Resin composition for carbon dioxide adsorbent, and carbon dioxide adsorbent

Abstract

The present invention relates to: a resin composition for a carbon dioxide adsorbent, the resin composition containing a polyamide polyamine (A) that is a product including a polyamine (a1) and a polycarboxylic acid (a2) as essential reaction components, and the component (a1) containing a polyamine and / or a polyalkyleneimine represented by a specific general formula; and a carbon dioxide adsorbent obtained by supporting the aforementioned composition on a porous carrier (B).

Description

Resin composition for carbon dioxide adsorbent, carbon dioxide adsorbent

[0001] This invention relates to a resin composition for carbon dioxide adsorbents and a carbon dioxide adsorbent.

[0002] The increasing emissions of carbon dioxide from manufacturing processes such as the combustion of fossil fuels are contributing to global warming, and in recent years, its adsorption and recovery have attracted attention, leading to the development of various adsorbent compositions and adsorbents.

[0003] Such compositions typically use amine compounds. For example, a carbon dioxide separation composition containing an amine compound having multiple tertiary amino groups, an amine compound having multiple secondary amino groups, and water is known (Patent Document 1).

[0004] However, while amine compounds can adsorb carbon dioxide, their poor heat resistance means that when the adsorbed carbon dioxide is recovered, the composition decomposes due to the heat, impairing its carbon dioxide adsorption performance and making it unsuitable for reuse.

[0005] Japanese Patent Publication No. 2023-159053

[0006] The present invention aims to provide a resin composition for carbon dioxide adsorbent that can sufficiently adsorb carbon dioxide even after being exposed to high temperatures.

[0007] The inventors, through diligent research, have found a solution to the aforementioned problems and have completed the present invention. Specifically, the present invention relates to the following resin composition for carbon dioxide adsorbents and carbon dioxide adsorbent.

[0008] <Item> 1. A resin composition for carbon dioxide adsorbent comprising a polyamide polyamine (A), which is a product of polyamine (a1) and polycarboxylic acid (a2) as essential reaction components, wherein the (a1) component comprises a polyamine and / or polyalkyleneimine represented by general formula (1). [Chemical Formula 1]H ２ N-CH ２ CH ２ -X...(1) (In equation (1), X represents an amino group that has a group that can react with component (a2) (where X = -NH) ２(except in the case of)) 2. The resin composition for a carbon dioxide adsorbent according to item 1 above, wherein the reaction component further contains a monocarboxylic acid (a3). 3. A carbon dioxide adsorbent obtained by supporting the resin composition for a carbon dioxide adsorbent according to item 1 or 2 above on a porous carrier (B).

[0009] According to the resin composition for a carbon dioxide adsorbent of the present invention, carbon dioxide can be sufficiently adsorbed even after being exposed to high temperatures. In addition, the carbon dioxide adsorbent obtained by supporting the composition on a porous carrier exhibits similar adsorption performance, and also has the effect that the adsorbed carbon dioxide can be desorbed and efficiently recovered.

[0010] The resin composition for a carbon dioxide adsorbent of the present invention contains a polyamide polyamine (A) (hereinafter referred to as component (A)), which is a product having specific polyamine (a1) (hereinafter referred to as component (a1)) and polycarboxylic acid (a2) (hereinafter referred to as component (a2)) as essential reaction components.

[0011] Component (a) is a polyamine, which is a compound having at least two or more amino groups. In the present invention, as component (a1), a polyamine represented by the general formula (1) and / or a polyalkyleneimine are used as essential components. These may be used alone or in combination of two or more.

[0012] [Chemical formula 1] H ２ N-CH ２ CH ２ -X... (1) (In formula (1), X represents an amino group having a group capable of reacting with component (a2) (however, X = -NH ２ is excluded).)

[0013] When X in the general formula (1) is an -NH ２ group, that is, in the case of ethylenediamine, the obtained product becomes difficult to adsorb carbon dioxide, which is not preferable.

[0014] Examples of the group represented by X in the general formula (1) include, for example, -NH-(CH ２ CH ２ ) ｍ -NH ２ (m represents an integer from 1 to 10), -NH-(CH ２CH ２ ) ｎ Examples include chain-like amino groups such as -OH (where n is an integer from 1 to 10); and cyclic amino groups such as 1-imidazolidinyl group, 2-imidazolidinyl group, 4-imidazolidinyl group, 1-pyrazolidinyl group, 2-pyrazolidinyl group, 3-pyrazolidinyl group, 2-aminopyrrolidinyl group, 3-aminopyrrolidinyl group, 2-aminopiperidinyl group, 3-aminopiperidinyl group, 4-aminopiperidinyl group, 1-piperazinyl group, 2-piperazinyl group, 3-piperazinyl group, and 1-(aminoethyl)piperazinyl group.

[0015] Examples of such (a1) components include polyethylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and hexaethyleneheptamine; and hydroxyethyl polyamines such as N-(2-hydroxyethyl)ethylenediamine (N-(2-aminoethyl)ethanolamine), N-(2-hydroxyethyl)diethylenetriamine, N-(2-hydroxyethyl)triethylenetetramine, N-(2-hydroxyethyl)tetraethylenepentamine, N-(2-hydroxyethyl)pentaethylenehexamine, and N-(2-hydroxyethyl)hexaethyleneheptamine. Examples include heterocyclic amines containing aminoethyl, such as 1-(2-aminoethyl)imidazolidine, 2-(2-aminoethyl)imidazolidine, 3-(2-aminoethyl)imidazolidine, 1-(2-aminoethyl)pyrazolidine, 2-(2-aminoethyl)pyrazolidine, 3-(2-aminoethyl)pyrazolidine, 1-(2-aminoethyl)piperazine, 2-(2-aminoethyl)piperazine, and 3-(2-aminoethyl)piperazine. These may be used individually or in combination of two or more.

[0016] In particular, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-(2-hydroxyethyl)ethylenediamine (N-(2-aminoethyl)ethanolamine), and 1-aminoethylpiperazine are preferred, and diethylenetriamine, tetraethylenepentamine, and N-(2-hydroxyethyl)ethylenediamine (N-(2-aminoethyl)ethanolamine) are more preferred, as they form an amide group or ester group when reacted with component (B) described later, and the unreacted secondary amino group derived from component (A) allows the resulting product to efficiently adsorb carbon dioxide.

[0017] Polyalkyleneimines are polymers obtained by polymerizing alkyleneimines, and are soluble in water, alcohol, etc. Among them, those that readily react with component (a2) described later are those containing a primary amino group (-NH) in their molecule. ２ ) and / or having multiple secondary amino groups (-NH-) is preferred. Examples of alkylenes include ethylene, propylene, and butylene. Among these, polyethyleneimine is preferred.

[0018] Examples of commercially available polyalkyleneimines include "Epomin SP-003," "Epomin SP-006," "Epomin SP-012," "Epomin SP-018," "Epomin SP-200," "Epomin HM-2000," "Epomin P-1000," "Epomin P-3000," "Epomin RP-20," and "Epomin PP-061" (all manufactured by Nippon Shokubai Co., Ltd.).

[0019] (a2) Component is a polycarboxylic acid, which is a compound having two or more carboxyl groups.

[0020] (a2) Components include, for example, saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, and 1,10-decanedicarboxylic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid; saturated aliphatic tricarboxylic acids such as 1,2,3-propanetricarboxylic acid, 1,2,4-butanetricarboxylic acid, and 1,3,5-pentanetricarboxylic acid; aliphatic polycarboxylic acids having hydroxyl groups such as malic acid, tartaric acid, and citric acid; saturated alicyclic dicarboxylic acids such as 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarbonate, hexahydrophthalic acid, and 4-methylhexahydrophthalic acid; Alicyclic tricarboxylic acids such as 1,2,4-cyclohexanetricarboxylic acid and 1,3,5-cyclohexanetricarboxylic acid; unsaturated alicyclic dicarboxylic acid such as 1,2,3,6-tetrahydrophthalic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, 2,3-naphthalenedicarboxylic acid, and 2,4-naphthalenedicarboxylic acid; aromatic tridicarboxylic acids such as trimellitic acid; aromatic tetracarboxylic acids such as pyromellitic acid;

[0021] Furthermore, as component (a2), salts of the polycarboxylic acid, acid anhydrides of the polycarboxylic acid, etc., can also be used. Examples of salts include alkali metal salts such as lithium salts, sodium salts, and potassium salts; and alkaline earth metal salts such as magnesium salts and calcium salts.

[0022] These (a2) components may be used individually or in combination of two or more. Among these, saturated aliphatic dicarboxylic acids and polycarboxylic acids having a hydroxyl group are preferred, and saturated aliphatic dicarboxylic acids are more preferred, as the obtained (A) component is more likely to efficiently adsorb carbon dioxide.

[0023] As the molar amount of the component (a2), from the viewpoint that the obtained component (A) is likely to efficiently adsorb carbon dioxide, 0.1 to 2 moles, more preferably 0.1 to 1 mole, and still more preferably 0.25 to 0.5 moles, are preferable with respect to 1 mole of the component (a1).

[0024] The reaction components may further contain a monocarboxylic acid (a3) (hereinafter referred to as the component (a3)). A monocarboxylic acid is a compound having one carboxy group.

[0025] Examples of the component (a3) include saturated aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid (hexanoic acid), enanthic acid (heptanoic acid), caprylic acid (octanoic acid), pelargonic acid (nonanoic acid), capric acid (decanoic acid), undecylic acid (undecanoic acid), lauric acid (dodecanoic acid), tridecanoic acid, myristic acid (tetradecanoic acid), pentadecanoic acid, palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid), isostearic acid, nonadecanoic acid; unsaturated aliphatic monocarboxylic acids such as acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, oleic acid; saturated alicyclic monocarboxylic acids such as cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cycloheptanecarboxylic acid, cyclooctanecarboxylic acid; aromatic carboxylic acids such as benzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, and the like.

[0026] Further, as the component (a3), salts of the monocarboxylic acid, acid anhydrides of the monocarboxylic acid, and the like can also be used. Examples of the salt include alkali metal salts such as lithium salt, sodium salt, potassium salt; alkaline earth metal salts such as magnesium salt, calcium salt, and the like.

[0027] These components (a3) may be used alone or in combination of two or more. Among them, saturated aliphatic monocarboxylic acids are preferable from the viewpoint that the obtained component (A) is likely to adsorb carbon dioxide.

[0028] When using the component (a3), the molar amount thereof is preferably in a molar ratio of the component (a2) to the component (a3) of (a2) / (a3) = 50 / 50 to 90 / 10, more preferably 60 / 40 to 85 / 15.

[0029] Further, in terms of the obtained component (A) being likely to adsorb carbon dioxide, the ratio of the molar amount of the component (a1) to the total molar amount of the components (a2) and (a3) is preferably {(molar amount of component (a1)) / (total molar amount of components (a2) and (a3))} = 0.1 to 5, more preferably 0.5 to 2.

[0030] The component (A) of the present invention can be obtained by various known methods. For example, the component (a1) and the component (a2), and optionally the component (a3) are mixed and reacted while dehydrating. Examples of the reaction conditions include a temperature of usually 100 to 250°C, preferably 130 to 200°C, and a time of usually 1 to 10 hours, preferably 2 to 5 hours.

[0031] The reaction may be carried out in the presence of a catalyst such as sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc., or may be carried out without the presence of a catalyst. Further, the obtained condensate is preferably diluted with water or an organic solvent. The non-volatile content concentration after dilution is preferably 20 to 80% by weight.

[0032] Examples of the water include pure water, ultrapure water, ion-exchanged water, tap water, industrial water, hard water, soft water, etc. These may be used alone or in combination of two or more.

[0033] Examples of the organic solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol, t-butanol; ketones such as methyl ethyl ketone; dimethyl sulfoxide, hexane, toluene, etc. These may be used alone or in combination of two or more.

[0034] Additives such as inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid; inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide; antifoaming agents, antioxidants, preservatives, leveling agents, viscosity modifiers, pH adjusters, bactericides, etc. may be added to the component (A) of the present invention.

[0035] The physical properties of the obtained component (A) include, for example, a weight-average molecular weight of preferably 500 to 50,000, more preferably 1,000 to 10,000, and even more preferably 1,000 to 5,000. Here, the weight-average molecular weight is a value measured by the GPC (Gene Permeation Control) method. When the weight-average molecular weight of component (A) is within this range, the obtained component (A) readily adsorbs carbon dioxide.

[0036] Furthermore, the number-average molecular weight of component (A) is preferably 250 to 30,000, more preferably 500 to 5,000, and even more preferably 500 to 3,000. Here, the number-average molecular weight is a value measured by the GPC (Gene Permeation Control) method. When the number-average molecular weight of component (A) is within this range, the obtained component (A) readily adsorbs carbon dioxide.

[0037] Furthermore, the viscosity of a solution of component (A) containing 50% by weight of nonvolatile content at a temperature of 25°C is preferably 1 to 1,000 mPa·s, more preferably 10 to 500 mPa·s, and even more preferably 10 to 100 mPa·s. Here, the viscosity is the value measured with a Brookfield type viscometer (Type B viscometer).

[0038] In addition, the non-volatile content concentration of component (A) is preferably 30 to 80% by weight, more preferably 40 to 70% by weight, and even more preferably 50 to 60% by weight.

[0039] The carbon dioxide adsorbent resin composition of the present invention can be used in liquid form or as a cured film of the composition. Furthermore, it can also be used as a carbon dioxide adsorbent in which the composition is supported on a porous carrier (B) described later.

[0040] When using the carbon dioxide adsorbent resin composition of the present invention in liquid form, one possible method is to bring the composition into contact with a gas containing carbon dioxide to adsorb the carbon dioxide, and then release the carbon dioxide by applying high temperature or reduced pressure (chemical adsorption method). The carbon dioxide adsorbent resin composition may be diluted with water or the like before use, and the concentration after dilution is not particularly limited.

[0041] Other components besides carbon dioxide contained in the aforementioned carbon dioxide-containing gas include, for example, argon, oxygen, air, hydrogen, nitrogen, nitrogen oxides (NOx), sulfur oxides (SOx), and the like.

[0042] When using the carbon dioxide adsorbent composition of the present invention as a cured film, one possible method is to apply the composition onto a support and dry it.

[0043] Examples of supports include synthetic polymers such as polysulfone, polyethersulfone, polyamide, polyimide, polyacrylonitrile, polybutadiene, polystyrene, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl chloride, polymethyl methacrylate, cellulose acetate, and polycarbonate; paper, glass, and the like.

[0044] Examples of coating methods include immersion coaters, spray coaters, spin coaters, curtain flow coaters, slot die coaters, extrusion die coaters, air doctor coaters, blade coaters, bead coaters, rod coaters, knife coaters, squeeze coaters, roll coaters, reverse roll coaters, bar coaters, gravure coaters, and comma coaters. Furthermore, the coating amount should be such that the thickness of the cured film after curing is preferably 1 to 100 μm, more preferably 10 to 50 μm.

[0045] For example, the drying conditions include a temperature of preferably 60 to 180°C, more preferably 80 to 130°C, and a drying time of preferably 1 to 6 hours, more preferably 3 to 4 hours.

[0046] One embodiment of the present invention is a carbon dioxide adsorbent, in which the resin composition for carbon dioxide adsorbent of the present invention is supported on a porous carrier (B) (hereinafter referred to as component (B)).

[0047] Examples of component (B) include silica, activated carbon, layered silicates, zeolites, aluminosilicates, vermiculite, molecular sieves, diatomaceous earth, porous metal-organic structures (MOF, PCP, etc.), alumina, ceramics, porous concrete, activated clay, and clay minerals. Among these, silica and alumina are preferred because they have a specific surface area and pore size that can support component (A).

[0048] As the aforementioned silica, crystalline silica, amorphous silica, silica gel, mesoporous silica, porous silica, and the like can be used.

[0049] (B) Examples of component shapes include granular, powdery, fibrous, plate-like, cylindrical, and honeycomb-like forms.

[0050] The average pore size of component (B) is preferably 100 nm or less, and more preferably 50 nm or less, in order to facilitate the adsorption of carbon dioxide by the resulting carbon dioxide adsorbent.

[0051] The adsorbent of the present invention can be obtained, for example, by adding the carbon dioxide adsorbent resin composition and component (B), and then immersing or mixing them. The method and order of addition are not particularly limited. The carbon dioxide adsorbent resin composition may be used as is, or it may be dissolved in water or an organic solvent as described above beforehand. After loading, water and organic solvents can be removed by heating, reduced-pressure drying, vacuum drying, etc.

[0052] The present invention will be described in more detail below through examples and comparative examples. However, the technical scope of the present invention is not limited by these descriptions. Unless otherwise specified, percentages in the examples are based on weight.

[0053] Production Example 1: In a reaction apparatus equipped with a thermometer, condenser, stirrer, and nitrogen inlet tube, 118.1 g (1 mole) of succinic acid and 120 g of deionized water were charged and stirred. After adding 189.3 g (1 mole) of tetraethylenepentamine dropwise from a dropping funnel, the temperature was increased while removing the generated water from the system, and the reaction was carried out at 120-200°C for 5 hours. Then, deionized water was gradually added to achieve a non-volatile content of 50% to obtain polyamide polyamine (A-1).

[0054] Production Examples 2 to 16, Comparative Production Examples 1 to 2, and Reference Comparative Examples 1 to 2: The reaction components and moles shown in Table 1 were changed, and the process was carried out in the same manner as in Production Example 1 to obtain polyamide polyamines (A-2) to (A-16) and (AC-1) and (AC-2) with a non-volatile content of 50%, respectively. Tetraethylenepentamine and polyethyleneimine (product name: "Epomin S-012", manufactured by Nippon Shokubai Co., Ltd.) were also used for comparison.

[0055] The weight-average molecular weight and number-average molecular weight of the polyamide polyamines and the amines in the reference comparative examples were measured under the following conditions. The results are shown in Table 1.

[0056] (Weight-average molecular weight and number-average molecular weight) Measured under the following conditions. GPC main unit: Tosoh Corporation Columns: Two TSKgel G6000PWXL-CP and one TSKgel guardcolumn PWXL-CP (both manufactured by Tosoh Corporation) (The temperature of each column was set to 40°C.) Eluent: 0.5 mol / L acetate buffer (aqueous solution of 0.5 mol / L acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) + 0.5 mol / L sodium acetate (manufactured by Kishida Chemical Co., Ltd.)) Flow rate: 0.6 ml / min Detector: RALLS method: TDA MODEL 301 manufactured by Viscotec (concentration detector, 90° light scattering detector and viscosity detector (The temperature of each detector was set to 40°C.)) Standard substance: Polyethylene oxide Measurement sample: Component A was diluted with the above eluent so that the non-volatile content concentration was 0.2% and measured.

[0057]

[0058] The abbreviations shown in Table 1 represent the following compounds: (Amines) ・TEPA: Tetraethylenepentamine ・DETA: Diethylenetriamine ・TETA: Triethylenetetramine ・PEI-1: Polyethyleneimine, trade name: "Epomin SP-012", manufactured by Nippon Shokubai Co., Ltd. ・PEI-2: Polyethyleneimine, trade name: "Epomin SP-003", manufactured by Nippon Shokubai Co., Ltd. ・AEEA: N-(2-aminoethyl)ethanolamine ・AEP: 1-aminoethylpiperazine ・EDA: Ethylenediamine ・1,3-PDA: 1,3-Propylenediamine (Carboxylic Acids) ・SA: Succinic acid ・ADA: Adipic acid ・CA: Citric acid ・StA: Stearic acid

[0059] <Evaluation of Resin Compositions for Carbon Dioxide Adsorbents> The polyamide polyamines from each production example and comparative production example, and the amine from the reference comparative example were used as carbon dioxide adsorbent resin compositions as they were, and the following evaluations were performed.

[0060] (Amount of carbon dioxide adsorbed) Examples 1-1 to 1-18, Comparative Examples 1-1 to 1-4 100 g of each carbon dioxide adsorbent resin composition was taken and mixed with deionized water to make a non-volatile content of 20% to prepare a diluted solution. 90 g of the diluted solution was placed in a 125 mL gas adsorption bottle and kept warm in a water bath to a liquid temperature of 40°C. A mixture of carbon dioxide at 200 mL / min and nitrogen at 300 mL / min was blown into the bottle for 1 hour, and the amount of carbon dioxide adsorbed (X) was measured using a gas flow meter. １ The amount of adsorption (unit: L) was measured. An adsorption amount of 25 L or more was considered good, and a larger value indicates better performance. The results are shown in Table 2 (the same applies below).

[0061] Separately from the above, 90 g of the diluent was placed in a 200 mL three-necked flask equipped with a thermometer and reflux tube, and heated to 100°C while bubbling with oxygen, and stirred for 20 hours. After cooling, it was placed in a 125 mL gas adsorption bottle, and the amount of carbon dioxide adsorbed (X) was measured in the same manner as above. ２ The amount of adsorption (unit: L) was measured. An adsorption amount of 10 L or more was considered good, and a larger value indicates better performance.

[0062] The reduction rate was calculated from the amount of carbon dioxide adsorbed as described above using the following formula. A smaller value indicates better carbon dioxide adsorption performance even when exposed to high temperatures. The results are shown in Table 2. (Formula 1) (Reduction Rate) = {(X １ -X ２ ) / X １} × 100

[0063]

[0064] <Preparation of Carbon Dioxide Adsorbent> Example 2-1 Deionized water was added and mixed with the (A-1) component obtained in Production Example 1 so that the non-volatile content concentration was 20%. 10 g of the above (A-1) component solution (non-volatile content: 2 g) was added to a 20 mL beaker and stirred. Then, 0.5 g of silica (product name: "CARiACT-G10", particle size: 10 nm, manufactured by Fuji Silicia Chemical Co., Ltd.) was added and stirred for 20 minutes. After filtering with a Kiriyama funnel, the mixture was vacuum-dried at 60°C for 3 hours to obtain a carbon dioxide adsorbent. The amount of (A-1) component supported on the silica (non-volatile content) was 17%. The amount of supported component is also shown in Table 3 (the same applies below).

[0065] Examples 2-2 to 2-20 and Comparative Examples 2-1 to 2-4: Using the components with the non-volatile content concentrations listed in Table 3, carbon dioxide adsorbents were obtained in the same manner as in Example 2-1.

[0066] (Heat resistance (oxidative decomposition temperature)) 50 mg of each carbon dioxide adsorbent was placed in a container and set in a simultaneous thermal and thermogravimetric analyzer (TG-DTA, instrument name: "DTG-60", manufactured by Shimadzu Corporation). After holding at 80°C for 15 minutes, the temperature was raised to 700°C at a rate of 20°C / min while flowing air at 100 mL / min, and then held for 5 minutes. The temperature at which the peak of heat quantity was maximized was read from the chart (horizontal axis: temperature, vertical axis: heat quantity). A higher oxidative decomposition temperature indicates higher heat resistance (less likely to decompose).

[0067] (Amount of carbon dioxide adsorbed) 100 mg of each carbon dioxide adsorbent was placed in a container and measured at 25°C using a commercially available gas adsorption measurement device (device name: "BELSORP MAX X", manufactured by Microtrac-Bel). The amount of carbon dioxide adsorbed at a pressure of 20 kPa (X) was obtained from the chart (horizontal axis: pressure, vertical axis: amount of carbon dioxide adsorbed).３ The value (unit: mmol / g) was read. An adsorption amount of 0.3 mmol / g or higher is considered good, and a larger value indicates better performance.

[0068] Separately from the above, 100 mg of each carbon dioxide adsorbent was placed in a container and set in a simultaneous thermal and thermogravimetric analyzer (TG-DTA, instrument name: "DTG-60", manufactured by Shimadzu Corporation), and heated at 125°C for 16 hours while circulating air. After cooling to 25°C, the amount of carbon dioxide adsorbed (X) was measured using the same method as described above. ４ The adsorption amount (unit: mmol / g) was measured. An adsorption amount of 0.2 mmol / g or higher was considered good, and a higher value indicates better performance.

[0069] (Decrease Rate) The decrease rate was calculated from the amount of carbon dioxide adsorbed as described above using the following Equation 2. A smaller value indicates higher carbon dioxide adsorption performance even when exposed to high temperatures. The results are shown in Table 3 (the same applies below). (Equation 2) (Decrease Rate) = {(X ３ -X ４ ) / X ３} × 100

[0070] (Desorption Rate) 10 mg of each carbon dioxide adsorbent was placed in a container and set in a simultaneous thermogravimetric analyzer (TG-DTA, manufactured by Shimadzu Corporation). The mixture was heated at 60°C for 3 hours while flowing nitrogen. After cooling to 25°C, the weight value on the chart (horizontal axis: time, vertical axis: weight) at this time was set to 0. Next, carbon dioxide was flowed at 25°C for 6 hours to allow adsorption, and the weight (Y) at saturation (when the value on the vertical axis became constant) was recorded from the chart. １ ) was read. Then, while flowing nitrogen, it was heated at 60°C for 12 hours to desorb carbon dioxide, and the weight (Y) was read from the chart 4 hours after desorption began. ２ The following equation 3 was used to calculate the desorption rate. A higher value indicates that carbon dioxide is being desorbed and recovered. (Equation 3) Desorption rate (%) = {(Y １ -Y ２ ) / Y １} × 100 Y １ : Weight when saturated with carbon dioxide Y ２ Weight 4 hours after starting the removal process

[0071]

[0072] The symbols for the porous carriers in Table 3 indicate the following components: • B-1-Silica, trade name: "CARiACT-G10", average pore size: 10 nm, manufactured by Fuji Silicia Chemical Co., Ltd. • B-2-Silica, trade name: "CARiACT-Q30", average pore size: 30 nm, manufactured by Fuji Silicia Chemical Co., Ltd. • B-3-Alumina, trade name: "Neobeat GB-13", average pore size: 11 nm, manufactured by Mizusawa Chemical Industry Co., Ltd.

Claims

1. A resin composition for carbon dioxide adsorbent comprising a polyamide polyamine (A), which is a product of polyamine (a1) and polycarboxylic acid (a2) as essential reaction components, wherein the (a1) component comprises a polyamine and / or polyalkyleneimine represented by general formula (1). [Chemical Formula 1]H ２ N-CH ２ CH ２ -X...(1) (In equation (1), X represents an amino group that has a group that can react with component (a2) (where X = -NH) ２ (Except in the case of...) 2. The resin composition for carbon dioxide adsorbent according to claim 1, wherein the reaction component further comprises a monocarboxylic acid (a3).

3. A carbon dioxide adsorbent comprising a porous carrier (B) on which the resin composition for carbon dioxide adsorbent according to claim 1 or 2 is supported.

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