ratio of hydroxylated N, N, N, -trimethyl-1-adamantanamine fluoride / silica (SiO ₂ ) component was 0.2, hydrofluoric acid (HF) / hydroxylated N, N, N The molar ratio of, -trimethyl-1-adamantanamine was 1.25, and the molar ratio of water / silica (SiO ₂ ) was 1.3.

  The fluororesin container removed from the hot stirrer was set in a stainless steel autoclave, and hydrothermal synthesis was performed at 150 ° C. for 24 hours. The pressure of hydrothermal synthesis was about 1 MPa. After the heat treatment, a powdery solid was formed in the fluororesin container. The powdery solid is taken out from the container, washed with water, dried, then heated to 680 ° C. at a rate of 1.0 ° C./min in the air at a rate of 1.0 ° C./min and held for 12 hours, at a rate of 1 ° C./min. Cooled to room temperature. Hereinafter, the same analysis as in Example 1 was performed on the powdered solid obtained by the same operation as in Example 1.

  As a result of powder X-ray diffraction of the CHA type pure silica zeolite crystal, only the diffraction peak of the CHA type zeolite was clearly detected, and no halo was observed in the region of 2θ = 18-30 ° (CuKα). It was confirmed that they were single crystals and aggregates of silica zeolite crystals. FIG. 3 is a scanning electron micrograph of the produced CHA type pure silica zeolite crystal. FIG. 4 is a diffraction chart obtained by powder X-ray diffraction. The yield of the CHA type pure silica zeolite was 96% with respect to the silica in the raw material silica sol.

(Example 6)
In Example 5, as described in Table 1, the same operation as in Example 5 was performed except that the content of each component in the raw material composition was changed. As a result, a very good pure silica zeolite was obtained.

(Comparative Example 1)
In Example 1, as described in Table 1, the same operation as in Example 1 was performed except that the content of each component in the raw material composition was changed. As a result, many crystals different from pure silica CHA were produced, and the synthesis was poor.
FIG. 5 is a scanning electron micrograph of the crystal produced in Comparative Example 1. Similarly, FIG. 6 is a diffraction chart obtained by powder X-ray diffraction.

(Comparative Example 2)
In Example 1, as described in Table 1, the same operation as in Example 1 was performed except that the content of each component in the raw material composition was changed. As a result, a large number of non-crystals different from pure silica CHA were produced, halo peaks were observed in X-ray diffraction, and the synthesis was quite poor.
FIG. 7 is a scanning electron micrograph of the crystal produced in Comparative Example 2. Similarly, FIG. 8 is a diffraction chart obtained by powder X-ray diffraction.

(Comparative Example 3)
In Example 5, as described in Table 1, the same operation as in Example 5 was performed except that the content of each component in the raw material composition was changed. As a result, many crystals different from pure silica CHA were produced, and the synthesis was poor.
FIG. 9 is a scanning electron micrograph of the crystal produced in Comparative Example 3. Similarly, FIG. 10 is a diffraction chart obtained by powder X-ray diffraction.

(Comparative Example 4)
In Example 5, as described in Table 1, the same operation as in Example 5 was performed except that the content of each component in the raw material composition was changed. As a result, many crystals different from pure silica CHA were produced, and the synthesis was poor.

(Comparative Example 5)
In Example 5, the same operation as in Example 5 was performed except that the temperature during hydrothermal synthesis was 175 ° C. and the content of each component in the raw material composition was changed as shown in Table 1. As a result, many crystals different from pure silica CHA were produced, and the synthesis was poor.

(Comparative Example 6)
In a fluororesin autoclave container (trade name: Double Reactor RW-20, manufactured by Hiro Co., Ltd., volume 20 ml), 0.43 g of hydroxylated N, N, N— produced from 1-adamantanamine (Aldrich) Trimethyl-1-adamantanamine powder and 0.28 g of silica sol (trade name: colloidal silica AS-40, manufactured by Aldrich, solid concentration 40% by mass) are mixed by lightly stirring, and 87 mg of fluorine is added to the mixture. Hydrohydric acid (46.9% by mass, manufactured by Wako Pure Chemical Industries, Ltd.) was added with vigorous stirring, and the composition was confirmed to be neutral with a universal test paper (pH test paper).
Put the fluororesin-coated rotor in the autoclave container containing the raw powder composition, set it on a hot stirrer (trade name: Program Hot Stirrer DP-2M, manufactured by ASONE Co., Ltd.), and set the temperature to 90 ° C. Stir at 800 rpm. A glass container (trade name: BELL JAR VKU-500, manufactured by Kiriyama Seisakusho Co., Ltd.) was placed thereon, and dried under reduced pressure using an aspirator (trade name: portable aspirator MDA-015, manufactured by ULVAC Kiko Co., Ltd.). Thereafter, the autoclave container was taken out from the glass container and dried under reduced pressure until the mass became 0.75 g to obtain a mixture. At this time, the molar ratio of the silica (SiO ₂ ) component in the water / silica sol was 5.9.

  The autoclave container removed from the hot stirrer was transferred to a stainless steel heat-resistant container, and hydrothermal synthesis was performed at 175 ° C. for 16 hours. After the heat treatment, a powdery solid was formed in the autoclave container. This powdery solid is taken out from the autoclave container, washed with water, dried, then heated to 580 ° C. at a rate of 1.0 ° C./min in the air at a rate of 1.0 ° C./min, held for 12 hours, and then at a rate of 1 ° C./min. At room temperature. As a result, a good pure silica zeolite was obtained.

  Table 1 shows the molar ratio of the components contained in the crystals obtained in each of the Examples and Comparative Examples and the evaluation results of the obtained crystals. The crystal was evaluated based on the peak obtained by the powder X-ray diffraction. The evaluation criteria were “：: very good (only the peak of the target structure was observed)”, “◯: good (the peak of the target structure was observed as the main peak, and other peaks were also slightly observed. ””, “Δ: Poor (the peak of the target structure and other peaks were observed to the same extent)”, “×: Synthesis not possible (the other peaks were larger than the peaks of the target structure.)” It is.

Table 1 shows the results of various measurements on the water vapor adsorption amount and the CO ₂ separation and recovery amount using the zeolites obtained in the examples and comparative examples as described above. The test equipment used to perform the performance test of zeolite is composed of an adsorbent filling container containing zeolite, a raw material gas cylinder, a vacuum pump, and a switching valve. By opening and closing a predetermined switching valve with a sequence controller. Tests such as adsorption / desorption of CO ₂ under constant temperature and pressure conditions are possible.
It can be confirmed by the following method that the CO ₂ separation and recovery composition of the present invention has a water vapor adsorption amount of less than 3 mol / kg and a CO ₂ separation and recovery amount of 2.5 mol / kg or more.

<Measurement of water vapor adsorption amount>
For the zeolites obtained in Examples 1 to 6 and Comparative Example 6 described above, a high-accuracy diaphragm pressure sensor is obtained by a constant volume method using an automatic gas / vapor adsorption measuring device Belsorp18-plus (manufactured by Nippon Bell Co., Ltd.). Was used to measure the amount of water vapor adsorbed at saturated vapor pressure, and a single component adsorption isotherm of water vapor was created and calculated under the following conditions.
Sample weight: 0.6g-1.8g
・ Measurement temperature: 40 ℃
・ Pretreatment: Evacuated at 200 ° C for 8 hours (heated at 10 ° C / min)
・ Measurement conditions: Adsorption equilibrium 500 sec
: Adsorption temperature 40 ℃
: Saturated vapor pressure 7.377 kPa
: Initial introduction pressure 0.400 kPa
: Maximum adsorption pressure P / Po = 0.9
: Minimum desorption pressure P / Po = 0.05
The results are shown in Table 1. It was revealed that the pure silica zeolites of Examples 1 to 6 had less water vapor adsorption than the zeolite of Comparative Example 6 at 40 ° C. That is, the water vapor adsorption amount of Comparative Example 6 is about 3.5 mol / kg (40 ° C., 97 kPa), whereas the saturated adsorption amounts of Examples 1 to 6 are all about 3.0 mol / kg (40 ° C., 97 kPa).
Although the content of the hydroxylated organic amine in the raw material composition is small compared with the conventional pure silica zeolite, the pure silica zeolite of Examples 1 to 5 has a water vapor adsorption amount as compared with the conventional pure silica zeolite. With fewer results.

<Measurement of CO ₂ separation and recovery>
Respect zeolites obtained in Examples 1 to 6, high-pressure gas 2 component adsorption apparatus (BEL Japan Inc., BELSORP HP) using a CO ₂ adsorption amount measured at a measurement temperature of 40 ° C., CO ₂ adsorption isotherms It was created. This device has a structure in which a balance is installed on a volumetric gas adsorption device that determines the amount of adsorption by a normal pressure change, and can measure the weight change at the same time as the pressure change during gas adsorption. It is possible to measure the amount of gas adsorption. For the coexistence measurement of water vapor, a method was adopted in which CO ₂ was introduced after saturated adsorption of water vapor on zeolite in advance.
The difference loading (loading of CO ₂ adsorption amount of the thus CO ₂ partial pressure 1000kPa from the steam pre-adsorbed -CO ₂ adsorption like hot springs obtained (mol / kg) CO ₂ adsorption amount of 100kPa from (mol / kg) Here, it is calculated as the amount of CO ₂ separated and recovered (mol / kg) by means of increasing and decreasing the pressure. The results are shown in Table 1.
<Conditions for CO ₂ adsorption measurement in the presence of water vapor in the above method>
Sample weight: 0.6 to 1.0 g
・ Measurement temperature: 40 ℃
Water vapor pre-adsorption: 7.3 kPa
・ Measurement pressure (total pressure): 0 to 2.0 MPa
・ CO ₂ recovery amount: 1000 → 100 kPa (CO ₂ partial pressure) Loading difference recovery amount mol / Kg

Moreover, with respect to the zeolite obtained in Comparative Example 6, the high-pressure gas two-component adsorption device MSB-BG-H10R (manufactured by Nippon Bell Co., Ltd.) was used and the zeolite obtained in Examples 1 to 6 was used. Similarly, CO ₂ adsorption (two-component simultaneous adsorption) in the presence of water vapor was measured. This device also has a structure with a magnetic suspension balance in the gas adsorption amount measuring device of the usual constant volume method. By combining the constant volume method and the gravimetric method, the amount of change is obtained from both and the two component gas adsorption amounts are obtained. Measurements were made to create adsorption isotherms.
Sample weight: 0.8g-1.0g
・ Measurement temperature: 40 ℃
・ Pretreatment: Evacuated at 250 ° C for 8 hours (heated at 5 ° C / min)
・ Measurement pressure (total pressure): 0 to 2.0 MPa
・ Steam coexistence conditions: Measurement after saturated water vapor adsorption at 40 ° C. beforehand ・ CO ₂ recovery amount: 1000 → 100 kPa (CO ₂ partial pressure) loading difference recovery amount mol / Kg
The results are shown in Table 1. It was revealed that the pure silica zeolite of Examples 1 to 6 did not impair the CO ₂ separation and recovery amount at 40 ° C. as compared with the zeolite of Comparative Example 6. That is, the CO ₂ separation and recovery amount of Comparative Example 6 is about 2.5 mol / kg (1000 → 100 kPa loading difference), whereas the CO ₂ adsorption amounts of Examples 1 to 6 are all about 2.5 mol / kg. More than (1000 → 100 kPa loading difference recovery amount).
The pure silica zeolite of Examples 1 to 5 in which the content of the hydroxylated organic amine in the raw material composition is small compared to the conventional pure silica zeolite, the CO ₂ adsorption amount of the conventional pure silica zeolite, the CO ₂ separation recovery amount The result was unimpaired.
Further, the water vapor adsorption amount can be suppressed to 3 mol / kg or less, and the carbon dioxide separation and recovery composition obtained by carrying out the present invention does not cause the CO ₂ adsorption ability to be significantly impaired by moisture adsorption. , CO ₂ adsorption capacity can be maintained.
Further, as can be seen from Table 1, when the present invention is carried out, the amount of the hydroxylated organic amine, which is an expensive material, can be significantly reduced during the production of the carbon dioxide separation and recovery composition, resulting in low cost. Can be achieved. Moreover, since it becomes possible to suppress the usage-amount of hydroxylated organic amine, the usage-amount of hydrofluoric acid can also be suppressed and the further low cost can also be achieved.

The CO ₂ separation / recovery composition of the present invention is low in cost because the amount of the structure directing agent (hydroxylated organic amine) used as a raw material is small compared to the conventional CO ₂ separation / recovery agent, and the amount of water vapor adsorption is small. It is not easily affected by moisture when adsorbing CO _2, has an excellent CO ₂ recovery capability, and can efficiently recover and separate CO ₂ .

Claims (11)

  In a raw material composition for producing a carbon dioxide separation and recovery composition containing silica, a hydroxylated organic amine, water and hydrofluoric acid, the content of the hydroxylated organic amine is 7 to 40 mol per 100 mol of silica. A raw material composition for producing a carbon dioxide separation and recovery composition, characterized in that the water content is 50 to 200 mol parts.   2. The raw material composition for producing a carbon dioxide gas separation and recovery composition according to claim 1, wherein the molar ratio of hydrofluoric acid / hydroxylated organic amine is 0.5 to 1.5.   A carbon dioxide separation and recovery composition produced by subjecting the raw material composition according to claim 1 to a heat treatment step.   The composition according to claim 3, wherein the water vapor adsorption amount of the carbon dioxide gas separation and recovery composition is less than 3 mol / kg, and the carbon dioxide separation and recovery amount is 2.5 mol / kg or more.   The composition according to any one of claims 1 to 4, wherein the carbon dioxide gas separation and recovery composition contains pure silica zeolite.   The composition according to claim 5, wherein the pure silica zeolite is of the CHA type.   The composition according to any one of claims 1 to 6, wherein the hydroxylated organic amine is hydroxylated N, N, N-trimethyl-1-adamantanamine.   The composition according to any one of claims 1 to 7, wherein one or more selected from the group consisting of colloidal silica, fumed silica, tetraethyl orthosilicate, and tetrapropyl orthosilicate are used as a silica source.   The composition according to any one of claims 2 to 8, wherein the heat treatment step heats the raw material composition according to claim 1 at 130 ° C to 200 ° C for 12 to 30 hours. A production method for producing a carbon dioxide separation and recovery composition from a raw material composition containing silica, a hydroxylated organic amine, water and hydrofluoric acid,
A step of preparing a raw material composition in which the content of the hydroxylated organic amine is 7 to 40 mol parts and the water content is 50 to 200 mol parts with respect to 100 mol parts of the silica;
And a step of heat-treating the raw material composition. A method for producing a carbon dioxide separation and recovery composition.   The method for producing a carbon dioxide gas separation and recovery composition according to claim 10, wherein the molar ratio of hydrofluoric acid / hydroxylated organic amine is 0.5 to 1.5.