JP2017047412A - Acid gas adsorption material, production method therefor, acid gas recovery method, acid gas recovery unit and acid gas recovery system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acid gas adsorption material capable of adsorbing selectively acid gas such as carbon dioxide by chemical absorption, and excellent in its adsorption amount.SOLUTION: An acid gas adsorption material contains a crosslinked product of a polyfunctional glycidyl ether type epoxy compound and an amine compound having a primary or secondary aliphatic amino group.SELECTED DRAWING: None

Description

  The present invention relates to an acid gas adsorbing material and a method for producing the same, an acid gas recovery method, an acid gas recovery unit, and an acid gas recovery system.

  Since the Industrial Revolution, the increase in the amount of carbon dioxide in the atmosphere accompanying the expansion of fossil fuel consumption is considered to cause global warming. Global warming countermeasures are being discussed between countries, and as one of the countermeasures, carbon dioxide capture and storage technology called CCS (Carbon Dioxide Capture and Storage) is drawing attention. CCS is a technology that reduces carbon dioxide emissions into the atmosphere by collecting and liquefying carbon dioxide in gas discharged from thermal power plants and the like and storing it in the ground or in the sea. However, since the carbon dioxide concentration in the exhaust gas is as low as about 10% and cannot be liquefied as it is, a step for collecting and concentrating the carbon dioxide in the exhaust gas is required.

  Carbon dioxide recovery methods include a chemical adsorption recovery method using a liquid absorbent containing a basic amine (see Patent Document 1), zeolite, activated carbon, and porous metal complex called MOF (Metal Organic Framework). A recovery method by physical adsorption using a solid adsorbent such as a material (see Patent Document 2 and Non-Patent Document 1) is known.

JP 2007-325996 A JP 2009-62268 A

Industrial & Engineering Chemistry Research, 2012, 51, 1438-1463

  However, in the absorbent described in Patent Document 1, since the amine in the absorbent volatilizes and is partially released into the atmosphere, there is a concern about the influence on the environment and the replenishment cost of the amine may increase. Therefore, for example, use of a solid adsorbent capable of chemical adsorption is desired, but a solid adsorbent capable of chemical adsorption excellent in the amount of adsorption is not necessarily realized.

  On the other hand, in the solid adsorbent described in Patent Document 2 or Non-Patent Document 1, a gas having a predetermined molecular size is separated by physical adsorption using van der Waals force. It is difficult to selectively adsorb only, and in the presence of water vapor, there is a possibility of competitive adsorption with water vapor and a decrease in adsorption performance.

  Accordingly, the present invention provides an acidic gas adsorbing material that can selectively adsorb an acidic gas such as carbon dioxide by chemical adsorption and has an excellent amount of adsorption, a method for producing the same, an acid gas recovery method, an acid gas recovery unit, and an acid gas An object is to provide a gas recovery system.

  One aspect of the present invention is an acid gas adsorbing material containing a cross-linked product of a polyfunctional glycidyl ether type solid epoxy compound and an amine compound having a primary or secondary aliphatic amino group.

  Another aspect of the present invention is an acid gas adsorbing material containing an aggregate of organic fine particles.

The specific surface area of the acid gas adsorbing material may be 1.0 m ² / g or more.

  Another aspect of the present invention is an acid gas recovery unit including the acid gas adsorbing material.

  Another aspect of the present invention is an acid gas recovery system including the acid gas recovery unit.

  In another aspect of the present invention, a step of introducing a gas containing an acid gas into an acid gas recovery unit including the acid gas adsorbing material described above to adsorb the acid gas to the acid gas adsorbing material; And a step of desorbing the acidic gas from the acidic gas adsorbing material by changing the temperature.

  Another aspect of the present invention includes a step of obtaining an acid gas adsorbing material by reacting a polyfunctional glycidyl ether type epoxy compound with an amine compound having a primary or secondary aliphatic amino group in an organic solvent, The compound is hardly soluble in an organic solvent, and the organic solvent is inactive with respect to the epoxy compound and the amine compound.

  In the above production method, the organic solvent may be at least one selected from the group consisting of an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, an aliphatic alcohol solvent, an ether solvent, and a halogen-containing organic solvent.

  In the said manufacturing method, an epoxy compound may show the solubility of 0.01-20 mass% with respect to the organic solvent.

  In the said manufacturing method, you may make an epoxy compound and an amine compound react so that the equivalent ratio of the epoxy compound with respect to an amine compound may be 0.7-1.2.

  According to the present invention, an acid gas adsorbing material that can selectively adsorb an acid gas such as carbon dioxide by chemical adsorption and has an excellent amount of adsorption, and a method for producing the same, an acid gas recovery method, an acid gas recovery unit, and an acid gas A gas recovery system can be provided.

It is a mimetic diagram showing one embodiment of an acid gas recovery system. It is a schematic diagram which shows one Embodiment of the collection | recovery method of acidic gas. 2 is a SEM photograph of the resin powder (acid gas adsorbing material) of Example 1. 3 is a SEM photograph of resin powder (acid gas adsorbing material) in Example 2. 4 is a SEM photograph of resin powder (acid gas adsorbing material) in Example 3. It is a SEM photograph of the resin powder (acid gas adsorption material) of Example 4. It is a SEM photograph of resin powder (acid gas adsorption material) of Example 5. It is a SEM photograph of resin powder (acid gas adsorption material) of Example 6. It is a SEM photograph of resin powder (acid gas adsorption material) of Example 7. 4 is a SEM photograph of a resin powder of Comparative Example 2. 6 is a SEM photograph of a resin powder of Comparative Example 3.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In this specification, the term “process” is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. It is. The numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. The content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.

<Acid Gas Adsorbing Material (First Embodiment)>
The acidic gas adsorbing material according to the first embodiment includes a polyfunctional glycidyl ether type solid epoxy compound (hereinafter also simply referred to as “polyfunctional epoxy compound”) and an amine compound having a primary or secondary aliphatic amino group (hereinafter referred to as “polyfunctional epoxy compound”). , And also referred to as “amine compound”). This crosslinked product is a crosslinked product having a three-dimensional crosslinked structure obtained by reacting a polyfunctional glycidyl ether type solid epoxy compound with an amine compound having a primary or secondary aliphatic amino group, and is a cured product. It can be said.

(Polyfunctional epoxy compound)
The polyfunctional glycidyl ether type solid epoxy compound has two or more glycidyl ether groups and is solid (solid) at room temperature (25 ° C.). The glycidyl ether group is a group represented by the following formula (1).

[In formula (1), * represents a bond. ]

  Since the polyfunctional epoxy compound has a Lewis basic ether structure, the interaction with the acid gas can be promoted, so that an acid gas adsorbing material having excellent adsorption characteristics can be obtained. By having a glycidyl ether group, the polyfunctional epoxy compound needs to form a crosslinked product with an amine compound having high nucleophilicity, and therefore preferably does not have a ketone structure or an ester structure in the molecule. In this case, it can be avoided that an imine structure or an amide structure is formed by the reaction with the amine compound.

  From the viewpoint that the polyfunctional epoxy compound can disperse the polyfunctional epoxy compound in the solvent and allow the amine compound and the polyfunctional epoxy compound slightly dissolved in the solvent to react with each other, and a cross-linked product can be suitably obtained. Solid at room temperature (25 ° C.). The polyfunctional epoxy compound is more preferably solid at the reaction temperature with the amine compound. Specifically, when the polyfunctional epoxy compound is a monomer or the like whose melting point can be measured, the melting point is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 100 ° C. or higher. It may be below ℃. When the polyfunctional epoxy compound is a polymer whose melting point cannot be measured, the softening point of the polyfunctional epoxy compound is preferably in the above range. The softening point of the polyfunctional epoxy compound in the present invention means a softening point measured by a ring and ball method according to JIS K7234-1986 "Testing method for softening point of epoxy resin".

  The polyfunctional epoxy compound preferably has an aromatic ring from the viewpoint of further excellent adsorption performance. It is presumed that when the polyfunctional epoxy compound has an aromatic ring, the acidic gas can permeate and adsorb not only on the surface of the acidic gas adsorbing material but also inside. In particular, when the acid gas adsorbing material has an aromatic ring in the main chain, the flexibility of the acid gas adsorbing material is lowered and it is difficult to adopt a close-packed structure. Therefore, as the free volume inside the cross-linked product (acid gas adsorbing material) increases, the permeability of the acid gas is improved and the adsorption capacity is improved. On the other hand, since the acid gas adsorbing material after the acid gas adsorption needs to be heated for regeneration, it is preferable that the acid gas adsorbing material also has chemical stability that does not decompose under heating conditions. In this respect, when the polyfunctional epoxy compound has an aromatic ring, an improvement in heat resistance of the crosslinked product (acid gas adsorbing material) can be expected.

  The aromatic ring is not particularly limited, and examples thereof include a benzene ring, naphthalene ring, anthracene ring, fluorene ring, thiophene ring, pyrrole ring, carbazole ring, pyridine ring, and imidazole ring. These aromatic rings may or may not have a substituent. The polyfunctional epoxy compound may have one of these aromatic rings or may have two or more.

Examples of such a polyfunctional epoxy compound include a compound represented by the following formula (2).

[In Formula (2), A ¹ represents an m-valent organic group having an aromatic ring, and m represents an integer of 2 or more. ]

The organic group represented by A ¹ preferably has at least one aromatic ring selected from a benzene ring, naphthalene ring, anthracene ring, fluorene ring, thiophene ring, pyrrole ring, carbazole ring, pyridine ring and imidazole ring. More preferably, it has a benzene ring. These aromatic rings may or may not have a substituent. m is preferably an integer of 2 to 4.

  As the polyfunctional epoxy compound represented by the formula (2), 9,9′-bis [4- (glycidyloxy) phenyl] fluorene, 1,4-diglycidyloxybenzene, 1,1 ′, 2,2 ′ -Tetrakis [4- (glycidyloxy) phenyl] ethane, 4,4 '-(diglycidyloxy) biphenyl, 1,5- (diglycidyloxy) naphthalene and the like.

When the organic group represented by A ¹ has a benzene ring, the polyfunctional epoxy compound is preferably a compound represented by the following formula (3) or (4).

In formula (3), A ² represents an m-valent organic group or m-valent hydrocarbon group having an aromatic ring, R ¹ represents a hydrogen atom or an alkyl group, and m is the same as m in formula (2) Represents the definition content. The organic group represented by A ² preferably has at least one kind selected from a naphthalene ring, an anthracene ring, a fluorene ring, a thiophene ring, a pyrrole ring, a carbazole ring, a pyridine ring and an imidazole ring as an aromatic ring. These aromatic rings may have a substituent, and the substituent may have at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom. The organic group represented by A ² may have a group containing at least one atom selected from an oxygen atom, a nitrogen atom and a sulfur atom in addition to the aromatic ring. The carbon number of the m-valent hydrocarbon group represented by A ² may be, for example, 1 to 5. When A ² is a divalent hydrocarbon group (m = 2), the hydrocarbon group may be, for example, an alkylene group having 1 to 5 carbon atoms, and preferably an alkylene group having 1 to 2 carbon atoms. R ¹ preferably represents a hydrogen atom, a methyl group or an ethyl group.

  As the polyfunctional epoxy compound represented by the formula (3), 9,9′-bis [4- (glycidyloxy) phenyl] fluorene, 1,1 ′, 2,2′-tetrakis [4- (glycidyloxy) Phenyl] ethane, bisphenol A type epoxy compound (epoxy resin), bisphenol F type epoxy compound (epoxy resin), bisphenol S type epoxy compound (epoxy resin), novolac type epoxy compound (epoxy resin) and the like.

In formula (4), R ¹ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom, a methyl group or an ethyl group. n represents an integer of 1 to 3. Examples of the polyfunctional epoxy compound represented by the formula (4) include 1,4-diglycidyloxybenzene, 4,4 ′-(diglycidyloxy) biphenyl, and the like.

  The above polyfunctional epoxy compounds may be used individually by 1 type, and may be used in combination of 2 or more type. When obtaining the acid gas adsorbing material (crosslinked product), other known epoxy compounds other than the polyfunctional epoxy compound may be used in combination for the purpose of adjusting the physical properties.

(Amine compound)
Since the amine compound has a primary or secondary aliphatic amino group, it becomes a tertiary amine after the addition reaction with the polyfunctional epoxy compound, which also acts as a catalyst for homopolymerization of the polyfunctional epoxy compound. At this time, since the basicity of the amino group after the reaction is maintained, the high molecular weight crosslinked product (acid gas adsorbing material) also exhibits basicity. Therefore, acidic gas such as carbon dioxide is adsorbed to the amino group present in the cross-linked product by a neutralization reaction. The primary aliphatic amino group is a group represented by —NH ₂ R ² , and the secondary aliphatic amino group is a group represented by —NHR ³ R ⁴ . Here, R ² , R ³ and R ⁴ each independently represent an aliphatic hydrocarbon group. Carbon number of this aliphatic hydrocarbon group may be 1-6, for example.

  On the other hand, when an amine compound having only a tertiary amino group is used, the homopolymerization of the polyfunctional epoxy compound is prioritized over the addition reaction to the polyfunctional epoxy compound, which makes it impossible to introduce an amino group into the crosslinked product. In addition, the adsorption characteristics of the acid gas adsorbing material are deteriorated. When an amine compound having only an aromatic amino group is used, the acid gas adsorbing material has a low basicity, so that a sufficient adsorption capacity for acid gas cannot be obtained.

  The amine compound may be an amine compound having two or more amino groups, and at least one of the amino groups is a primary or secondary aliphatic amino group. When the amine compound has two or more amino groups, if at least one of the amino groups is a primary or secondary aliphatic amino group, the other amino group is an aromatic amino group, a tertiary amino group, or the like. May be.

  Examples of such amine compounds include ethylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tris (2-aminoethyl) amine, N, N′-bis (3-aminopropyl) ethylenediamine, piperazine and the like.

  The amine compound is preferably an amine compound having two or more amino groups, more preferably two or more primary or secondary, from the viewpoint of easily forming a stable three-dimensional crosslinked structure with less polyfunctional epoxy compound. An amine compound having an aliphatic amino group, more preferably an aliphatic amine compound having two or more primary or secondary aliphatic amino groups. Among these amine compounds, an amine compound further having an ethylenediamine structure is particularly preferable. Since the ethylenediamine structure can form a chelate-type bidentate structure with respect to acidic gas, formation of a more stable adsorption structure can be expected.

  The acid gas adsorbing material may consist of a cross-linked product of a polyfunctional epoxy compound and an amine compound, and in addition to the cross-linked product, further contains other components such as a polymer in which only the polyfunctional epoxy compound is polymerized with each other. You may do it.

<Acid Gas Adsorbing Material (Second Embodiment)>
The acidic gas adsorbing material according to the second embodiment contains an aggregate of organic fine particles. The shape of the organic fine particles is not particularly limited. Here, the organic fine particles are fine particles composed of an organic compound and are, for example, 100 μm or less or 50.0 μm or less, preferably 20.0 μm or less, more preferably 15.0 μm or less, and even more preferably 10.0 μm or less. Particularly preferably, it means fine particles having an average primary particle diameter of 5.0 μm or less. The average primary particle diameter of the organic fine particles may be, for example, 0.01 μm or more, 0.1 μm or more, or 0.5 μm or more. The average primary particle diameter of the organic fine particles means an area average primary particle diameter measured by appearance observation with a scanning electron microscope.

  The aggregate is formed by aggregation of organic fine particles. The shape of the aggregate is not particularly limited. The average diameter of the aggregate is preferably 1.0 to 2000 μm, more preferably 5.0 to 500 μm, and still more preferably 10.0 to 100 μm, for example, from the viewpoint of reducing pressure loss and dead volume when packed in a column. It is. The average diameter of the aggregate means an area average diameter measured by a laser light scattering diffraction method.

The organic fine particles contain, for example, a cured product (crosslinked product) of a resin having a partial structure represented by the following formula (5).

In formula (5), R ⁵ represents a hydrogen atom or an aliphatic hydrocarbon group, and * represents a bond. The number of carbon atoms of the aliphatic hydrocarbon group represented by R ⁵ may be 1 to 6, for example.

The organic fine particles preferably contain a cured product (crosslinked product) of a resin having a partial structure represented by the following formula (6).

In formula (6), A ¹ and m each represent the same definition as A ¹ and m in formula (2), R ⁶ represents a hydrogen atom or an aliphatic hydrocarbon group, and X ¹ represents a q-valent organic compound. Represents a group, q represents an integer of 2 or more, and * represents a bond. A plurality of R ⁶ may be the same as or different from each other, and a plurality of R ⁶ may be bonded to each other. The number of carbon atoms of the aliphatic hydrocarbon group represented by R ⁶ may be 1 to 6, for example. q is preferably an integer of 2 to 4, more preferably 2.

The organic group represented by X ¹ is preferably a hydrocarbon group or an amino group, more preferably an aliphatic hydrocarbon group or an aliphatic amino group. The number of carbon atoms in the organic group represented by X ¹ may be, for example, 1-6. The organic group represented by X ^1, and specific examples thereof include groups represented by any one of the following formulas (7) to (11). In formulas (7) to (11), * represents a bond.

  The organic fine particles more preferably contain a cured product (crosslinked product) of a resin having a partial structure represented by the following formula (12) or (13).

In formula (12), R ⁶ , X ¹ and q each represent the same definition as R ⁶ , X ¹ and q in formula (6), and A ² , R ¹ and m each represent A in formula (3). ^It represents the same definition as ² and m, and * represents a bond.

In the formula (13), represents the same definition as ^{R 6} and ^{X 1} in ^{R 6} and ^{X 1} are each formula (6), ^{R 1} and n are the same definition as ^{R 1} and n in each formula (4) Indicates the content, and * indicates a bond.

  The cured product (crosslinked product) of the resin described above may be a crosslinked product of the polyfunctional epoxy compound and the amine compound described in the first embodiment. The organic fine particles may consist of the cured product (crosslinked product) of the resin described above, and in addition to the cured product (crosslinked product) of the resin, only the polyfunctional epoxy compound described in the first embodiment is polymerized with each other. It may further contain other components such as a polymer.

  Below, the matter common to the acidic gas adsorption material which concerns on 1st and 2nd embodiment mentioned above is demonstrated (henceforth, the word "acid gas adsorption material" means the acidic gas which concerns on 1st and 2nd embodiment. Meaning both adsorbent materials).

  The nitrogen content in the acid gas adsorbing material is preferably 1.0% by mass or more, more preferably 5.0% by mass or more, based on the total amount of the acid gas adsorbing material, from the viewpoint of further excellent acid gas adsorption amount. More preferably, it is 10.0 mass% or more. The nitrogen content may be, for example, 20.0% by mass or less based on the total amount of the acid gas adsorbing material. The nitrogen content in the present invention is measured by elemental analysis using a VARIO MICRO cube manufactured by Elementar.

The specific surface area of the acid gas adsorbing material is preferably 1.0 m ² / g or more, more preferably 5.0 m ² / g or more, and still more preferably 10.0 m ² / g, from the viewpoint of further excellent acid gas adsorption. That's it. The specific surface area may be, for example, 1000 m ² / g or less. The specific surface area in the present invention means a specific surface area measured by a constant volume method using nitrogen gas as an adsorption gas and calculated by the BET multipoint method.

  The heat mass retention rate at 300 ° C. of the acid gas adsorbing material is preferably 85% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more, from the viewpoint of excellent thermal stability of the acid gas adsorbing material. is there. The thermal mass retention at 300 ° C. in the present invention is the change in mass when the acidic gas adsorbing material is heated from room temperature (25 ° C.) to 300 ° C. at a rate of temperature increase of 10 ° C./min (mass after heating / before heating). Mass × 100 (%)).

  The glass transition temperature of the acid gas adsorbing material is preferably 100 ° C. or higher, more preferably 150 ° C. or higher, further preferably 200 ° C. or higher, from the viewpoint of excellent thermal stability of the acid gas adsorbing material. The glass transition temperature may be 250 ° C. or lower, for example. The glass transition temperature in the present invention means a temperature corresponding to a loss tangent (tan δ) peak measured using a dynamic viscoelasticity measuring apparatus (the largest peak when two or more peaks are present). The measurement conditions may be, for example, a temperature range: 30 to 250 ° C., a heating rate: 5 ° C./min, and a frequency: 1 Hz.

<Method for producing acid gas adsorbing material>
In the method for producing an acid gas adsorbing material according to the present embodiment, a polyfunctional glycidyl ether type epoxy compound and an amine compound having a primary or secondary aliphatic amino group are reacted in an organic solvent to produce the acid gas adsorbing material. A obtaining step.

  The polyfunctional glycidyl ether type epoxy compound has two or more glycidyl ether groups and may be hardly soluble in an organic solvent.

  The solubility of the polyfunctional glycidyl ether type epoxy compound in the organic solvent is preferably 0.1 to 20.0 mass%, 0.1 to 10.0 mass%, 0.1 to 5.0 mass%, and 0.0. 5 to 20.0 mass%, 0.5 to 10.0 mass%, 0.5 to 5.0 mass%, 1.0 to 20.0 mass%, 1.0 to 10.0 mass%, or 1. It is 0-5.0 mass%.

The solubility in this invention means the solubility with respect to the organic solvent in 25 degreeC, and is specifically measured as follows, for example. A polyfunctional glycidyl ether type epoxy compound is added to an organic solvent at 25 ° C. until it remains undissolved to prepare a saturated solution, which is heated to 60 ° C., then cooled again to 25 ° C. and left for 12 hours. The supernatant is filtered through a syringe filter, the filtrate is weighed, dried at 150 ° C. for 1 hour, and the dry mass is measured to calculate the solid mass and the solution mass, and the solubility is determined according to the following equation.
Solubility (mass%) = solid mass / solution mass × 100

  The polyfunctional glycidyl ether type epoxy compound may be the polyfunctional glycidyl ether type solid epoxy compound described in the first embodiment. The amine compound having a primary or secondary aliphatic amino group may be the amine compound having a primary or secondary aliphatic amino group described in the first embodiment.

  An organic solvent will not be specifically limited if it is a solvent inactive with respect to a polyfunctional glycidyl ether type epoxy compound and an amine compound. Specifically, the organic solvent may be an organic solvent other than ketones, esters, amines, carboxylic acids and the like. The organic solvent is preferably selected from an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, an aliphatic alcohol solvent, an ether solvent and a halogen-containing organic solvent. These solvents may be used alone or in combination of two or more solvents for the purpose of adjusting the boiling point of the solvent and the solubility of the epoxy compound.

  Examples of the aliphatic hydrocarbon solvent include n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, isooctane, petroleum ether, benzine and the like.

  Examples of the aromatic hydrocarbon solvent include toluene, xylene, mesitylene, benzene and the like.

  Examples of the aliphatic alcohol solvent include methanol, ethanol, isopropanol, butanol, cyclohexanol, ethylene glycol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol, and the like.

  Examples of the ether solvent include diethyl ether, diisopropyl ether, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, anisole and the like. In addition, a compound in which only a part of the hydroxy group of the aliphatic polyhydric alcohol is etherified (that is, a compound having at least one hydroxy group), such as propylene glycol monomethyl ether, is classified as an aliphatic alcohol. Shall.

  Examples of the halogen-containing organic solvent include dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene and the like.

  The organic solvent is preferably a solvent in which the polyfunctional glycidyl ether type epoxy compound exhibits a predetermined solubility as described above while dissolving the amine compound well. By using such an organic solvent, it is possible to maintain an environment in which the amine compound is excessive with respect to the polyfunctional glycidyl ether type epoxy compound in the solution and to ensure the reactivity between the epoxy compound and the amine compound.

  The solubility of the polyfunctional epoxy compound in the organic solvent is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and still more preferably 0.1% by mass from the viewpoint of ensuring reactivity with the amine compound. Above, especially preferably 0.5% by mass or more, and most preferably 1.0% by mass or more. The solubility of the polyfunctional epoxy compound in the organic solvent is preferably 20% by mass or less, more preferably 10% by mass or less, from the viewpoint of suppressing the runaway reaction while maintaining an excessive environment of the amine compound in the solution. More preferably, it is 5 mass% or less. The solubility of the polyfunctional epoxy compound in the organic solvent is preferably from the viewpoint of ensuring reactivity with the amine compound and suppressing the runaway reaction while maintaining an excessive environment in the solution. 01-20 mass%, 0.01-10 mass%, 0.01-5 mass%, 0.02-20 mass%, 0.02-10 mass%, 0.02-5 mass%, 0.1 20 mass%, 0.1-10 mass%, 0.1-5 mass%, 0.5-20 mass%, 0.5-10 mass%, 0.5-5 mass%, 1.0-20 mass% %, 1.0 to 10% by mass, or 1.0 to 5% by mass.

  The solubility of the polyfunctional epoxy compound in the organic solvent is measured as follows. That is, first, for example, in a sample tube, a polyfunctional epoxy compound is added to an organic solvent at 25 ° C. until it remains undissolved to prepare a saturated solution. The solution is heated to 60 ° C. To do. Next, the supernatant is filtered with a syringe filter, and about 5 g of the filtrate is added to a 5 cmφ aluminum dish and weighed. Then, the filtrate is dried at 150 ° C. for 1 hour, and the dry weight is measured to calculate the solid weight and the solution weight. Measure twice and take the average value as solubility.

  The boiling point of the organic solvent is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, and still more preferably 100 ° C. or higher. In this case, it is possible to suppress a reduction in reactivity due to a risk of ignition and a lack of temperature during heating and reflux. The boiling point of the organic solvent is preferably 180 ° C. or lower, more preferably 150 ° C. or lower, and still more preferably 120 ° C. or lower. In this case, in addition to facilitating removal of the residual solvent after drying, the temperature of the reaction solution does not rise to the boiling point of the organic solvent even when an unexpected temperature rise occurs due to the reaction heat of the epoxy compound, etc. Therefore, rapid reaction with the amine compound due to dissolution of the epoxy compound or runaway reaction due to homopolymerization of the epoxy compounds can be suppressed. The boiling point of the organic solvent may be 60 to 180 ° C, 80 to 150 ° C, or 100 to 120 ° C.

  After preparing solutions using different solvents for the epoxy compound and the amine compound as the organic solvent, the solutions may be mixed to react the epoxy compound and the amine compound. In this case, each solvent is preferably compatible.

  The polyfunctional glycidyl ether type epoxy compound and the amine compound are preferably capable of introducing as many amino groups as acid gas adsorption sites into the acid gas adsorbing material as much as possible. Is reacted at a rate such that.

  The equivalent ratio of the polyfunctional glycidyl ether type epoxy compound to the amine compound (epoxy compound / amine compound) is preferably 0.7 or more from the viewpoint of easy formation of a three-dimensional cross-linked structure and excellent thermal stability of the acid gas adsorbing material. More preferably, it is 0.8 or more, More preferably, it is 1.0 or more. The equivalent ratio (epoxy compound / amine compound) is preferably 2.0 or less, more preferably 1 from the viewpoint of increasing the amount of amino groups in the acid gas adsorbing material and further improving the amount of acid gas adsorbed. .5 or less, more preferably 1.2 or less. The equivalent ratio (epoxy compound / amine compound) is preferably 0.7 to 2.0, 0.7 to 1 from the viewpoint of achieving both improvement in thermal stability of the acid gas adsorbing material and improvement in the amount of adsorption. .5, 0.7-1.2, 0.8-2.0, 0.8-1.5, 0.8-1.2, 1.0-2.0, 1.0-1.5 Or 1.0-1.2.

  The equivalent ratio of the glycidyl group of the polyfunctional glycidyl ether type epoxy compound to the amino group of the amine compound (glycidyl group / amino group) is easy to form a three-dimensional crosslinked structure, from the viewpoint of excellent thermal stability of the acid gas adsorbing material, Preferably it is 0.5 or more, More preferably, it is 0.7 or more, More preferably, it is 1.0 or more. The equivalent ratio (glycidyl group / amino group) is preferably 2.3 or less, more preferably 2. from the viewpoint of further increasing the amount of acid gas adsorbed by increasing the amount of amino groups in the acid gas adsorbing material. 0 or less, more preferably 1.5 or less, and still more preferably 1.2 or less. The equivalent ratio (glycidyl group / amino group) is preferably 0.5 to 2.3, 0.5 to 2 from the viewpoint of achieving both improvement in thermal stability of the acid gas adsorbing material and improvement in adsorption amount. 0.0, 0.5-1.5, 0.5-1.2, 0.7-2.3, 0.7-2.0, 0.7-1.5, 0.7-1.2 1.0 to 2.3, 1.0 to 2.0, 1.0 to 1.5, or 1.0 to 1.2. In addition, the equivalent ratio of the glycidyl group of the polyfunctional glycidyl ether type epoxy compound to the primary or secondary aliphatic amino group of the amine compound (glycidyl group / primary or secondary aliphatic amino group) falls within the above range. Is more preferable.

  The reaction between the polyfunctional glycidyl ether type epoxy compound and the amine compound in an organic solvent is preferably 20 to 120 ° C, more preferably 30 to 60 ° C, preferably 2 to 24 hours, more preferably 4 to 12 hours. Done.

  The reaction dispersion liquid thus obtained may be filtered, for example, and the filtrate may be vacuum dried. Next, for example, the solid after vacuum drying is pulverized with a blender or the like, and classified using a sieve or the like, so that a powdered acidic gas adsorbing material can be obtained.

  The acidic gas adsorbing material according to the first or second embodiment is obtained by the manufacturing method as described above. In this production method, an epoxy compound dissolved in an organic solvent reacts with an amine compound under high dilution conditions, so that the resulting acid gas adsorbent material is finely divided and has a large specific surface area. Indicates.

  In addition, in the conventional method, in order to make it react in the environment where an amine compound is excess, the solution containing an epoxy compound is dripped at the solution containing an amine compound in many cases. However, the polyfunctional glycidyl ether type epoxy compound used in this embodiment has low solubility in a solvent and is difficult to add dropwise as an epoxy compound solution. Therefore, in the manufacturing method of the present embodiment, an amine compound is added to the epoxy compound dispersion using an organic solvent in which the epoxy compound is difficult to dissolve, so that the amine compound is excessive in the epoxy compound that is difficult to be dropped as a solution. It can be reacted under certain circumstances. The present inventors consider a more detailed reason as follows.

  Generally, a hardly soluble epoxy compound such as a solid epoxy compound reacts with an amine compound on a solid surface in an amine compound solution, and thus the reaction is very slow and hardly proceeds. Therefore, in this reaction system, a slightly dissolved low concentration epoxy compound reacts with the amine compound, and the epoxy compound can always react with the amine compound in an environment where the amine compound is excessive. In addition, since this production method uses an amine compound having a primary or secondary aliphatic amino group, the amine compound has high fat solubility, and as a result, the solubility of the reaction product of the epoxy compound and the amine compound is also high. Therefore, the reaction proceeds until a desired crosslinked structure is formed without precipitation of the reaction product.

<Acid gas recovery system and acid gas recovery method>
FIG. 1 is a schematic diagram showing an embodiment of an acid gas recovery system (acid gas recovery device). As shown in FIG. 1, an acid gas recovery system (acid gas recovery device) 1 includes a gas inflow path 2, a first acid gas recovery unit 3a, a first gas outflow path 4a connected thereto, and a second Acid gas recovery unit 3b and a second gas outflow passage 4b connected thereto.

  The gas inflow path 2 allows gas containing acid gas to flow in from the outside, for example. The gas inflow path 2 is connected to the first acid gas via the first two-way valve 5a so that the introduced gas can be introduced into the first acid gas recovery unit 3a and the second acid gas recovery unit 3b. The recovery unit 3a is connected to the second acidic gas recovery unit 3b via the second two-way valve 5b.

  The 1st and 2nd gas outflow paths 4a and 4b are connected so that gas can be made to flow out from the 1st and 2nd acidic gas recovery units 3a and 3b, respectively. The first gas outflow passage 4a has a first three-way valve 6a and two gas outlets 7a and 8a, and one of the two gas outlets 7a and 8a is determined by the first three-way valve 6a. For example, gas is allowed to flow outside. Similarly, the second gas outflow passage 4b has a second three-way valve 6b and two gas outlets 7b and 8b. The second three-way valve 6b allows the two gas outlets 7b and 8b to be connected to each other. Gas is allowed to flow out from either one, for example.

  The first and second acidic gas recovery units 3a and 3b include first and second acidic gas adsorbing materials 9a and 9b, respectively, disposed in, for example, containers. The acid gas adsorbing material according to the first or second embodiment described above is used for the first and second acid gas adsorbing materials 9a and 9b. The form of the first and second acid gas adsorbing materials 9a and 9b is not particularly limited, and may be, for example, a powder, a pellet, a foam, a sheet, or a composite supported on a porous substrate.

  In this acidic gas recovery system 1, first, as shown in FIG. 2A, for example, gas containing acidic gas is introduced from the outside through the gas inflow path 2. At this time, by opening the first two-way valve 5a and closing the second two-way valve 5b, gas is introduced only into the first acid gas recovery unit 3a.

  Of the gas introduced into the first acidic gas recovery unit 3a, only the acidic gas is selectively adsorbed on the first acidic gas adsorbing material 9a. At this time (at the time of adsorption), the temperature of the first acidic gas adsorbing material 9a may be, for example, 20 to 100 ° C. At this time, by opening the first three-way valve 6a toward the one gas outlet 7a, gas other than the acid gas out of the gases introduced into the first acidic gas recovery unit 3a is supplied to one gas outlet. For example, it flows out from 7a to the outside.

  Next, as shown in FIG. 2 (b), the first two-way valve 5a is closed and the second two-way valve 5b is opened. If it does so, the gas containing the acidic gas which flowed in through the gas inflow path 2 will be introduce | transduced only into the 2nd acidic gas collection | recovery unit 3b. Similarly to the above-described first acidic gas recovery unit, in the second acidic gas recovery unit 3b, only the acidic gas is selectively adsorbed on the second acidic gas adsorbing material 9b, and the second three-way By opening the valve 6b toward the one gas outlet 7b, a gas other than the acid gas is allowed to flow out from the one gas outlet 7b, for example, to the outside.

  On the other hand, in the first acid gas recovery unit 3a (first acid gas adsorbing material 9a), a temperature change is performed by a temperature change device (not shown). The temperature change device may be a heating device using an electric heater, boiler steam, or the like, and the temperature inside the first acidic gas recovery unit 3a (first acidic gas adsorbing material 9a) is raised by these heating devices. When the temperature of the first acid gas adsorbing material 9a rises, the acid gas adsorbed on the first acid gas adsorbing material 9a is desorbed. At this time (at the time of desorption), the temperature of the first acidic gas adsorbing material 9a may be, for example, 80 to 200 ° C.

  At this time, by opening the first three-way valve 6a toward the other gas outlet 8a, the acid gas desorbed from the first acid gas adsorbing material 9a can be recovered, for example, from the other gas outlet 8a. It is made to flow out to a container (not shown), and acidic gas is collect | recovered.

  As shown in FIG. 2 (b), the first and second acidic gas adsorbing materials 9a and 9b perform the step of performing adsorption and desorption of acidic gas in parallel with the first acidic gas adsorbing material 9a and the second acidic gas adsorbing material 9a. By repeating adsorption and desorption alternately with the acid gas adsorbing material 9b, the acid gas can be continuously recovered.

  As described above, according to the acidic gas recovery system 1, the acidic gas can be selectively adsorbed and recovered in an excellent adsorption amount by chemical adsorption by a so-called temperature swing method that is industrially low cost. That is, in the case of the temperature swing method, the acid gas can be adsorbed and desorbed using waste heat, so that, for example, gas selectivity and adsorption characteristics can be maintained even in the presence of water vapor. Moreover, according to this acidic gas collection | recovery system 1, the collection process of acidic gas can be simplified and the collection | recovery cost of acidic gas can be reduced. Furthermore, the acid gas adsorbing materials 9a and 9b can be produced by an industrially simple method, and are relatively inexpensive and excellent in mass productivity, so that the acid gas recovery cost can be reduced.

  In the above-described embodiment, a so-called adsorption tower in which a gas containing an acidic gas is introduced at a temperature at which the acidic gas adsorbing material adsorbs the acidic gas, and a high-purity acidic acid at a temperature at which the acidic gas is desorbed from the acidic gas adsorbing material. Although a method (batch method) in which acid gas is recovered by alternately switching to a so-called desorption tower from which gas is taken out is used, a method of recovering acid gas may be a continuous method.

  The continuous type means, for example, that acid gas adsorption and desorption are continuously performed by continuously circulating an acid gas adsorbing material inside a container in which a low temperature part for performing an adsorption process and a high temperature part for performing a desorption process exist. It is a method to be performed automatically. As a method for circulating the acid gas adsorbing material, for example, a fluidized bed, a honeycomb rotor system or the like can be used.

  As mentioned above, although embodiment of this invention was described, these are the illustrations for description of this invention, and are not the meaning which limits the scope of the present invention only to these embodiment. The present invention can be implemented in various modes different from the above-described embodiments without departing from the gist thereof.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to an Example.

<Example 1>
A 500 mL 4-neck round bottom separable flask was equipped with a stirring blade, a cooling pipe, a thermocouple thermometer, and a liquid feed pump tube, and a three-way cock was attached to the upper part of the cooling pipe and connected to a nitrogen pipe. In a separable flask, 1,4-bis (glycidyloxy) benzene (Nagase ChemteX Corporation, product name “EX203”, epoxy equivalent 115 g / eq.) 56 g (0.5 mol) and toluene (Wako Pure Chemical Industries, Ltd.) After adding 100 mL and substituting with nitrogen, the stirring blade was stirred at 500 rpm with a three-one motor (As One Co., Ltd., model number “BLW600”), and ethylenediamine with a liquid feed pump (Yamato Scientific Co., Ltd., product number “7554-80”). Monohydrate (Wako Pure Chemical Industries, Ltd.) 20 g (0.25 mol) and 1-butanol (Wako Pure Chemical Industries, Ltd.) 100 mL were added dropwise at 25 ° C. over 30 minutes. When stirring was continued at the room temperature (25 ° C.) after completion of the dropwise addition, the solution temperature rose due to the heat of reaction, and after 4 hours, the temperature rose to 36 ° C. After further stirring for 2 hours, the mixture was heated to reflux at 120 ° C. for 1 hour. After the reaction suspension was cooled to room temperature, the reaction dispersion was filtered. The filtrate was put in a Teflon (registered trademark) coating vat and vacuum-dried at 100 ° C. and 100 Pa in a vacuum dryer (Espec Corp., model “LCV-232”). After drying until the weight loss is 2% / 30 minutes or less, the solid is pulverized with a blender (Waring, model “7012S”), and classified to a particle size of 100 μm or less using a sieve with an opening of 100 μm. As a result, 66 g (yield 86%) of resin powder (acid gas adsorbing material) which is a cross-linked product of an epoxy compound and an amine compound was obtained. The SEM photograph of the obtained resin powder (acid gas adsorbing material) is shown in FIG. 3 ((a) 5000 times, (b) 1000 times).

<Example 2>
1,1,2,2-tetrakis [4- (glycidyloxy) phenyl] ethane (Asahi Organic Material Industries Co., Ltd., product name “TEP-G”, epoxy equivalent 156 g / eq.) 78 g (0.5 mol) and toluene Example except that 20 g (0.25 mol) of ethylenediamine monohydrate (Wako Pure Chemical Industries, Ltd.) and 100 mL of 1-butanol (Wako Pure Chemical Industries, Ltd.) were added dropwise to 100 mL (Wako Pure Chemical Industries, Ltd.) In the same manner as in Example 1, 96 g (yield 98%) of resin powder (acid gas adsorbing material) was obtained. The SEM photograph of the obtained resin powder (acid gas adsorbing material) is shown in FIG. 4 ((a) 5000 times, (b) 1000 times).

<Example 3>
Mixture of 4,4′-bis (glycidyloxy) biphenyl and 4,4′-bis (glycidyloxy) -3,3 ′, 5,5′-tetramethylbiphenyl (Mitsubishi Chemical Corporation, product name “YL-6121H ”, Epoxy equivalent 163 g / eq.) 82 g (0.50 mol) and toluene (Wako Pure Chemical Industries, Ltd.) 100 mL, ethylenediamine monohydrate (Wako Pure Chemical Industries, Ltd.) 20 g (0.25 mol) and 1- 92 g (yield 94%) of a resin powder (acid gas adsorbing material) was obtained in the same manner as in Example 1 except that 100 mL of butanol (Wako Pure Chemical Industries, Ltd.) was added dropwise. The SEM photograph of the obtained resin powder (acid gas adsorption material) is shown in FIG. 5 ((a) 5000 times, (b) 1000 times).

<Example 4>
Ethylenediamine was added to 100 mL of 1,4-bis (glycidyloxy) benzene (Nagase ChemteX Corporation, product name “EX203”, epoxy equivalent 115 g / eq.) 28 g (0.25 mol) and heptane (Wako Pure Chemical Industries, Ltd.). Resin powder (acid gas adsorption) in the same manner as in Example 1 except that 10 g (0.13 mol) of monohydrate (Wako Pure Chemical Industries, Ltd.) and 20 mL of 1-butanol (Wako Pure Chemical Industries, Ltd.) were added dropwise. Material) 34 g (yield 96%) was obtained. The SEM photograph of the obtained resin powder (acid gas adsorbing material) is shown in FIG. 6 ((a) 5000 times, (b) 1000 times).

<Example 5>
To 100 mL of 1,4-bis (glycidyloxy) benzene (Nagase ChemteX Corporation, product name “EX203”, epoxy equivalent 115 g / eq.) 28 g (0.25 mol) and dibutyl ether (Wako Pure Chemical Industries, Ltd.) Resin powder (acid gas) in the same manner as in Example 1 except that 20 g (0.13 mol) of ethylenediamine monohydrate (Wako Pure Chemical Industries, Ltd.) and 20 mL of 1-butanol (Wako Pure Chemical Industries, Ltd.) were added dropwise. 33 g (yield 94%) of adsorbent material was obtained. The SEM photograph of the obtained resin powder (acid gas adsorption material) is shown in FIG. 7 ((a) 5000 times, (b) 1000 times).

<Example 6>
1,4-bis (glycidyloxy) benzene (Nagase ChemteX Corporation, product name “EX203”, epoxy equivalent 115 g / eq.) 28 g (0.25 mol) and 1-butanol (Wako Pure Chemical Industries, Ltd.) 100 mL Resin powder (acid gas) in the same manner as in Example 1 except that 10 g (0.13 mol) of ethylenediamine monohydrate (Wako Pure Chemical Industries, Ltd.) and 100 mL of 1-butanol (Wako Pure Chemical Industries, Ltd.) were added dropwise. 34 g (yield 95%) of adsorbent material was obtained. The SEM photograph of the obtained resin powder (acid gas adsorbing material) is shown in FIG. 8 ((a) 5000 times, (b) 1000 times).

<Example 7>
Piperazine was added to 100 mL of 1,4-bis (glycidyloxy) benzene (Nagase ChemteX Corporation, product name “EX203”, epoxy equivalent 115 g / eq.) 56 g (0.5 mol) and toluene (Wako Pure Chemical Industries, Ltd.). (Wako Pure Chemical Industries, Ltd.) 38 g of resin powder (acid gas adsorbing material) in the same manner as in Example 1 except that 11 g (0.13 mol) and 1-butanol (Wako Pure Chemical Industries, Ltd.) 100 mL were added dropwise. Yield 97%). The SEM photograph of the obtained resin powder (acid gas adsorption material) is shown in FIG. 9 ((a) 5000 times, (b) 1000 times).

<Comparative Example 1>
1,4-bis (glycidyloxycarbonyl) benzene (Nagase ChemteX Corporation, product name “EX711”, epoxy equivalent 138 g / eq.) 69 g (0.5 mol) and toluene (Wako Pure Chemical Industries, Ltd.) 100 mL with ethylenediamine 76 g of resin powder was obtained in the same manner as in Example 1 except that 20 g (0.25 mol) of monohydrate (Wako Pure Chemical Industries, Ltd.) and 100 mL of 1-butanol (Wako Pure Chemical Industries, Ltd.) were added dropwise. . However, the obtained resin powder was not a crosslinked product but a thermoplastic resin powder. As a result of confirming the absorption derived from the carbonyl group by FT-IR measurement, absorption was observed in the vicinity of 1700 cm ⁻¹ in the raw material epoxy compound, whereas absorption was observed in the vicinity of 1650 cm ⁻¹ in the obtained resin powder. It was found that the group was changed to an amide group. That is, the target product (crosslinked product of epoxy compound and amine compound) was not obtained.

<Comparative example 2>
A 500 mL 4-neck round bottom separable flask was equipped with a stirring blade, a cooling pipe, a thermocouple thermometer, and a liquid feed pump tube, and a three-way cock was attached to the upper part of the cooling pipe and connected to a nitrogen pipe. After adding 20 g (0.25 mol) of ethylenediamine monohydrate (Wako Pure Chemical Industries, Ltd.) and 63 g of 1-butanol (Wako Pure Chemical Industries, Ltd.) to the separable flask and substituting with nitrogen, the stirring blade was replaced with a three-one motor (As One). 50% phenol novolak epoxy resin (Dow Chemical Company, product name “Dow Chemical Company,” with a liquid feed pump (Yamato Scientific Co., Ltd., model “7554-80”) while stirring at 500 rpm with a model number “BLW600”). DEN431 ”, epoxy equivalent of 175 g / eq.) In toluene (Wako Pure Chemical Industries, Ltd.) solution was added dropwise to react. Since the heat was generated by dropping, the dropping speed was adjusted so that the solution temperature did not exceed 85 ° C. When 66 g of “DEN431” was dropped, the reaction solution gelled. After the completion of gelation, the temperature was raised to 120 ° C., and stirring was continued while heating under reflux for 1 hour to grind the gel. The gel pulverized product was cooled to room temperature, then dispersed in 200 g of distilled water, further pulverized with a dissolver, and then the gel dispersion solution was filtered. The filtrate was placed in a Teflon (registered trademark) coating vat and vacuum dried at 150 ° C. and 100 Pa in a vacuum dryer (Espec Corp., model “LCV-232”). After drying until the weight loss is within 2% / 30 minutes, the solid is pulverized with a blender (Waring, model “7012S”) and classified to a particle size of 300 μm or less using a sieve having an opening of 300 μm. Thus, 56 g (yield 66%) of resin powder was obtained. The SEM photograph of the obtained resin powder is shown in FIG. 10 ((a) 5000 times, (b) 1000 times).

<Comparative Example 3>
To 35 g (0.45 mol) of ethylenediamine monohydrate and 80 g of 1-butanol, a toluene solution of 50% by mass of ethylene glycol diglycidyl ether (Tokyo Chemical Industry Co., Ltd., “EGDE”, epoxy equivalent 87 g / eq.) Was added dropwise. Then, 57 g (yield 51%) of resin powder was obtained in the same manner as in Comparative Example 2, except that 77 g of “EGDE” was dropped. The SEM photograph of the obtained resin powder is shown in FIG. 11 ((a) 5000 times, (b) 1000 times).

<Comparative example 4>
To 10 g (0.13 mol) of ethylenediamine monohydrate and 80 g of 1-butanol, a solution of 77 g (0.51 mol) of phenylglycidyl ether (abbreviation: PGE (Wako Pure Chemical Industries, Ltd.)) and 77 g of toluene was added dropwise and heated. The same operation as in Example 1 was performed except that refluxing was performed for 2 hours. However, the reaction solution did not gel, and the target product (crosslinked product of an epoxy compound and an amine compound) could not be obtained.

  Various conditions in Examples and Comparative Examples are summarized in Tables 1 and 2. The solubility of the epoxy compound was measured according to the following procedure.

(Solubility)
In a sample tube, each epoxy compound was added to the solvent used in each example at 25 ° C. until it remained undissolved to prepare a saturated solution, which was heated to 60 ° C., then cooled again to 25 ° C. and left for 12 hours. . The supernatant was filtered with a syringe filter, and about 5 g of the filtrate was added to a 5 cmφ aluminum dish and weighed. Then, the filtrate was dried at 150 ° C. for 1 hour, the dry weight was measured, and the solid content weight and the solution weight were calculated. Measurement was performed twice, and the average value was taken as the solubility.

  The resin powder obtained in the examples was evaluated as follows. The results are shown in Tables 1-3.

(Thermal stability)
About 10 mg of each resin powder was put into a 6 mmφ platinum pan and heated in an air atmosphere at a heating rate of 10 ° C./min, and the weight change was measured using a thermogravimetric analyzer (TGA) (Hitachi High-Tech Science Co., Ltd., product name “ TG / DTA7200 "), and the weight retention (mass%) at 300 ° C was used as an index of thermal stability.

(Specific surface area)
Each resin powder was vacuum degassed at 25 ° C. for 16 hours using an automatic specific surface area / pore size distribution measuring device (Bell Japan, product name “BELSORP-mini II”), and then pretreated at room temperature (25 The specific surface area was calculated by the BET multipoint method.

(Area average diameter of aggregate)
Using a laser diffraction / scattering particle size distribution measuring apparatus (BECMAN COULTER, product name “LS13320”), a dispersion in which each resin powder is dispersed in pure water is measured, and an area percentage is calculated to obtain a particle size distribution. Asked. The arithmetic average value of the obtained particle size distribution was defined as the area average diameter of the aggregate.

(Area average primary particle size of organic fine particles)
The area average primary particle size of the organic fine particles was measured using a scanning electron microscope (JEOL, product name “JCM-5000”). Specifically, three straight lines in the vertical direction and three in the horizontal direction are randomly drawn on the photographed SEM image, and the distances of the primary particles passing through the straight lines are measured. The primary particle diameter di of i was defined. The surface area Si of each particle i was calculated by the following formula (14) on the assumption that the primary particles are spherical. The area average primary particle diameter MA was calculated by the following formula (15) using the primary particle diameter di of each particle i and the surface area Si of each particle i. An SEM photograph at an appropriate magnification was used so that the number of observation data i at this time was 50 to 100.

(Carbon dioxide adsorption and chemical adsorption)
Using a thermogravimetric analyzer (TGA), the carbon dioxide (CO ₂ ) adsorption amount and chemical adsorption of each resin powder were evaluated according to the following procedure.
First, about 10 mg of resin powder is put into a 6 mmφ platinum pan, dried under a nitrogen stream of 200 mL / min at 150 ° C. until there is no weight change, and then the nitrogen stream is switched to a carbon dioxide stream of 200 mL / min, and the temperature is set to 50. The amount of weight increase when the temperature was lowered to ° C. was defined as the carbon dioxide adsorption amount. Also, the amount of carbon dioxide adsorbed at this time is 100 parts by mass, and then the carbon dioxide stream is switched to a nitrogen stream of 200 mL / min while maintaining at 50 ° C. The desorption amount was calculated. When the desorption amount of carbon dioxide is 20 parts by mass or less with respect to the adsorption amount, it is determined that there is no dependency on the partial pressure of adsorption and there is chemical adsorption (indicated by “A” in the table), and 20 parts by mass When exceeding, it was judged that there was no chemical adsorption (indicated by “B” in the table).

From Tables 1 and 2, a cross-linked product of a polyfunctional glycidyl ether type solid epoxy compound and an amine compound having a primary or secondary aliphatic amino group showed a good CO ₂ adsorption amount. When a glycidyl ester type solid epoxy compound was used (Comparative Example 1), the cross-linking reaction was inhibited due to a side reaction in which an amine and an ester reacted to form an amide, and gelation did not occur. When the solubility of the polyfunctional glycidyl ether type epoxy compound is 0.1 to 5.0% by mass and the equivalent ratio of epoxy compound / amine compound is in the range of 0.7 to 1.2 (Comparative Example 3) Particularly good CO ₂ adsorption was shown. This is considered to be because the particle diameter was reduced and the specific surface area was increased accordingly.

  DESCRIPTION OF SYMBOLS 1 ... Acid gas recovery system, 3a, 3b ... Acid gas recovery unit, 9a, 9b ... Acid gas adsorption material.

Claims (10)

  An acid gas adsorbing material comprising a cross-linked product of a polyfunctional glycidyl ether type solid epoxy compound and an amine compound having a primary or secondary aliphatic amino group.   An acid gas adsorbing material containing aggregates of organic fine particles. The acidic gas adsorbing material according to claim 1 or 2, wherein the specific surface area is 1.0 m ² / g or more.   An acid gas recovery unit comprising the acid gas adsorbing material according to claim 1.   An acid gas recovery system comprising the acid gas recovery unit according to claim 4. Introducing a gas containing an acidic gas into an acidic gas recovery unit comprising the acidic gas adsorbing material according to any one of claims 1 to 3, and causing the acidic gas adsorbing material to adsorb the acidic gas;
A step of changing the temperature in the acidic gas recovery unit to desorb the acidic gas from the acidic gas adsorbing material. Comprising a step of reacting a polyfunctional glycidyl ether type epoxy compound with an amine compound having a primary or secondary aliphatic amino group in an organic solvent to obtain an acid gas adsorbing material;
The method for producing an acidic gas adsorbing material, wherein the epoxy compound is hardly soluble in the organic solvent, and the organic solvent is inert to the epoxy compound and the amine compound.   The acidic gas adsorption according to claim 7, wherein the organic solvent is at least one selected from the group consisting of an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, an aliphatic alcohol solvent, an ether solvent, and a halogen-containing organic solvent. Material manufacturing method.   The manufacturing method of the acidic gas adsorption material of Claim 7 or 8 with which the said epoxy compound shows the solubility of 0.01-20 mass% with respect to the said organic solvent.   The acidic gas according to any one of claims 7 to 9, wherein the epoxy compound and the amine compound are reacted so that an equivalent ratio of the epoxy compound to the amine compound is 0.7 to 1.2. Production method of adsorbent material.