Carbon dioxide separation material, method for separating or recovering carbon dioxide, and method for manufacturing carbon dioxide separation material.

Abstract

To provide a low-cost and high-performance carbon dioxide separation material having high resistance to oxidation deterioration, and to separate or recover carbon dioxide with high efficiency.SOLUTION: Provided is a carbon dioxide separation material containing a polyamine. The polyamine includes a propyl polyamine component having a hydrogen atom or a functional group that bonds to a nitrogen atom and having three or more propyl groups which bond to respective nitrogen atoms within a molecule. At least one of the propyl groups is a hydroxypropyl group having a hydroxy group, and the hydroxypropyl group bonds to a nitrogen atom that constitutes a tertiary amine. The hydroxy group bonds to a secondary carbon atom. Two or more of the propyl groups are unsubstituted isopropyl groups which do not have a hydroxy group.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This invention relates to a carbon dioxide separation material, a method for separating or recovering carbon dioxide, and a method for manufacturing a carbon dioxide separation material. [Background technology]

[0002] Patent Document 1 proposes a carbon dioxide separation material containing a polyamine support in which a polyamine having at least two isopropyl groups on a nitrogen atom is supported on a support, and a method for separating or recovering carbon dioxide using the carbon dioxide separation material.

[0003] Patent document 2 proposes a method for preparing alkylalkanolamines, which involves the reaction of a carbonyl compound with a hydroxylalkylamine in the presence of hydrogen and a catalyst.

[0004] Patent Document 3 proposes a core-shell type amine-based carbon dioxide adsorbent having a porous support on which an amine compound is immobilized as a core, an amine layer as a shell that is resistant to inactivation by sulfur dioxide, and containing a chelating agent that suppresses oxidative decomposition of the amine and is resistant to oxygen and sulfur dioxide.

[0005] Patent document 4 proposes a renewable solid sorbent comprising a modified polyamine and a solid support for adsorbing carbon dioxide from a gas mixture containing air. The modified polyamine is a reaction product of an amine and an epoxide. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2014 / 208712 [Patent Document 2] Special Publication No. 2012-530771 (Patent No. 5678050) [Patent Document 3] U.S. Patent No. 10654025 [Patent Document 4] U.S. Patent Publication No. 2019 / 0168185 [Overview of the project] [Problems that the invention aims to solve]

[0007] As mentioned above, several materials have been developed for adsorbing carbon dioxide, but there is a need for reduced manufacturing costs and further improvements in performance. For example, it is desirable to increase the resistance of carbon dioxide separation materials with polyamines supported on a support to oxidative degradation, and to suppress the reduction due to volatilization of polyamines. This is because carbon dioxide separation materials are expected to be used in an oxygen-containing atmosphere (especially air) at temperatures of around 60°C. [Means for solving the problem]

[0008] One aspect of the present invention relates to a carbon dioxide separation material comprising a polyamine, wherein the polyamine comprises a propyl polyamine component having a hydrogen atom or functional group bonded to a nitrogen atom and three or more propyl groups bonded to each other nitrogen atom in the molecule, wherein at least one of the propyl groups is a hydroxypropyl group having a hydroxyl group, the hydroxypropyl group is bonded to a nitrogen atom constituting a tertiary amine, the hydroxyl group is bonded to a secondary carbon atom, and two or more of the propyl groups are unsubstituted isopropyl groups without a hydroxyl group.

[0009] Another aspect of the present invention relates to a method for separating or recovering carbon dioxide, comprising a first step of contacting a gas to be treated with the carbon dioxide separation material to absorb carbon dioxide, and a second step of decarbonizing the carbon dioxide from the carbon dioxide separation material that absorbed carbon dioxide in the first step, wherein the second step comprises one or more of the following: (A) a step of placing the carbon dioxide separation material under reduced pressure conditions to decarbonize carbon dioxide (pressure swing method), (B) a step of contacting the carbon dioxide separation material with at least one of water vapor and an inert gas (preferably a gas that does not contain carbon dioxide) to decarbonize carbon dioxide, and (C) a step of heating the carbon dioxide separation material to decarbonize carbon dioxide (temperature swing method).

[0010] A further aspect of the present invention relates to a method for producing a carbon dioxide separation material, comprising the steps of: preparing a polyamine; and contacting the polyamine with a support to obtain a polyamine support comprising the polyamine and the support on which the polyamine is supported, wherein the polyamine comprises a propyl polyamine component having a hydrogen atom or functional group bonded to a nitrogen atom and three or more propyl groups bonded to each other nitrogen atom in the molecule, at least one of the propyl groups being a hydroxypropyl group having a hydroxyl group, the hydroxypropyl group being bonded to a nitrogen atom constituting a tertiary amine, the hydroxyl group being bonded to a secondary carbon atom, and two or more of the propyl groups being unsubstituted isopropyl groups without a hydroxyl group. [Effects of the Invention]

[0011] The polyamines according to this disclosure allow for easy control of reactants in the production reaction, and the carbon dioxide separation material supported by these polyamines exhibits high resistance to oxidative degradation, suppresses reduction due to polyamine volatilization, and has excellent carbon dioxide adsorption and desorption performance. Therefore, a low-cost, high-performance carbon dioxide separation material can be provided. Furthermore, by using the carbon dioxide separation material according to this disclosure, carbon dioxide can be separated or recovered with high efficiency. [Brief explanation of the drawing]

[0012] [Figure 1] It is a diagram showing the adsorption behavior of carbon dioxide by the fresh polyamine carriers of Example 2, 4 and Comparative Examples 1, 2. [Figure 2] It is a diagram showing the adsorption behavior of carbon dioxide by the polyamine carriers after heating in air at 100 ° C for 42 hours in Example 2, 4 and Comparative Examples 1, 2. [Figure 3] It is a diagram showing a comparison of the adsorption behavior of carbon dioxide by the polyamine carriers before and after heating in air at 100 ° C for 42 hours in Example 2, 4 and Comparative Examples 1, 2. [Figure 4] It is a diagram showing the adsorption and desorption behavior of carbon dioxide by the fresh polyamine carrier of Example 4. [Figure 5] It is a diagram showing the adsorption and desorption behavior of carbon dioxide by the polyamine carrier after heating in air at 100 ° C for 42 hours in Example 4.

Mode for Carrying Out the Invention

[0013] Hereinafter, the carbon dioxide separation material according to the embodiment of the present invention will be described, but the carbon dioxide separation material is not limited to the following embodiments.

[0014] The carbon dioxide separation material contains polyamine, and the polyamine contains at least a propyl polyamine component.

[0015] Here, the propyl polyamine component has a hydrogen atom or a functional group bonded to a nitrogen atom and has three or more propyl groups bonded to different nitrogen atoms in the molecule. Examples of the functional group bonded to the nitrogen atom include a hydroxyl group (N-OH), an alkyl group (N-R (R is an alkyl group such as a methyl group or an ethyl group)), and the like.

[0016] However, at least one propyl group is a hydroxypropyl group having a hydroxyl group. The hydroxypropyl group is bonded to the nitrogen atom constituting the tertiary amine. In the hydroxypropyl group, the hydroxyl group is bonded to the secondary carbon atom. That is, the hydroxypropyl group is a 2-hydroxy-n-propyl group (-CH2CH(OH)CH3). In addition, two or more propyl groups are unsubstituted isopropyl groups (-CH(CH3)CH3) that do not have a hydroxyl group. The introduction of unsubstituted isopropyl groups loosens the chemical bond between N and CO2, allowing CO2 to be removed with less energy (e.g., at low temperatures). Hereafter, such propyl polyamine components will also be referred to as "PO-IP-polyamine components".

[0017] Here, when simply referring to a "propyl group," the term "propyl group" is used as a general term encompassing both "hydroxypropyl groups" (which have a hydroxyl group) and "unsubstituted propyl groups (especially isopropyl groups)" (which do not have a hydroxyl group).

[0018] Hereinafter, a propyl group bonded to a nitrogen atom will also be referred to as "propyl group N". PO-IP-polyamine components contain three or more nitrogen atoms in their molecule. Of the three or more propyl groups N in a PO-IP-polyamine component, at least one is a hydroxypropyl group, and two or more are unsubstituted isopropyl groups.

[0019] In the PO-IP-polyamine component, two or more of the three or more nitrogen atoms are bonded to a hydrogen atom. Alternatively, all but one of the nitrogen atoms may be bonded to a hydrogen atom.

[0020] The nitrogen atom bonded to the hydrogen atom may form a secondary amino group bonded to one hydrogen atom, or a primary amino group bonded to two hydrogen atoms.

[0021] The propyl polyamine component may contain only a single polyamine component or may contain multiple polyamine components. That is, the propyl polyamine component may be a mixture of multiple polyamine components or may contain only a purified single polyamine component. The propyl polyamine component may contain only a PO-IP-polyamine component or may contain polyamine components other than a PO-IP-polyamine component. The propyl polyamine component may contain a polyamine component that does not have a hydroxypropyl group and only has an unsubstituted isopropyl group, or it may not contain such a component.

[0022] A polyamine component that does not have a hydroxypropyl group and only has an unsubstituted isopropyl group may be a polyamine obtained by substituting the hydroxypropyl group of a PO-IP-polyamine component with a hydrogen atom. Hereinafter, such a propyl polyamine component will also be referred to as an "IP-polyamine component".

[0023] The PO-IP-polyamine component may have a linear structure, a branched structure, or a ring structure containing a nitrogen atom. Among these, the linear PO-IP-polyamine component is preferable because it has many CO2 adsorption sites.

[0024] A carbon dioxide separation material supported with a propyl polyamine component as a mixture containing PO-IP-polyamine and IP-polyamine components as essential components exhibits particularly excellent stability. Specifically, it has high resistance to oxidative degradation, suppresses reduction due to polyamine volatilization, and has high carbon dioxide adsorption and desorption performance.

[0025] Among propyl polyamine components, the PO-IP-polyamine component is considered to play a significant role in enhancing the stability of carbon dioxide separation materials. This is because polyamines containing both PO-IP-polyamine and IP-polyamine components have significantly higher resistance to oxidative degradation and lower vapor pressure than polyamines containing only IP-polyamine components, and their volatilization is suppressed. Such carbon dioxide separation materials are suitable for long-term use.

[0026] The content of the PO-IP-polyamine component in the propyl polyamine component is preferably 50 mol% or less, but may be between 10 mol% and 50 mol%. The content of the IP-polyamine component in the propyl polyamine component is preferably 50 mol% or more, and preferably 90 mol% or less.

[0027] The propyl group N can bond to a nitrogen atom constituting a secondary amine or a tertiary amine, but it is preferable for the unsubstituted isopropyl group to bond to a nitrogen atom constituting a secondary amine in order to enhance carbon dioxide detachment. On the other hand, the hydroxypropyl group can bond to a nitrogen atom constituting a tertiary amine. It is preferable for the hydroxypropyl group to bond to a nitrogen atom constituting a tertiary amine that is located outside the terminal end of the polyamine molecule.

[0028] It is preferable that the unsubstituted isopropyl group is bonded to the ends of the polyamine molecule. For example, in the case of a linear polyamine molecule, isopropyl groups may be bonded to two ends. In the case of a branched polyamine molecule, isopropyl groups may be bonded to the ends of all branched chains.

[0029] The isopropyl group bonded to the nitrogen atom constituting the secondary amine may be formed, for example, by the reaction of an isopropyl group N as a starting material with a primary amino group. For example, acetone can be used as the starting material for the isopropyl group.

[0030] The hydroxypropyl group bonded to the nitrogen atom constituting the tertiary amine may be formed, for example, by the reaction of a hydroxypropyl group starting material with a secondary amino group. For example, propylene oxide can be used as the starting material for the hydroxypropyl group.

[0031] PO-IP polyamine components can be produced, for example, by introducing two or more isopropyl groups to the primary amino group (-NH2 group) and -NH- group of a polyamine that is commercially available or obtained by known methods, and then introducing one or more hydroxypropyl groups to the secondary amino group of the polyamine.

[0032] One method for introducing an isopropyl group is to react the -NH2 group with an isopropyl group N starting material such as acetone. Another method for introducing a hydroxypropyl group is to react the -NH group with a hydroxypropyl group starting material such as propylene oxide. In this case, by controlling the molar ratio of polyamine to propylene oxide, a mixture of PO-IP-polyamine components and IP-polyamine can be obtained in any desired composition.

[0033] Specifically, platinum oxide catalyst and anhydrous ethanol are placed in a reaction vessel such as a flask, the inside of the reaction vessel is purged with hydrogen, and then hydrogen is added until the pressure reaches 100 kPa to 150 kPa, and the mixture is stirred for a predetermined time to reduce the platinum oxide catalyst. Next, a polyamine having a primary amino group (-NH2 group) and an -NH- group, acetone, and anhydrous ethanol are placed in the reaction vessel containing the reduced catalyst, the inside of the reaction vessel is purged with hydrogen, and then hydrogen is added until the pressure reaches approximately 200 kPa to 350 kPa, and then the mixture is stirred while supplying hydrogen until there is no further pressure drop. At this time, the N=C bond formed by the reaction of acetone and NH2 and the dehydration of water is hydrogenated. After filtering the solution to remove the catalyst, the ethanol is removed under reduced pressure, and the resulting colorless liquid is further dried under vacuum to obtain the IP-polyamine component. In the reaction between acetone and the primary amino group (first reaction), an unsubstituted isopropyl group is formed.

[0034] Next, the IP-polyamine component is dissolved in water, propylene oxide is added dropwise and mixed, and the mixture is stirred at room temperature for 12 hours. Then, the mixture is heated to 60°C and held for a further 2 hours. The PO-IP-polyamine component can be obtained by removing the water under reduced pressure from the resulting liquid and then vacuum drying. In the reaction between propylene oxide and the secondary amino group (second reaction), a hydroxypropyl group is formed.

[0035] Acetone preferentially reacts with primary amino groups, generating nitrogen atoms that constitute secondary amines containing NH groups. In other words, isopropyl groups preferentially bond to the nitrogen atoms that make up secondary amines. Therefore, the reactants in the first reaction are easily controlled, and a greater number of NH groups that adsorb and desorb carbon dioxide can be secured.

[0036] The following shows an example structure of a PO-IP-polyamine component (hereinafter referred to as "PO-IP-TEPA") produced by bonding tetraethylenepentamine (TEPA), a skeletal amine, with 2 moles of isopropyl groups and 1 mole of hydroxypropyl groups per mole of TEPA.

[0037] [ka]

[0038] PO-IP-TEPA can be obtained, for example, by the process shown in the following scheme. First, tetraethylenepentamine (TEPA) is reacted with 2 molecules of acetone per molecule of TEPA to add two isopropyl groups to the TEPA. The isopropylated TEPA obtained at this time is also called "IP-TEPA". Subsequently, one or less molecules of propylene oxide are reacted with one molecule of IP-TEPA to add a hydroxypropyl group. For example, by reacting 1 mole or less (e.g., 0.5 mole or less) of propylene oxide per mole of IP-TEPA, a mixture of PO-IP-TEPA and IP-TEPA having only unsubstituted isopropyl groups and no hydroxypropyl groups can be obtained.

[0039] [ka]

[0040] Like PO-IP-TEPA, the PO-IP-polyamine component may have two isopropyl groups bonded to nitrogen atoms constituting a different secondary amine and a hydroxypropyl group bonded to a nitrogen atom constituting a tertiary amine. In the hydroxypropyl group, the hydroxyl group is bonded to the secondary carbon atom.

[0041] Hereafter, the polyamine component IP produced by reacting 0.25 mol (or 0.5 mol) of propylene oxide per mol of IP-TEPA will be referred to as "0.25PO-IP-TEPA" ("0.50PO-IP-TEPA"), etc.

[0042] Furthermore, while the vapor pressure of IP-TEPA at 60°C is 1.80 kPa, the vapor pressure of 0.5PO-IP-TEPA is reduced to 1.47 kPa.

[0043] Next, as another example of a PO-IP-polyamine component, the structure of an example of a polyamine component (hereinafter referred to as "PO-IP-PEHA") produced by reacting the skeletal amine pentaethylenehexamine (PEHA) with 2 moles of acetone and 1 mole of propylene oxide per mole of PEHA is shown. Here again, by setting the amount of propylene oxide reacted with 1 mole of IP-PEPA to 1 mole or less (for example, 0.5 mole or less), a mixture of PO-IP-PEHA and IP-PEHA having only unsubstituted isopropyl groups and no hydroxypropyl groups can be obtained.

[0044] [ka]

[0045] Next, as yet another example of a PO-IP-polyamine component, the structure of an example of a polyamine component (hereinafter referred to as "PO-IP-HEHA") produced by reacting the skeletal amine hexaethyleneheptamine (HEHA) with 2 moles of acetone and 1 mole of propylene oxide per mole of HEHA is shown. Here again, by setting the amount of propylene oxide reacted with 1 mole of IP-HEHA to 1 mole or less (for example, 0.5 mole or less), a mixture of PO-IP-HEHA and IP-HEHA having only unsubstituted isopropyl groups and no hydroxypropyl groups can be obtained.

[0046] [ka]

[0047] The structure of the PO-IP polyamine component (polyamine molecule) is preferably one having two or more NH groups and one or more alkylene groups interposed between nitrogen atoms. From the viewpoint of increasing the carbon dioxide adsorption capacity, the more NH groups contained in one polyamine molecule the better. Preferably, the number of NH groups contained in one polyamine molecule is 2 to 50, and more preferably 3 to 30. On the other hand, considering the handling of the polyamine molecule, preferably, the number of NH groups contained in one polyamine molecule is 3 to 20, more preferably 4 to 10, and even more preferably 4 to 7.

[0048] In the PO-IP-polyamine component, the alkylene group interposed between nitrogen atoms is preferably an alkylene group having 1 to 6 carbon atoms, specifically methylene, ethylene, propylene, and butylene groups. The number of alkylene groups contained in one polyamine molecule can be selected according to the number of NH groups contained in one polyamine molecule. One polyamine molecule may contain only one type of alkylene group, or it may contain two or more types of alkylene groups.

[0049] Specifically, the PO-IP-polyamine component is defined by general formula (1):

[0050] [Chemical formula]

[0051] It may have a skeleton represented by. However, R in formula (1) represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylamino group having 1 to 6 carbon atoms, A represents an alkylene group having 2 to 6 carbon atoms, m represents an integer of 2 to 50, and a plurality of Rs may be the same or different from each other, and at least one R is a hydrogen atom or an alkylamino group having 1 to 6 carbon atoms, and a plurality of As may be the same or different from each other.

[0052] The PO-IP-polyamine component can be represented, for example, by the general formula (2):

[0053] [Chemical formula]

[0054] It can be represented by.

[0055] In formula (2), R A represents R 6 or the group: -A-NR 6 R 7 represents R B or the group: -A-NR 8 R 8 R 9 represents A represents an alkylene group having 2 to 6 carbon atoms, n represents an integer of 1 to 5 (for example, 2 or more), and p and q each independently represent 0 or 1.

[0056] A plurality of As may be the same or different from each other, and when there are a plurality of Rs 5 may be the same or different from each other.

[0057] R 1 R 2 R 7 and R 9 represent an unsubstituted isopropyl group, R 3 R4 , R 6 and R 8 R represents a hydrogen atom. 5 At least one (preferably two or fewer, more preferably one) of the hydroxypropyl group, R 5 The remainder represents hydrogen atoms.

[0058] Examples of polyamine skeleton amines include at least one selected from the group consisting of monopolymers of ethyleneimine, propyleneimine, 2-ethylaziridine, 2-propylaziridine, and 2-butylaziridine, and copolymers of at least two of these. Here, monopolymers and copolymers include oligomers with a polymerization number of 10 or less (e.g., 7 or less). For example, at least one selected from the group consisting of tetraethylenepentamine, spermine, N,N,N',N'-tetrakis(3-aminopropyl)-1,4-butanediamine, pentaethylenehexamine, hexaethyleneheptamine, and triethylenetetramine. A polyamine skeleton amine refers to a polyamine having a primary amino group that reacts with an isopropyl group starting material when generating an isopropyl group bonded to the nitrogen atom constituting a secondary amine.

[0059] Specific examples of IP-polyamine components that serve as raw materials for PO-IP-polyamine components include diisopropylated polyamines such as diisopropylated tetraethylenepentamine, diisopropylated spermine, diisopropylated pentaethylenehexamine, diisopropylated hexaethyleneheptamine, and diisopropylated triethylenetetramine; and tetraisopropylated polyamines such as tetraisopropylated N,N,N',N'-tetrakis(3-aminopropyl)-1,4-butanediamine. More specifically, 1,11-B Examples include su(isopropylamino)-3,6,9-triazoundecane, N,N'-bis(3-(isopropylamino)propyl)-1,4-butanediamine, N,N,N',N'-tetrakis(3-(isopropylamino)propyl)-1,4-butanediamine, 1,14-bis(isopropylamino)-3,6,9,12-tetraazatetradecane, 1,17-bis(isopropylamino)-3,6,9,12,15-pentazaheptadecane, and 1,8-bis(isopropylamino)-3,6,-diazaoctane.

[0060] Here, diisopropylated polyamine is a polyamine in which a total of two isopropyl groups are substituted on two or more nitrogen atoms of the polyamine, and tetraisopropylated polyamine is a polyamine in which a total of four isopropyl groups are substituted on two or more nitrogen atoms of the polyamine. By reacting such an IP-polyamine component with, for example, propylene oxide, a PO-IP-polyamine component is obtained in which a hydroxypropyl group is bonded to the nitrogen atom constituting the tertiary amine of the above IP-polyamine component.

[0061] The boiling point of polyamines (especially propyl polyamine components) at 760 mmHg is 320°C or higher. In this case, carbon dioxide separation materials containing polyamines can be used stably even at high temperatures (e.g., around 60°C). If the boiling point is 320°C or higher at 760 mmHg, the polyamine can remain supported on the support even if the boiling point decreases due to reduced pressure (e.g., around 0.2 Pa). Therefore, by using these polyamines, the operating temperature can be set higher than room temperature, and carbon dioxide can be efficiently removed.

[0062] <Support> The support material can be any material capable of supporting polyamines (especially propyl polyamine components) and withstanding the conditions of carbon dioxide separation and recovery. For example, ceramics, porous materials, carbon materials, and resin materials can be used. Specifically, examples include silica, polymethyl methacrylate, alumina, silica-alumina, clay minerals, magnesia, zirconia, zeolites, zeolite-related compounds, natural minerals, waste solids, activated carbon, and carbon molecular sieves. The support material may be used alone or in combination of two or more types.

[0063] The support material may be a commercially available product as is, or a support material synthesized by a known method may be used. Examples of commercially available products include mesostructured silica MSU-F from Sigma-Aldrich, SIPENNAT® 50S from Evonik, and CARiACT® Q10, Q30, and Q50 from Fuji Silysia Chemical Co., Ltd.

[0064] The support material is preferably porous with a large specific surface area and pore volume in order to support a large amount of polyamine. The specific surface area (BET) is 50 m². 2 / g or more 2000m 2 Less than / g is preferable, 100m 2 / g or more 1000m 2 A value of less than / g is preferable. The pore volume is 0.1 cm³. 3 / g or more 2.3cm 3 Less than / g is preferable, and 0.7cm 3 / g or more 2.3cm3 Less than / g is preferable.

[0065] Specific surface area and pore volume can be measured, for example, using a specific surface area / pore diameter distribution analyzer (ASAP2420: manufactured by Shimadzu Corporation) with a constant volume method. A more specific method for measuring gas adsorption using a specific surface area / pore diameter distribution analyzer involves, for example, pre-treating the sample by heating and vacuum evacuation, and weighing approximately 0.1 g of the sample into a sample tube. Then, the sample is heated to 40°C, vacuum evacuation is performed for 6 hours, and the sample is cooled to room temperature before weighing the sample mass. For measurement, the liquid nitrogen temperature is set and the pressure range is specified. Specific surface area, pore volume, and pore diameter can be calculated by analyzing the obtained nitrogen adsorption isotherm.

[0066] <Polyamine carriers> A polyamine-supported material is a polyamine supported on a support. A polyamine-supported material includes a polyamine (particularly a propyl polyamine component) and a support on which it is supported.

[0067] Polyamine support structures can be manufactured by a manufacturing method comprising the steps of preparing polyamines and obtaining polyamine support structures. In the step of obtaining polyamine support structures, polyamines can be brought into contact with a support to create a support structure on which polyamines are supported.

[0068] Polyamine supports can be produced, for example, by mixing a support with a solution of polyamine (particularly a propyl polyamine component), stirring at room temperature, and then distilling off the solvent (e.g., water, alcohol). One method for distilling off the solvent is to heat the mixture under reduced pressure using an evaporator or the like.

[0069] By supporting polyamines (particularly propyl polyamine components) on a support, it becomes possible to apply the material to pressure swing and temperature swing methods, which are not applicable to aqueous carbon dioxide separation materials. The pressure swing method includes a step of placing the carbon dioxide separation material under reduced pressure conditions to remove carbon dioxide. The temperature swing method includes a step of heating the carbon dioxide separation material to remove carbon dioxide.

[0070] <Carbon dioxide separation material> The carbon dioxide separation material includes, for example, a polyamine carrier and a binder for granulating the polyamine carrier. That is, the carbon dioxide separation material may include a polyamine carrier as a granulated product using a binder. By granulating the polyamine carrier using a binder, vibration resistance and abrasion resistance can be imparted, and stability in water can be further improved.

[0071] As the binder, at least one selected from the group consisting of silica, alumina, silica-alumina, clay minerals, fluororesins, cellulose derivatives, and epoxy resins may be used. Examples of fluororesins include polytetrafluoroethylene. Examples of cellulose derivatives include hydroxypropyl methylcellulose, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and hydroxyethylated starch. Examples of epoxy resins include diglycerol polyglycidyl ether and sorbitol polyglycidyl ether, which may be used as a mixture with an epoxy resin curing agent (modified polyamide resin, etc.). Other polymers (polyvinyl alcohol, polyethylene oxide, sodium polyacrylate, polyacrylamide, etc.) may also be used. These compounds are commercially available or can be easily manufactured by known methods. The binder may be used alone or in combination of two or more types.

[0072] As binders, commercially available options include Snowtec 30 and AS-200 from Nissan Chemical Corporation, Polyflon PTFE D-210C from Daikin Industries, Ltd., NEOVISCO MC RM4000 from Sansho Co., Ltd., AQ Nylon P-70 from Toray Industries, Inc., and Denacol EX-421 from Nagase ChemteX Corporation.

[0073] The amount of binder in the carbon dioxide separation material is not particularly limited as long as it is in an amount that allows for granulation, but it is preferable to keep it small in order to prevent a decrease in the polyamine content.

[0074] When granulation is performed using a binder, the average particle size of the granules is preferably 0.1 mm to 2.0 mm, from the viewpoint of reducing pressure loss when gas is supplied to the adsorbent-packed bed.

[0075] The content of polyamines (especially propyl polyamine components) in the carbon dioxide separation material is not particularly limited, but from the viewpoint of efficiently separating and recovering carbon dioxide, the polyamine content is preferably, for example, 15% by mass or more, and particularly preferably 20% by mass or more. The polyamine content may also be, for example, 70% by mass or less.

[0076] <Methods for separating or recovering carbon dioxide> The carbon dioxide separation (recovery) method processes gases containing carbon dioxide. These gases may include, for example, exhaust gases emitted from thermal power plants that use coal, heavy oil, natural gas, etc. as fuel; blast furnaces in steel mills that reduce iron oxide with coke; converters in steel mills that burn carbon in pig iron to produce steel; boilers in various manufacturing plants; kilns in cement plants; and even exhaust gases emitted from transportation equipment such as automobiles, ships, and aircraft that use gasoline, heavy oil, light oil, etc. as fuel. These gases may also include carbon dioxide emitted in enclosed spaces such as submersible research vessels, space stations, buildings, offices, etc., due to human respiration or energy conversion by equipment. In addition, carbon dioxide in the atmosphere may also be used.

[0077] The carbon dioxide separation or recovery method described herein is characterized by the use of a carbon dioxide separation material.

[0078] The carbon dioxide separation (recovery) method includes a first step of bringing the gas to be treated into contact with a carbon dioxide separation material to absorb carbon dioxide, and a second step of decarbonizing the carbon dioxide from the carbon dioxide separation material that absorbed carbon dioxide in the first step.

[0079] The carbon dioxide content and temperature of the gas to be treated in the first step are not particularly limited, as long as the conditions can be withstood by the carbon dioxide separation material. For example, the partial pressure of carbon dioxide may be 100 kPa or less, and the temperature may be 10°C to 60°C. Specifically, examples include operating conditions expected in thermal power plants, etc. (partial pressure of carbon dioxide: 7 to 100 kPa, temperature: 40 to 60°C) and operating conditions expected in space stations, etc. (partial pressure of carbon dioxide: 0 to 1 kPa, temperature: 20 to 25°C). The gas to be treated may be at atmospheric pressure or pressurized.

[0080] The gas to be processed in the first step may contain water vapor. Since the carbon dioxide separation material has excellent carbon dioxide adsorption properties even when the gas to be processed contains water vapor, the dehumidification operation can be omitted.

[0081] Methods for removing carbon dioxide in the second step include (A) a step of removing carbon dioxide by placing the carbon dioxide separation material under reduced pressure conditions (pressure swing method), (B) a step of removing carbon dioxide by contacting the carbon dioxide separation material with at least one of water vapor and an inert gas (preferably a gas that does not contain carbon dioxide (or a gas with a low carbon dioxide content)), and (C) a step of removing carbon dioxide by heating the carbon dioxide separation material (temperature swing method).

[0082] In the method including step (A), it is preferable to reduce the pressure to about 0.2 Pa in terms of the amount of carbon dioxide desorbed and the stability of the carbon dioxide separation material. The carbon dioxide separation material or the container containing it may be heated during the depressurization. If heating is performed, the temperature should preferably be up to about 60°C, in which case it is preferable to reduce the pressure to about 0.5 Pa. The method including step (A) is suitable when the gas to be treated has a temperature of 20 to 60°C and a carbon dioxide partial pressure of 100 kPa or less.

[0083] In the method including step (B), for example, carbon dioxide partial pressure can be reduced and carbon dioxide can be desorbed by bringing an inert gas, water vapor, or a gas that does not contain carbon dioxide into contact with the carbon dioxide separation material. The gas to be brought into contact with the carbon dioxide separation material only needs to be stable in that gas, and inert gases such as argon, nitrogen, and water vapor are preferred, with depressurized water vapor being more preferred.

[0084] In the method including step (C), carbon dioxide can be desorbed by raising the temperature above the temperature at which it was absorbed. In this case, the temperature at which carbon dioxide was absorbed may be, for example, 10 to 40°C, and the temperature at which carbon dioxide was desorbed may be, for example, around 60°C.

[0085] [Examples] Next, the present disclosure will be described in detail using examples, but the present invention is not limited to the following examples. Furthermore, the polyamine load (mass%) is expressed as the percentage of the mass of polyamine relative to the mass of the carbon dioxide separation material (polyamine loader) excluding carbon dioxide (here, it is the ratio of polyamine to the total of polyamine and support).

[0086] The following instruments were used to measure the physicochemical properties of the synthesized polyamines. Liquid Chromatography Mass Spectrometer (LC-MS): Alliance LC / MS system manufactured by Waters Japan Ltd.

[0087] Hereinafter, the description of "xPO" such as "xPO-IP-TEPA" indicates that the number of moles of propylene oxide reacted per 1 mol of the skeletal amine (in this example, TEPA) is x mol. For example, the description of "0.25PO" such as "0.25PO-IP-TEPA" indicates that the number of moles of propylene oxide reacted per 1 mol of the skeletal amine is 0.25 mol.

[0088] Also, "IP" in "0.25PO-IP-TEPA" etc. indicates that two primary amino groups of the skeletal amine are isopropylated to form diisopropylamine (in other words, the number of moles of acetone reacted per molecule is 2 mol).

[0089] Also, for example, "(29) / Q30" in the description of "0.25PO-IP-TEPA(29) / Q30" etc. indicates that the content rate of the polyamine component contained in the polyamine carrier is 29% by mass and the carrier is Q30.

[0090] 《Example 1》 <Synthesis of IP-polyamine component> Synthesis of diisopropylatetetraethylenepentamine (alias: 1,11-diisopropylamino-3,6,9-triazadecane) (IP-TEPA)

[0091] Put 2 g of platinum oxide catalyst and 100 ml of commercially available absolute ethanol into a 1 L flask. After replacing the inside of the flask with hydrogen, hydrogen was introduced until it reached 150 kPa, and it was stirred at 500 rpm for 15 to 20 minutes to reduce the platinum oxide catalyst.

[0092] Next, 189.31 g (1.0 mol) of tetraethylenepentamine (TEPA), 121.97 g (2.1 mol) of acetone (CH3-CO-CH3), and 150 ml of absolute ethanol were put into the flask containing the reduced catalyst.

[0093] After replacing the inside of the flask with hydrogen, hydrogen was introduced until it reached about 200 kPa. The theoretical amount of hydrogen (2 mol) was absorbed, causing the pressure to drop. Subsequently, the solution was stirred until it was confirmed that no absorption occurred for 10 hours.

[0094] After filtering the solution to remove the catalyst, ethanol was removed under reduced pressure at 40 °C. The resulting colorless liquid was further dried under vacuum (10 -1 mmHg) at 50 °C overnight to obtain IP-TEPA (yield 95%).

[0095] <Synthesis of PO-IP-Polyamine Component> 0.5 mol of propylene oxide per mole of IP-TEPA was added dropwise and mixed. The mixture was stirred at room temperature for 12 hours, and then heated to 60 °C and held for an additional 2 hours. Water was removed from the resulting liquid under reduced pressure, and it was further dried under vacuum to obtain 0.5PO-IP-TEPA.

[0096] <Preparation of Carbon Dioxide Separation Material (Polyamine Support)> A predetermined amount of 0.5PO-IP-TEPA was weighed and dissolved in 20 g of methanol (manufactured by Wako Pure Chemical Industries, Ltd.; special grade) placed in a 300 cm 3 eggplant-shaped flask.

[0097] Subsequently, a predetermined amount of support Q30 (CARiACT Q30 manufactured by Fuji Silysia Chemical Ltd.; specific surface area 100 m 2 / g, average pore diameter 30 nm, pore volume 0.9 mL / g) was placed in the eggplant-shaped flask and stirred at room temperature for 2 hours. Then, while heating to 40 °C with a rotary evaporator (manufactured by EYELA; N-1000), the pressure inside the system was reduced to 0.03 MPa to remove the methanol solvent, obtaining a polyamine support (0.5PO-IP-TEPA(25) / Q30) containing 25% by mass of 0.5PO-IP-TEPA.

[0098] The removal of the methanol solvent was completed when a mass reduction of 20 g corresponding to the methanol solvent was confirmed after pre-weighing the total weight of the flask and reagents. The prepared polyamine support was stoppered in an eggplant flask and stored in a desiccator until used for the evaluation test.

[0099] 《Example 2》 A polyamine support (0.5PO-IP-TEPA(29) / Q30) was obtained in the same manner as in Example 1, except that the content of 0.5PO-IP-TEPA was changed to 29% by mass.

[0100] 《Example 3》 <Synthesis of PO-IP-polyamine component> 0.25PO-IP-TEPA was obtained (yield 95%) in the same manner as in Example 1, except that the propylene oxide reacted per mole of IP-TEPA was changed to 0.25 mol. Also, a polyamine support (0.25PO-IP-TEPA(25) / Q30) containing 25% by mass of 0.25PO-IP-TEPA was obtained in the same manner as in Example 1.

[0101] 《Example 4》 A polyamine support (0.25PO-IP-TEPA(29) / Q30) was obtained in the same manner as in Example 3, except that the content of 0.25PO-IP-TEPA was changed to 29% by mass.

[0102] 《Example 5》 <Synthesis of IP-polyamine> Synthesis of​​​​​​​​​0.25PO-IP-DEDP was obtained (yield 95%) in the same manner as in Example 1, except that it was reacted with 0.25 mol of propylene oxide per mole of IP-DEDP. Also, a polyamine carrier containing 29% by mass of 0.25PO-IP-DEDP (0.25PO-IP-DEDP(29) / Q30) was obtained in the same manner as in Example 1.

[0105] 《Example 6》 <Synthesis of IP-polyamine> IP-PEHA was obtained (yield 95%) in the same manner as in Example 1, except that 1.0 mol of pentaethylenehexamine (PEHA) as the skeletal amine and 2.1 mol of acetone as the starting material for the isopropyl group were placed in the flask containing the reduced catalyst.

[0106] <Synthesis of PO-IP-polyamine component> 0.25PO-IP-PEHA was obtained (yield 95%) in the same manner as in Example 1, except that it was reacted with 0.25 mol of propylene oxide per mole of IP-PEHA. Also, a polyamine carrier containing 29% by mass of 0.25PO-IP-PEHA (0.25PO-IP-PEHA(29) / Q30) was obtained in the same manner as in Example 1.

[0107] 《Example <Synthesis of IP-polyamine> IP-HEHA was obtained (yield 95%) in the same manner as in Example 1, except that 1.0 mol of hexaethyleneheptamine (HEHA) as the skeletal amine and 2.1 mol of acetone as the starting material for the isopropyl group were placed in the flask containing the reduced catalyst.

[0108] <Synthesis of PO-IP-polyamine component> 0.25PO-IP-HEHA was obtained (yield 95%) in the same manner as in Example 1, except that it was reacted with 0.25 mol of propylene oxide per mole of IP-HEHA. Also, a polyamine carrier containing 29% by mass of 0.25PO-IP-HEHA (0.25PO-IP-HEHA(29) / Q30) was obtained in the same manner as in Example 1.

[0109] Comparative Example 1 TEPA (skeletal amine) was directly supported on Q30 at a content of 29% by mass to obtain a polyamine support (TEPA(29) / Q30).

[0110] Comparative Example 2 IP-TEPA was directly supported on Q30 at a content of 29% by mass to obtain a polyamine-supported material (IP-TEPA(29) / Q30).

[0111] Comparative Example 3 DEDP (skeletal amine) was directly supported on Q30 at a content of 29% by mass to obtain a polyamine support (DEDP(29) / Q30).

[0112] Comparative Example 4 IP-DEDP was directly supported on Q30 at a content of 29% by mass to obtain a polyamine-supported material (DEDP(29) / Q30).

[0113] Comparative Example 5 PEHA (skeletal amine) was directly supported on Q30 at a content of 29% by mass to obtain a polyamine support (PEHA(29) / Q30).

[0114] Comparative Example 6 IP-PEHA was directly supported on Q30 at a content of 29% by mass to obtain a polyamine-supported material (PEHA(29) / Q30).

[0115] Comparative Example 7 A polyamine support (HEHA(29) / Q30) was obtained by directly supporting HEHA (skeletal amine) on Q30 at a content of 29% by mass.

[0116] Comparative Example 8 IP-HEHA was directly supported on Q30 at a content of 29% by mass to obtain a polyamine-supported material (HEHA(29) / Q30).

[0117] Table 1 summarizes the composition of the polyamine support for each example and comparative example.

[0118] [Table 1]

[0119] <Evaluation Test 1> For the polyamine supports of the examples and comparative examples, the amount of carbon dioxide absorbed at each pressure at a predetermined temperature was measured using a breakthrough curve measuring device (manufactured by GL Sciences Co., Ltd.).

[0120] Approximately 1 g of the sample was weighed into a sample tube, and the sample was pre-treated by flowing argon through it at 80°C for 6 hours, after which the sample temperature was maintained at 60°C. Carbon dioxide was flowed through the sample tube at a partial pressure of 13 kPa, and the outlet gas composition was measured by gas chromatography. The amount of absorption was determined from the integration of the time from the start of CO2 absorption to saturation and the outlet gas concentration.

[0121] The amount of carbon dioxide removed (recovered) was determined by the cumulative effect of the time from switching the gas to argon until carbon dioxide was no longer detected in the outlet gas, and the outlet gas concentration.

[0122] The amount of carbon dioxide absorbed and the amount of desorption (recovery) by reduced pressure of the polyamine supports obtained in Example 4 and Comparative Examples 1 and 2 were measured. The results are shown in Table 2.

[0123] In the table below, the unit for carbon dioxide absorption is the amount absorbed per 1 kg of polyamine carrier (mol). Furthermore, the absorption amount (mol / kg) shown in (A) represents the absorption of a fresh sample at 60°C and 13 kPa, while the desorption (recovery) amount shown in (B) is the amount desorbed (recovered) at 60°C by flowing argon gas.

[0124] [Table 2]

[0125] <Evaluation Test 2> For the polyamine supports of the examples and comparative examples, the equilibrium absorption of carbon dioxide at various pressures at specified temperatures was measured by the constant-volume method. A ChemiSorb HTP manufactured by Micromerities was used as the measuring apparatus. Unless otherwise specified, the measurement methods for evaluation tests 2 to 4 were as follows: Approximately 0.1 g of the sample was weighed into a sample tube, and the sample was pretreated by flowing helium at 80°C for 6 hours, after which the sample temperature was maintained at 40°C. Carbon dioxide was gradually introduced into the sample tube, and the relationship between the partial pressure of carbon dioxide and the absorption amount at each measurement temperature was obtained by specifying a pressure range up to 100 kPa. The equilibrium absorption amount at 13 kPa was read from the obtained isotherms.

[0126] Oxidative degradation of the polyamine support was performed using a packed-bed reactor. 1.0 g of the polyamine support was packed into a quartz tube and pretreated by flowing nitrogen at 100°C for 3 hours. Then, degradation treatment was performed by flowing simulated air (21% O2-N2 balance) at 100°C for 42 hours. Subsequently, carbon dioxide was introduced at 40°C using the same method as above, and an isotherm was obtained. The amount of carbon dioxide absorbed was read from the equilibrium absorption at 13 kPa.

[0127] The amount of carbon dioxide absorbed by the fresh polyamine support obtained in Examples 1-7 and Comparative Examples 1-8, as well as the carbon dioxide absorption retention rate of the degraded polyamine support relative to the fresh polyamine support, was measured. The results are shown in Table 3.

[0128] [Table 3]

[0129] Figures 1-3 also show the results for fresh samples and samples after degradation treatment in Examples 2 and 4 and Comparative Examples 1 and 2. In Figures 1 and 2, the horizontal axis (Absolute pressure) corresponds to the absolute or partial pressure of CO2, and the vertical axis (CO2 absorbed) shows the amount of CO2 absorbed. Figure 3 is a bar graph summarizing the results from Figures 1 and 2.

[0130] <Evaluation Test 3> The amount of carbon dioxide absorbed was read from the isotherm obtained using the same method as in Evaluation Test 2, and this was determined as the amount of carbon dioxide absorbed.

[0131] Isotherms of the degraded polyamine support were obtained using the same method as in Evaluation Test 2. The amount of carbon dioxide absorbed was measured at 100 kPa.

[0132] The amount of carbon dioxide absorbed by the fresh polyamine support obtained in Examples 1-7 and Comparative Examples 1-8, as well as the carbon dioxide absorption retention rate of the degraded polyamine support relative to the fresh polyamine support, was measured. The results are shown in Table 4.

[0133] [Table 4]

[0134] <Evaluation Test 4> After Evaluation Test 2, samples of the fresh polyamine support from Example 4 and the polyamine support after degradation treatment were evacuated under reduced pressure for 20 minutes. Then, carbon dioxide was introduced at 40°C using the same method as in Evaluation Test 2, and isotherms were measured. The amount of carbon dioxide absorbed was read at 100 kPa.

[0135] Figures 4 and 5 show the results for fresh samples and samples after degradation treatment. In each figure, the horizontal axis (Absolute pressure) corresponds to the absolute or partial pressure of CO2, and the vertical axis (CO2 absorbed) shows the amount of CO2 absorbed. The results are shown in Table 5.

[0136] [Table 5]

[0137] <Evaluation Test 5: Examination of the effects of water vapor> Since polyamine carriers are also used to separate carbon dioxide from mixed gases containing water vapor in addition to carbon dioxide, the effect of water vapor was investigated. The amount of carbon dioxide absorbed under humidified conditions was measured using a breakthrough curve analyzer (GL Sciences Co., Ltd.).

[0138] Approximately 1 g of fresh polyamine supports from Examples 4 and 7 was weighed into a sample tube and pretreated by drying and degassing by flowing argon at 80°C for 6 hours, after which the sample temperature was maintained at 60°C. Next, a mixed gas of H2O / Ar was flowed to allow the polyamine supports to absorb water.

[0139] After water absorption reached saturation, carbon dioxide was introduced at a partial pressure of 13 kPa, and the outlet gas composition was simultaneously measured using a gas chromatograph to obtain a breakthrough curve.

[0140] After the carbon dioxide absorption reached saturation, argon gas was flowed through the system, and the outlet gas composition was measured by gas chromatography. In this measurement, instead of depressurizing with a vacuum pump, argon gas was flowed through the system to lower the partial pressure of carbon dioxide in the system and thus desorb the carbon dioxide.

[0141] The amount of absorption was determined from the sum of the time from the start of absorption to saturation and the outlet concentration. The amount of desorption was determined from the sum of the time from the time of switching to argon gas until carbon dioxide was no longer detected in the outlet gas and the outlet concentration. The results are shown in Table 6. For evaluation under dry conditions, the amount of carbon dioxide absorbed was measured at 60°C and 13kPa, and the amount of desorption was measured at 60°C.

[0142] [Table 6] [Industrial applicability]

[0143] The carbon dioxide separation material described herein is efficient and practical, and suitable for reuse, as it increases the amount of carbon dioxide absorbed and can separate and recover a large amount of carbon dioxide with short-term depressurization. Furthermore, the carbon dioxide separation material described herein can separate and recover carbon dioxide using either the pressure swing method or the temperature swing method in the carbon dioxide absorption and desorption process, allowing for the selection of carbon dioxide absorption and desorption processes suitable for various operating environments. In addition, the carbon dioxide separation material described herein has high resistance to oxidative degradation and is less susceptible to reduction due to the volatilization of polyamines. Moreover, even in the presence of water vapor, the absorption, desorption, and reabsorption performance does not deteriorate, and a dehumidification process is not required, thus enabling the construction of energy-saving systems and cost reduction through miniaturization of equipment.

Claims

1. Contains polyamines, The polyamine comprises a propyl polyamine component having a hydrogen atom or functional group bonded to a nitrogen atom, and three or more propyl groups bonded to different nitrogen atoms within the molecule. At least one of the propyl groups is a hydroxypropyl group having a hydroxyl group, The hydroxypropyl group is bonded to the nitrogen atom constituting the tertiary amine, The aforementioned hydroxyl group is bonded to a secondary carbon atom, A carbon dioxide separation material wherein two or more of the propyl groups are unsubstituted isopropyl groups that do not have a hydroxyl group.

2. The carbon dioxide separation material according to claim 1, wherein the unsubstituted isopropyl group is bonded to a nitrogen atom constituting a secondary amine.

3. The carbon dioxide separation material according to claim 1 or 2, wherein the propyl polyamine component has two or more NH groups and one or more alkylene groups interposed between nitrogen atoms.

4. The propyl polyamine component is defined by general formula (1): It has a skeleton represented by, In formula (1), R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylamino group having 1 to 6 carbon atoms. A represents an alkylene group having 2 to 6 carbon atoms. m represents an integer between 2 and 50. The multiple R groups may be the same or different, and at least one R is a hydrogen atom or an alkylamino group having 1 to 6 carbon atoms. The carbon dioxide separation material according to any one of claims 1 to 3, wherein the multiple A's may be the same or each may be different.

5. The aforementioned propyl polyamine component is general formula (2): It is expressed as, in equation (2), R Ａ R ６ Or base: -A-NR ６ R ７ Show, R Ｂ R ８ Or base: -A-NR ８ R ９ Show, A represents an alkylene group having 2 to 6 carbon atoms. n represents an integer from 1 to 5. p and q each independently represent either 0 or 1. The multiple instances of A may be the same or they may be different. R in the case of multiple ５ They may be the same or different from each other R １ , R 2 , R 7 and R 9 R represents the unsubstituted isopropyl group, 3 , R 4 , R 6 and R 8 This represents a hydrogen atom. R 5 At least one of them represents the hydroxypropyl group, R 5 The carbon dioxide separation material according to claim 4, wherein the remainder represents hydrogen atoms.

6. The carbon dioxide separation material according to any one of claims 1 to 5, wherein the boiling point of the polyamine at 760 mmHg is 320°C or higher.

7. The carbon dioxide separation material according to any one of claims 1 to 6, wherein the amine skeleton of the polyamine is at least one selected from the group consisting of monopolymers of ethyleneimine, propyleneimine, 2-ethylaziridine, 2-propylaziridine, and 2-butylaziridine, and copolymers of at least two of these.

8. The carbon dioxide separator according to any one of claims 1 to 7, wherein the skeletal amine of the polyamine is at least one selected from the group consisting of tetraethylenepentamine, spermine, N,N,N',N'-tetrakis(3-aminopropyl)-1,4-butanediamine, pentaethylenehexamine, hexaethyleneheptamine, and triethylenetetramine.

9. The carbon dioxide separation material includes a polyamine carrier, The carbon dioxide separation material according to any one of claims 1 to 8, wherein the polyamine support comprises the polyamine and a support on which the polyamine is supported.

10. The carbon dioxide separation material according to claim 9, wherein the support is at least one selected from the group consisting of silica, polymethyl methacrylate, alumina, silica-alumina, clay minerals, magnesia, zirconia, zeolite, zeolite-related compounds, natural minerals, waste solids, activated carbon, and carbon molecular sieves.

11. The support has a specific surface area (BET) of 50 m². ２ / g or more 1000m ２ The amount is less than or equal to / g, and the pore volume is 0.1 cm³. ３ / g ~ 2.3cm ３ The carbon dioxide separation material according to claim 9 or 10, wherein the amount is / g.

12. A carbon dioxide separation material according to any one of claims 9 to 11, comprising the polyamine support and a binder for granulating the polyamine support.

13. The carbon dioxide separator according to claim 12, wherein the binder is at least one selected from the group consisting of silica, alumina, silica-alumina, clay minerals, fluororesins, cellulose derivatives, and epoxy resins.

14. A first step involves bringing the gas to be treated into contact with a carbon dioxide separation material according to any one of claims 1 to 13, thereby absorbing carbon dioxide, and A second step involves decarbonizing the carbon dioxide from the carbon dioxide separation material that absorbed carbon dioxide in the first step. A method for separating or recovering carbon dioxide containing, The second step is (A) A step of placing the carbon dioxide separation material under reduced pressure conditions and removing carbon dioxide (pressure swing method), (B) A step of contacting the carbon dioxide separation material with at least one of water vapor and an inert gas to remove carbon dioxide, and (C) A step of heating the carbon dioxide separation material to remove carbon dioxide (temperature swing method) A method for separating or recovering carbon dioxide, which includes one or more of the following.

15. The method for separating or recovering carbon dioxide according to claim 14, wherein the gas to be processed is a gas with a temperature of 20 to 60°C and a partial pressure of carbon dioxide of 100 kPa or less.

16. The process of preparing polyamines, A step of bringing the polyamine into contact with a support to obtain a polyamine support comprising the polyamine and the support on which the polyamine is supported, It is equipped with, The polyamine comprises a propyl polyamine component having a hydrogen atom or functional group bonded to a nitrogen atom, and three or more propyl groups bonded to different nitrogen atoms within the molecule. At least one of the propyl groups is a hydroxypropyl group having a hydroxyl group, The hydroxypropyl group is bonded to the nitrogen atom constituting the tertiary amine, The aforementioned hydroxyl group is bonded to a secondary carbon atom, A method for producing a carbon dioxide separation material, wherein two or more of the propyl groups are unsubstituted isopropyl groups that do not have a hydroxyl group.

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