WO2022085789A1

WO2022085789A1 - Method for recovering carbon dioxide, method for absorbing carbon dioxide, and method for desorbing carbon dioxide

Info

Publication number: WO2022085789A1
Application number: PCT/JP2021/039122
Authority: WO
Inventors: 誠司山添; 大樹三浦; 哲也宍戸; 裕宇藤木; 純平山; 玄加藤; 聡一吉川; 和志天本
Original assignee: 東京都公立大学法人
Priority date: 2020-10-23
Filing date: 2021-10-22
Publication date: 2022-04-28
Also published as: JP7441557B2; JPWO2022085789A1

Abstract

A method for recovering carbon dioxide, said method comprising: a step (A1) wherein carbon dioxide is absorbed by a carbon dioxide adsorbing/desorbing liquid agent that contains a compound represented by general formula (1), so that a reaction product of the compound and the carbon dioxide is precipitated in the carbon dioxide adsorbing/desorbing liquid agent; and a step (B1) wherein the carbon dioxide is desorbed from the carbon dioxide adsorbing/desorbing liquid agent by subjecting the carbon dioxide adsorbing/desorbing liquid agent after the precipitation of the reaction product to a heat treatment. (Meanwhile, the cases where m is 0, p1 is 2, and two amino groups, to which p1 is attached, are arranged in the meta position to each other are excluded).

Description

Carbon dioxide recovery method, carbon dioxide absorption method, and carbon dioxide release method

The present invention relates to a method for recovering carbon dioxide, a method for absorbing carbon dioxide, and a method for releasing carbon dioxide.
This application claims priority based on Japanese Patent Application No. 2020-178243 filed in Japan on October 23, 2020, the contents of which are incorporated herein by reference.

Carbon dioxide gas is a greenhouse gas, and its concentration in the atmosphere rises, causing global warming. So far, the progress of civilization has continued to consume large amounts of fossil fuels on the earth, and carbon dioxide emissions have continued to increase. In contrast, plants absorb carbon dioxide and release oxygen through photosynthesis. However, logging is progressing on a global scale, large amounts of plants are being lost, and carbon dioxide consumption continues to decline. As a result, the concentration of carbon dioxide in the atmosphere is increasing, and various harmful effects thought to be caused by global warming are recognized on a global scale. Against this background, various techniques for absorbing and immobilizing carbon dioxide in the atmosphere have been studied.

For example, a carbon dioxide absorber containing 1,3-diaminocyclohexane or a derivative in which 1 to 3 hydrogen atoms in the cyclohexane ring conformation are substituted with an alkyl group having 1 to 4 carbon atoms is disclosed. (See Patent Document 1). In this carbon dioxide absorber, 1,3-diaminocyclohexane and its derivative react with carbon dioxide at the amino group (-NH ₂ ) in it, and the amino group is a carboxyamino group (-NH-C (=). By becoming a carbamic acid derivative that has become O) -OH), it is in a state of absorbing carbon dioxide.

Japanese Patent Publication No. 2019-520201

However, 1,3-diaminocyclohexane and its derivatives are known to be easily polymerized by themselves, and have a problem that the carbon dioxide absorption capacity is likely to decrease.
On the other hand, carbon dioxide is not only used for photosynthesis of plants, but also as a raw material for producing high-performance materials. Therefore, in recent years, the development of carbon dioxide recovery technology that absorbs carbon dioxide and releases the absorbed carbon dioxide has been promoted. On the other hand, it is uncertain whether 1,3-diaminocyclohexane and its derivatives described in Patent Document 1 have sufficient carbon dioxide emitting ability.

An object of the present invention is to provide a carbon dioxide absorbing / releasing agent having sufficient carbon dioxide absorbing / releasing ability and a novel method for recovering carbon dioxide.

The present invention adopts the following configuration.
[1]. It is a method for recovering carbon dioxide, and the method for recovering carbon dioxide is described in the following general formula (1).

(In the formula, m is 0 or 1; R ¹ and R ² are independently an alkyl group, an alkoxy group, a carboxy group, an alkyloxycarbonyl group, a formyl group, an alkylcarbonyl group, an alkylthio group and a sulfo group, respectively. It is an alkyloxysulfonyl group, a nitro group, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group may have a substituent; p ₁ and p ₂ are independently 1 or 2, respectively. Yes; if m is 0, q ₁ is an integer from 0 to 11, where p ₁ + q ₁ is less than or equal to 12, and if m is 1, q ₁ is an integer from 0 to 10. However, when p ₁ + q ₁ is 11 or less, q ₂ is an integer of 0 to 10, and q ₁ is an integer of 2 or more, two or more R ^1s may be the same or different from each other. Well, when q ₂ is an integer of 2 or more, two or more R ^2s may be the same or different from each other, q ₁ is an integer of 2 or more, and two or more R ^1s are. In the case of the alkyl group which may have a substituent, the two or more R ^1s may be bonded to each other to form a ring, and q ₂ is an integer of 2 or more. Moreover, when two or more R ^2s are the alkyl groups which may have a substituent, the two or more R ^2s may be bonded to each other to form a ring.)
By allowing a liquid carbon dioxide absorbing / releasing agent containing the compound represented by the above to absorb carbon dioxide, the reaction product of the compound represented by the general formula (1) and the carbon dioxide is formed into the liquid. Step (A1) of precipitating in the carbon dioxide absorption / release agent of
Step (B1) of absorbing the carbon dioxide and releasing the carbon dioxide from the liquid carbon dioxide absorbing / releasing agent by heat-treating the liquid carbon dioxide absorbing / releasing agent after the reactant is precipitated (B1). A method for recovering carbon dioxide (where m is 0, p ₁ is 2, and two amino groups with p ₁ are arranged in meta positions with each other. Excluding carbon dioxide recovery methods).
[2]. The method for recovering carbon dioxide according to [1], wherein the step (B1) is performed in the coexistence of a base catalyst.
[3]. It is a method for recovering carbon dioxide, and the method for recovering carbon dioxide is described in the following general formula (1).

(In the formula, m is 0 or 1; R ¹ and R ² are independently an alkyl group, an alkoxy group, a carboxy group, an alkyloxycarbonyl group, a formyl group, an alkylcarbonyl group, an alkylthio group and a sulfo group, respectively. It is an alkyloxysulfonyl group, a nitro group, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group may have a substituent; p ₁ and p ₂ are independently 1 or 2, respectively. Yes; if m is 0, q ₁ is an integer from 0 to 11, where p ₁ + q ₁ is 12 or less, and if m is 1, q ₁ is an integer from 0 to 10. However, when p ₁ + q ₁ is 11 or less, q ₂ is an integer of 0 to 10, and q ₁ is an integer of 2 or more, two or more R ^1s may be the same or different from each other. Well, when q ₂ is an integer of 2 or more, two or more R ^2s may be the same or different from each other, q ₁ is an integer of 2 or more, and two or more R ^1s are. In the case of the alkyl group which may have a substituent, the two or more R ^1s may be bonded to each other to form a ring, and q ₂ is an integer of 2 or more. Moreover, when two or more R ^2s are the alkyl groups which may have a substituent, the two or more R ^2s may be bonded to each other to form a ring.)
In the step (A) of absorbing carbon dioxide into a carbon dioxide absorbing / releasing agent containing the compound represented by the above, and in the coexistence of a base catalyst, the carbon dioxide absorbing / releasing agent after absorbing the carbon dioxide is heat-treated. A method for recovering carbon dioxide (where m is 0, p ₁ is 2, and p ₁ is), which comprises a step (B2) of releasing the carbon dioxide from the carbon dioxide absorbing / releasing agent. Except for the method of recovering carbon dioxide when the two attached amino groups are arranged at the meta positions of each other).
[4]. The compound represented by the general formula (1) is the following general formula (11A), (12A) or (11B).

(In the formula, R ¹¹ , R ¹² , R ¹³ and R ²¹ are independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a carboxy group and an alkyloxy having 2 to 11 carbon atoms, respectively. Carbonyl group, formyl group, alkylcarbonyl group with 2 to 11 carbon atoms, alkylthio group with 1 to 10 carbon atoms, sulfo group, alkyloxysulfonyl group with 1 to 10 carbon atoms, nitro group, hydroxyl group, thiol group, cyano group or It is a halogen atom and the alkyl group may have an amino group as the substituent; q ₁₁ and q ₁₂ are independently integers of 0 to 6 and q ₁₁ is an integer of 2 or more. In some cases, the two or more R ^11s may be the same or different from each other, and if q ₁₂ is an integer of two or more, the two or more R ^12s may be the same or different from each other. When q ₁₁ is an integer of 2 or more and 2 or more R ^11s are the alkyl groups which may have an amino group as the substituent, the two or more R ^11s are mutual. The alkyl group may be bonded to to form a ring, q ₁₂ may be an integer of 2 or more, and R ¹² of 2 or more may have an amino group as the substituent. In some cases, the two or more R ^12s may be coupled to each other to form a ring; q ₁₃ and q ₂₁ are independently integers from 0 to 4, and q ₁₃ is 2 or more. If the integers of, the two or more R ^13s may be the same or different from each other, and if q ₂₁ is an integer of two or more, the two or more R ^21s may be the same or different from each other. Also, when q ₁₃ is an integer of 2 or more and 2 or more R ¹³ are the alkyl groups which may have an amino group as the substituent, the two or more Rs may be used. ¹³ may be bonded to each other to form a ring, q ₂₁ may be an integer of 2 or more, and 2 or more R ²¹ may have an amino group as the substituent. When it is a group, the two or more R ^21s may be bonded to each other to form a ring.)
The method for recovering carbon dioxide according to any one of [1] to [3], which is a compound represented by (However, in the above general formula (12A), the carbon atom constituting the cyclohexane ring skeleton is used. Except for the method of carbon dioxide recovery when two directly bonded amino groups are located at the meta positions of each other).
[5]. The compound represented by the general formula (11A), (12A) or (11B) is the following general formula (111A), (121A), (122A) or (111B).

(In the formula, R ¹¹¹ , R ¹²¹ , R ¹²² , R ¹³¹ and R ²¹¹ are independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms and an alkyloxy group having 2 to 6 carbon atoms, respectively. It is a carbonyl group, a formyl group, an alkylcarbonyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 5 carbon atoms, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group has an amino group as the substituent. Independently, q ₁₁₁ , q ₁₂₁ and q ₁₂₂ are integers of 0 to 4, and when q ₁₁₁ is an integer of 2 or more, the two or more R ^111s are the same as each other. However, if q ₁₂₁ is an integer of 2 or more, the two or more R ^121s may be the same or different from each other, and if q ₁₂₂ is an integer of 2 or more, 2 or more. The number of R ^122s may be the same or different from each other, q ₁₁₁ may be an integer of 2 or more, and two or more R ^111s may have an amino group as the substituent. When is, the two or more R ^111s may be coupled to each other to form a ring, q ₁₂₁ is an integer of 2 or more, and two or more R ^121s are the substituents. In the case of the alkyl group which may have an amino group, the two or more R ^121s may be bonded to each other to form a ring, and q ₁₂₂ is an integer of 2 or more. In addition, when the two or more R ^122s are the alkyl groups which may have an amino group as the substituent, the two or more R ^122s are bonded to each other to form a ring. May; q ₁₃₁ and q ₂₁₁ are independently integers of 0 to 2, and if q ₁₃₁ is 2, the two R ^131s may be the same or different from each other, q ₂₁₁ . When is 2, the two R ^211s may be the same or different from each other, even if q ₁₃₁ is 2 and the two R ^131s have an amino group as the substituent. In the case of a good alkyl group, the two R ^131s may be bonded to each other to form a ring, q ₂₁₁ is 2, and the two R ^211s are the substituents. In the case of the alkyl group which may have an amino group, the two R ^211s may be bonded to each other to form a ring), which is a compound represented by [4]. ] The method for recovering carbon dioxide described in.
[6]. The method for recovering carbon dioxide according to any one of [1] to [5], wherein the step (A1) and the step (B1), or the step (A) and the step (B2) are repeated two or more times. ..
[7]. It is a method of absorbing carbon dioxide, and the method of absorbing carbon dioxide is described in the following general formula (1).

(In the formula, m is 0 or 1; R ¹ and R ² are independently an alkyl group, an alkoxy group, a carboxy group, an alkyloxycarbonyl group, a formyl group, an alkylcarbonyl group, an alkylthio group and a sulfo group, respectively. It is an alkyloxysulfonyl group, a nitro group, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group may have a substituent; p ₁ and p ₂ are independently 1 or 2, respectively. Yes; if m is 0, q ₁ is an integer from 0 to 11, where p ₁ + q ₁ is 12 or less, and if m is 1, q ₁ is an integer from 0 to 10. However, when p ₁ + q ₁ is 11 or less, q ₂ is an integer of 0 to 10, and q ₁ is an integer of 2 or more, two or more R ^1s may be the same or different from each other. Well, when q ₂ is an integer of 2 or more, two or more R ^2s may be the same or different from each other, q ₁ is an integer of 2 or more, and two or more R ^1s are. In the case of the alkyl group which may have a substituent, the two or more R ^1s may be bonded to each other to form a ring, and q ₂ is an integer of 2 or more. Moreover, when two or more R ^2s are the alkyl groups which may have a substituent, the two or more R ^2s may be bonded to each other to form a ring.)
By allowing a liquid carbon dioxide absorbing / releasing agent containing the compound represented by the above to absorb carbon dioxide, the reaction product of the compound represented by the general formula (1) and the carbon dioxide is formed into the liquid. A method for absorbing carbon dioxide having a step (a1) of precipitating in the carbon dioxide absorbing / releasing agent (where m is 0, p ₁ is 2 and p ₁ is attached to the two amino groups. Except for the method of absorbing carbon dioxide when they are placed in meta positions with each other).
[8]. A method for releasing carbon dioxide, wherein the method for releasing carbon dioxide is based on the following general formula (1).

(In the formula, m is 0 or 1; R ¹ and R ² are independently an alkyl group, an alkoxy group, a carboxy group, an alkyloxycarbonyl group, a formyl group, an alkylcarbonyl group, an alkylthio group and a sulfo group, respectively. It is an alkyloxysulfonyl group, a nitro group, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group may have a substituent; p ₁ and p ₂ are independently 1 or 2, respectively. Yes; if m is 0, q ₁ is an integer from 0 to 11, where p ₁ + q ₁ is less than or equal to 12, and if m is 1, q ₁ is an integer from 0 to 10. However, when p ₁ + q ₁ is 11 or less, q ₂ is an integer of 0 to 10, and q ₁ is an integer of 2 or more, two or more R ^1s may be the same or different from each other. Well, when q ₂ is an integer of 2 or more, two or more R ^2s may be the same or different from each other, q ₁ is an integer of 2 or more, and two or more R ^1s are. In the case of the alkyl group which may have a substituent, the two or more R ^1s may be bonded to each other to form a ring, and q ₂ is an integer of 2 or more. Moreover, when two or more R ^2s are the alkyl groups which may have a substituent, the two or more R ^2s may be bonded to each other to form a ring.)
By heat-treating a liquid carbon dioxide-releasing agent containing a reaction product of a compound represented by A method for releasing carbon dioxide, which comprises a step (b1) of releasing carbon dioxide.
[9]. It is a method of releasing carbon dioxide, and the method of releasing carbon dioxide is described in the following general formula (1).

(In the formula, m is 0 or 1; R ¹ and R ² are independently an alkyl group, an alkoxy group, a carboxy group, an alkyloxycarbonyl group, a formyl group, an alkylcarbonyl group, an alkylthio group and a sulfo group, respectively. It is an alkyloxysulfonyl group, a nitro group, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group may have a substituent; p ₁ and p ₂ are independently 1 or 2, respectively. Yes; if m is 0, q ₁ is an integer from 0 to 11, where p ₁ + q ₁ is less than or equal to 12, and if m is 1, q ₁ is an integer from 0 to 10. However, when p ₁ + q ₁ is 11 or less, q ₂ is an integer of 0 to 10, and q ₁ is an integer of 2 or more, two or more R ^1s may be the same or different from each other. Well, when q ₂ is an integer of 2 or more, two or more R ^2s may be the same or different from each other, q ₁ is an integer of 2 or more, and two or more R ^1s are. In the case of the alkyl group which may have a substituent, the two or more R ^1s may be bonded to each other to form a ring, and q ₂ is an integer of 2 or more. Moreover, when two or more R ^2s are the alkyl groups which may have a substituent, the two or more R ^2s may be bonded to each other to form a ring.)
A step of releasing the carbon dioxide from the carbon dioxide releasing agent by heat-treating the carbon dioxide releasing agent containing a reaction product of the compound represented by (b2) and carbon dioxide in the coexistence of a base catalyst (b2). ), A method of releasing carbon dioxide.

According to the present invention, a carbon dioxide absorbing / releasing agent having sufficient carbon dioxide absorbing / releasing ability and a novel method for recovering carbon dioxide are provided.

It is a graph which shows the carbon dioxide removal efficiency in Example 1 together with the imaging data of the carbon dioxide absorption and release agent. It is a ¹³ C-NMR spectrum of a component in a carbon dioxide sink when carbon dioxide is flowing in, a standard of cyclohexylamine, and a standard of N-cyclohexylcarbamic acid. It is a graph which shows the carbon dioxide removal efficiency in Example 2. FIG. It is a graph which shows the carbon dioxide removal efficiency in Example 3. FIG. It is a graph which shows the carbon dioxide removal efficiency in Example 4. FIG. It is a graph which shows the carbon dioxide removal efficiency in Example 5. FIG. 6 is spectral data of weight loss at the time of thermogravimetric analysis-mass spectrometry for the carbon dioxide emitting agent in Example 6. FIG. 6 is spectral data of ionic strength at the time of thermogravimetric analysis-mass spectrometry for the carbon dioxide emitting agent in Example 6. It is a graph which shows the measurement result of the concentration of carbon dioxide in the exhaust gas in the 1st carbon dioxide emission experiment in Examples 7-8. It is a graph which shows the measurement result of the concentration of carbon dioxide in the exhaust gas in the 2nd carbon dioxide emission experiment in Examples 7-8. It is a graph which shows the measurement result of the concentration of carbon dioxide in the exhaust gas at the time of absorption of carbon dioxide in the 1st cycle to the 2nd cycle in Example 9. It is a graph which shows the measurement result of the concentration of carbon dioxide in the exhaust gas at the time of the release of carbon dioxide in the 1st cycle to the 2nd cycle in Example 9. It is a graph which shows the measurement result of the concentration of carbon dioxide in the exhaust gas at the time of absorption of carbon dioxide in the 1st cycle to the 4th cycle in Example 10. It is a graph which shows the measurement result of the concentration of carbon dioxide in the exhaust gas at the time of the release of carbon dioxide in the 1st cycle to the 4th cycle in Example 10. ¹³ C-NMR spectra of N-cyclohexylcarbamic acid obtained in Example 11 and regenerated cyclohexylamine. ¹³ C-NMR spectra of the (2-aminocyclohexyl) carbamic acid obtained in Example 13 and the regenerated 1,2-cyclohexanediamine. ¹³ C-NMR spectra of the (4-aminocyclohexyl) carbamic acid obtained in Example 14 and the regenerated 1,4-cyclohexanediamine. ¹³ C-NMR spectra of the (3-aminomethyl-3,5,5-trimethylcyclohexyl) carbamic acid obtained in Example 15 and the regenerated isophorone diamine. It is a graph which shows the measurement result of the concentration of carbon dioxide in the exhaust gas at the time of the release of carbon dioxide in Examples 18-19. It is a graph which shows the measurement result of the concentration of carbon dioxide in the exhaust gas at the time of absorption of carbon dioxide in Example 19. It is a graph which shows the measurement result of the concentration of carbon dioxide in the exhaust gas at the time of absorption of carbon dioxide in Example 20. It is a graph which shows the measurement result of the concentration of carbon dioxide in the exhaust gas at the time of the release of carbon dioxide in Examples 18 and 20. It is a graph which shows the measurement result of the concentration of carbon dioxide in the exhaust gas at the time of absorption of carbon dioxide in Example 21. It is a graph which shows the measurement result of the concentration of carbon dioxide in the exhaust gas at the time of the release of carbon dioxide in Examples 18 and 21. It is a graph which shows the measurement result of the concentration of carbon dioxide in the exhaust gas at the time of absorption of carbon dioxide in Example 22. It is a graph which shows the measurement result of the concentration of carbon dioxide in the exhaust gas at the time of the release of carbon dioxide in Examples 18 and 22. It is a graph which shows the measurement result of the concentration of carbon dioxide in the exhaust gas at the time of absorption of carbon dioxide in Example 23. It is a graph which shows the measurement result of the concentration of carbon dioxide in the exhaust gas at the time of the release of carbon dioxide in Examples 18 and 23. It is a graph which shows the measurement result of the concentration of carbon dioxide in the exhaust gas at the time of absorption of carbon dioxide in Example 24. It is a graph which shows the measurement result of the concentration of carbon dioxide in the exhaust gas at the time of the release of carbon dioxide in Example 24. It is a graph which shows the measurement result of the concentration of carbon dioxide in the exhaust gas at the time of absorption of carbon dioxide in Example 25. It is a graph which shows the measurement result of the concentration of carbon dioxide in the exhaust gas at the time of the release of carbon dioxide in Example 25. It is a graph which shows the carbon dioxide removal efficiency in Examples 26-28. It is a graph which shows the carbon dioxide removal efficiency in Examples 29-32. It is a graph which shows the carbon dioxide removal efficiency in Examples 28, 31 and 33. It is a graph which shows the carbon dioxide removal efficiency in Examples 28, 34-35. It is a graph which shows the carbon dioxide removal efficiency in Examples 28, 36-39.

<< Carbon dioxide absorption and release agent >>
The carbon dioxide absorbing / releasing agent according to the embodiment of the present invention is a carbon dioxide absorbing / releasing agent that absorbs carbon dioxide and releases the absorbed carbon dioxide, and has the following general formula (1).

(In the formula, m is 0 or 1; R ¹ and R ² are independently an alkyl group, an alkoxy group, a carboxy group, an alkyloxycarbonyl group, a formyl group, an alkylcarbonyl group, an alkylthio group and a sulfo group, respectively. It is an alkyloxysulfonyl group, a nitro group, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group may have a substituent; p ₁ and p ₂ are independently 1 or 2, respectively. Yes; if m is 0, q ₁ is an integer from 0 to 11, where p ₁ + q ₁ is less than or equal to 12, and if m is 1, q ₁ is an integer from 0 to 10. However, when p ₁ + q ₁ is 11 or less, q ₂ is an integer of 0 to 10, and q ₁ is an integer of 2 or more, two or more R ^1s may be the same or different from each other. Well, when q ₂ is an integer of 2 or more, two or more R ^2s may be the same or different from each other, q ₁ is an integer of 2 or more, and two or more R ^1s are. In the case of the alkyl group which may have a substituent, the two or more R ^1s may be bonded to each other to form a ring, and q ₂ is an integer of 2 or more. Moreover, when two or more R ^2s are the alkyl groups which may have a substituent, the two or more R ^2s may be bonded to each other to form a ring.)
(However, m is 0, p ₁ is 2, and p ₁ is attached) containing a compound represented by (in the present specification, it may be referred to as “compound (1)”). Except for carbon dioxide absorption and release agents when two amino groups are located at the meta positions of each other).

In the carbon dioxide absorption / release agent of the present embodiment, the active ingredient that absorbs carbon dioxide and releases carbon dioxide after absorption is compound (1). That is, the compound (1) has reactivity with carbon dioxide (in other words, absorbable), and the reactant of the compound (1) and carbon dioxide has the property of releasing carbon dioxide.

More specifically, the compound (1) reacts with carbon dioxide at the amino group (-NH ₂ ) in the compound (1), and the amino group becomes a carboxyamino group (-NH-C (= O) -OH). By becoming a carbamic acid derivative, carbon dioxide is absorbed. At this time, depending on the conditions under which the carbamic acid derivative is placed, the carboxyamino group may be a group represented by the formula "-NH-C (= O) ^-O- " or the formula "-NH ₂ ⁺ -C (=). It may be the basis represented by "O) ^-O- ". Further, the carbamic acid derivative, which is a reaction product of compound (1) and carbon dioxide, releases carbon dioxide from the carboxyamino group in the derivative to form an amino group. As a result, the carbamic acid derivative returns to compound (1).
After absorbing and releasing this carbon dioxide, the compound (1) can absorb and release carbon dioxide again by the same reaction mechanism. That is, compound (1) can repeatedly absorb and release carbon dioxide.

<Compound (1)>
The compound (1) is represented by the general formula (1).
In the general formula (1), m is 0 or 1.
m defines the presence or absence of one cyclohexane ring skeleton mediated by a methylene group in compound (1).
That is, when m is 0, the compound (1) is a cyclohexane derivative and is represented by the following general formula (1A) (in the present specification, this compound may be referred to as “compound (1A)”). (However, excluding compounds in which p ₁ is 2 and two (p ₁ ) amino groups with p ₁ are arranged at the meta positions of each other).
When m is 1, compound (1) is a dicyclohexylmethane derivative and is represented by the following general formula (1B) (in the present specification, this compound may be referred to as “compound (1B)”).

(In the formula, R ¹ , R ² , p ₁ , p ₂ , q ₁ and q ₂ are the same as above.)

In the present specification, when a structure in which one or more hydrogen atoms are substituted with a group other than a hydrogen atom is assumed in a specific compound, the compound having such a substituted structure is referred to as the above-mentioned specific compound. It is referred to as a "derivative" of the compound of.
As used herein, the term "group" includes not only an atomic group formed by bonding a plurality of atoms but also one atom, unless otherwise specified.

In the general formula (1), R ¹ and R ² are independently an alkyl group, an alkoxy group, a carboxy group (-C (= O) -OH), an alkyloxycarbonyl group, and a formyl group (-C (= O), respectively. ) -H), alkylcarbonyl group (acyl group), alkylthio group, sulfo group (-SO _3H ), alkyloxysulfonyl group, nitro group (-NO ₂ ), hydroxyl group (-OH), thiol group (mercapto group, -SH), a cyano (-CN) group or a halogen atom, and the alkyl group may have a substituent. That is, these groups in R ¹ and R ² may be the same or different from each other.

The alkyl group in R ¹ and R ² may be linear, branched or cyclic.

The carbon number of the linear or branched alkyl group in R ¹ and R ² is not particularly limited, but is preferably 1 to 20.
Examples of such linear or branched alkyl groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. n-Pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3- Dimethylbutyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethyl Pentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group , Heptadecyl group, octadecyl group, nonadecil group, icosyl group and the like.
The number of carbon atoms of the linear or branched alkyl group is more preferably 1 to 10, and may be, for example, any of 1 to 7, 1 to 5, and 1 to 3.

The cyclic alkyl group in R ¹ and R ² may be either monocyclic or polycyclic.
The number of carbon atoms of the cyclic alkyl group is not particularly limited as long as it is 3 or more, but it is preferably 3 to 20.
Examples of the cyclic alkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group and 2-. Examples thereof include an adamantyl group and a tricyclodecyl group.
The cyclic alkyl group preferably has 3 to 15 carbon atoms, and may be, for example, any of 3 to 10, 3 to 7, and 3 to 5, or 5 to 15, 5 to 10. , And any of 5 to 7.

The alkyl group in R ¹ and R ² may be a mixture of a linear or branched chain structure and a cyclic structure.
Examples of the alkyl group in which such a chain structure and a cyclic structure are mixed include the above-mentioned linear or branched chain such as a cyclopentylmethyl group, a 1-cyclopentylethyl group, a cyclohexylmethyl group, and a 1-cyclohexylethyl group. A monovalent group having a structure in which one or more hydrogen atoms in the alkyl group in the form are substituted with the cyclic alkyl group described above; a methylcyclopentyl group, an ethylcyclopentyl group, a methylcyclohexyl group, an ethylcyclohexyl group, Examples thereof include a monovalent group having a structure in which one or more hydrogen atoms in the above-mentioned cyclic alkyl group, such as a dimethylcyclohexyl group, are substituted with the above-mentioned linear or branched alkyl group. Be done.
The number of carbon atoms of the alkyl group in which the chain structure and the cyclic structure are mixed is not particularly limited as long as it is 4 or more, but is preferably 4 to 25, and is preferably any of 6 to 15, and 6 to 10, for example. There may be.

In the present specification, the alkyl group having only a chain structure and not having a cyclic structure is a chain alkyl group, and the alkyl group having a cyclic structure is cyclic regardless of the presence or absence of the chain structure. It is an alkyl group.

The alkyl groups in R ¹ and R ² are independently alkyl groups having 1 to 10 carbon atoms (chain alkyl groups having 1 to 10 carbon atoms and cyclic alkyl groups having 3 to 10 carbon atoms). It is more preferable that the alkyl groups have 1 to 5 carbon atoms (chain alkyl groups having 1 to 5 carbon atoms and cyclic alkyl groups having 3 to 5 carbon atoms) independently of each other.

The alkyl group in R ¹ and R ² may have a substituent.
The fact that the alkyl group has a substituent means that one or more hydrogen atoms in the alkyl group are substituted with a group other than the hydrogen atom.

When the number of hydrogen atoms substituted in the alkyl group is two or more, the substituents may be all the same, all may be different, or only a part thereof may be the same. ..

In the alkyl group, the substitution position of the hydrogen atom is not particularly limited.
For example, when two or more hydrogen atoms that can be substituted with a substituent are bonded to one carbon atom in the alkyl group, only one of them may be substituted with the substituent. However, two or more may be substituted with a substituent.
For example, when the alkyl group has a chain structure, the substitution position may be a carbon atom at the end of the chain structure or a non-terminal carbon atom.

When the alkyl group in R ¹ and R ² has a substituent, the number of substituents depends on the number of hydrogen atoms that can be substituted, but is usually preferably 1 to 3 or 1 or. It is more preferable that the number is two.

Examples of the substituent include an amino group, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), a hydroxyl group and the like.

Among the alkyl groups having a substituent, for example, an aminoalkyl group having an amino group as a substituent is mentioned, and a more preferable one is, for example, a chain (linear or branched). Examples thereof include an aminoalkyl group in which an amino group is bonded to a carbon atom at the end of the alkyl group.

The alkoxy group in R ¹ and R ² may be linear, branched or cyclic.
Examples of the alkoxy group in R ¹ and R ² include a methoxy group (CH ₃ -O-), a cyclopropyloxy group (C ₃ H ₅ -O-), and a cyclopentylmethyl oxy group (C ₅ H ₉ -CH ₂ ). -O-), methylcyclopentyloxy group (CH ₃ -C ₅ H ₈ -O-), etc., the linear, branched or cyclic alkyl groups in R ¹ and R ² described above become oxygen atoms. Examples thereof include monovalent groups having a bonded structure.

The linear or branched alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, for example, 1 to 7, 1 to 5, and 1 to 3. It may be either.
The cyclic alcoholic group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and may be, for example, any of 3 to 10, 3 to 7, and 3 to 5. It may be any of 5 to 15, 5 to 10, and 5 to 7.
The number of carbon atoms of the alkoxy group in which the chain structure and the cyclic structure are mixed is not particularly limited as long as it is 4 or more, but is preferably 4 to 25, and is preferably any of 6 to 15, and 6 to 10, for example. There may be.

In the present specification, the alkoxy group having only a chain structure and not having a cyclic structure is a chain alkoxy group, and the alkoxy group having a cyclic structure is cyclic regardless of the presence or absence of the chain structure. It is an alkoxy group.

The alkoxy groups in R ¹ and R ² are independently alkoxy groups having 1 to 10 carbon atoms (chain alkoxy groups having 1 to 10 carbon atoms and cyclic alkoxy groups having 3 to 10 carbon atoms). It is more preferable that the alkoxy groups have 1 to 5 carbon atoms (chain alkoxy groups having 1 to 5 carbon atoms and cyclic alkoxy groups having 3 to 5 carbon atoms) independently of each other.

Examples of the alkyloxycarbonyl group in R ¹ and R ² include a methoxycarbonyl group (CH ₃ -OC (= O)-) and a cyclopropyloxycarbonyl group (C ₃ H5-OC ₍ = O)). )-), Cyclopentylmethyloxycarbonyl group (C ₅ H ₉ -CH ₂ -OC (= O)-), Methylcyclopentyl oxycarbonyl group (CH ₃ -C ₅ H ₈ -OC (= O)-) ), Etc., the linear, branched or cyclic alkyl group in R ¹ and R ² described above is a carbonyl group (-C (=) in an oxycarbonyl group (-OC (= O)-). Examples thereof include monovalent groups having a structure bonded to oxygen atoms that do not constitute O)-).

When the alkyl group is linear or branched, the number of carbon atoms of the alkyloxycarbonyl group is preferably 2 to 21, more preferably 2 to 11, for example, 2 to 8, It may be any of 2 to 6 and 2 to 4.
When the alkyl group is cyclic, the alkyloxycarbonyl group preferably has 4 to 21 carbon atoms, more preferably 4 to 16 carbon atoms, for example, 4 to 11, 4 to 8 and 4 carbon atoms. It may be any of 6 to 6, 6 to 16, 6 to 11 and 6 to 8.
When the alkyl group is a mixture of a chain structure and a cyclic structure, the carbon number of the alkyloxycarbonyl group is not particularly limited as long as it is 5 or more, but is preferably 5 to 26, for example, 7. It may be any of 16 and 7-11.

The alkyloxycarbonyl group in R ¹ and R ² is preferably an alkyloxycarbonyl group having 2 to 11 carbon atoms independently, and each independently has an alkyloxycarbonyl group having 2 to 6 carbon atoms. Is more preferable.

Examples of the alkylcarbonyl group in R ¹ and R ² include a methylcarbonyl group (acetyl group, CH ₃ _- C (= O)-) and a cyclopropylcarbonyl group (C3 _H5 -C (= O)-). , Cyclopentylmethylcarbonyl group (C ₅ H ₉ -CH ₂ -C (= O)-), methylcyclopentylcarbonyl group (CH ₃ ^- C ₅ H ₈ -C (= O)-), etc. Examples thereof include a monovalent group having a structure in which the linear, branched or cyclic alkyl group in ^R2 is bonded to a carbon atom in a carbonyl group (-C (= O)-).

When the alkyl group is linear or branched, the number of carbon atoms of the alkylcarbonyl group is preferably 2 to 21, more preferably 2 to 11, for example, 2 to 8 and 2. It may be any of 6 and 2-4.
When the alkyl group is cyclic, the number of carbon atoms of the alkylcarbonyl group is preferably 4 to 21, more preferably 4 to 16, for example, 4 to 11, 4 to 8, and 4 to 4. It may be any of 6, or 6 to 16, 6 to 11, and 6 to 8.
When the alkyl group is a mixture of a chain structure and a cyclic structure, the number of carbon atoms of the alkylcarbonyl group is not particularly limited as long as it is 5 or more, but is preferably 5 to 26, for example, 7 to 26. It may be any of 16 and 7-11.

The alkylcarbonyl groups in R ¹ and R ² are preferably independent alkylcarbonyl groups having 2 to 11 carbon atoms, and more preferably independent alkylcarbonyl groups having 2 to 6 carbon atoms. ..

The alkylthio group in R ¹ and R ² may be linear, branched or cyclic.
Examples of the alkylthio group in R ¹ and R ² include a methyl thio group (CH ₃ -S-), a cyclopropyl thio group (C ₃ H ₅ -S-), and a cyclopentyl methyl thio group (C ₅ H ₉ -CH _2- The linear, branched or cyclic alkyl group in ^R1 and ^R2 described above, such as S-), methylcyclopentylthio group ₍ CH ₃ -C ₅ H8-S-), is attached to a sulfur atom. Examples thereof include monovalent groups having the above-mentioned structure.
The linear or branched alkylthio group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, for example, 1 to 7, 1 to 5 and 1 to 3 carbon atoms. It may be either.
The cyclic alkylthio group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and may be, for example, any of 3 to 10, 3 to 7, and 3 to 5. It may be any of 5 to 15, 5 to 10, and 5 to 7.
The number of carbon atoms of the alkylthio group in which the chain structure and the cyclic structure are mixed is not particularly limited as long as it is 4 or more, but is preferably 4 to 25, and is preferably any of 6 to 15, and 6 to 10, for example. There may be.

In the present specification, the alkylthio group having only a chain structure and not having a cyclic structure is a chain alkylthio group, and the alkylthio group having a cyclic structure is cyclic regardless of the presence or absence of the chain structure. It is an alkylthio group.

The alkylthio groups in R ¹ and R ² are independently alkyl thio groups having 1 to 10 carbon atoms (chain alkyl thio groups having 1 to 10 carbon atoms and cyclic alkyl thio groups having 3 to 10 carbon atoms). It is more preferable that the alkylthio groups have 1 to 5 carbon atoms (chain alkylthio groups having 1 to 5 carbon atoms and cyclic alkylthio groups having 3 to 5 carbon atoms) independently of each other.

Examples of the alkyloxysulfonyl group in ^R1 and ^R2 include a methyloxysulfonyl group (methoxysulfonyl group _, CH ₃ -O-SO _2- ) and a cyclopropyloxysulfonyl group (C3 H5 _- O-SO ₂ ). -), Cyclopentylmethyloxysulfonyl group (C ₅ H ₉ -CH ₂ -O-SO _2- ), methylcyclopentyloxysulfonyl group (CH ₃ -C ₅ H ₈ -O-SO _2- ), etc. The linear, branched or cyclic alkyl group in ¹ and R ² is bonded to an oxygen atom that does not constitute a sulfonyl group (-SO _2- ) in an oxysulfonyl group (-O-SO _2- ). Examples thereof include monovalent groups having the above-mentioned structure.

When the alkyl group is linear or branched, the number of carbon atoms of the alkyloxysulfonyl group is preferably 1 to 20, more preferably 1 to 10, and for example, 1 to 7. It may be any one of 1 to 5 and 1 to 3.
When the alkyl group is cyclic, the number of carbon atoms of the alkyloxysulfonyl group is preferably 3 to 20, more preferably 3 to 15, for example, 3 to 10, 3 to 7, and 3. It may be any of 5 to 5, 5 to 15, 5 to 10, and 5 to 7.
When the alkyl group is a mixture of a chain structure and a cyclic structure, the number of carbon atoms of the alkyloxysulfonyl group is not particularly limited as long as it is 4 or more, but is preferably 4 to 25, for example, 6. It may be any of ~ 15, and 6-10.

It is preferable that the alkyloxysulfonyl groups in R ¹ and R ² are independently alkylcarbonyl groups having 1 to 10 carbon atoms, and each independently is an alkylcarbonyl group having 1 to 5 carbon atoms. preferable.

Examples of the halogen atom in R ¹ and R ² include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

R ¹ and R ² each independently may have an amino group as the substituent, and may have an alkyl group having 1 to 10 carbon atoms (chain alkyl group having 1 to 10 carbon atoms, 3 to 10 carbon atoms). 10 cyclic alkyl group), an alkoxy group having 1 to 10 carbon atoms (chain alkoxy group having 1 to 10 carbon atoms, cyclic alkoxy group having 3 to 10 carbon atoms), a carboxy group, and 2 carbon atoms. Alkyloxycarbonyl groups of ~ 11 (alkyloxycarbonyl groups having 2 to 11 carbon atoms when the alkyl group is linear or branched, and alkyloxycarbonyl groups having 4 to 11 carbon atoms when the alkyl group is cyclic) Group), a formyl group, an alkylcarbonyl group having 2 to 11 carbon atoms (an alkylcarbonyl group having 2 to 11 carbon atoms when the alkyl group is linear or branched, and a cyclic group when the alkyl group is cyclic). An alkylcarbonyl group having 4 to 11 carbon atoms), an alkylthio group having 1 to 10 carbon atoms (chain alkylthiogroup having 1 to 10 carbon atoms, a cyclic alkylthio group having 3 to 10 carbon atoms), a sulfo group, and the like. Alkyloxysulfonyl group having 1 to 10 carbon atoms (alkyloxysulfonyl group having 1 to 10 carbon atoms when the alkyl group is linear or branched, and 4 to 11 carbon atoms when the alkyl group is cyclic). It is preferably one or more selected from the group consisting of an alkyloxysulfonyl group), a nitro group, a hydroxyl group, a thiol group, a cyano group, and a halogen atom.
R ¹ and R ² each independently may have an amino group as the substituent, and may have an alkyl group having 1 to 5 carbon atoms (chain alkyl group having 1 to 5 carbon atoms, 3 to 3 carbon atoms). A cyclic alkyl group having 5 carbon atoms), an alkoxy group having 1 to 5 carbon atoms (chain alkoxy group having 1 to 5 carbon atoms, a cyclic alkoxy group having 3 to 5 carbon atoms), and an alkyl having 2 to 6 carbon atoms. An oxycarbonyl group (an alkyloxycarbonyl group having 2 to 6 carbon atoms when the alkyl group is linear or branched, and an alkyloxycarbonyl group having 4 to 6 carbon atoms when the alkyl group is cyclic) and A formyl group and an alkylcarbonyl group having 2 to 6 carbon atoms (an alkylcarbonyl group having 2 to 6 carbon atoms when the alkyl group is linear or branched, and 4 to 4 carbon atoms when the alkyl group is cyclic). 6 alkylcarbonyl group), an alkylthio group having 1 to 5 carbon atoms (chain alkylthiogroup having 1 to 5 carbon atoms, a cyclic alkylthio group having 3 to 3 carbon atoms), a hydroxyl group, a thiol group, and cyano. More preferably, it is one or more selected from the group consisting of a group and a halogen atom.

In the general formula ( ₁ ), p1 and p2 are independently 1 or ₂ , respectively. That is, p ₁ and p ₂ may be the same as each other or may be different from each other.
p ₁ defines the number of amino groups directly bonded to the carbon atom constituting one of the cyclohexane ring skeletons in compound (1).
p ₂ defines the number of amino groups directly bonded to the carbon atom constituting the other cyclohexane ring skeleton in compound (1).

In the general formula (1), when m is 0, q ₁ is an integer of 0 to 11, where p ₁ + q ₁ is 12 or less. On the other hand, when m is 1, q ₁ is an integer of 0 to 10, where p ₁ + q ₁ is 11 or less.
q ₁ defines the number of R ^1s in compound (1) that are directly bonded to the carbon atoms constituting one of the cyclohexane ring conformations.

In both cases where m is 0 and q ₁ is an integer of 2 or more (2 to 11), or m is 1 and q ₁ is an integer of 2 or more (2 to 10). Two or more R1s may be the same or different from ^each other. That is, two or more R ^1s may be all the same, all may be different, or only a part may be the same.

In the general formula (1), q ₂ is an integer of 0 to 10.
q ₂ defines the number of R ² directly bonded to the carbon atom constituting the other cyclohexane ring skeleton in compound (1).

When q ₂ is an integer of 2 or more (2 to 10), the two or more R ^2s may be the same or different from each other. That is, two or more R ^2s may be all the same, all may be different, or only a part may be the same.

When m is 0, q ₁ is an integer of 2 or more (2 to 11), and 2 or more R ^1s are alkyl groups which may have a substituent, and m is. 1 and q ₁ is an integer of 2 or more (2 to 10), and 2 or more R ^1s are alkyl groups which may have a substituent. , The two or more R ^1s (alkyl groups which may have substituents) are attached to each other to form a ring together with the groups in the cyclohexane ring skeleton to which these R ^1s are attached. May be.
The ring formed by bonding two or more R ^1s to each other is an aliphatic ring containing only a carbon atom as an atom forming a ring skeleton.
When the ring is formed, the bonding position between ^two or more R1s is not particularly limited. For example, when R ¹ has a chain structure, the bond position may be a carbon atom at the end of the chain structure or a non-terminal carbon atom.
When the ring is formed, the number of binding sites between R1s may be ¹ or 2 or more. That is, the ring may be either monocyclic or polycyclic.

When q ₂ is an integer of 2 or more (2 to 10) and two or more R ^2s are alkyl groups which may have a substituent, the two or more R ^2s (substitutions) Alkyl groups (which may have groups) may be attached to each other to form a ring with the groups in the cyclohexane ring skeleton to which these ^R2s are attached.
The mode in which two or more R ^2s are bonded to each other to form a ring is the same as the above-mentioned mode in which two or more R ^1s are bonded to each other to form a ring. That is, examples of the ring formed by connecting two or more R ^2s to each other include the same ring formed by connecting two or more R ^1s to each other as described above. The rings may be the same or different from each other.

For example, when m is 0, q ₁ and q ₂ are preferably 0 to 6, and more preferably 0 to 4.
For example, when m is 1, the q ₁ and q ₂ are preferably 0 to 4, and more preferably 0 to 2.

However, in the carbon dioxide sink of the present embodiment, in the general formula (1), m is 0, p ₁ is 2, and two (p ₁ ) amino groups are arranged at the meta positions of each other. Those containing the above-mentioned compounds are not included.
That is, in the carbon dioxide sink of the present embodiment, in the compound (1), when m is 0 and p ₁ is 2, two (p ₁ ) amino groups are in meta positions with each other. It will not be placed.

Compound (1) is the following general formula (11A), (12A) or (11B).

(In the formula, R ¹¹ , R ¹² , R ¹³ and R ²¹ are independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a carboxy group and an alkyloxy having 2 to 11 carbon atoms, respectively. Carbonyl group, formyl group, alkylcarbonyl group with 2 to 11 carbon atoms, alkylthio group with 1 to 10 carbon atoms, sulfo group, alkyloxysulfonyl group with 1 to 10 carbon atoms, nitro group, hydroxyl group, thiol group, cyano group or It is a halogen atom and the alkyl group may have an amino group as the substituent; q ₁₁ and q ₁₂ are independently integers of 0 to 6 and q ₁₁ is an integer of 2 or more. In some cases, the two or more R ^11s may be the same or different from each other, and if q ₁₂ is an integer of two or more, the two or more R ^12s may be the same or different from each other. When q ₁₁ is an integer of 2 or more and 2 or more R ^11s are the alkyl groups which may have an amino group as the substituent, the two or more R ^11s are mutual. The alkyl group may be bonded to to form a ring, q ₁₂ may be an integer of 2 or more, and R ¹² of 2 or more may have an amino group as the substituent. In some cases, the two or more R ^12s may be coupled to each other to form a ring; q ₁₃ and q ₂₁ are independently integers from 0 to 4, and q ₁₃ is 2 or more. If the integers of, the two or more R ^13s may be the same or different from each other, and if q ₂₁ is an integer of two or more, the two or more R ^21s may be the same or different from each other. Also, when q ₁₃ is an integer of 2 or more and 2 or more R ¹³ are the alkyl groups which may have an amino group as the substituent, the two or more Rs may be used. ¹³ may be bonded to each other to form a ring, q ₂₁ may be an integer of 2 or more, and 2 or more R ²¹ may have an amino group as the substituent. When it is a group, the two or more R ^21s may be bonded to each other to form a ring.)
Compounds represented by (in the present specification, they may be referred to as "compound (11A)", "compound (12A)" or "compound (11B)", respectively, corresponding to the reference numerals attached to them) (However, , In the general formula (12A), the compound in which the two amino groups directly bonded to the carbon atoms constituting the cyclohexane ring skeleton are arranged at the meta positions of each other is excluded).

In the general formula (11A), (12A) or (11B), R ¹¹ , R ¹² , R ¹³ and R ²¹ are independently alkyl groups having 1 to 10 carbon atoms and alkoxy groups having 1 to 10 carbon atoms, respectively. Carboxy group, alkyloxycarbonyl group with 2 to 11 carbon atoms, formyl group, alkylcarbonyl group with 2 to 11 carbon atoms, alkylthio group with 1 to 10 carbon atoms, sulfo group, alkyloxysulfonyl group with 1 to 10 carbon atoms, It is a nitro group, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group may have an amino group as the substituent. That is, these groups in R ¹¹ , R ¹² , R ¹³ and R ²¹ may be the same or different from each other.

The alkyl groups having 1 to 10 carbon atoms in R ¹¹ , R ¹² , R ¹³ and R ²¹ are linear or branched (that is, chain) alkyl groups having 1 to 10 carbon atoms and 3 to 3 carbon atoms. It may be any of 10 cyclic alkyl groups.
Examples of the alkyl group having 1 to 10 carbon atoms include those having 1 to 10 carbon atoms among the alkyl groups in R ¹ and R ² .

When the alkyl group in R ¹¹ , R ¹² , R ¹³ or R ²¹ has a substituent, the embodiment having a substituent is the same as the case where the alkyl group in R ¹ and R ² has a substituent.

The alkoxy groups having 1 to 10 carbon atoms in R ¹¹ , R ¹² , R ¹³ and R ²¹ are linear or branched (ie, chain) alkoxy groups having 1 to 10 carbon atoms and 3 to 3 carbon atoms. It may be any of 10 cyclic alkoxy groups.
Examples of the alkoxy group having 1 to 10 carbon atoms include alkoxy groups having 1 to 10 carbon atoms among the alkoxy groups in R ¹ and R ² .

The alkyl group in the alkyloxycarbonyl group having 2 to 11 carbon atoms in R ¹¹ , R ¹² , R ¹³ and R ²¹ is a linear or branched (that is, chain) alkyl group having 1 to 10 carbon atoms. And a cyclic alkyl group having 3 to 10 carbon atoms.
As the alkyloxycarbonyl groups having 2 to 11 carbon atoms in R ¹¹ , R ¹² , R ¹³ and R ²¹ , among the alkyl oxycarbonyl groups in R ¹ and R ² , those having 2 to 11 carbon atoms are used. Can be mentioned.

The alkyl groups in the alkylcarbonyl groups having 2 to 11 carbon atoms in R ¹¹ , R ¹² , R ¹³ and R ²¹ are linear or branched (that is, chain) alkyl groups having 1 to 10 carbon atoms. , A cyclic alkyl group having 3 to 10 carbon atoms, or any of the above.
Examples of the alkylcarbonyl group having 2 to 11 carbon atoms in R ¹¹ , R ¹² , R ¹³ and R ²¹ include those having 2 to 11 carbon atoms among the alkyl carbonyl groups in R ¹ and R ² . ..

The alkylthio groups having 1 to 10 carbon atoms in R ¹¹ , R ¹² , R ¹³ and R ²¹ are linear or branched (that is, chain) alkyl thio groups having 1 to 10 carbon atoms and 3 to 3 carbon atoms. It may be any of 10 cyclic alkylthio groups.
Examples of the alkylthio group having 1 to 10 carbon atoms in R ¹¹ , R ¹² , R ¹³ and R ²¹ include those having 1 to 10 carbon atoms among the alkyl thio groups in R ¹ and R ² .

The alkyl group in the alkyloxysulfonyl group having 1 to 10 carbon atoms in R ¹¹ , R ¹² , R ¹³ and R ²¹ is a linear or branched (that is, chain) alkyl group having 1 to 10 carbon atoms. And a cyclic alkyl group having 3 to 10 carbon atoms.
As the alkyloxysulfonyl groups having 1 to 10 carbon atoms in R ¹¹ , R ¹² , R ¹³ and R ²¹ , among the alkyl oxysulfonyl groups in R ¹ and R ² , those having 1 to 10 carbon atoms are used. Can be mentioned.

R ¹¹ , R ¹² , R ¹³ and R ²¹ each independently may have an amino group as the substituent and have an alkyl group having 1 to 5 carbon atoms (chain alkyl having 1 to 5 carbon atoms). A group, a cyclic alkyl group having 3 to 5 carbon atoms), an alkoxy group having 1 to 5 carbon atoms (chain alkoxy group having 1 to 5 carbon atoms, a cyclic alkoxy group having 3 to 5 carbon atoms), and carbon. Alkyloxycarbonyl group of number 2 to 6 (alkyloxycarbonyl group having 2 to 6 carbon atoms when the alkyl group is linear or branched, and alkyl having 4 to 6 carbon atoms when the alkyl group is cyclic The oxycarbonyl group), the formyl group, the alkylcarbonyl group having 2 to 6 carbon atoms (the alkylcarbonyl group having 2 to 6 carbon atoms when the alkyl group is linear or branched, and the alkyl group are cyclic). In the case of an alkylcarbonyl group having 4 to 6 carbon atoms), an alkylthio group having 1 to 5 carbon atoms (chain alkylthiogroup having 1 to 5 carbon atoms, a cyclic alkylthio group having 3 to 3 carbon atoms), and a hydroxyl group. , A thiol group, a cyano group, and a halogen atom, preferably one or more selected from the group.

In the compound (11B), both R ¹³ and R ²¹ may have an amino group as the substituent, and are alkyl groups having 1 to 5 carbon atoms (chain alkyl groups having 1 to 5 carbon atoms, etc.). A cyclic alkyl group having 3 to 5 carbon atoms), an alkoxy group having 1 to 5 carbon atoms (chain alkoxy group having 1 to 5 carbon atoms, a cyclic alkoxy group having 3 to 5 carbon atoms), and 2 carbon atoms. Alkyloxycarbonyl group of ~ 6 (alkyloxycarbonyl group having 2 to 6 carbon atoms when the alkyl group is linear or branched, and alkyloxycarbonyl group having 4 to 6 carbon atoms when the alkyl group is cyclic) Group), a formyl group, an alkylcarbonyl group having 2 to 6 carbon atoms (an alkylcarbonyl group having 2 to 6 carbon atoms when the alkyl group is linear or branched, and a cyclic group when the alkyl group is cyclic). An alkylcarbonyl group having 4 to 6 carbon atoms), an alkylthio group having 1 to 5 carbon atoms (a chain alkylthio group having 1 to 5 carbon atoms, a cyclic alkylthio group having 3 to 3 carbon atoms), a hydroxyl group, and a thiol group. It is preferably one or more selected from the group consisting of a group, a cyano group and a halogen atom.

In the general formula (11A) or (12A), q ₁₁ and q ₁₂ are independently integers of 0 to 6, preferably 0 to 4.

When q ₁₁ is an integer of 2 or more (2 to 6), the two or more R ^11s may be the same or different from each other. That is, two or more R ^11s may be all the same, all may be different, or only a part may be the same.

When q ₁₂ is an integer of 2 or more (2 to 6), the two or more R ^12s may be the same or different from each other. That is, two or more R ^12s may be all the same, all may be different, or only a part may be the same.

When q ₁₁ is an integer of 2 or more (2 to 6) and two or more R ^11s are alkyl groups which may have an amino group as a substituent, the two or more Rs are mentioned. ¹¹ (an alkyl group which may have an amino group as a substituent) may be bonded to each other to form a ring together with the group in the cyclohexane ring skeleton to which these R ^11s are bonded. ..
The mode in which two or more R ^11s are bonded to each other to form a ring is the same as the above-mentioned mode in which two or more R ^1s are bonded to each other to form a ring.

When q ₁₂ is an integer of 2 or more (2 to 6) and two or more R ^12s are alkyl groups which may have an amino group as a substituent, two or more R ^12s are used. (Alkyl groups which may have an amino group as a substituent) may be bonded to each other to form a ring together with the group in the cyclohexane ring skeleton to which these R ^12s are bonded.
The mode in which two or more R ^12s are bonded to each other to form a ring is the same as the above-mentioned mode in which two or more R ^1s are bonded to each other to form a ring.

In the general formula (11B), q ₁₃ and q ₂₁ are each independently an integer of 0 to 4, preferably 0 to 2.

When q ₁₃ is an integer of 2 or more (2 to 4), the two or more R ^13s may be the same or different from each other. That is, two or more R ^13s may be all the same, all may be different, or only a part may be the same.

When q ₂₁ is an integer of 2 or more (2 to 4), the two or more R ^21s may be the same or different from each other. That is, two or more R ^21s may be all the same, all may be different, or only a part may be the same.

When q ₁₃ is an integer of 2 or more (2 to 4) and two or more R ^13s are alkyl groups which may have an amino group as a substituent, the two or more Rs are mentioned. ¹³ (an alkyl group which may have an amino group as a substituent) may be bonded to each other to form a ring together with the group in the cyclohexane ring skeleton to which these R ^13s are bonded. ..
The embodiment in which two or more R ^13s are coupled to each other to form a ring is the same as the above-mentioned embodiment in which two or more R ^1s are coupled to each other to form a ring.

When q ₂₁ is an integer of 2 or more (2 to 4) and two or more R ^21s are alkyl groups which may have an amino group as a substituent, the two or more Rs are mentioned. ²¹ (an alkyl group which may have an amino group as a substituent) may be bonded to each other to form a ring together with the group in the cyclohexane ring skeleton to which these R ^21s are bonded. ..
The mode in which two or more R ^21s are bonded to each other to form a ring is the same as the above-mentioned mode in which two or more R ^1s are bonded to each other to form a ring.

However, in the carbon dioxide absorption / release agent of the present embodiment, in the general formula (12A), two amino groups directly bonded to the carbon atoms constituting the cyclohexane ring skeleton are arranged at the meta positions of each other. Those containing the compound are not included.
That is, in compound (12A), the two amino groups directly bonded to the carbon atoms constituting the cyclohexane ring skeleton are not arranged at the meta positions of each other.

The compound (11A), the compound (12A) or the compound (11B) is the following general formula (111A), (121A), (122A) or (111B).

(In the formula, R ¹¹¹ , R ¹²¹ , R ¹²² , R ¹³¹ and R ²¹¹ are independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms and an alkyloxy group having 2 to 6 carbon atoms, respectively. It is a carbonyl group, a formyl group, an alkylcarbonyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 5 carbon atoms, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group has an amino group as the substituent. Independently, q ₁₁₁ , q ₁₂₁ and q ₁₂₂ are integers of 0 to 4, and when q ₁₁₁ is an integer of 2 or more, the two or more R ^111s are the same as each other. However, if q ₁₂₁ is an integer of 2 or more, the two or more R ^121s may be the same or different from each other, and if q ₁₂₂ is an integer of 2 or more, 2 or more. The number of R ^122s may be the same or different from each other, q ₁₁₁ may be an integer of 2 or more, and two or more R ^111s may have an amino group as the substituent. When is, the two or more R ^111s may be coupled to each other to form a ring, q ₁₂₁ is an integer of 2 or more, and two or more R ^121s are the substituents. In the case of the alkyl group which may have an amino group, the two or more R ^121s may be bonded to each other to form a ring, and q ₁₂₂ is an integer of 2 or more. In addition, when the two or more R ^122s are the alkyl groups which may have an amino group as the substituent, the two or more R ^122s are bonded to each other to form a ring. May; q ₁₃₁ and q ₂₁₁ are independently integers of 0 to 2, and if q ₁₃₁ is 2, the two R ^131s may be the same or different from each other, q ₂₁₁ . When is 2, the two R ^211s may be the same or different from each other, even if q ₁₃₁ is 2 and the two R ^131s have an amino group as the substituent. In the case of a good alkyl group, the two R ^131s may be bonded to each other to form a ring, q ₂₁₁ is 2, and the two R ^211s are the substituents. In the case of the alkyl group which may have an amino group, the two R ^211s may be bonded to each other to form a ring) (in the present specification). Corresponds to the assigned reference numerals, respectively. 111A) ”,“ compound (121A) ”, compound“ (122A) ”or compound“ (111B) ”) is preferred.

In the general formula (111A), (121A), (122A) or (111B), R ¹¹¹ , R ¹²¹ , R ¹²² , R ¹³¹ and R ²¹¹ each independently have an alkyl group having 1 to 5 carbon atoms and a carbon number of carbon atoms. An alkoxy group of 1 to 5, an alkyloxycarbonyl group of 2 to 6 carbons, a formyl group, an alkylcarbonyl group of 2 to 6 carbons, an alkylthio group of 1 to 5 carbons, a hydroxyl group, a thiol group, a cyano group or a halogen atom. The alkyl group may have an amino group as the substituent. That is, these groups in R ¹¹¹ , R ¹²¹ , R ¹²² , R ¹³¹ and R ²¹¹ may be the same or different from each other.

The alkyl groups having 1 to 5 carbon atoms in R ¹¹¹ , R ¹²¹ , R ¹²² , R ¹³¹ and R ²¹¹ are linear or branched (that is, chain) alkyl groups having 1 to 5 carbon atoms and carbon. It may be any of the cyclic alkyl groups of the number 3 to 5.
Examples of the alkyl group having 1 to 5 carbon atoms include those having 1 to 5 carbon atoms among the alkyl groups in R ¹ and R ² .

When the alkyl group in R ¹¹¹ , R ¹²¹ , R ¹²² , R ¹³¹ or R ²¹¹ has a substituent, the embodiment having a substituent is the same as when the alkyl group in R ¹ and R ² has a substituent. ..

The alkoxy groups having 1 to 5 carbon atoms in R ¹¹¹ , R ¹²¹ , R ¹²² , R ¹³¹ and R ²¹¹ are linear or branched (ie, chain) alkoxy groups having 1 to 5 carbon atoms and carbon. It may be any of the cyclic alkoxy groups of the number 3 to 5.
Examples of the alkoxy group having 1 to 5 carbon atoms include alkoxy groups having 1 to 5 carbon atoms among the alkoxy groups in R ¹ and R ² .

The alkyl groups in the alkyloxycarbonyl groups having 2 to 6 carbon atoms in R ¹¹¹ , R ¹²¹ , R ¹²² , R ¹³¹ and R ²¹¹ are linear or branched chains (that is, chain-like) having 1 to 5 carbon atoms. It may be either an alkyl group of the above or a cyclic alkyl group having 3 to 5 carbon atoms.
As the alkyloxycarbonyl group having 2 to 6 carbon atoms in R ¹¹¹ , R ¹²¹ , R ¹²² , R ¹³¹ and R ²¹¹ , among the alkyloxycarbonyl groups in R ¹ and R ² , the carbon number is 2 to 6. Some are mentioned.

In R ¹¹¹ , R ¹²¹ , R ¹²² , R ¹³¹ and R ²¹¹ , the alkyl groups among the alkylcarbonyl groups having 2 to 6 carbon atoms are linear or branched (that is, chain-like) having 1 to 5 carbon atoms. It may be either an alkyl group or a cyclic alkyl group having 3 to 5 carbon atoms.
As the alkylcarbonyl group having 2 to 6 carbon atoms in R ¹¹¹ , R ¹²¹ , R ¹²² , R ¹³¹ and R ²¹¹ , among the alkyl carbonyl groups in R ¹ and R ² , the number of carbon atoms is 2 to 6. Can be mentioned.

The alkylthio groups having 1 to 5 carbon atoms in R ¹¹¹ , R ¹²¹ , R ¹²² , R ¹³¹ and R ²¹¹ are linear or branched (that is, chain) alkyl thio groups having 1 to 5 carbon atoms and carbon. It may be any of the cyclic alkylthio groups of the number 3 to 5.
The alkylthio groups having 1 to 5 carbon atoms in R ¹¹¹ , R ¹²¹ , R ¹²² , R ¹³¹ and R ²¹¹ include the alkylthio groups having 1 to 5 carbon atoms in R ¹ and R ² . Can be mentioned.

In the general formula (111A), (121A) or (122A), q ₁₁₁ , q ₁₂₁ and q ₁₂₂ are each independently an integer of 0 to 4.
When q ₁₁₁ is an integer of 2 or more (2 to 4), the two or more R ^111s may be the same or different from each other. That is, two or more R ^111s may be all the same, all may be different, or only a part may be the same.
When q ₁₁₁ is an integer of 2 or more (2 to 4) and two or more R ^111s are alkyl groups which may have an amino group as a substituent, the two or more Rs are mentioned. ¹¹¹ (an alkyl group which may have an amino group as a substituent) may be bonded to each other to form a ring together with the group in the cyclohexane ring skeleton to which these R ^111s are bonded. ..
The embodiment in which two or more R ^111s are coupled to each other to form a ring is the same as the above-described embodiment in which two or more R ^1s are coupled to each other to form a ring.

When q ₁₂₁ is an integer of 2 or more (2 to 4), the two or more R ^121s may be the same or different from each other. That is, two or more R ^121s may be all the same, all may be different, or only a part may be the same.
When q ₁₂₁ is an integer of 2 or more (2 to 4) and two or more R ^121s are alkyl groups which may have an amino group as a substituent, the two or more Rs are mentioned. ¹²¹ (an alkyl group which may have an amino group as a substituent) may be bonded to each other to form a ring together with the group in the cyclohexane ring skeleton to which these R ^121s are bonded. ..
The mode in which two or more R ^121s are bonded to each other to form a ring is the same as the above-mentioned mode in which two or more R ^1s are bonded to each other to form a ring.

When q ₁₂₂ is an integer of 2 or more (2 to 4), the two or more R ^122s may be the same or different from each other. That is, two or more R ^122s may be all the same, all may be different, or only a part may be the same.
When q ₁₂₂ is an integer of 2 or more (2 to 4) and two or more R ^122s are alkyl groups which may have an amino group as a substituent, the two or more Rs are mentioned. ¹²² (an alkyl group which may have an amino group as a substituent) may be bonded to each other to form a ring together with the group in the cyclohexane ring skeleton to which these R ^122s are bonded. ..
The embodiment in which two or more R ^122s are coupled to each other to form a ring is the same as the above-mentioned embodiment in which two or more R ^1s are coupled to each other to form a ring.

In the general formula (111B), q ₁₃₁ and q ₂₁₁ are independently integers of 0 to 2.
When q ₁₃₁ is 2, the two R ^131s may be the same or different from each other.
When q ₁₃₁ is 2 and the two R ^131s are alkyl groups which may have an amino group as a substituent, the two R ^131s (having an amino group as a substituent) Alkyl groups (which may be present) may be attached to each other to form a ring together with the groups in the cyclohexane ring skeleton to which these R ^131s are attached.
The mode in which two or more R ^131s are bonded to each other to form a ring is the same as the above-mentioned mode in which two or more R ^1s are bonded to each other to form a ring.

When q ₂₁₁ is 2, the two R ^211s may be the same or different from each other.
When q ₂₁₁ is 2 and the two R ^211s are alkyl groups which may have an amino group as a substituent, the two R ^211s (having an amino group as a substituent) Alkyl groups (which may be present) may be attached to each other to form a ring together with the groups in the cyclohexane ring skeleton to which these R ^211s are attached.
The embodiment in which two or more R ^211s are coupled to each other to form a ring is the same as the above-mentioned embodiment in which two or more R ^1s are coupled to each other to form a ring.

Among the compounds (1), examples of those belonging to the compound (111A) include those represented by the following formulas (cyclohexylamine, isophoronediamine).

Among the compounds (1), an example of the compound belonging to the compound (121A) is a compound (1,2-cyclohexanediamine) represented by the following formula.

Among the compounds (1), an example of the compound belonging to the compound (122A) is a compound (1,4-cyclohexanediamine) represented by the following formula.

Among the compounds (1), an example of the compound belonging to the compound (111B) is a compound represented by the following formula (4,4'-methylenebis (2-methylcyclohexylamine)).

The compound (1) contained in the carbon dioxide absorption / release agent may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof are for the purpose. It can be selected arbitrarily according to the situation.
For example, some compounds (1) have steric isomers, but in the present embodiment, the steric isomers are treated as the same type of compound (1).

In compound (1), either one or both of R ¹ and R ² may be an alkyl group having an amino group as a substituent. That is, the compound (1) has a group other than the amino group directly bonded to the carbon atom constituting the cyclohexane ring conformation (in this specification, it may be referred to as "first amino group"). In addition, there are those having an amino group (in this specification, sometimes referred to as "second amino group") which is not directly bonded to the carbon atom constituting the cyclohexane ring skeleton. In the compound (1) having such two kinds of amino groups, the first amino group tends to react more easily with carbon dioxide than the second amino group.

The carbon dioxide absorption / release agent of the present embodiment contains the compound (1) and may contain only the compound (1) (in other words, it may be composed of the compound (1)). However, the compound (1) and a component other than the compound (1) may be contained.
For example, the liquid carbon dioxide absorbing / releasing agent containing the compound (1) and a solvent is preferable in that the absorption and release of carbon dioxide are easier.

<Solvent>
The solvent is not particularly limited, but is preferably one that dissolves compound (1), and more preferably one that dissolves compound (1) at a temperature of room temperature or lower. As described above, the carbon dioxide absorbing / releasing agent in which the compound (1) is dissolved in the solvent can more easily absorb carbon dioxide.

In the present specification, "normal temperature" means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 30 ° C.

The solvent may or may not dissolve the reaction product (the carbamic acid derivative) of the compound (1) and carbon dioxide. For example, in a composition containing the carbamic acid derivative and a solvent, when the carbamic acid derivative is not dissolved under any of the temperature conditions, the carbamic acid derivative, that is, the carbon dioxide releasing agent described later is more easily used. Can be taken out.

Examples of the solvent include organic solvents, water and the like.
Examples of the organic solvent include sulfoxides such as dimethylsulfoxide (DMSO); amides such as N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMAc); and lactams such as N-methyl-2-pyrrolidone. (Cyclic amide); alcohols such as methanol, ethanol, 2-propanol (IPA); hydrocarbons such as toluene, o-xylene, m-xylene, p-xylene (aromatic hydrocarbons); tetrahydrofuran (THF), 1, Ethers such as 4-dioxane, tetrahydropyran, dibutyl ether, 1,2-dimethoxyethane (compounds having an ether bond); nitriles such as propionitrile and acetonitrile (compounds having a cyano group); ethyl acetate, butyl acetate and the like. Examples thereof include esters (carboxylic acid esters).
Preferred solvents include polar solvents (water, polar organic solvents).

The solvent preferably has a high boiling point and a low vapor pressure at room temperature. By using such a solvent, the vaporization of the solvent can be suppressed in the steps (A), (B), (a) and (b) described later, and these steps can be performed more stably. can.
From such a viewpoint, the boiling point of the solvent is preferably 100 ° C. or higher, and may be, for example, 190 ° C. or higher.
The upper limit of the boiling point of the solvent is not particularly limited. For example, a solvent having a boiling point of 200 ° C. or lower is relatively easy to obtain.

The solvent contained in the carbon dioxide absorption / release agent may be only one type, may be two or more types, and when two or more types are used, the combination and ratio thereof are arbitrary depending on the purpose. Can be selected.
For example, the two or more kinds of solvents may be an aqueous mixed solvent composed of water and one kind or two or more kinds of organic solvents, or a non-aqueous mixed solvent composed of two or more kinds of organic solvents. May be good.

The concentration of the carbon dioxide absorbing / releasing agent compound (1) when containing a solvent is not particularly limited, but is preferably 0.05 to 5M, for example, 0.05 to 3.5M, and 0. It may be any of .05 to 2M.

In the present specification, the concentration unit "M" represents "mol / L", and the concentration unit "mM" represents "mmol / L".

The carbon dioxide absorption / release agent may contain the compound (1), a solvent, and other components that do not fall under any of the above, as long as the effects of the present invention are not impaired.
The other components can be arbitrarily selected depending on the intended purpose, and are not particularly limited.

The other components contained in the carbon dioxide absorbing / releasing agent may be only one kind, two or more kinds, and when two or more kinds, the combination and ratio thereof are intended. It can be selected arbitrarily according to the situation.

In the carbon dioxide absorbing / releasing agent (carbon dioxide absorbing / releasing agent before starting absorption of carbon dioxide), the content (parts by mass) of the other components with respect to the total mass (parts by mass) of the carbon dioxide absorbing / releasing agent. The ratio is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, and particularly preferably 1% by mass or less. .. When the ratio is not more than the upper limit value regardless of the presence or absence of the solvent, the ability of the carbon dioxide absorbing / releasing agent to absorb and release carbon dioxide becomes higher.
In other words, in the carbon dioxide absorption / release agent (carbon dioxide absorption / release agent before starting absorption of carbon dioxide), the total content of the compound (1) and the solvent is contained with respect to the total mass (part by mass) of the carbon dioxide absorption / release agent. The ratio of the amount (part by mass) is not particularly limited, but is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 97% by mass or more, and 99% by mass or more. Is particularly preferable.

The carbon dioxide absorption / release agent of the present embodiment has an excellent effect in that carbon dioxide can be easily absorbed and the absorbed carbon dioxide can be easily released.
Conventional carbon dioxide sinks, for example, can easily absorb carbon dioxide but are difficult to release carbon dioxide, or can easily release carbon dioxide but can absorb carbon dioxide. It was difficult. That is, the conventional carbon dioxide absorption / release agent could not practically achieve both absorption and release of carbon dioxide.
On the other hand, the carbon dioxide absorption / release agent of the present embodiment contains a compound (1) having a structure in a specific range as an active ingredient that absorbs carbon dioxide and releases carbon dioxide after absorption. It solves the conventional problems.

The carbon dioxide absorption / release agent of the present embodiment containing the compound (1) and other components (solvent or the other component) can be produced by mixing these components.

<< Carbon dioxide recovery method >>
The method for recovering carbon dioxide according to an embodiment of the present invention is described in the following general formula (1).

(In the formula, m is 0 or 1; R ¹ and R ² are independently an alkyl group, an alkoxy group, a carboxy group, an alkyloxycarbonyl group, a formyl group, an alkylcarbonyl group, an alkylthio group and a sulfo group, respectively. It is an alkyloxysulfonyl group, a nitro group, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group may have a substituent; p ₁ and p ₂ are independently 1 or 2, respectively. Yes; if m is 0, q ₁ is an integer from 0 to 11, where p ₁ + q ₁ is less than or equal to 12, and if m is 1, q ₁ is an integer from 0 to 10. However, when p ₁ + q ₁ is 11 or less, q ₂ is an integer of 0 to 10, and q ₁ is an integer of 2 or more, two or more R ^1s may be the same or different from each other. Well, when q ₂ is an integer of 2 or more, two or more R ^2s may be the same or different from each other, q ₁ is an integer of 2 or more, and two or more R ^1s are. In the case of the alkyl group which may have a substituent, the two or more R ^1s may be bonded to each other to form a ring, and q ₂ is an integer of 2 or more. Moreover, when two or more R ^2s are the alkyl groups which may have a substituent, the two or more R ^2s may be bonded to each other to form a ring.)
In the step (A) of causing a carbon dioxide absorbing / releasing agent containing a compound represented by (that is, compound (1)) to absorb carbon dioxide,
It has a step (B) of releasing the carbon dioxide from the carbon dioxide absorbing / releasing agent by heat-treating the carbon dioxide absorbing / releasing agent after absorbing the carbon dioxide (however, m is 0). , Except for the method of recovering carbon dioxide when p ₁ is 2 and the two amino groups with p ₁ are arranged at the meta positions of each other).

In the method for recovering carbon dioxide of the present embodiment, the carbon dioxide absorbing / releasing agent according to the above-described embodiment of the present invention is used. Therefore, in the above recovery method, in the general formula (1), m is 0, p ₁ is 2, and two (p ₁ ) amino groups are arranged at the meta positions of each other. Does not include those using a carbon dioxide absorbing / releasing agent containing.
According to the method for recovering carbon dioxide of the present embodiment, by using the carbon dioxide absorbing / releasing agent, carbon dioxide can be easily absorbed and the absorbed carbon dioxide can be easily released, so that carbon dioxide can be easily recovered. ..

<Process (A)>
In the step (A), the carbon dioxide absorbing / releasing agent containing the compound (1) absorbs carbon dioxide. In the step (A), the compound (1) in the carbon dioxide absorption / release agent reacts with carbon dioxide at the amino group thereof to become the carbamic acid derivative, so that carbon dioxide is absorbed. ..

In the step (A), for example, carbon dioxide gas may be brought into contact with the carbon dioxide absorbing / releasing agent. Above all, the step (A) can be carried out more easily by using a liquid carbon dioxide absorption / release agent containing the compound (1) and the solvent. The liquid carbon dioxide sink is the one described above.

The carbon dioxide (gas) may be absorbed by the carbon dioxide absorbing / releasing agent alone, or may be absorbed by the carbon dioxide absorbing / releasing agent in the state of a mixed gas with another gas.
As the mixed gas, for example, the gaseous target substance to be recovered of carbon dioxide may be used as it is, or the target substance may be further mixed with another gas and diluted. For example, air may be used as the mixed gas, and dry air is more suitable as a target for recovering carbon dioxide. Examples of the other mixed gas include a mixed gas containing carbon dioxide gas and an inert gas. However, the mixed gas mentioned here is an example.

Examples of the inert gas include nitrogen gas, helium gas, argon gas and the like. Among these, nitrogen gas is particularly suitable because it is inexpensive.

The concentration of carbon dioxide in the gas containing carbon dioxide to be brought into contact with the carbon dioxide absorbing / releasing agent may be 100% by volume or less, for example, 80% by volume or less, 60% by volume or less, 40% by volume or less, 32 volumes. It may be any of% or less, 25% by volume or less, 15% by volume or less, and 5% by volume or less.
The concentration of carbon dioxide in the carbon dioxide-containing gas in contact with the carbon dioxide absorbing / releasing agent may be, for example, 0.04% by volume (400 ppm) or more.
In the recovery method of the present embodiment, by using the carbon dioxide absorbing / releasing agent, not only carbon dioxide can be easily absorbed, but also a gas having a wide range of carbon dioxide concentration can be used as described above, which is useful. expensive.

The concentration of carbon dioxide in the mixed gas containing carbon dioxide (gas) is not particularly limited, but is preferably 0.04 to 32% by volume, for example, 0.04 to 25% by volume and 0.04 to 15% by volume. It may be any of% by volume and 0.04 to 5% by volume, 5 to 32% by volume, 15 to 32% by volume, and 25 to 32% by volume, 5 It may be up to 25% by volume. When the concentration is equal to or higher than the lower limit, the amount of carbon dioxide absorbed becomes larger. When the concentration is not more than the upper limit value, the absorption leakage of carbon dioxide is further suppressed.
In the recovery method of the present embodiment, by using the carbon dioxide absorbing / releasing agent, not only carbon dioxide can be easily absorbed, but also the mixed gas having a wide carbon dioxide concentration as described above can be used, which is useful. High in sex.

The flow rate of carbon dioxide gas when the carbon dioxide is absorbed by the carbon dioxide absorbing / releasing agent can be arbitrarily selected according to the purpose.
The flow rate is 0.01 to 20 mol / h per 1 mol of the amount of the compound (1) in the carbon dioxide absorbing / releasing agent, regardless of whether carbon dioxide is used alone or as a mixed gas. It is preferable that the gas is, for example, either 0.01 to 10 mol / h, 0.01 to 5 mol / h, and 0.01 to 1 mol / h, or 0.1 to 20 mol / h, 1 It may be either ~ 20 mol / h and 10 to 20 mol / h. When the flow rate is equal to or higher than the lower limit, the amount of carbon dioxide absorbed becomes larger. When the flow rate is not more than the upper limit value, absorption leakage of carbon dioxide is further suppressed.
In the recovery method of the present embodiment, by using the carbon dioxide absorbing / releasing agent, not only carbon dioxide can be easily absorbed, but also the flow rate of carbon dioxide gas can be widely set as described above, which is highly useful.

The temperature of the carbon dioxide absorbing / releasing agent when the carbon dioxide is absorbed by the carbon dioxide absorbing / releasing agent can be appropriately selected depending on the type of the carbon dioxide absorbing / releasing agent, and is not particularly limited.
The temperature is preferably -18 to 30 ° C, and may be, for example, -18 to 25 ° C, -18 to 15 ° C, and -18 to 5 ° C, or -8 to 30 ° C. , 8-30 ° C, and 18-30 ° C, or -8-25 ° C, and 8-15 ° C. When the temperature is equal to or higher than the lower limit, the amount of carbon dioxide absorbed becomes larger. When the temperature is not more than the upper limit value, the absorption leakage of carbon dioxide is further suppressed.

In the step (A), when a liquid carbon dioxide absorption / release agent is used, carbon dioxide is used as a liquid carbon dioxide absorption / release agent regardless of whether carbon dioxide is used alone or as a mixed gas. It is preferable to bubbling by directly flowing into the inside. By doing so, the absorption efficiency of carbon dioxide can be improved.
Further, when carbon dioxide is directly flowed into the liquid carbon dioxide absorption / release agent, the carbon dioxide absorption / release agent may be stirred by a known method. By doing so, it may be possible to improve the absorption efficiency of carbon dioxide.

In the present embodiment, the step (A) may be completed when a part of the compound (1) has not reacted with carbon dioxide, or the whole amount of the compound (1) may be reacted with carbon dioxide. The step (A) may be completed.
The amount of the compound (1) in the carbon dioxide absorption / release agent at the end of the step (A) with respect to the amount (number of moles) of the compound (1) in the carbon dioxide absorption / release agent at the start of the step (A). The ratio of (number of moles) is preferably 20 mol% or less, and may be, for example, 10 mol% or less, 5 mol% or less, 1 mol% or less, or 0 mol%. You may. When the ratio is not more than the upper limit value, the amount of carbon dioxide released in the subsequent step (B) is further increased.

In the step (A), when a liquid carbon dioxide absorbing / releasing agent is used, the solid reaction product (the carbamic acid derivative) depends on the carbon dioxide absorption conditions such as the type of the solvent contained therein. May or may not precipitate.
More specifically, the reaction temperature at the time of reaction between the compound (1) and carbon dioxide is lowered, and the concentration of the compound (1) in the liquid carbon dioxide absorption / release agent is increased (the amount of the solvent used is reduced). One or both of the above and the increase in the amount of the compound (1) used), the solvent having a small solubility of the reaction product, and the compound (1) having a diamine (amino). The reaction product can be easily precipitated in a liquid carbon dioxide absorption / release agent by using (the one having two groups) or the like. However, the adjustment of conditions is not limited to these.
When the reaction product precipitates (the liquid carbon dioxide absorbing / releasing agent is a suspension), the increase in the amount of carbon dioxide absorbed can be visually confirmed by increasing the amount of the precipitate.
In the present embodiment, the subsequent step (B) can be satisfactorily performed regardless of the presence or absence of precipitation of the solid reaction product.

In the step (A), the reaction product (reaction product of the compound (1) and carbon dioxide) is precipitated in the liquid carbon dioxide absorbing / releasing agent, so that the reaction between the compound (1) and carbon dioxide is further carried out. It is promoted and the absorption of carbon dioxide of the carbon dioxide absorption / release agent is promoted.

<Process (B)>
In the step (B), the carbon dioxide absorbing / releasing agent after absorbing carbon dioxide is heat-treated to release the carbon dioxide from the carbon dioxide absorbing / releasing agent. In the step (B), the carbamic acid derivative produced in the step (A) releases carbon dioxide, and the amino group is regenerated. As a result, the carbamic acid derivative returns to compound (1).

In the step (B), the temperature at which the carbon dioxide absorption / release agent after absorbing carbon dioxide is heat-treated is appropriately determined in consideration of, for example, the type of the compound (1), the type when a solvent is used, and the like. Can be adjusted. The temperature at the time of the heat treatment is preferably, for example, lower than the boiling point of the compound (1), and when a solvent is used, it is preferably lower than the boiling point of the solvent. When the temperature at the time of the heat treatment is in such a range, the dissipation of the compound (1) or the solvent can be suppressed.

More specifically, the temperature at the time of the heat treatment is preferably, for example, 100 ° C. or lower, and is any one of 90 ° C. or lower, 80 ° C. or lower, 70 ° C. or lower, 60 ° C. or lower, and 50 ° C. or lower. You may. When the temperature is not more than the upper limit value, carbon dioxide can be released with a smaller amount of energy and in a shorter time.
The lower limit of the temperature at the time of the heat treatment is not particularly limited. The temperature is preferably 30 ° C. or higher in that the release of carbon dioxide proceeds more smoothly.
In the step (B), the carbamic acid derivative releases a sufficient amount of carbon dioxide even if the temperature at the time of the heat treatment is lower than that in the case of the conventional method. As described above, the recovery method of the present embodiment is highly useful in that the temperature at the time of heat treatment is low.

In the present embodiment, the step (B) may be performed in the coexistence of a base catalyst. By performing the heat treatment in the coexistence of a base catalyst, the release of carbon dioxide proceeds more smoothly.

The base catalyst may be either a solid or a liquid at room temperature, for example.
The base catalyst may or may not be dissolved in the carbon dioxide absorbing / releasing agent, for example, when the carbon dioxide absorbing / releasing agent after absorbing carbon dioxide is in a liquid state. When not dissolved, for example, the base catalyst can be easily separated from the carbon dioxide absorbing / releasing agent after the completion of step (B). From this point of view, the base catalyst is preferably solid at room temperature.

The base catalyst may be either an inorganic base or an organic base.

Among the base catalysts, examples of the inorganic base include metal oxides, and basic metal oxides or polyvalent anionic metal oxide clusters are preferable.

The polyvalent anion metal oxide cluster preferably has a metal species of Group 5 or Group 6 metal.
Examples of such a multivalent anion metal oxide cluster include _{K8 Nb 6} _O ₁₉ .

Examples of the basic metal oxide include magnesium oxide (MgO), lanthanum oxide (La ₂ O ₃ ), zirconium oxide (ZrO ₂ ), cerium oxide (IV) (CeO ₂ ), and aluminum oxide (Al ₂ O ₃ ). ), Layered Double Hydroxide (LDH) and the like.

Among the base catalysts, examples of the organic base include amines (primary amines, secondary amines, and tertiary amines).
More specifically, the amines include, for example, hexylamine (n-hexylamine), dihexylamine (di-n-hexylamine), trihexylamine (tri-n-hexylamine), and heptylamine (n-heptyl). Amine), diheptylamine (di-n-heptylamine), triheptylamine (tri-n-heptylamine), octylamine (n-octylamine), dioctylamine (di-n-octylamine), trioctylamine (Tri-n-octylamine), 2-ethylhexylamine, N, N-diisopropylethylamine and other aliphatic primary to tertiary amines; aniline (also known as phenylamine), diphenylamine, triphenylamine and the like (fragrance) Group primary to tertiary amines); diazabicycloundecene (also known as 1,8-diazabicyclo [5.4.0] -7-undecene, abbreviated as DBU), diazabicyclononen (also known as 1, Examples thereof include nitrogen-containing fused ring compounds such as 5-diazabicyclo [4.3.0] -5-nonen, abbreviated as DBN) and 1,4-diazabicyclo [2.2.2] octane (abbreviation: DABCO). ..

The base catalyst used in the step (B) may be only one type, may be two or more types, and when two or more types are used, the combination and ratio thereof are arbitrarily selected according to the purpose. can.

In the step (B), the amount of the base catalyst used is 0.001 to 0.1 times the molar amount of the amount of the carbamic acid derivative which is a reaction product of the compound (1) and carbon dioxide. Is preferable, and the molar amount is more preferably 0.005 to 0.05 times. When the amount of the base catalyst used is equal to or greater than the lower limit, the release of carbon dioxide proceeds more smoothly. When the amount of the base catalyst used is not more than the upper limit, the overuse of the base catalyst is suppressed.

In the present embodiment, the step (B) may be performed in the coexistence of an acid. By performing the heat treatment in the coexistence of an acid, the release of carbon dioxide proceeds more smoothly.

The acid may be either an organic acid or an inorganic acid, but is preferably an inorganic acid.
Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid and the like.

In the step (B), the amount of the acid used is preferably 1 to 3 times the molar amount of the amount of the carbamic acid derivative which is a reaction product of the compound (1) and carbon dioxide. When the amount of the acid used is equal to or higher than the lower limit, the release of carbon dioxide proceeds more smoothly. When the amount of the acid used is not more than the upper limit, the excessive use of the acid is suppressed.

In the step (B), when the liquid carbon dioxide absorption / release agent after absorbing carbon dioxide is used, it is preferable that the inert gas is directly flowed into the liquid carbon dioxide absorption / release agent for bubbling. Although a sufficient amount of carbon dioxide can be discharged by heat treatment without bubbling, the released carbon dioxide can be discharged together with the inert gas by heat treatment while bubbling in this way. It can be collected efficiently. Here, the inert gas is the one described above.
Further, when the inert gas is directly flowed into the liquid carbon dioxide absorbing / releasing agent, the carbon dioxide absorbing / releasing agent may be stirred by a known method. By doing so, it may be possible to improve the efficiency of carbon dioxide collection.

In the step (B), when the inert gas is directly flowed into the liquid carbon dioxide absorbing / releasing agent and bubbling, the flow rate of the inert gas is the carbamic acid in the liquid carbon dioxide absorbing / releasing agent. The amount is preferably 20 to 100 L / min, more preferably 35 to 85 L / min per 1 mol of the acid derivative. When the flow rate of the inert gas is at least the lower limit, the released carbon dioxide can be collected more efficiently. When the flow rate of the inert gas is not more than the upper limit, the vaporization of the solvent and the vaporization of the compound (1) can be further suppressed.

The carbon dioxide absorbing / releasing agent after absorbing carbon dioxide does not fall under any of the carbamic acid derivative, the solvent, the base catalyst, and the acid, as long as the effects of the present invention are not impaired. May contain the components of.
The other components can be arbitrarily selected depending on the intended purpose, and are not particularly limited.

The other components contained in the carbon dioxide absorbing / releasing agent after absorbing carbon dioxide may be only one kind, two or more kinds, or a combination thereof when two or more kinds are used. And the ratio can be arbitrarily selected according to the purpose.

In the carbon dioxide absorption / release agent after absorbing carbon dioxide (carbon dioxide absorption / release agent before starting the emission of carbon dioxide), the content of the other components with respect to the total mass (parts by mass) of the carbon dioxide absorption / release agent. The ratio of the amount (part by mass) is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, and 1% by mass or less. Is particularly preferable. When the ratio is not more than the upper limit value regardless of the presence or absence of the solvent, the carbon dioxide absorbing / releasing agent has a higher ability to release carbon dioxide.
In other words, in the carbon dioxide absorbing / releasing agent after absorbing carbon dioxide (the carbon dioxide absorbing / releasing agent before starting the emission of carbon dioxide), the carbamate with respect to the total mass (part by mass) of the carbon dioxide absorbing / releasing agent. The ratio of the total content (parts by mass) of the derivative and the solvent is not particularly limited, but is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 97% by mass or more. It is preferably 99% by mass or more, and particularly preferably 99% by mass or more.

In the recovery method, the step (A) and the step (B) may be performed only once or may be repeated twice or more.
As described above, by performing the step (B), the carbamic acid derivative, which is a reaction product of the compound (1) and carbon dioxide, releases carbon dioxide and returns to the compound (1). The regenerated compound (1) can be used again for absorption and release of carbon dioxide. Therefore, in the recovery method, the step (A) and the step (B) can be repeated twice or more.

When the step (A) and the step (B) are repeated, the step (A) and the step (A) and the step (A) are performed by terminating the step (A) when a part of the compound (1) has not reacted with carbon dioxide. (B) can be performed more smoothly, and the entire process of carbon dioxide recovery may be performed in a shorter time. Here, the "stage in which a part of compound (1) has not reacted with carbon dioxide" is, for example, a stage represented by the ratio (mol%) of the amount (number of moles) of compound (1) described above. Is.

When the step (A) and the step (B) are repeated, neither the step (A) nor the step (B) is applicable after the completion of the step (B) of the first cycle, if necessary. Step (C) may be performed.

For example, when the acid is used in the step (B), the acid is contained in the carbon dioxide absorption / release agent after the carbon dioxide is released. In such a case, the amino group in the compound (1) forms a salt in the carbon dioxide absorbing / releasing agent. If the compound (1) is left as it is, the carbon dioxide absorbing / releasing agent is difficult to absorb carbon dioxide in the step (A) of the second cycle (the compound (1) is difficult to react with carbon dioxide). Therefore, in this case, the carbon dioxide absorption / release agent is regenerated by adding a base to the carbon dioxide absorption / release agent so that the amino group of compound (1) is in a free state (a state in which no salt is formed). Is preferable. Therefore, as the step (C), for example, adding a base to the acid-containing carbon dioxide absorption / release agent after the carbon dioxide is released, which is performed after the step (B) is performed in the coexistence of the acid. This includes a step of neutralizing the acid.

The base used in the step (C) may be either an organic base or an inorganic base, but is preferably an inorganic base.
Examples of the inorganic base include metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide.

In the step (C), the amount of the base used may be any amount as long as it can neutralize the acid in the carbon dioxide absorbing / releasing agent.

When a base is used in the step (C), a salt not involved in the compound (1) is newly produced by neutralization with the acid. In the step (C), the salt (newly generated salt) may be further removed. That is, the step (C) is performed, for example, by adding a base to the acid-containing carbon dioxide absorption / release agent after the carbon dioxide is released, which is performed after the step (B) is performed in the coexistence of the acid. It may be a step of neutralizing the acid and then removing the salt newly generated by the neutralization from the carbon dioxide absorbing / releasing agent after the acid is neutralized.

The salt newly generated by neutralization may be removed from the carbon dioxide absorbing / releasing agent by a known method. For example, when the salt is precipitated in the carbon dioxide absorbing / releasing agent after neutralizing the acid, the salt can be removed from the carbon dioxide absorbing / releasing agent by filtration.

The recovery method may have other steps that do not fall under any of step (A), step (B), and step (C) as long as the effects of the present invention are not impaired. ..
The type and number of the other steps and the timing of performing the other steps can be arbitrarily selected according to the purpose and are not particularly limited.

<< Carbon dioxide recovery method (M1) >>
As an example of the method for recovering carbon dioxide according to the embodiment of the present invention, the following general formula (1)

(In the formula, m is 0 or 1; R ¹ and R ² are independently an alkyl group, an alkoxy group, a carboxy group, an alkyloxycarbonyl group, a formyl group, an alkylcarbonyl group, an alkylthio group and a sulfo group, respectively. It is an alkyloxysulfonyl group, a nitro group, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group may have a substituent; p ₁ and p ₂ are independently 1 or 2, respectively. Yes; if m is 0, q ₁ is an integer from 0 to 11, where p ₁ + q ₁ is less than or equal to 12, and if m is 1, q ₁ is an integer from 0 to 10. However, when p ₁ + q ₁ is 11 or less, q ₂ is an integer of 0 to 10, and q ₁ is an integer of 2 or more, two or more R ^1s may be the same or different from each other. Well, when q ₂ is an integer of 2 or more, two or more R ^2s may be the same or different from each other, q ₁ is an integer of 2 or more, and two or more R ^1s are. In the case of the alkyl group which may have a substituent, the two or more R ^1s may be bonded to each other to form a ring, and q ₂ is an integer of 2 or more. Moreover, when two or more R ^2s are the alkyl groups which may have a substituent, the two or more R ^2s may be bonded to each other to form a ring.)
By allowing a liquid carbon dioxide absorbing / releasing agent containing the compound represented by the above to absorb carbon dioxide, the compound represented by the general formula (1) (that is, the compound (1)), the carbon dioxide, and the carbon dioxide can be obtained. In the step (A1) of precipitating the reaction product of the above in the liquid carbon dioxide absorption / release agent,
Step (B1) of absorbing the carbon dioxide and releasing the carbon dioxide from the liquid carbon dioxide absorbing / releasing agent by heat-treating the liquid carbon dioxide absorbing / releasing agent after the reactant is precipitated (B1). A method for recovering carbon dioxide (where m is 0, p ₁ is 2, and two amino groups with p ₁ are arranged in meta positions with each other. (Excluding the method for recovering carbon dioxide) (in the present specification, it may be referred to as "method for recovering carbon dioxide (M1)").

In the step (A1) of the carbon dioxide recovery method (M1), the carbon dioxide absorption / release agent is limited to a liquid in the step (A) of the carbon dioxide recovery method described above, and the compound ( This is a step in which the reaction product of 1) and carbon dioxide is limited to those that precipitate in a liquid carbon dioxide absorbing / releasing agent.

In order to carry out the step (A1), the step (A) in the carbon dioxide recovery method described above may be carried out reflecting the above-mentioned limitation.
For example, in the step (A1), the liquid carbon dioxide absorption / release agent preferably contains the compound (1) and a solvent.

In the carbon dioxide recovery method (M1), the above step (A1) is performed to precipitate a reaction product of the compound (1) and carbon dioxide in a liquid carbon dioxide absorption / release agent (liquid carbon dioxide absorption / release). By using the agent as a suspension), the reaction between the compound (1) and carbon dioxide is promoted, and the absorption of carbon dioxide by the carbon dioxide absorption / release agent is promoted.

In the step (A1), for example, the conditions for allowing the liquid carbon dioxide absorbing / releasing agent containing the compound (1) to absorb carbon dioxide (in other words, the reaction conditions between the compound (1) and carbon dioxide) are adjusted. By doing so, the reaction product of compound (1) and carbon dioxide can be precipitated in a liquid carbon dioxide absorption / release agent. For example, lowering the reaction temperature during the reaction between compound (1) and carbon dioxide, increasing the concentration of compound (1) in the liquid carbon dioxide absorption / release agent (reducing the amount of the solvent used, and so on. Increasing the amount of compound (1) used, one or both of them), using a liquid carbon dioxide absorption / release agent having a low solubility of the reaction product, compound (1). As a result, a reaction product of compound (1) and carbon dioxide can be easily precipitated in a liquid carbon dioxide absorbing / releasing agent by using a diamine (having two amino groups) or the like. However, the adjustment of conditions is not limited to these.

The compound (1) used in the step (A1) is the following general formula (11A), (12A) or (11B).

(In the formula, R ¹¹ , R ¹² , R ¹³ and R ²¹ are independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a carboxy group and an alkyloxy having 2 to 11 carbon atoms, respectively. Carbonyl group, formyl group, alkylcarbonyl group with 2 to 11 carbon atoms, alkylthio group with 1 to 10 carbon atoms, sulfo group, alkyloxysulfonyl group with 1 to 10 carbon atoms, nitro group, hydroxyl group, thiol group, cyano group or It is a halogen atom and the alkyl group may have an amino group as the substituent; q ₁₁ and q ₁₂ are independently integers of 0 to 6 and q ₁₁ is an integer of 2 or more. In some cases, the two or more R ^11s may be the same or different from each other, and if q ₁₂ is an integer of two or more, the two or more R ^12s may be the same or different from each other. When q ₁₁ is an integer of 2 or more and 2 or more R ^11s are the alkyl groups which may have an amino group as the substituent, the two or more R ^11s are mutual. The alkyl group may be bonded to to form a ring, q ₁₂ may be an integer of 2 or more, and R ¹² of 2 or more may have an amino group as the substituent. In some cases, the two or more R ^12s may be coupled to each other to form a ring; q ₁₃ and q ₂₁ are independently integers from 0 to 4, and q ₁₃ is 2 or more. If the integers of, the two or more R ^13s may be the same or different from each other, and if q ₂₁ is an integer of two or more, the two or more R ^21s may be the same or different from each other. Also, when q ₁₃ is an integer of 2 or more and 2 or more R ¹³ are the alkyl groups which may have an amino group as the substituent, the two or more Rs may be used. ¹³ may be bonded to each other to form a ring, q ₂₁ may be an integer of 2 or more, and 2 or more R ²¹ may have an amino group as the substituent. When it is a group, the two or more R ^21s may be bonded to each other to form a ring.)
Compound represented by (Compound (11A), Compound (12A) or Compound (11B)) (However, in the above general formula (12A), two compounds directly bonded to the carbon atom constituting the cyclohexane ring skeleton. It is preferable that the amino groups of the above are (excluding compounds in which the meta-positions of each other are arranged).

The compound (11A), compound (12A) or compound (11B) used in the step (A1) is the following general formula (111A), (121A), (122A) or (111B).

(In the formula, R ¹¹¹ , R ¹²¹ , R ¹²² , R ¹³¹ and R ²¹¹ are independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms and an alkyloxy group having 2 to 6 carbon atoms, respectively. It is a carbonyl group, a formyl group, an alkylcarbonyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 5 carbon atoms, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group has an amino group as the substituent. Independently, q ₁₁₁ , q ₁₂₁ and q ₁₂₂ are integers of 0 to 4, and when q ₁₁₁ is an integer of 2 or more, the two or more R ^111s are the same as each other. However, if q ₁₂₁ is an integer of 2 or more, the two or more R ^121s may be the same or different from each other, and if q ₁₂₂ is an integer of 2 or more, 2 or more. The number of R ^122s may be the same or different from each other, q ₁₁₁ may be an integer of 2 or more, and two or more R ^111s may have an amino group as the substituent. When is, the two or more R ^111s may be coupled to each other to form a ring, q ₁₂₁ is an integer of 2 or more, and two or more R ^121s are the substituents. In the case of the alkyl group which may have an amino group, the two or more R ^121s may be bonded to each other to form a ring, and q ₁₂₂ is an integer of 2 or more. In addition, when the two or more R ^122s are the alkyl groups which may have an amino group as the substituent, the two or more R ^122s are bonded to each other to form a ring. May; q ₁₃₁ and q ₂₁₁ are independently integers of 0 to 2, and if q ₁₃₁ is 2, the two R ^131s may be the same or different from each other, q ₂₁₁ . When is 2, the two R ^211s may be the same or different from each other, even if q ₁₃₁ is 2 and the two R ^131s have an amino group as the substituent. In the case of a good alkyl group, the two R ^131s may be bonded to each other to form a ring, q ₂₁₁ is 2, and the two R ^211s are the substituents. In the case of the alkyl group which may have an amino group, the two R ^211s may be bonded to each other to form a ring) (“Compound (111A)”. ) ”,“ Compound (121A) ”, Compound“ (12A) ” 2A) ”or compound“ (111B) ”) is preferred.

The step (B1) in the carbon dioxide recovery method (M1) is the carbon dioxide absorption / release after absorbing carbon dioxide, which is the target of the heat treatment in the step (B) of the carbon dioxide recovery method described above. This is a step in which the agent is limited to a liquid and a reaction product of the compound (1) and carbon dioxide is precipitated.

In order to carry out the step (B1), the step (B) in the carbon dioxide recovery method described above may be carried out reflecting the above-mentioned limitation.
For example, the step (B1) may be performed in the coexistence of the base catalyst.

The carbon dioxide recovery method (M1) is the method for recovering carbon dioxide described above, in which the step (A) is limited to the step (A1) and the step (B) is limited to the step (B1). be.
For example, in the carbon dioxide recovery method (M1), the steps (A1) and (B1) may be repeated twice or more, and the steps (A1) and (B1) in this case may be repeated twice or more. The mode of repeating the steps is the same as the mode of repeating the steps (A) and (B) two or more times in the method for recovering carbon dioxide described above.

The description of the carbon dioxide recovery method (M1) is the same as the description of the carbon dioxide recovery method (the carbon dioxide recovery method having the steps (A) and (B)) except that the above limitation is applied. Is. Therefore, further detailed description of the carbon dioxide recovery method (M1) will be omitted.

<< Carbon dioxide recovery method (M2) >>
As another example of the method for recovering carbon dioxide according to the embodiment of the present invention, the following general formula (1)

(In the formula, m is 0 or 1; R ¹ and R ² are independently an alkyl group, an alkoxy group, a carboxy group, an alkyloxycarbonyl group, a formyl group, an alkylcarbonyl group, an alkylthio group and a sulfo group, respectively. It is an alkyloxysulfonyl group, a nitro group, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group may have a substituent; p ₁ and p ₂ are independently 1 or 2, respectively. Yes; if m is 0, q ₁ is an integer from 0 to 11, where p ₁ + q ₁ is less than or equal to 12, and if m is 1, q ₁ is an integer from 0 to 10. However, when p ₁ + q ₁ is 11 or less, q ₂ is an integer of 0 to 10, and q ₁ is an integer of 2 or more, two or more R ^1s may be the same or different from each other. Well, when q ₂ is an integer of 2 or more, two or more R ^2s may be the same or different from each other, q ₁ is an integer of 2 or more, and two or more R ^1s are. In the case of the alkyl group which may have a substituent, the two or more R ^1s may be bonded to each other to form a ring, and q ₂ is an integer of 2 or more. Moreover, when two or more R ^2s are the alkyl groups which may have a substituent, the two or more R ^2s may be bonded to each other to form a ring.)
In the step (A) of causing a carbon dioxide absorbing / releasing agent containing a compound represented by (that is, compound (1)) to absorb carbon dioxide,
It comprises a step (B2) of releasing the carbon dioxide from the carbon dioxide absorbing / releasing agent by heat-treating the carbon dioxide absorbing / releasing agent after absorbing the carbon dioxide in the coexistence of a base catalyst. Carbon dioxide recovery method (However, carbon dioxide recovery method when m is 0, p ₁ is 2, and two amino groups with p ₁ are arranged at the meta positions of each other. (Except for) (in this specification, it may be referred to as "carbon dioxide recovery method (M2)").

The step (A) in the carbon dioxide recovery method (M2) is the same as the step (A) in the carbon dioxide recovery method described above.

As an example, the compound (1) used in the step (A) in the carbon dioxide recovery method (M2) is the following general formula (11A), (12A) or (11B).

As an example, the compound (11A), the compound (12A) or the compound (11B) used in the step (A) in the carbon dioxide recovery method (M2) is described in the following general formulas (111A), (121A) and (122A). Or (111B)

Further detailed description of the step (A) in the carbon dioxide recovery method (M2) will be omitted.

In the step (B2) of the carbon dioxide recovery method (M2), in the step (B) of the carbon dioxide recovery method described above, the heat treatment of the carbon dioxide absorbing / releasing agent after absorbing carbon dioxide is performed as a base. This process is limited to those performed in the coexistence of a catalyst. That is, in order to carry out the step (B2), the step (B) in the carbon dioxide recovery method described above may be carried out reflecting the above-mentioned limitation.
For example, the base catalyst used in the step (B2) is the same as the base catalyst used in the step (B).

According to the carbon dioxide recovery method (M2), in the step (B2), by performing the heat treatment in the coexistence of a base catalyst, the release of carbon dioxide proceeds more smoothly.

The carbon dioxide recovery method (M2) is a method for recovering carbon dioxide described above, in which the step (B) is limited to the step (B2).
For example, in the carbon dioxide recovery method (M2), the steps (A) and (B2) may be repeated twice or more, and the steps (A) and (B2) in this case may be repeated twice or more. The mode of repeating the steps is the same as the mode of repeating the steps (A) and (B) two or more times in the method for recovering carbon dioxide described above.

The description of the carbon dioxide recovery method (M2) is the same as the description of the carbon dioxide recovery method (the carbon dioxide recovery method having the steps (A) and (B)) except that the above limitation is applied. Is. Therefore, further detailed description of the carbon dioxide recovery method (M2) will be omitted.

<< Carbon dioxide absorption method >>
The method for absorbing carbon dioxide according to an embodiment of the present invention is described in the following general formula (1).

(In the formula, m is 0 or 1; R ¹ and R ² are independently an alkyl group, an alkoxy group, a carboxy group, an alkyloxycarbonyl group, a formyl group, an alkylcarbonyl group, an alkylthio group and a sulfo group, respectively. It is an alkyloxysulfonyl group, a nitro group, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group may have a substituent; p ₁ and p ₂ are independently 1 or 2, respectively. Yes; if m is 0, q ₁ is an integer from 0 to 11, where p ₁ + q ₁ is less than or equal to 12, and if m is 1, q ₁ is an integer from 0 to 10. However, when p ₁ + q ₁ is 11 or less, q ₂ is an integer of 0 to 10, and q ₁ is an integer of 2 or more, two or more R ^1s may be the same or different from each other. Well, when q ₂ is an integer of 2 or more, two or more R ^2s may be the same or different from each other, q ₁ is an integer of 2 or more, and two or more R ^1s are. In the case of the alkyl group which may have a substituent, the two or more R ^1s may be bonded to each other to form a ring, and q ₂ is an integer of 2 or more. Moreover, when two or more R ^2s are the alkyl groups which may have a substituent, the two or more R ^2s may be bonded to each other to form a ring.)
The carbon dioxide absorbing / releasing agent containing the compound represented by (that is, the compound (1)) has a step (a) of absorbing carbon dioxide (where m is 0, p ₁ is 2 and p. Except for the method of absorbing carbon dioxide when the two amino groups marked with ₁ are arranged at the meta positions of each other).

The step (a) in the present embodiment is the same as the step (A) in the carbon dioxide recovery method according to the above-described embodiment of the present invention. Therefore, the detailed description of the step (a) will be omitted here.

Also in the method for absorbing carbon dioxide of the present embodiment, the carbon dioxide absorbing / releasing agent according to the above-described embodiment of the present invention is used. Therefore, in the above absorption method, in the general formula (1), m is 0, p ₁ is 2, and two (p ₁ ) amino groups are arranged at the meta positions of each other. Does not include those using a carbon dioxide absorbing / releasing agent containing.
According to the method for absorbing carbon dioxide of the present embodiment, carbon dioxide can be easily absorbed by using the carbon dioxide absorbing / releasing agent.

The method for absorbing carbon dioxide of the present embodiment may have other steps that do not correspond to step (a) as long as the effects of the present invention are not impaired.
The type and number of the other steps and the timing of performing the other steps can be arbitrarily selected according to the purpose and are not particularly limited.

<< Carbon dioxide absorption method (α1) >>
As an example of the method for absorbing carbon dioxide according to the embodiment of the present invention, the following general formula (1)

(In the formula, m is 0 or 1; R ¹ and R ² are independently an alkyl group, an alkoxy group, a carboxy group, an alkyloxycarbonyl group, a formyl group, an alkylcarbonyl group, an alkylthio group and a sulfo group, respectively. It is an alkyloxysulfonyl group, a nitro group, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group may have a substituent; p ₁ and p ₂ are independently 1 or 2, respectively. Yes; if m is 0, q ₁ is an integer from 0 to 11, where p ₁ + q ₁ is less than or equal to 12, and if m is 1, q ₁ is an integer from 0 to 10. However, when p ₁ + q ₁ is 11 or less, q ₂ is an integer of 0 to 10, and q ₁ is an integer of 2 or more, two or more R ^1s may be the same or different from each other. Well, when q ₂ is an integer of 2 or more, two or more R ^2s may be the same or different from each other, q ₁ is an integer of 2 or more, and two or more R ^1s are. In the case of the alkyl group which may have a substituent, the two or more R ^1s may be bonded to each other to form a ring, and q ₂ is an integer of 2 or more. Moreover, when two or more R ^2s are the alkyl groups which may have a substituent, the two or more R ^2s may be bonded to each other to form a ring.)
By allowing a liquid carbon dioxide absorbing / releasing agent containing the compound represented by (that is, compound (1)) to absorb carbon dioxide, the compound represented by the general formula (1), the carbon dioxide, and the carbon dioxide A method for absorbing carbon dioxide (where m is 0, p ₁ is 2 and p ₁ is attached), which comprises a step (a1) of precipitating the reaction product of the above in the liquid carbon dioxide absorbing / releasing agent. Except for the method of absorbing carbon dioxide when the two amino groups are arranged at the meta positions of each other) (in the present specification, it may be referred to as "method of absorbing carbon dioxide (α1)"). Can be mentioned.

The step (a1) in the carbon dioxide absorption method (α1) is the same as the step (A1) in the carbon dioxide recovery method (M1) described above.
Further, in the step (a1), in the step (A) of the carbon dioxide recovery method described above, the carbon dioxide absorbing / releasing agent is limited to a liquid one, and the reaction between the compound (1) and carbon dioxide. This is a process limited to those that precipitate in a liquid carbon dioxide absorbing / releasing agent.
Further, in the step (a1), in the step (a) of the carbon dioxide absorption method described above, the carbon dioxide absorption / release agent is limited to a liquid one, and the reaction between the compound (1) and carbon dioxide. This is a process limited to those that precipitate in a liquid carbon dioxide absorbing / releasing agent.
Therefore, the detailed description of the step (a1) will be omitted here.

In the carbon dioxide absorption method (α1), the above step (a1) is performed in the same manner as in the case of the carbon dioxide recovery method (M1), and the reaction product of the compound (1) and carbon dioxide is converted into liquid carbon dioxide. Precipitation in the absorption / release agent (using a liquid carbon dioxide absorption / release agent as a suspension) promotes the reaction between the compound (1) and carbon dioxide, and the carbon dioxide absorption / release agent absorbs carbon dioxide. Is promoted.

After the reaction product is precipitated in the liquid carbon dioxide absorption / release agent by the carbon dioxide absorption method (α1), the reaction product can be easily taken out from the liquid carbon dioxide absorption / release agent. By taking out the reactant in this way, for example, the reactant can be stably stored.

The reaction product precipitated in the liquid carbon dioxide absorption / release agent can be taken out from the carbon dioxide absorption / release agent by applying a known solid-liquid separation method such as filtration.
After taking out, the reaction product may be washed once or twice or more by a known method, if necessary.
The reaction product after being taken out or the reaction product after washing can be dried by a known method.

The description of the carbon dioxide absorption method (α1) is the same as the description of the carbon dioxide absorption method (carbon dioxide absorption method having the step (a)) except that it has the above-mentioned limitation. Therefore, further detailed description of the carbon dioxide absorption method (α1) will be omitted.

<< Carbon dioxide release method >>
The method for releasing carbon dioxide according to an embodiment of the present invention is described in the following general formula (1).

(In the formula, m is 0 or 1; R ¹ and R ² are independently an alkyl group, an alkoxy group, a carboxy group, an alkyloxycarbonyl group, a formyl group, an alkylcarbonyl group, an alkylthio group and a sulfo group, respectively. It is an alkyloxysulfonyl group, a nitro group, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group may have a substituent; p ₁ and p ₂ are independently 1 or 2, respectively. Yes; if m is 0, q ₁ is an integer from 0 to 11, where p ₁ + q ₁ is less than or equal to 12, and if m is 1, q ₁ is an integer from 0 to 10. However, when p ₁ + q ₁ is 11 or less, q ₂ is an integer of 0 to 10, and q ₁ is an integer of 2 or more, two or more R ^1s may be the same or different from each other. Well, when q ₂ is an integer of 2 or more, two or more R ^2s may be the same or different from each other, q ₁ is an integer of 2 or more, and two or more R ^1s are. In the case of the alkyl group which may have a substituent, the two or more R ^1s may be bonded to each other to form a ring, and q ₂ is an integer of 2 or more. Moreover, when two or more R ^2s are the alkyl groups which may have a substituent, the two or more R ^2s may be bonded to each other to form a ring.)
A step of releasing the carbon dioxide from the carbon dioxide emitting agent by heat-treating the carbon dioxide releasing agent containing a reaction product of the compound represented by (that is, the compound (1)) and carbon dioxide (that is, the compound (1)). b).

In the present embodiment, the reaction product of the above-mentioned compound (1) and carbon dioxide is, for example, the carbon atom constituting the cycloalkyl ring skeleton in the compound (1) as described above. Examples thereof include a reaction product of a directly bonded amino group and carbon dioxide. However, unlike the above-mentioned carbon dioxide absorption / release agent, carbon dioxide recovery method, and carbon dioxide absorption method, in the carbon dioxide release method of the present embodiment, m is 0 as the reactant. Those using compound (1) in the case where p ₁ is 2 and two (p ₁ ) amino groups are arranged at the meta positions of each other are not excluded. That is, in the method for releasing carbon dioxide of the present embodiment, the reaction product contained in the carbon dioxide releasing agent has m of 0, p1 of ₂ , and ₂ (p1) amino groups. Can include a reactant of compound (1) and carbon dioxide when they are located in meta positions with each other.
More specifically, the reactants include, for example, the following general formula (2).

(In the formula, R ¹ , R ² , p ₁ , p ₂ , q ₁ , q ₂ and m are the same as above; X ¹ and X ² are independently hydrogen atoms or carboxy groups, respectively. If p ₁ is 2, the two X ^1s may be the same or different from each other, and if p ₂ is 2, the two X ^2s may be the same or different from each other. Well, however, if m is 0, then ^one or two X1s are carboxy groups, and if m is 1, then one or two X1s and ^one or two. Of the X ² , one or more are carboxy groups; when X ¹ or X ² is a carboxy group, the group represented by the formula "-NHCOOH" is of the formula "-". It may be either a group represented by " ^NHCOO- " or a group represented by the formula "-NH ₂ ⁺ ^COO- ").
(In the present specification, it may be referred to as "compound (2)").

In the general formula (2), R ¹ , R ² , p ₁ , p ₂ , q ₁ , q ₂ and m are R ¹ , R ² , p ₁ , p ₂ , q ₁ and m in the general formula (1). Same as q ₂ and m.
When p ₁ is 2, the two X ^1s may be the same or different from each other, and when p ₂ is 2, the two X ^2s may be the same or different from each other. good.

In the general formula (2), X ¹ and X ² are independently hydrogen atoms or carboxy groups (-C (= O) -OH). That is, X ¹ and X ² may be the same as each other or may be different from each other.

When X ¹ is a carboxy group, the group represented by the formula "-NHX ¹ ", that is, the formula " ^-NHCOOH " may be a group represented by the formula "-NHCOO-" or the formula "-NHCOO-". -It may be a group represented by "NH ₂ ⁺ ^COO- ".
Similarly, when X ² is a carboxy group, the group represented by the formula "-NHX ² ", that is, the formula " ^-NHCOOH " may be the group represented by the formula "-NHCOO-". , May be a group represented by the formula "-NH ₂ ⁺ ^COO- ".

However, the compound (2) is a carboxyamino group (-NHCOOH) directly bonded to the carbon atom constituting the cyclohexane ring skeleton, a group represented by the formula "-NHCOO-" ^, or a group represented by the formula "-NH ₂ ". It has one or two or more groups represented by " ⁺ ^COO- ".
More specifically, in the general formula (2), when m is 0, ^one or two X1s are a carboxy group (-C (= O) -OH) or a carboxylate anion (-). C (= O) ^-O- ). When m is 1, X ¹ with the code p ₁ (ie, one or two) and X ² with the code p ₂ (ie, one or two). Of the total of 2 to 4 X ^1s or X ^2s , one or more are carboxy groups or carboxylate anions.

The reaction product of the compound (1) and carbon dioxide when m is 0 is represented by, for example, the following general formula (2A) (in the present specification, this compound is referred to as “compound (2A)”. May be referred to).
The reaction product of the compound (1) and carbon dioxide when m is 1 is represented by the following general formula (2B) (in the present specification, this compound is referred to as “compound (2B)”. There is).

(In the formula, R ¹ , R ² , p ₁ , p ₂ , q ₁ , q ₂ , X ¹ and X ² are the same as above.)

In the general formula (2A) or (2B), R ¹ , R ² , p ₁ , p 2, p ₂ , q ₁ , q ₂ , X ¹ and X ² are R ¹ , R ² , p in the general formula (2). Same as ₁ , p ₂ , q ₁ , q ₂ , X ¹ and X ² .
Therefore, when q ₁ is an integer of 2 or more, two or more R ^1s may be the same or different from each other, and when q ₂ is an integer of 2 or more, two or more R ^2s may be different from each other. May be the same or different from each other. Further, when q ₁ is an integer of 2 or more and 2 or more R ^1s are the alkyl groups which may have a substituent, the two or more R ^1s (substituents are used). The alkyl group) may be bonded to each other to form a ring, q ₂ is an integer of 2 or more, and R ² of 2 or more has a substituent. In the case of the above-mentioned alkyl group, the two or more ^R2 (the above-mentioned alkyl group which may have a substituent) may be bonded to each other to form a ring. Further, when p ₁ is 2, the two X ^1s may be the same or different from each other, and when p ₂ is 2, the two X ^2s may be the same or different from each other. You may. Then, in the general formula (2A), one or two X ^1s are carboxy groups, and in the general formula (2B), one or two X ^1s and one or two X ^2s . One or more of the above are carboxy groups. When X ¹ or X ² is a carboxy group, the group represented by the formula " ^-NHCOOH " is a group represented by the formula "-NHCOO-" and the formula "-NH ₂ ⁺ ^COO- ". It may be any of the groups represented by.

The reaction product of the compound (11A) described above and carbon dioxide is represented by, for example, the following general formula (21A) (in the present specification, this compound is referred to as "compound (21A)". There is).
The reaction product of the compound (12A) and carbon dioxide described above is represented by, for example, the following general formula (22A) (in the present specification, this compound is referred to as “compound (22A)”. There is).
The reaction product of the compound (11B) described above and carbon dioxide is represented by the following general formula (21B). (In the present specification, this compound may be referred to as "compound (21B)").

(In the formula, R ¹¹ , R ¹² , R ¹³ , R ²¹ , q ₁₁ , q ₁₂ , q ₁₃ , q ₂₁ , X ¹ and X ² are the same as above.)

In the general formula (21A), (22A) or (21B), R ¹¹ , R ¹² , R ¹³ , R ²¹ , q ₁₁ , q ₁₂ , q ₁₃ and q ₂₁ are the general formulas (11A), (12A) or It is the same as R ¹¹ , R ¹² , R ¹³ , R ²¹ , q ₁₁ , q ₁₂ , q ₁₃ and q ₂₁ in (11B).
In the general formula (21A), (22A) or (21B), X ¹ and X ² are the same as X ¹ and X ² in the general formula (2).
Therefore, if q ₁₁ is an integer of 2 or more, the two or more R ^11s may be the same or different from each other, and if q ₁₂ is an integer of 2 or more, the two or more R ^12s may be the same or different. May be the same or different from each other. Further, when q ₁₁ is an integer of 2 or more and 2 or more R ^11s are the alkyl groups which may have a substituent, the two or more R ^11s (substituents are used). The alkyl group) may be bonded to each other to form a ring, q ₁₂ is an integer of 2 or more, and R ¹² of 2 or more has a substituent. In the case of the above-mentioned alkyl group, the two or more R ^12s (the above-mentioned alkyl group which may have a substituent) may be bonded to each other to form a ring. Further, when q ₁₃ is an integer of 2 or more, two or more R ^13s may be the same or different from each other, and when q ₂₁ is an integer of 2 or more, two or more R ^21s may be different from each other. May be the same or different from each other. Further, when q ₁₃ is an integer of 2 or more and 2 or more R ¹³ are the alkyl groups which may have a substituent, the two or more R ¹³ (substituents are used). The alkyl group) may be bonded to each other to form a ring, q ₂₁ is an integer of 2 or more, and 2 or more R ²¹ have a substituent. In the case of the above-mentioned alkyl group, the two or more R ^21s (the above-mentioned alkyl group which may have a substituent) may be bonded to each other to form a ring.

The reaction product of the compound (111A) and carbon dioxide described above is represented by, for example, the following general formula (211A) (in the present specification, this compound is referred to as “compound (211A)”. There is).
The reaction product of the compound (121A) described above and carbon dioxide is represented by, for example, the following general formula (221A) (in the present specification, this compound is referred to as “compound (221A)”. There is).
The reaction product of the compound (122A) and carbon dioxide described above is represented by, for example, the following general formula (222A) (in the present specification, this compound is referred to as “compound (222A)”. There is).
The reaction product of the compound (111B) and carbon dioxide described above is represented by, for example, the following general formula (211B) (in the present specification, this compound is referred to as “compound (211B)”. There is).

(In the formula, R ¹¹¹ , R ¹²¹ , R ¹²² , R ¹³¹ , R ²¹¹ , q ₁₁₁ , q ₁₂₁ , q ₁₂₂ , q ₁₃₁ , q ₂₁₁ , X ¹ and X ² are the same as above.)

In the general formulas (211A), (221A), (222A) or (211B), R ¹¹¹ , R ¹²¹ , R ¹²² , R ¹³¹ , R ²¹¹ , q ₁₁₁ , q ₁₂₁ , q ₁₂₂ , q ₁₃₁ and q ₂₁₁ are Same as R ¹¹¹ , R ¹²¹ , R ¹²² , R ¹³¹ , R ²¹¹ , q ₁₁₁ , q ₁₂₁ , q ₁₂₂ , q ₁₃₁ and q ₂₁₁ in the general formulas (111A), (121A), (122A) or (111B). Is.
In the general formula (211A), (221A), (222A) or (211B), X ¹ and X ² are the same as X ¹ and X ² in the general formula (2).
Therefore, when q ₁₁₁ is an integer of 2 or more, two or more R ^111s may be the same or different from each other, and when q ₁₂₁ is an integer of 2 or more, two or more R ^121s may be different from each other. May be the same or different from each other, and when q ₁₂₂ is an integer of 2 or more, two or more R ^122s may be the same or different from each other. Further, when q ₁₁₁ is an integer of 2 or more and the two or more R ^111s are the alkyl groups which may have an amino group as the substituent, the two or more R ^111s . (The alkyl group which may have the substituent) may be bonded to each other to form a ring, q ₁₂₁ is an integer of 2 or more, and R ¹²¹ of 2 or more is the said. In the case of the alkyl group which may have an amino group as a substituent, the two or more R ^121s (the alkyl group which may have the substituent) are bonded to each other and have a ring. In the case where q ₁₂₂ is an integer of 2 or more and two or more R ^122s are the alkyl groups which may have an amino group as the substituent. Two or more R ^122s (the alkyl groups which may have the substituents) may be bonded to each other to form a ring. Further, when q ₁₃₁ is 2, the two R ^131s may be the same or different from each other, and when q ₂₁₁ is 2, the two R ^211s may be the same or different from each other. good. Further, when q ₁₃₁ is 2 and the two R ^131s are the alkyl groups which may have an amino group as the substituents, the two R ^131s (the substituents are used). The alkyl group (which may have the alkyl group) may be bonded to each other to form a ring, q ₂₁₁ is 2, and the two R ^211s have an amino group as the substituent. In the case of the above-mentioned alkyl group, the two R ^211s (the above-mentioned alkyl group which may have the above-mentioned substituent) may be bonded to each other to form a ring.

In the step (b) of the present embodiment, the carbon dioxide according to the above-described embodiment of the present invention is used, except that the carbon dioxide-releasing agent is used instead of the carbon dioxide-absorbing and releasing agent after absorbing the carbon dioxide. It is the same as the step (B) in the recovery method of. The carbon dioxide emitting agent in the present embodiment has m as 0, p ₁ as 2, and two (p ₁ ) amino groups as a reaction product of compound (1) and carbon dioxide. Carbon dioxide absorption after absorption of carbon dioxide in the above step (B), except that it may contain a reactant of compound (1) and carbon dioxide when it is arranged at the meta position. Same as release agent.

In the carbon dioxide emitting agent of the present embodiment, the active components that release carbon dioxide are a reaction product of compound (1) and carbon dioxide, m is 0, p ₁ is 2, and two (2). The compound in the above-mentioned step (B) except that it may be a reaction product of the compound ( ₁ ) in the case where the amino groups of p1) are arranged at the meta positions of each other and carbon dioxide. It is the same as the reaction product (the above-mentioned carbamic acid derivative) of (1) and carbon dioxide.

<Carbon dioxide release agent>
The carbon dioxide-releasing agent contains a reaction product of compound (1) and carbon dioxide (the carbamate derivative), and may contain only the reaction product (in other words, the reaction product consists of the reaction product). It may contain the reactants and components other than the reactants.
For example, the liquid carbon dioxide emitting agent containing the reaction product and the solvent is preferable in that carbon dioxide is released more easily.

Examples of the liquid carbon dioxide releasing agent include the same as the liquid carbon dioxide absorbing / releasing agent after absorbing the carbon dioxide described above. However, in the above-mentioned release method, in the general formula (1), m is 0, p ₁ is 2, and two (p ₁ ) amino groups are arranged at the meta positions of each other. Also included are those using a carbon dioxide emitting agent containing.

Even if the carbon dioxide emitting agent contains the carbamic acid derivative, the solvent, the base catalyst, and other components that do not correspond to any of the acids, as long as the effects of the present invention are not impaired. good.
The other components can be arbitrarily selected depending on the intended purpose, and are not particularly limited.

The other components contained in the carbon dioxide emitting agent may be only one kind, two or more kinds, and when two or more kinds, the combination and the ratio thereof depend on the purpose. It can be selected arbitrarily.

In the carbon dioxide releasing agent (carbon dioxide releasing agent before starting the emission of carbon dioxide), the ratio of the content (parts by mass) of the other components to the total mass (parts by mass) of the carbon dioxide releasing agent is. Although not particularly limited, it is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, and particularly preferably 1% by mass or less. When the ratio is equal to or less than the upper limit value regardless of the presence or absence of the solvent, the carbon dioxide emitting agent has a higher ability to release carbon dioxide.
In other words, in the carbon dioxide releasing agent (carbon dioxide releasing agent before starting the emission of carbon dioxide), the total content (mass) of the carbamate derivative and the solvent with respect to the total mass (parts by mass) of the carbon dioxide releasing agent. Part) is not particularly limited, but is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 97% by mass or more, and 99% by mass or more. Is particularly preferable.

According to the method for releasing carbon dioxide of the present embodiment, carbon dioxide can be easily released by using the carbon dioxide releasing agent.

Except for the points described so far, the step (b) in the present embodiment is the same as the step (B) in the carbon dioxide recovery method according to the above-described embodiment of the present invention. Therefore, further detailed description of the step (b) will be omitted here.

The carbon dioxide releasing agent can be produced, for example, by causing the carbon dioxide absorbing / releasing agent to absorb carbon dioxide by the method for absorbing carbon dioxide according to the embodiment of the present invention described above. Then, in this case, carbon dioxide containing the compound (1) in the case where m is 0, p ₁ is 2, and two (p ₁ ) amino groups are arranged at the meta positions of each other. A release agent may be used.
Further, the carbon dioxide emitting agent can be used, for example, by producing the carbamic acid derivative by another method, and if necessary, using the carbamic acid derivative and other components (solvent or the other component). It can also be manufactured by mixing.

The method for releasing carbon dioxide of the present embodiment may have other steps that do not correspond to step (b) as long as the effects of the present invention are not impaired.
The type and number of the other steps and the timing of performing the other steps can be arbitrarily selected according to the purpose and are not particularly limited.

<< Carbon dioxide release method (β1) >>
As an example of the method for releasing carbon dioxide according to the embodiment of the present invention, the following general formula (1)

(In the formula, m is 0 or 1; R ¹ and R ² are independently an alkyl group, an alkoxy group, a carboxy group, an alkyloxycarbonyl group, a formyl group, an alkylcarbonyl group, an alkylthio group and a sulfo group, respectively. It is an alkyloxysulfonyl group, a nitro group, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group may have a substituent; p ₁ and p ₂ are independently 1 or 2, respectively. Yes; if m is 0, q ₁ is an integer from 0 to 11, where p ₁ + q ₁ is less than or equal to 12, and if m is 1, q ₁ is an integer from 0 to 10. However, when p ₁ + q ₁ is 11 or less, q ₂ is an integer of 0 to 10, and q ₁ is an integer of 2 or more, two or more R ^1s may be the same or different from each other. Well, when q ₂ is an integer of 2 or more, two or more R ^2s may be the same or different from each other, q ₁ is an integer of 2 or more, and two or more R ^1s are. In the case of the alkyl group which may have a substituent, the two or more R ^1s may be bonded to each other to form a ring, and q ₂ is an integer of 2 or more. Moreover, when two or more R ^2s are the alkyl groups which may have a substituent, the two or more R ^2s may be bonded to each other to form a ring.)
By heat-treating a liquid carbon dioxide-releasing agent containing a reaction product of the compound represented by (that is, compound (1)) and carbon dioxide and in which the reaction product is precipitated, the liquid carbon dioxide release agent is formed. Examples thereof include a method for releasing carbon dioxide (in the present specification, it may be referred to as “method for releasing carbon dioxide (β1)”), which comprises a step (b1) for releasing the carbon dioxide from the carbon dioxide emitting agent.

The step (b1) in the carbon dioxide release method (β1) is the carbon dioxide release after absorbing carbon dioxide, which is the target of the heat treatment in the step (b) of the carbon dioxide release method described above. This is a step in which the agent is limited to a liquid and a reaction product of the compound (1) and carbon dioxide is precipitated. That is, in order to carry out the step (b1), the step (b) in the carbon dioxide emission method described above may be carried out reflecting the above-mentioned limitation.

The liquid carbon dioxide emitting agent in which the reactant is precipitated used in the step (b1) is, for example, the above-mentioned after absorbing carbon dioxide obtained by the above-mentioned carbon dioxide absorption method (α1). The same as the liquid carbon dioxide absorption / release agent in which the reaction product is precipitated can be mentioned.
When such a carbon dioxide emitting agent is used, carbon dioxide can be released with higher efficiency by the carbon dioxide releasing method (β1).

Further, as the liquid carbon dioxide-releasing agent in which the reactant is precipitated, which is used in the step (b1), for example, by the above-mentioned carbon dioxide absorption method (α1), carbon dioxide is added to the carbon dioxide-absorbing and releasing agent. By absorbing the above, the reaction product of compound (1) and carbon dioxide is precipitated in the liquid carbon dioxide absorption / release agent, and then the reaction product is taken out from the liquid carbon dioxide absorption / release agent, if necessary. The reaction product after removal was washed once or twice or more, and if necessary, the reaction product after removal or the reaction product after washing was dried and taken out as necessary. After storing the later reaction product, the washed reaction product, or the dried reaction product, the reaction product (the carbamate derivative), the solvent, and, if necessary, other components (the above-mentioned). Other components) and those obtained by mixing with each other can also be mentioned.
When such a carbon dioxide release agent is used, the conditions of the step (b1) can be adjusted in a wide range by extracting the reaction product from the liquid carbon dioxide absorption / release agent. In addition, carbon dioxide can be released with higher efficiency.

Further, as the liquid carbon dioxide release agent in which the reactant is precipitated, which is used in the step (b1), for example, the reactant (in other words, the carbamic acid derivative) is produced by another method. Examples thereof include those obtained by mixing the obtained reaction product (the carbamic acid derivative), the solvent, and, if necessary, components other than these (the other components).
Even when such a carbon dioxide emitting agent is used, the conditions of the step (b1) can be adjusted in a wide range by using the reaction product once taken out. In addition, carbon dioxide can be released with higher efficiency.

However, no matter what kind of liquid carbon dioxide emitting agent is used as the liquid carbon dioxide emitting agent in which the reactant is precipitated, m is used in the general formula (1) as the carbon dioxide releasing method (β1). Carbon dioxide containing a reaction product of compound (1) and carbon dioxide when 0, p ₁ is 2, and two (p ₁ ) amino groups are arranged at the meta positions of each other. Also included is a method using a release agent.

The description of the carbon dioxide release method (β1) is the same as the description of the carbon dioxide release method (carbon dioxide release method having the step (b)) except that it has the above-mentioned limitation. Therefore, further detailed description of the carbon dioxide emission method (β1) will be omitted.

<< Carbon dioxide release method (β2) >>
As another example of the method for releasing carbon dioxide according to the embodiment of the present invention, the following general formula (1)

(In the formula, m is 0 or 1; R ¹ and R ² are independently an alkyl group, an alkoxy group, a carboxy group, an alkyloxycarbonyl group, a formyl group, an alkylcarbonyl group, an alkylthio group and a sulfo group, respectively. It is an alkyloxysulfonyl group, a nitro group, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group may have a substituent; p ₁ and p ₂ are independently 1 or 2, respectively. Yes; if m is 0, q ₁ is an integer from 0 to 11, where p ₁ + q ₁ is less than or equal to 12, and if m is 1, q ₁ is an integer from 0 to 10. However, when p ₁ + q ₁ is 11 or less, q ₂ is an integer of 0 to 10, and q ₁ is an integer of 2 or more, two or more R ^1s may be the same or different from each other. Well, when q ₂ is an integer of 2 or more, two or more R ^2s may be the same or different from each other, q ₁ is an integer of 2 or more, and two or more R ^1s are. In the case of the alkyl group which may have a substituent, the two or more R ^1s may be bonded to each other to form a ring, and q ₂ is an integer of 2 or more. Moreover, when two or more R ^2s are the alkyl groups which may have a substituent, the two or more R ^2s may be bonded to each other to form a ring.)
By heat-treating a carbon dioxide-releasing agent containing a reaction product of the compound represented by (that is, compound (1)) and carbon dioxide in the coexistence of a base catalyst, the carbon dioxide-releasing agent can be used as the carbon dioxide. Examples thereof include a method for releasing carbon dioxide (in the present specification, it may be referred to as “method for releasing carbon dioxide (β2)”), which comprises a step of releasing carbon (b2).

The step (b2) in the carbon dioxide release method (β2) is a carbon dioxide containing a reaction product of the compound (1) and carbon dioxide in the step (b) of the carbon dioxide release method described above. This step is limited to those in which the heat treatment of the release agent is performed in the coexistence of a base catalyst. That is, in order to carry out the step (b2), the step (b) in the carbon dioxide emission method described above may be carried out reflecting the above-mentioned limitation.
For example, the base catalyst used in the step (b2) is the same as the base catalyst used in the step (B).

As the carbon dioxide emitting agent used in the step (b2) to be used in combination with the base catalyst, for example, it can be obtained by the carbon dioxide absorbing method described above (the carbon dioxide absorbing method having the step (a)). The same as the carbon dioxide absorbing / releasing agent after absorbing carbon dioxide can be mentioned. However, in the carbon dioxide emission method (β2), in the general formula (1), m is 0, p ₁ is 2, and two (p ₁ ) amino groups are arranged at the meta positions of each other. Also included is a method using a carbon dioxide emitting agent containing a reaction product of the compound (1) and carbon dioxide in the above case.

According to the carbon dioxide release method (β2), the carbon dioxide release proceeds more smoothly by performing the heat treatment in the coexistence of a base catalyst in the step (b2).

The description of the carbon dioxide release method (β2) is the same as the description of the carbon dioxide release method (carbon dioxide release method having the step (b)) except that it has the above-mentioned limitation. Therefore, further detailed description of the carbon dioxide emission method (β2) will be omitted.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the examples shown below.

[Example 1]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing cyclohexylamine and methanol, a methanol solution of cyclohexylamine having a concentration of cyclohexylamine of 0.5 M was prepared, and this was used as a carbon dioxide absorption / release agent.

<< Absorption of carbon dioxide >>
A methanol solution (2 mL) of cyclohexylamine obtained above was placed in a test tube, and a three-way cock was attached to the opening of the test tube. A metal thin tube was passed through the inside of the test tube from the gas inlet of the three-way cock, and the end of the thin tube on the inner side of the test tube was placed in the methanol solution. As described above, the gas is directly flowed from the outside of the test tube into the methanol solution inside the test tube from the gas inlet of the three-way cock through the thin tube, and the gas in the gas phase part inside the test tube is introduced. , The device was assembled so that it could be discharged to the outside of the test tube from the gas outlet of the three-way cock.

Then, using the above device at room temperature, a mixed gas containing 1% by volume of carbon dioxide and 99% by volume of nitrogen was added to the test tube at a flow rate of 20 mL / min (0.54 mmol / h of carbon dioxide). From the outside, the gas inside the test tube is flowed into the methanol solution inside the test tube for bubbling (steps (a) and (a1)), and the gas inside the test tube is discharged from the gas outlet of the three-way cock to the test tube. It was discharged to the outside. Then, this exhaust gas was analyzed by a gas chromatography (TCD-GC) method using a thermal conductivity detector (TCD), and carbon dioxide in the exhaust gas was quantified. Then, the amount of carbon dioxide absorbed by the methanol solution (that is, the carbon dioxide absorbing / releasing agent) is calculated from the amount of carbon dioxide inflow and emission, and the following formula [carbon dioxide removal efficiency (%)] = [carbon dioxide Absorption amount] / [Carbon dioxide inflow amount] x 100
The carbon dioxide removal efficiency (absorption efficiency) was calculated. The results are shown in FIG. FIG. 1 shows not only the efficiency of removing carbon dioxide, but also the imaging data of the methanol solution at the start of inflow of carbon dioxide (0 minutes after the start of inflow) and at the stage of 60 minutes after the start of inflow.

As time passed from the start of the inflow of carbon dioxide, a white solid substance was formed in the methanol solution. As described above, the methanol solution became a methanol suspension. This white solid was a reaction product of cyclohexylamine and carbon dioxide (that is, N-cyclohexylcarbamic acid). ¹³ in heavy water ₍ D2O) of the components in the methanol solution when carbon dioxide is flowing in, the cyclohexylamine standard, the reactant, and the N-cyclohexylcarbamic acid standard. The analysis result (NMR spectrum) by C-NMR is shown in FIG. From these analysis results, it was possible to identify that the reaction product was N-cyclohexylcarbamic acid.

At the stage 60 minutes after the start of the inflow of carbon dioxide, the methanol solution was considerably cloudy.
As is clear from FIG. 1, immediately after the start of the inflow of carbon dioxide, the carbon dioxide removal efficiency was close to 100%, and the methanol solution absorbed carbon dioxide with high efficiency. Then, with the passage of time, the amount of cyclohexylamine that can react with carbon dioxide decreased, the efficiency of removing carbon dioxide decreased, and about 120 minutes after the start of inflow of carbon dioxide, carbon dioxide was not removed. ..
As described above, it was confirmed that the methanol solution has a sufficient ability to absorb carbon dioxide for a gas having a relatively high concentration of carbon dioxide.

<< Manufacturing of carbon dioxide absorption / release agent, absorption of carbon dioxide >>
[Example 2]
A carbon dioxide absorbing / releasing agent is produced by the same method as in Example 1 except that dry air (containing about 400 ppm of carbon dioxide on a volume basis) is used instead of the mixed gas to absorb carbon dioxide. I let you. The calculation result of the carbon dioxide removal efficiency at this time is shown in FIG.

As in the case of Example 1, as time passed from the start of the inflow of carbon dioxide, a white solid substance (a reaction product of cyclohexylamine and carbon dioxide) was generated in the methanol solution, and a methanol suspension was formed. ..
As is clear from FIG. 3, immediately after the start of the inflow of carbon dioxide, the carbon dioxide removal efficiency was close to 100%, and the methanol solution absorbed carbon dioxide with high efficiency. Then, with the passage of time, the amount of cyclohexylamine that can react with carbon dioxide decreased, and the efficiency of removing carbon dioxide decreased. However, since the concentration of carbon dioxide in the dry air was low, the rate of decrease in the amount of cyclohexylamine capable of reacting with carbon dioxide was slower than in the case of Example 1, and the decrease in carbon dioxide removal efficiency was gradual. ..
As described above, it was confirmed that the methanol solution has a sufficient ability to absorb carbon dioxide with respect to air.
It was confirmed by analysis by ¹³ C-NMR that the obtained reaction product was N-cyclohexylcarbamic acid.

Further, from the results of Examples 1 and 2, it was confirmed that the methanol solution can be selected from a gas having a wide concentration of carbon dioxide as the gas to be applied.

[Example 3]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing isophorone diamine and dimethyl sulfoxide (DMSO), a DMSO solution of isophorone diamine having a concentration of isophorone diamine of 1 M was prepared, and this was used as a carbon dioxide absorption / release agent.

<< Absorption of carbon dioxide >>
A DMSO solution (15 mL) of the isophorone diamine obtained above was placed in a test tube, and the same apparatus as in Example 1 was assembled.
Then, using the above device at room temperature, a mixed gas containing 30% by volume of carbon dioxide and 70% by volume of nitrogen was added at a flow rate of 20 mL / min (16 mmol / h of carbon dioxide) from the outside of the test tube. , Inflow into the DMSO solution inside the test tube and bubbling (step (a), step (a1)), and at the same time, the gas inside the test tube is discharged from the gas outlet of the three-way cock to the outside of the test tube. It was discharged. Then, the amount of carbon dioxide absorbed by the DMSO solution (that is, the carbon dioxide absorption / release agent) was calculated by the same method as in the case of Example 1, and the carbon dioxide removal efficiency (absorption efficiency) was calculated. The results are shown in FIG.

As time passes from the start of the inflow of carbon dioxide, a reaction product of isophorone diamine and carbon dioxide (that is, (3-aminomethyl-3,5,5-trimethylcyclohexyl)) is added to the DMSO solution as a white solid. Carbamic acid) was produced. As described above, the DMSO solution became a DMSO suspension.
As is clear from FIG. 4, immediately after the start of the inflow of carbon dioxide, the carbon dioxide removal efficiency was close to 100%, and the DMSO solution absorbed carbon dioxide with high efficiency. Approximately 35 minutes after the start of inflow of carbon dioxide, a sharp decrease in carbon dioxide removal efficiency begins, and about 50 minutes after the start of inflow of carbon dioxide, the decrease in carbon dioxide removal efficiency becomes gradual and the inflow of carbon dioxide starts. About 100 minutes after that, carbon dioxide was not removed.
It was confirmed by analysis by ¹³ C-NMR that the obtained reaction product was (3-aminomethyl-3,5,5-trimethylcyclohexyl) carbamic acid.

[Example 4]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing isophorone diamine and toluene, a toluene solution of isophorone diamine having a concentration of isophorone diamine of 0.18 M was prepared, and this was used as a carbon dioxide absorption / release agent.

<< Absorption of carbon dioxide >>
A toluene solution (3 mL) of the isophorone diamine obtained above was placed in a test tube, and the same apparatus as in Example 1 was assembled.
Then, using the above device at room temperature, a mixed gas containing 1% by volume of carbon dioxide and 99% by volume of nitrogen was added to the test tube at a flow rate of 20 mL / min (0.54 mmol / h of carbon dioxide). Along with bubbling by flowing into the toluene solution inside the test tube from the outside (step (a), step (a1)), the gas inside the test tube is discharged from the gas outlet of the three-way cock to the test tube. It was discharged to the outside. Then, the amount of carbon dioxide absorbed by the toluene solution (that is, the carbon dioxide absorption / release agent) was calculated by the same method as in the case of Example 1, and the carbon dioxide removal efficiency (absorption efficiency) was calculated. The results are shown in FIG.

As time passed from the start of the inflow of carbon dioxide, a reaction product of isophorone diamine and carbon dioxide was generated as a white solid in the toluene solution. As described above, the toluene solution became a toluene suspension.
As is clear from FIG. 5, immediately after the start of the inflow of carbon dioxide, the carbon dioxide removal efficiency was close to 100%, and the toluene solution absorbed carbon dioxide with high efficiency. Approximately 60 minutes after the start of inflow of carbon dioxide, a sharp decrease in carbon dioxide removal efficiency begins, and about 85 minutes after the start of inflow of carbon dioxide, the decrease in carbon dioxide removal efficiency becomes gradual and the inflow of carbon dioxide starts. About 120 minutes after that, carbon dioxide was not removed.
It was confirmed by analysis by ¹³ C-NMR that the obtained reaction product was (3-aminomethyl-3,5,5-trimethylcyclohexyl) carbamic acid.

[Example 5]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing isophorone diamine and dimethyl sulfoxide (DMSO), a DMSO solution of isophorone diamine having a concentration of isophorone diamine of 1 M was prepared, and this was used as a carbon dioxide absorption / release agent.

<< Absorption of carbon dioxide >>
The DMSO solution (1 mL) of the isophorone diamine obtained above was placed in a test tube, and the same apparatus as in Example 1 was assembled.
Then, at room temperature, using the above device, dry air (containing about 400 ppm of carbon dioxide by volume) was introduced from the outside of the test tube at a flow rate of 20 mL / min (carbon dioxide is 22 μmol / h). Along with bubbling by flowing into the DMSO solution inside (steps (a) and (a1)), the gas inside the test tube was discharged to the outside of the test tube from the gas discharge port of the three-way cock. Then, the amount of carbon dioxide absorbed by the DMSO solution (that is, the carbon dioxide absorption / release agent) was calculated by the same method as in the case of Example 1, and the carbon dioxide removal efficiency (absorption efficiency) was calculated. The results are shown in FIG.

As time passed from the start of the inflow of carbon dioxide, a reaction product of isophorone diamine and carbon dioxide was generated as a white solid in the DMSO solution. As described above, the DMSO solution became a DMSO suspension.
As is clear from FIG. 6, immediately after the start of the inflow of carbon dioxide, the carbon dioxide removal efficiency was close to 100%, and the DMSO solution absorbed carbon dioxide with high efficiency. Then, this state was maintained until 50 hours after the start of the inflow of carbon dioxide.
It was confirmed by analysis by ¹³ C-NMR that the obtained reaction product was (3-aminomethyl-3,5,5-trimethylcyclohexyl) carbamic acid.

<< Release of carbon dioxide >>
[Example 6]
Solid (3-aminomethyl-3,5,5-trimethylcyclohexyl) carbamic acid at a heating rate of 10 ° C./min while flowing nitrogen gas using a thermogravimetric analysis-mass spectrometer (TG-MS). By heat-treating (carbon dioxide emitting agent) (step (b)), thermogravimetric measurement and mass spectrometry were performed at the same time. The results are shown in FIGS. 7 to 8. FIG. 7 is the spectral data of weight loss, and FIG. 8 is the spectral data of ionic strength.
In addition, in this specification, a simple description of "nitrogen gas" means nitrogen gas having a purity of 100%.

As is clear from these results, the weight of the carbon dioxide emitting agent started to decrease after about 60 ° C., and the peak corresponding to carbon dioxide (m / z = 44) was detected, followed by isophorone diamine. A corresponding peak (m / z = 138) was detected.
It was also confirmed by analysis by ¹³ C-NMR that the obtained reaction product was isophorone diamine.

[Example 7]
<< Manufacture of carbon dioxide release agent >>
Concentration of the isophorone diamine derivative by mixing (3-aminomethyl-3,5,5-trimethylcyclohexyl) carbamic acid (hereinafter, may be abbreviated as "isophorone diamine derivative") and dimethyl sulfoxide (DMSO). A DMSO suspension of an isophorone diamine derivative having a value of 0.2 M was prepared and used as a carbon dioxide releasing agent.

<< Release of carbon dioxide >>
A DMSO suspension (5 mL) of the isophorone diamine derivative obtained above was placed in a test tube, and the same apparatus as in Example 1 was assembled.
Then, using the device, 60 of the DMSO suspension was blown by flowing nitrogen gas from the outside of the test tube into the DMSO suspension inside the test tube at a flow rate of 50 mL / min. After heat treatment at ° C. (step (b)), the gas inside the test tube was discharged to the outside of the test tube from the gas discharge port of the three-way cock. Then, the concentration of carbon dioxide in the exhaust gas was measured using a Fourier transform infrared spectrophotometer (FT-IR) (first time). The results are shown in FIG.
In addition, the unit "%" attached to "CO ₂ CONCENTRATION" (concentration of carbon dioxide) in the graphs after FIG. 9 means "volume%".

Furthermore, the same operation as above was repeated, and the concentration of carbon dioxide in the exhaust gas was measured again (second time) to confirm the reproducibility. The results are shown in FIG.

As is clear from FIGS. 9 to 10, the concentration of carbon dioxide in the exhaust gas has increased with the passage of time from the start of the heat treatment, and carbon dioxide from the DMSO suspension (carbon dioxide releasing agent) has increased. Was being released. Approximately 8 minutes after the start of the heat treatment, the concentration of the carbon dioxide became maximum, and then the concentration of the carbon dioxide decreased.

In the first carbon dioxide release experiment, the amount of carbon dioxide released 60 minutes after the start of the heat treatment was about 0.85 mmol, which was calculated using this release amount and the amount of the isophorone diamine derivative used. The carbon dioxide emission rate was about 85%.
The carbon dioxide release rate from the start of the heat treatment to the maximum concentration of carbon dioxide was 51 μmol / min in the first release experiment and 49 μmol / min in the second release experiment. ..

The transition of the carbon dioxide concentration is almost the same between the first carbon dioxide release experiment and the second carbon dioxide release experiment, and the carbon dioxide release from the carbon dioxide release agent (step (b)). The reproducibility of was high.
In the first and second carbon dioxide emission experiments, it was confirmed by ¹³ C-NMR analysis that the obtained reaction product was isophorone diamine.

[Example 8]
<< Manufacture of carbon dioxide release agent, release of carbon dioxide >>
By mixing (3-aminomethyl-3,5,5-trimethylcyclohexyl) carbamate (the isophorone diamine derivative), _{K8 Nb 6} _O ₁₉ (base catalyst), and dimethyl sulfoxide (DMSO), A DMSO suspension of an isophorone diamine derivative having a concentration of the isophorone diamine derivative of 0.2 M, a concentration of the base catalyst of 0.002 M, and a precipitate of the isophorone diamine derivative was prepared, and this was distilled off. It was used as a carbon release agent.
The concentration of carbon dioxide in the exhaust gas was repeatedly measured by the same method as in Example 7 except that the carbon dioxide emitting agent was used. The first measurement result is shown in FIG. 9, and the second measurement result is shown in FIG.

As is clear from FIGS. 9 to 10, the transition of the concentration of carbon dioxide in the exhaust gas is almost the same as in the case of Example 7, and even if a base catalyst is used, carbon dioxide from the carbon dioxide emitting agent is used. The reproducibility of the release (step (b), step (b2)) was high. However, the maximum value of the carbon dioxide concentration was higher in Example 8 than in Example 7, which was presumed to be the effect of using the base catalyst.
The carbon dioxide release rate from the start of the heat treatment to the maximum concentration of carbon dioxide was 56 μmol / min in the first release experiment and 54 μmol / min in the second release experiment. ..
In the first and second carbon dioxide emission experiments, it was confirmed by ¹³ C-NMR analysis that the obtained reaction product was isophorone diamine.

[Example 9]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing isophorone diamine and dimethyl sulfoxide (DMSO), a DMSO solution of isophorone diamine having a concentration of isophorone diamine of 0.2 M was prepared, and this was used as a carbon dioxide absorption / release agent.

<< Recovery of carbon dioxide >>
<Absorption of carbon dioxide (1st cycle)>
A DMSO solution (5 mL) of the isophorone diamine obtained above was placed in a test tube, and the same apparatus as in Example 1 was assembled.
Then, using the above device at room temperature, a mixed gas containing 1% by volume of carbon dioxide and 99% by volume of nitrogen was added to the test tube at a flow rate of 10 mL / min (0.27 mmol / h of carbon dioxide). Along with bubbling by flowing into the DMSO solution inside the test tube from the outside (step (A), step (A1)), the gas inside the test tube is discharged from the gas outlet of the three-way cock to the test tube. It was discharged to the outside. Then, using FT-IR, the concentration of carbon dioxide in this exhaust gas was measured (first cycle). The results are shown in FIG.

As time passed from the start of the inflow of carbon dioxide, a white solid substance was formed in the DMSO solution. This was the isophorone diamine derivative. As described above, the DMSO solution became a DMSO suspension.
As is clear from FIG. 11, the concentration of carbon dioxide in the exhaust gas is close to 0% by volume from immediately after the start of the inflow of carbon dioxide to about 230 minutes later, in other words, the efficiency of removing carbon dioxide is high. Nearly 100%, the DMSO solution absorbed carbon dioxide with high efficiency. After that, with the passage of time, the amount of isophorone diamine capable of reacting with carbon dioxide decreased, and the concentration of carbon dioxide in the exhaust gas increased (the efficiency of removing carbon dioxide decreased). Approximately 360 minutes after the start of inflow of carbon dioxide, the concentration of carbon dioxide in the exhaust gas became about 1% by volume, and carbon dioxide was not removed.

After confirming that carbon dioxide was no longer removed, the inflow of the mixed gas into the DMSO suspension was stopped.
The amount of carbon dioxide absorbed by the DMSO solution (carbon dioxide absorbing / releasing agent) from the start to the stop of the inflow of carbon dioxide was calculated to be 1.27 mmol. Since isophorone diamine has two amino groups in one molecule, the amount of carbon dioxide absorbed by the DMSO solution can be up to 2 mmol in consideration of the amount used. However, here, it was confirmed that in isophoronediamine, it was mainly the amino group directly bonded to the carbon atom constituting the cyclohexyl ring skeleton that reacted with carbon dioxide. That is, in isophorone diamine, some amino groups were not involved in the reaction with carbon dioxide. As explained above, the corrected absorption rate of carbon dioxide (first cycle) when the amino group having such a limited arrangement form is used as a reference (in other words, the amino group is limited) is determined. It was judged to be 100%. The absorption rate of carbon dioxide (first cycle) was 64% when the amino group was not limited and the correction was not performed.

<Carbon dioxide release (1st cycle)>
Next, the DMSO suspension was heat-treated at 60 ° C. by flowing nitrogen gas from the outside of the test tube into the DMSO suspension inside the test tube at a flow rate of 50 mL / min and bubbling. Step (B), Step (B1)), the gas inside the test tube was discharged to the outside of the test tube from the gas discharge port of the three-way cock. Then, the concentration of carbon dioxide in the exhaust gas was measured using FT-IR (first cycle). The results are shown in FIG.

As is clear from FIG. 12, as time has passed from the start of the heat treatment, the concentration of carbon dioxide in the exhaust gas has increased, and carbon dioxide is released from the DMSO suspension (carbon dioxide absorbing / releasing agent). It had been. Approximately 10 minutes after the start of the heat treatment, the concentration of the carbon dioxide became maximum, and then the concentration of the carbon dioxide decreased.

The amount of carbon dioxide released from the start of the heat treatment to 200 minutes later was 1.2 mmol. The corrected emission rate (1st cycle) of carbon dioxide when the amino group was limited, which was calculated using this emission amount, was determined to be 100%. The carbon dioxide emission rate (first cycle) without correction, which was calculated using the above-mentioned carbon dioxide absorption amount and emission amount, was 94%.
In the present specification, the "carbon dioxide release rate" calculated using the amount of carbon dioxide absorbed and released is the following formula [carbon dioxide release rate (%)] = [carbon dioxide] unless otherwise specified. Amount of carbon dioxide released] / [Amount of carbon dioxide absorbed] x 100
Means what is calculated by.
By the heat treatment, the white solid was finally lost in the DMSO suspension, and the DMSO solution was regenerated.

<Absorption of carbon dioxide (2nd cycle)>
Next, the mixed gas is again flowed into the carbon dioxide absorbing / releasing agent (DMSO solution) regenerated by the release of carbon dioxide by the same method as in the case of the first cycle described above, and bubbling is performed (step (step). A), along with the step (A1)), the gas inside the test tube was discharged to the outside of the test tube from the gas discharge port of the three-way cock. Then, the concentration of carbon dioxide in this exhaust gas was measured by the same method as in the case of the first cycle (second cycle). The results are shown in FIG. By this step, the DMSO solution became a DMSO suspension.

As is clear from FIG. 11, the transition of the carbon dioxide concentration is almost the same between the absorption of carbon dioxide in the first cycle and the absorption of carbon dioxide in the second cycle, and the carbon dioxide produced by the carbon dioxide absorbing / releasing agent is used. The reproducibility of absorption (step (A), step (A1)) was high.

After confirming that carbon dioxide was no longer removed, the inflow of the mixed gas into the DMSO suspension was stopped.
The amount of carbon dioxide absorbed by the DMSO solution (carbon dioxide absorbing / releasing agent) from the start to the stop of the inflow of carbon dioxide was calculated to be 1.21 mmol. The corrected absorption rate of carbon dioxide (second cycle) when the amino group was limited, which was calculated using this absorption amount and the amount of isophorone diamine used, was determined to be 100%. The absorption rate of carbon dioxide (second cycle) was 61% when the amino group was not limited and no correction was performed.

<Carbon dioxide release (2nd cycle)>
Then, as in the case of the first cycle described above, the DMSO suspension is mixed with the DMSO suspension after the inflow of the mixed gas is stopped, while the nitrogen gas is flowed in again and bubbling. Heat treatment was performed at 60 ° C. (step (B), step (B1)), and the concentration of carbon dioxide in the exhaust gas was measured (second cycle). The results are shown in FIG.

As is clear from FIG. 12, the transition of the carbon dioxide concentration is almost the same between the release of carbon dioxide in the first cycle and the release of carbon dioxide in the second cycle, and the carbon dioxide produced by the carbon dioxide absorbing / releasing agent is used. The reproducibility of the release of carbon dioxide (step (B), step (B1)) was high.

The amount of carbon dioxide released from the start of the heat treatment to 200 minutes later was 1.2 mmol. The corrected emission rate (second cycle) of carbon dioxide when the amino group was limited, which was calculated using this emission amount, was determined to be 100%. The carbon dioxide emission rate (second cycle) without correction, which was calculated using the above-mentioned carbon dioxide absorption amount and emission amount, was 99%.
By the heat treatment, the white solid was finally lost in the DMSO suspension, and the DMSO solution was regenerated.

It was confirmed by ¹³ C-NMR analysis that the reaction product obtained during the absorption of carbon dioxide in the first and second cycles was (3-aminomethyl-3,5,5-trimethylcyclohexyl) carbamic acid.
It was confirmed by ¹³ C-NMR analysis that the reaction product obtained during the release of carbon dioxide in the first and second cycles was isophorone diamine.

[Example 10]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing isophorone diamine and dimethyl sulfoxide (DMSO), a DMSO solution of isophorone diamine having a concentration of isophorone diamine of 0.07 M was prepared, and this was used as a carbon dioxide absorption / release agent.

<< Recovery of carbon dioxide >>
<Absorption of carbon dioxide (1st cycle)>
A DMSO solution (15 mL) of the isophorone diamine obtained above was placed in a test tube, and the same apparatus as in Example 1 was assembled.
Next, except that the flow rate of the mixed gas was changed to 20 mL / min instead of 10 mL / min (the flow rate of carbon dioxide was changed to 0.54 mmol / h instead of 0.27 mmol / h), 1 of Example 9 Step (A) (step (A1)) was performed in the same manner as in the case of the first cycle, and the concentration of carbon dioxide in the exhaust gas was measured (first cycle). The results are shown in FIG.

As time passed from the start of the inflow of carbon dioxide, a white solid substance was formed in the DMSO solution. This was the isophorone diamine derivative. As described above, the DMSO solution became a DMSO suspension.
As is clear from FIG. 13, the concentration of carbon dioxide in the exhaust gas is close to 0% by volume from immediately after the start of the inflow of carbon dioxide to about 15 minutes later, in other words, the efficiency of removing carbon dioxide is high. Nearly 100%, the DMSO solution absorbed carbon dioxide with high efficiency. After that, with the passage of time, the amount of isophorone diamine capable of reacting with carbon dioxide decreased, and the concentration of carbon dioxide in the exhaust gas gradually increased (the efficiency of removing carbon dioxide gradually decreased). The amount of carbon dioxide absorbed by the DMSO solution (carbon dioxide absorbing / releasing agent) was calculated to be 1.0 mmol from the start of the inflow of carbon dioxide to about 120 minutes later. The corrected absorption rate (1st cycle) of carbon dioxide when the amino group was limited, which was calculated by using this absorption amount and the amount of isophorone diamine used, was 100%. The absorption rate of carbon dioxide (first cycle) was 50% when the amino group was not limited and no correction was performed.

<Carbon dioxide release (1st cycle)>
Then, as in the case of the first cycle of Example 9, the DMSO suspension was bubbling by flowing nitrogen gas into the DMSO suspension inside the test tube from the outside of the test tube. Heat treatment was performed at 60 ° C. (step (B), step (B1)), and the concentration of carbon dioxide in the exhaust gas was measured (first cycle). The results are shown in FIG.

As is clear from FIG. 14, as time has passed from the start of the heat treatment, the concentration of carbon dioxide in the exhaust gas has increased, and carbon dioxide is released from the DMSO suspension (carbon dioxide absorbing / releasing agent). It had been. Approximately 10 minutes after the start of the heat treatment, the concentration of the carbon dioxide became maximum, and then the concentration of the carbon dioxide decreased.

The amount of carbon dioxide released 120 minutes after the start of the heat treatment was 0.94 mmol. Corrected emission rate of carbon dioxide (1st cycle) when the amino group is limited, which is calculated using this emission amount, and correction, which is calculated using the above-mentioned absorption amount and emission amount of carbon dioxide, are performed. The carbon dioxide emission rate (1st cycle) in the absence was 94% in each case.
By the heat treatment, the white solid was finally lost in the DMSO suspension, and the DMSO solution was regenerated.

As is clear from FIG. 13, the transition of the carbon dioxide concentration is almost the same between the absorption of carbon dioxide in the first cycle and the absorption of carbon dioxide in the second cycle. The reproducibility of absorption (step (A), step (A1)) was high.

Approximately 120 minutes after the start of the inflow of carbon dioxide, the inflow of the mixed gas into the DMSO suspension was stopped.
The amount of carbon dioxide absorbed by the DMSO solution (carbon dioxide absorbing / releasing agent) from the start to the stop of the inflow of carbon dioxide was calculated to be 1.0 mmol. The corrected absorption rate (second cycle) of carbon dioxide when the amino group was limited, which was calculated using this absorption amount and the amount of regenerated isophorone diamine used, was 100%. The absorption rate of carbon dioxide (second cycle) was 50% when the amino group was not limited and the correction was not performed.

As is clear from FIG. 14, the transition of the carbon dioxide concentration is almost the same between the release of carbon dioxide in the first cycle and the release of carbon dioxide in the second cycle, and the carbon dioxide produced by the carbon dioxide absorbing / releasing agent is used. The reproducibility of the release of carbon dioxide (step (B), step (B1)) was high.

The amount of carbon dioxide released from the start of the heat treatment to 200 minutes later was 0.96 mmol. The corrected emission rate of carbon dioxide (second cycle) when the amino group is limited, which is calculated using this emission amount, and the correction, which is calculated using the above-mentioned absorption amount and emission amount of carbon dioxide, are performed. The carbon dioxide emission rate (second cycle) in the absence was 96% in each case.
By the heat treatment, the white solid was finally lost in the DMSO suspension, and the DMSO solution was regenerated.

<Absorption of carbon dioxide (3rd cycle), release of carbon dioxide (3rd cycle)>
Then, using this regenerated carbon dioxide absorption / release agent (DMSO solution), carbon dioxide absorption (third cycle) and carbon dioxide release (three cycles) are performed again in the same manner as in the case of the second cycle described above. Eyes) were performed in sequence.

As is clear from FIG. 13, in the absorption of carbon dioxide in the first to third cycles, the transition of the concentration of carbon dioxide is almost the same, and the absorption of carbon dioxide by the carbon dioxide absorbing / releasing agent (step (A), step. The reproducibility of (A1)) was high.
The amount of carbon dioxide absorbed by the DMSO solution (carbon dioxide absorbing / releasing agent) from the start to the stop of the inflow of carbon dioxide was calculated to be 1.0 mmol. The corrected absorption rate (third cycle) of carbon dioxide when the amino group was limited, which was calculated using this absorption amount and the amount of regenerated isophorone diamine used, was 100%. The absorption rate of carbon dioxide (third cycle) was 50% when the amino group was not limited and no correction was performed.

As is clear from FIG. 14, in the carbon dioxide release in the first to third cycles, the transition of the carbon dioxide concentration is almost the same, and the carbon dioxide release by the carbon dioxide absorbing / releasing agent (step (B), step The reproducibility of (B1)) was high.
The amount of carbon dioxide released from the start of the heat treatment to 200 minutes later was 1.0 mmol. The corrected emission rate of carbon dioxide (third cycle) when the amino group is limited, which is calculated using this emission amount, and the correction, which is calculated using the above-mentioned absorption amount and emission amount of carbon dioxide, are performed. The carbon dioxide emission rate (third cycle) in the absence was 100% in each case.
Also in the third cycle, the white solid was finally disappeared in the DMSO suspension by the heat treatment, and the DMSO solution was regenerated.

<Absorption of carbon dioxide (4th cycle), release of carbon dioxide (4th cycle)>
Then, using this regenerated carbon dioxide absorbing / releasing agent (DMSO solution), the absorption of carbon dioxide (4th cycle) and the release of carbon dioxide (4 cycles) are performed again in the same manner as in the case of the 2nd cycle described above. Eyes) were performed in sequence.
Also in the fourth cycle, the DMSO solution becomes a DMSO suspension by the step (A) (step (A1)), and the final DMSO suspension is obtained by the step (B) (step (B1)). The white solid had disappeared and the DMSO solution had been regenerated.

As is clear from FIG. 13, in the absorption of carbon dioxide in the 1st to 4th cycles, the transition of the concentration of carbon dioxide is almost the same, and the absorption of carbon dioxide by the carbon dioxide absorbing / releasing agent (step (A), step The reproducibility of (A1)) was high.
The amount of carbon dioxide absorbed by the DMSO solution (carbon dioxide absorbing / releasing agent) from the start to the stop of the inflow of carbon dioxide was calculated to be 1.0 mmol. The corrected absorption rate (second cycle) of carbon dioxide when the amino group was limited, which was calculated using this absorption amount and the amount of regenerated isophorone diamine used, was 100%. The absorption rate of carbon dioxide (second cycle) was 50% when the amino group was not limited and no correction was performed.

As is clear from FIG. 14, in the carbon dioxide release in the 1st to 4th cycles, the transition of the carbon dioxide concentration is almost the same, and the carbon dioxide release by the carbon dioxide absorbing / releasing agent (step (B), step The reproducibility of (B1)) was high.
The amount of carbon dioxide released from the start of the heat treatment to 200 minutes later was 1.0 mmol. The corrected emission rate of carbon dioxide (4th cycle) when the amino group is limited, which is calculated using this emission amount, and the correction, which is calculated using the above-mentioned absorption amount and emission amount of carbon dioxide, are performed. The carbon dioxide emission rate (4th cycle) in the absence was 100% in each case.

It was confirmed by ¹³ C-NMR analysis that the reaction product obtained during the absorption of carbon dioxide in the 1st to 4th cycles was (3-aminomethyl-3,5,5-trimethylcyclohexyl) carbamic acid.
It was confirmed by ¹³ C-NMR analysis that the reaction product obtained at the time of carbon dioxide release in the 1st to 4th cycles was isophorone diamine.

[Example 11]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing cyclohexylamine and N, N-dimethylformamide (DMF), a DMF solution of cyclohexylamine having a concentration of cyclohexylamine of 0.07 M was prepared, and this was used as a carbon dioxide absorption / release agent.

<< Recovery of carbon dioxide >>
<Absorption of carbon dioxide>
The DMF solution (15 mL) of cyclohexylamine obtained above was placed in a test tube, and the same apparatus as in Example 1 was assembled.
Then, under the temperature condition of -15 ° C., using the above-mentioned device, 20 mL / min (0.54 mmol / h of carbon dioxide) of the mixed gas containing 1% by volume of carbon dioxide and 99% by volume of nitrogen was added. At a flow rate, the gas inside the test tube is bubbling by flowing into the DMF solution inside the test tube from the outside of the test tube (step (A)), and the gas inside the test tube is discharged from the gas outlet of the three-way cock to the test tube. It was discharged to the outside of. Then, using FT-IR, the concentration of carbon dioxide in this exhaust gas was measured.

Unlike the case of Example 1, a reaction product of cyclohexylamine and carbon dioxide (that is, N-cyclohexylcarbamic acid) is precipitated in the DMF solution even after a lapse of time from the start of inflow of carbon dioxide. There was no.

After confirming that carbon dioxide was no longer removed, the inflow of the mixed gas into the DMF solution was stopped.
The amount of carbon dioxide absorbed by the DMF solution (carbon dioxide absorbing / releasing agent) from the start to the stop of the inflow of carbon dioxide was calculated to be 0.841 mmol. The absorption rate of carbon dioxide calculated by using this absorption amount and the amount of cyclohexylamine used was 84.1%.
The analysis result (NMR spectrum) by ¹³ C _- NMR in heavy water (D2O) of the obtained reaction product is shown in FIG. From this analysis result, it was possible to identify that the reaction product was N-cyclohexylcarbamic acid.

<Carbon dioxide release>
Next, the DMF solution was heat-treated at 60 ° C. while bubbling by flowing nitrogen gas from the outside of the test tube into the DMF solution inside the test tube at a flow rate of 50 mL / min (step (B)). ), The gas inside the test tube was discharged to the outside of the test tube from the gas outlet of the three-way cock. Then, using FT-IR, the concentration of carbon dioxide in the exhaust gas was measured.

The amount of carbon dioxide released after the start of the heat treatment was 0.453 mmol. The carbon dioxide emission rate calculated by using this emission amount and the above-mentioned carbon dioxide absorption amount was 54%.
FIG. 15 shows the analysis result (NMR spectrum) of the reaction product after the release of carbon dioxide in heavy water (D2O) by ¹³ C _- NMR. From this analysis result, it was possible to identify that the reaction product after releasing carbon dioxide was cyclohexylamine.

[Example 12]
<< Manufacture of carbon dioxide absorption / release agent >>
The carbon dioxide absorption / release agent (4) was used in the same manner as in Example 11 except that the same amount (number of moles) of 4,4'-methylenebis (2-methylcyclohexylamine) was used instead of cyclohexylamine. , 4'-Methylenebis (2-methylcyclohexylamine) DMF solution) was prepared.

<< Recovery of carbon dioxide >>
<Absorption of carbon dioxide>
Step (A) (step (A1)) is performed in the same manner as in Example 11 except that the carbon dioxide absorbing / releasing agent obtained above is used, and the concentration of carbon dioxide in the exhaust gas is measured. bottom.
As time passed from the start of the inflow of carbon dioxide, a reaction product of 4,4'-methylenebis (2-methylcyclohexylamine) and carbon dioxide was formed as a white solid in the DMF solution. As described above, the DMF solution became a DMF suspension.

After confirming that carbon dioxide was no longer removed, the inflow of the mixed gas into the DMF suspension was stopped.
The amount of carbon dioxide absorbed by the DMF solution (carbon dioxide absorbing / releasing agent) from the start to the stop of the inflow of carbon dioxide was calculated to be 1.38 mmol. Since 4,4'-methylenebis (2-methylcyclohexylamine) has two amino groups in one molecule, the amount of carbon dioxide absorbed by the DMF solution is determined in consideration of the amount used. Since the maximum amount was 2 mmol, the absorption rate of carbon dioxide was 69%. That is, in 4,4'-methylenebis (2-methylcyclohexylamine), some amino groups were not involved in the reaction with carbon dioxide.
It was confirmed by analysis by ¹³ C-NMR that the obtained reaction product was mainly (4- (4-amino-3-methylcyclohexyl) methyl-2-methyl) carbamic acid.

<Carbon dioxide release>
Next, the DMF suspension was heat-treated at 60 ° C. while flowing nitrogen gas from the outside of the test tube into the DMF suspension inside the test tube at a flow rate of 75 mL / min and bubbling. Step (B), Step (B1)), the gas inside the test tube was discharged to the outside of the test tube from the gas discharge port of the three-way cock. Then, using FT-IR, the concentration of carbon dioxide in the exhaust gas was measured. During this time, the amount of the white solid in the DMF suspension decreased with the passage of time and finally disappeared, and the DMF solution was regenerated.

The amount of carbon dioxide released after the start of the heat treatment was 1.23 mmol. The carbon dioxide emission rate calculated by using this emission amount and the above-mentioned carbon dioxide absorption amount was 89%.
It was confirmed by analysis by ¹³ C-NMR that the obtained reaction product was 4,4'-methylenebis (2-methylcyclohexylamine).

[Example 13]
<< Manufacture of carbon dioxide absorption / release agent >>
Carbon dioxide absorption and release in the same manner as in Example 11 except that the same amount (number of moles) of 1,2-cyclohexanediamine (also known as 1,2-diaminocyclohexane) was used instead of cyclohexylamine. An agent (DMF solution of 1,2-cyclohexanediamine) was produced.

<< Recovery of carbon dioxide >>
<Absorption of carbon dioxide>
Step (A) (step (A1)) is performed in the same manner as in Example 11 except that the carbon dioxide absorbing / releasing agent obtained above is used, and the concentration of carbon dioxide in the exhaust gas is measured. bottom.
As time passed from the start of the inflow of carbon dioxide, a reaction product of 1,2-cyclohexanediamine and carbon dioxide was produced as a white solid in the DMF solution. As described above, the DMF solution became a DMF suspension.

After confirming that carbon dioxide was no longer removed, the inflow of the mixed gas into the DMF suspension was stopped.
The amount of carbon dioxide absorbed by the DMF solution (carbon dioxide absorbing / releasing agent) from the start to the stop of the inflow of carbon dioxide was calculated to be 1.22 mmol. Since 1,2-cyclohexanediamine has two amino groups in one molecule, the maximum amount of carbon dioxide absorbed by the DMF solution is 2 mmol in consideration of the amount used. The absorption rate of carbon dioxide was 61%. That is, in 1,2-cyclohexanediamine, some amino groups were not involved in the reaction with carbon dioxide.
The analysis result (NMR spectrum) by ¹³ C _- NMR in heavy water (D2O) of the obtained reaction product is shown in FIG. From this analysis result, it was possible to identify that the reaction product was mainly (2-aminocyclohexyl) carbamic acid.

The amount of carbon dioxide released after the start of the heat treatment was 1.26 mmol. The carbon dioxide emission rate calculated by using this emission amount and the above-mentioned carbon dioxide absorption amount was determined to be 100%.
FIG. 16 shows the analysis result (NMR spectrum) of the reaction product after the release of carbon dioxide in heavy water (D2O) by ¹³ C _- NMR. From this analysis result, it was possible to identify that the reaction product after releasing carbon dioxide was 1,2-cyclohexanediamine.

[Example 14]
<< Manufacture of carbon dioxide absorption / release agent >>
Carbon dioxide absorption and release in the same manner as in Example 11 except that the same amount (number of moles) of 1,4-cyclohexanediamine (also known as 1,4-diaminocyclohexane) was used instead of cyclohexylamine. An agent (DMF solution of 1,4-cyclohexanediamine) was produced.

<< Recovery of carbon dioxide >>
<Absorption of carbon dioxide>
Step (A) (step (A1)) is performed in the same manner as in Example 11 except that the carbon dioxide absorbing / releasing agent obtained above is used, and the concentration of carbon dioxide in the exhaust gas is measured. bottom.
As time passed from the start of the inflow of carbon dioxide, a reaction product of 1,4-cyclohexanediamine and carbon dioxide was produced as a white solid in the DMF solution. As described above, the DMF solution became a DMF suspension.

After confirming that carbon dioxide was no longer removed, the inflow of the mixed gas into the DMF suspension was stopped.
The amount of carbon dioxide absorbed by the DMF solution (carbon dioxide absorbing / releasing agent) from the start to the stop of the inflow of carbon dioxide was calculated to be 1.16 mmol. Since 1,4-cyclohexanediamine has two amino groups in one molecule, the maximum amount of carbon dioxide absorbed by the DMF solution is 2 mmol in consideration of the amount used. The absorption rate of carbon dioxide was 58%. That is, in 1,4-cyclohexanediamine, some amino groups were not involved in the reaction with carbon dioxide.
The analysis result (NMR spectrum) by ¹³ C _- NMR in heavy water (D2O) of the obtained reaction product is shown in FIG. From this analysis result, it was possible to identify that the reaction product was mainly (4-aminocyclohexyl) carbamic acid.

The amount of carbon dioxide released after the start of the heat treatment was 1.02 mmol. The carbon dioxide emission rate calculated by using this emission amount and the above-mentioned carbon dioxide absorption amount was 88%.
FIG. 17 shows the analysis result (NMR spectrum) of the reaction product after the release of carbon dioxide in heavy water (D2O) by ¹³ C _- NMR. From this analysis result, it was possible to identify that the reaction product after releasing carbon dioxide was 1,4-cyclohexanediamine.

[Example 15]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing isophorone diamine and water, an aqueous solution of isophorone diamine having a concentration of isophorone diamine of 0.07 M was prepared, and this was used as a carbon dioxide absorption / release agent.

<< Recovery of carbon dioxide >>
<Absorption of carbon dioxide>
An aqueous solution (15 mL) of the isophorone diamine obtained above was placed in a test tube, and the same apparatus as in Example 1 was assembled.
Then, under the temperature condition of room temperature, the mixed gas containing 1% by volume of carbon dioxide and 99% by volume of nitrogen was added at a flow rate of 20 mL / min (0.54 mmol / h of carbon dioxide) using the above device. , From the outside of the test tube, flow into the aqueous solution inside the test tube for bubbling (step (A)), and at the same time, let the gas inside the test tube flow from the gas outlet of the three-way cock to the outside of the test tube. It was discharged. Then, using FT-IR, the concentration of carbon dioxide in this exhaust gas was measured.

Unlike the case of Example 1, the reaction product of isophorone diamine and carbon dioxide did not precipitate in the aqueous solution even after a lapse of time from the start of the inflow of carbon dioxide.

After confirming that carbon dioxide was no longer removed, the inflow of the mixed gas into the aqueous solution was stopped.
The amount of carbon dioxide absorbed by the aqueous solution (carbon dioxide absorbing / releasing agent) from the start to the stop of the inflow of carbon dioxide was calculated to be 1.17 mmol. It was determined that the corrected absorption rate of carbon dioxide when the amino group was limited, which was calculated using this absorption amount and the amount of isophorone diamine used, was 100%. The absorption rate of carbon dioxide was 59% when the amino group was not limited and the correction was not performed.
The analysis result (NMR spectrum) by ¹³ C _- NMR in heavy water (D2O) of the obtained reaction product is shown in FIG. From this analysis result, it was possible to identify that the reaction product was mainly (3-aminomethyl-3,5,5-trimethylcyclohexyl) carbamic acid. The reaction product also contained a part of dicarbamic acid produced by reacting with carbon dioxide together with two amino groups in one molecule of isophorone diamine.

<Carbon dioxide release>
Next, the aqueous solution was heat-treated at 60 ° C. while bubbling by flowing nitrogen gas from the outside of the test tube into the aqueous solution inside the test tube at a flow rate of 75 mL / min (step (B)). The gas inside the test tube was discharged to the outside of the test tube from the gas outlet of the three-way cock. Then, using FT-IR, the concentration of carbon dioxide in the exhaust gas was measured.

The amount of carbon dioxide released after the start of the heat treatment was 1.02 mmol. The corrected emission rate of carbon dioxide when the amino group was limited, which was calculated using this emission amount, was determined to be 100%. The carbon dioxide emission rate without correction, which was calculated using the above-mentioned carbon dioxide absorption amount and emission amount, was 87%.
FIG. 18 shows the analysis result (NMR spectrum) of the reaction product after the release of carbon dioxide in heavy water (D2O) by ¹³ C _- NMR. From this analysis result, it was possible to identify that the reaction product after releasing carbon dioxide was isophorone diamine.

[Example 16]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing isophorone diamine and 2-propanol (IPA), an IPA solution of isophorone diamine having a concentration of isophorone diamine of 0.07 M was prepared, and this was used as a carbon dioxide absorption / release agent.

<< Recovery of carbon dioxide >>
<Absorption of carbon dioxide>
Step (A) was carried out in the same manner as in Example 15 except that the carbon dioxide absorbing / releasing agent obtained above was used, and the concentration of carbon dioxide in the exhaust gas was measured.
As in the case of Example 15, the reaction product of isophorone diamine and carbon dioxide did not precipitate in the IPA solution even after a lapse of time from the start of the inflow of carbon dioxide.

After confirming that carbon dioxide was no longer removed, the inflow of the mixed gas into the IPA solution was stopped.
The amount of carbon dioxide absorbed by the IPA solution (carbon dioxide absorbing / releasing agent) from the start to the stop of the inflow of carbon dioxide was calculated to be 0.33 mmol. The corrected absorption rate of carbon dioxide when the amino group was limited, which was calculated by using this absorption amount and the amount of isophorone diamine used, was 33%. The absorption rate of carbon dioxide was 17% when the amino group was not limited and the correction was not performed.

<Carbon dioxide release>
Next, the IPA solution was heat-treated at 60 ° C. while bubbling by flowing nitrogen gas from the outside of the test tube into the IPA solution inside the test tube at a flow rate of 75 mL / min (step (B)). ), The gas inside the test tube was discharged to the outside of the test tube from the gas outlet of the three-way cock. Then, using FT-IR, the concentration of carbon dioxide in the exhaust gas was measured.

The amount of carbon dioxide released after the start of the heat treatment was 0.121 mmol. The corrected emission rate of carbon dioxide when the amino group was limited, which was calculated using this emission amount, was 12%. The carbon dioxide emission rate without correction, which was calculated using the above-mentioned carbon dioxide absorption amount and emission amount, was 37%.

[Example 17]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing isophorone diamine and DMF, a DMF solution of isophorone diamine having a concentration of isophorone diamine of 0.07 M was prepared, and this was used as a carbon dioxide absorption / release agent.

<< Recovery of carbon dioxide >>
<Absorption of carbon dioxide>
Step (A) (step (A1)) is performed in the same manner as in Example 15 except that the carbon dioxide absorbing / releasing agent obtained above is used, and the concentration of carbon dioxide in the exhaust gas is measured. bottom.
As time passed from the start of the inflow of carbon dioxide, a reaction product of isophorone diamine and carbon dioxide was generated as a white solid in the DMF solution. As described above, the DMF solution became a DMF suspension.

After confirming that carbon dioxide was no longer removed, the inflow of the mixed gas into the DMF suspension was stopped.
The amount of carbon dioxide absorbed by the DMF solution (carbon dioxide absorbing / releasing agent) from the start to the stop of the inflow of carbon dioxide was calculated to be 0.661 mmol. The corrected absorption rate of carbon dioxide when the amino group was limited, which was calculated by using this absorption amount and the amount of isophorone diamine used, was 66%. The absorption rate of carbon dioxide was 33% when the amino group was not limited and the correction was not performed.

The amount of carbon dioxide released after the start of the heat treatment was 0.429 mmol. The corrected emission rate of carbon dioxide when the amino group was limited, which was calculated using this emission amount, was 43%. The carbon dioxide emission rate without correction, which was calculated using the above-mentioned carbon dioxide absorption amount and emission amount, was 65%.

[Example 18]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing isophorone diamine and dimethyl sulfoxide (DMSO) in the same manner as in Example 10, a DMSO solution of isophorone diamine having a concentration of isophorone diamine of 0.07 M was prepared, and this was used as carbon dioxide. It was used as an absorption / release agent.

<< Recovery of carbon dioxide >>
<Absorption of carbon dioxide>
Step (A) (step (A1)) was performed in the same manner as in the case of the first cycle of Example 10, and the concentration of carbon dioxide in the exhaust gas was measured.

As a result, the concentration of carbon dioxide in the exhaust gas showed the same tendency as in the case of the first cycle of Example 10 from the start of the inflow of carbon dioxide to about 120 minutes. The amount of carbon dioxide absorbed by the DMSO solution (carbon dioxide absorbing / releasing agent) was calculated to be 1.25 mmol from the start of the inflow of carbon dioxide to about 240 minutes later. It was determined that the corrected absorption rate of carbon dioxide when the amino group was limited, which was calculated using this absorption amount and the amount of isophorone diamine used, was 100%. The absorption rate of carbon dioxide was 63% when the amino group was not limited and the correction was not performed.
By this step, the DMSO solution became a DMSO suspension.

<Carbon dioxide release>
Then, step (B) (step (B1)) was performed in the same manner as in the case of the first cycle of Example 10, and the concentration of carbon dioxide in the exhaust gas was measured. The results are shown in FIG.

As is clear from FIG. 19, the concentration of carbon dioxide in the exhaust gas showed the same tendency as in the case of the first cycle of Example 10. For example, about 10 minutes after the start of the heat treatment, the concentration of the carbon dioxide became maximum, and then the concentration of the carbon dioxide decreased.

The amount of carbon dioxide released 120 minutes after the start of the heat treatment was 1.12 mmol. The corrected emission rate of carbon dioxide when the amino group was limited, which was calculated using this emission amount, was determined to be 100%. The carbon dioxide emission rate without correction, which was calculated using the above-mentioned carbon dioxide absorption amount and emission amount, was 90%.
By this step, in the DMSO suspension, the white solid was finally disappeared, and the DMSO solution was regenerated.

[Example 19]
<< Manufacture of carbon dioxide absorption / release agent >>
The carbon dioxide absorbing / releasing agent was produced in the same manner as in Example 18.

<< Recovery of carbon dioxide >>
<Absorption of carbon dioxide>
Step (A) (step (A1)) was carried out in the same manner as in the case of Example 18, and the concentration of carbon dioxide in the exhaust gas was measured. The results are shown in FIG.

As is clear from FIG. 20, the concentration of carbon dioxide in the exhaust gas showed the same tendency as in the case of the first cycle of Example 10 from the start of the inflow of carbon dioxide to about 120 minutes. Then, in the time zone after that, which was unconfirmed in Example 10, the concentration of carbon dioxide in the exhaust gas increased significantly, and finally became about 1% by volume, and carbon dioxide was not removed. The above tendency was the same as in Example 18. The amount of carbon dioxide absorbed by the DMSO solution (carbon dioxide absorbing / releasing agent) was calculated to be 1.25 mmol from the start of the inflow of carbon dioxide to about 240 minutes later. It was determined that the corrected absorption rate of carbon dioxide when the amino group was limited, which was calculated using this absorption amount and the amount of isophorone diamine used, was 100%. The absorption rate of carbon dioxide was 63% when the amino group was not limited and the correction was not performed.
By this step, the DMSO solution became a DMSO suspension.

<Carbon dioxide release>
Then, by adding n-hexylamine (base catalyst) to the DMSO solution after performing step (A) (step (A1)), the concentration of n-hexylamine is 0.7 mM. A turbid liquid was obtained.
Next, step (B) (corresponding to both step (B1) and step (B2)) was performed in the same manner as in Example 18 except that this DMSO suspension was used, and the exhaust gas was discharged. The concentration of carbon dioxide was measured. The results are shown in FIG.

As is clear from FIG. 19, the concentration of carbon dioxide in the exhaust gas showed the same tendency as in the case of the first cycle of Example 10 and the case of Example 18. For example, about 10 minutes after the start of the heat treatment, the concentration of the carbon dioxide became maximum, and then the concentration of the carbon dioxide decreased. However, the maximum value of the carbon dioxide concentration was higher in Example 19 than in Example 18, which was presumed to be the effect of using the base catalyst.

[Example 20]
<< Manufacture of carbon dioxide absorption / release agent >>
The carbon dioxide absorbing / releasing agent was produced in the same manner as in Example 18.

As is clear from FIG. 21, the concentration of carbon dioxide in the exhaust gas showed the same tendency as in the case of Example 18. The concentration of carbon dioxide in the exhaust gas eventually became about 1% by volume, and carbon dioxide was not removed. The amount of carbon dioxide absorbed by the DMSO solution (carbon dioxide absorbing / releasing agent) was calculated to be 1.23 mmol from the start of the inflow of carbon dioxide to about 240 minutes later. It was determined that the corrected absorption rate of carbon dioxide when the amino group was limited, which was calculated using this absorption amount and the amount of isophorone diamine used, was 100%. The absorption rate of carbon dioxide was 62% when the amino group was not limited and the correction was not performed.
By this step, the DMSO solution became a DMSO suspension.

<Carbon dioxide release>
Then, by adding di-n-hexylamine (base catalyst) to the DMSO suspension after performing step (A) (step (A1)), the concentration of di-n-hexylamine is 0. A DMSO suspension of 0.7 mM was obtained.
Next, step (B) (corresponding to both step (B1) and step (B2)) was performed in the same manner as in Example 18 except that this DMSO suspension was used, and the exhaust gas was discharged. The concentration of carbon dioxide was measured. The results are shown in FIG. The results of Example 18 are also shown in FIG. 22.

As is clear from FIG. 22, the concentration of carbon dioxide in the exhaust gas showed the same tendency as in the case of Example 18. For example, about 10 minutes after the start of the heat treatment, the concentration of the carbon dioxide became maximum, and then the concentration of the carbon dioxide decreased. However, the maximum value of the carbon dioxide concentration was higher in Example 20 than in Example 18, which was presumed to be the effect of using the base catalyst.

The amount of carbon dioxide released 120 minutes after the start of the heat treatment was 1.20 mmol. The corrected emission rate of carbon dioxide when the amino group was limited, which was calculated using this emission amount, was determined to be 100%. The carbon dioxide emission rate without correction, which was calculated using the above-mentioned carbon dioxide absorption amount and emission amount, was 98%.
By this step, in the DMSO suspension, the white solid was finally disappeared, and the DMSO solution was regenerated.

[Example 21]
<< Manufacture of carbon dioxide absorption / release agent >>
The carbon dioxide absorbing / releasing agent was produced in the same manner as in Example 18.

As is clear from FIG. 23, the concentration of carbon dioxide in the exhaust gas showed the same tendency as in the case of Example 18. The concentration of carbon dioxide in the exhaust gas eventually became about 1% by volume, and carbon dioxide was not removed. The amount of carbon dioxide absorbed by the DMSO solution (carbon dioxide absorbing / releasing agent) was calculated to be 1.23 mmol from the start of the inflow of carbon dioxide to about 240 minutes later. It was determined that the corrected absorption rate of carbon dioxide when the amino group was limited, which was calculated using this absorption amount and the amount of isophorone diamine used, was 100%. The absorption rate of carbon dioxide was 62% when the amino group was not limited and the correction was not performed.
By this step, the DMSO solution became a DMSO suspension.

<Carbon dioxide release>
Then, by adding tri-n-hexylamine (base catalyst) to the DMSO suspension after performing step (A) (step (A1)), the concentration of tri-n-hexylamine is 0. A DMSO suspension of 0.7 mM was obtained.
Next, step (B) (corresponding to both step (B1) and step (B2)) was performed in the same manner as in Example 18 except that this DMSO suspension was used, and the exhaust gas was discharged. The concentration of carbon dioxide was measured. The results are shown in FIG. The results of Example 18 are also shown in FIG. 24.

As is clear from FIG. 24, the concentration of carbon dioxide in the exhaust gas showed the same tendency as in the case of Example 18. For example, about 10 minutes after the start of the heat treatment, the concentration of the carbon dioxide became maximum, and then the concentration of the carbon dioxide decreased. The maximum value of the carbon dioxide concentration was slightly higher in Example 21 than in Example 18. In addition, the time required for the carbon dioxide concentration to reach 0% by volume was shorter in Example 21 than in Example 18.

The amount of carbon dioxide released 120 minutes after the start of the heat treatment was 0.95 mmol. The corrected emission rate of carbon dioxide when the amino group was limited, which was calculated using this emission amount, was 95%. The carbon dioxide emission rate without correction, which was calculated using the above-mentioned carbon dioxide absorption amount and emission amount, was 77%.
By this step, in the DMSO suspension, the white solid was finally disappeared, and the DMSO solution was regenerated.

[Example 22]
<< Manufacture of carbon dioxide absorption / release agent >>
The carbon dioxide absorbing / releasing agent was produced in the same manner as in Example 18.

As is clear from FIG. 25, the concentration of carbon dioxide in the exhaust gas showed the same tendency as in the case of Example 18. The concentration of carbon dioxide in the exhaust gas eventually became about 1% by volume, and carbon dioxide was not removed. The amount of carbon dioxide absorbed by the DMSO solution (carbon dioxide absorbing / releasing agent) was calculated to be 1.18 mmol from the start of the inflow of carbon dioxide to about 240 minutes later. It was determined that the corrected absorption rate of carbon dioxide when the amino group was limited, which was calculated using this absorption amount and the amount of isophorone diamine used, was 100%. The absorption rate of carbon dioxide was 59% when the amino group was not limited and the correction was not performed.
By this step, the DMSO solution became a DMSO suspension.

<Carbon dioxide release>
Next, by adding diazabicycloundecene (DBU, base catalyst) to the DMSO suspension after performing step (A) (step (A1)), the concentration of DBU is 0.7 mM. A DMSO suspension was obtained.
Next, step (B) (corresponding to both step (B1) and step (B2)) was performed in the same manner as in Example 18 except that this DMSO suspension was used, and the exhaust gas was discharged. The concentration of carbon dioxide was measured. The results are shown in FIG. The results of Example 18 are also shown in FIG. 26.

As is clear from FIG. 26, the concentration of carbon dioxide in the exhaust gas showed the same tendency as in the case of Example 18. For example, about 10 minutes after the start of the heat treatment, the concentration of the carbon dioxide became maximum, and then the concentration of the carbon dioxide decreased. The maximum value of the carbon dioxide concentration was slightly higher in Example 22 than in Example 18. Further, when compared at the same time, the carbon dioxide concentration tends to be higher in Example 22 than in Example 18 until the carbon dioxide concentration becomes maximum, and the carbon dioxide concentration tends to be higher. After reaching the maximum, the concentration of carbon dioxide in Example 22 tended to be lower than that in Example 18.

The amount of carbon dioxide released 120 minutes after the start of the heat treatment was 1.06 mmol. The corrected emission rate of carbon dioxide when the amino group was limited, which was calculated using this emission amount, was determined to be 100%. The carbon dioxide emission rate without correction, which was calculated using the above-mentioned carbon dioxide absorption amount and emission amount, was 90%.
By this step, in the DMSO suspension, the white solid was finally disappeared, and the DMSO solution was regenerated.

[Example 23]
<< Manufacture of carbon dioxide absorption / release agent >>
The carbon dioxide absorbing / releasing agent was produced in the same manner as in Example 18.

As is clear from FIG. 27, the concentration of carbon dioxide in the exhaust gas showed the same tendency as in the case of Example 18. The concentration of carbon dioxide in the exhaust gas eventually became about 1% by volume, and carbon dioxide was not removed. The amount of carbon dioxide absorbed by the DMSO solution (carbon dioxide absorbing / releasing agent) was calculated to be 1.27 mmol within about 240 minutes after the start of the inflow of carbon dioxide. It was determined that the corrected absorption rate of carbon dioxide when the amino group was limited, which was calculated using this absorption amount and the amount of isophorone diamine used, was 100%. The absorption rate of carbon dioxide was 64% when the amino group was not limited and the correction was not performed.
By this step, the DMSO solution became a DMSO suspension.

<Carbon dioxide release>
Next, by adding magnesium oxide (base catalyst) to the DMSO suspension after performing step (A) (step (A1)), the concentration of magnesium oxide is 24.8 mM. Got
Next, step (B) (corresponding to both step (B1) and step (B2)) was performed in the same manner as in Example 18 except that this DMSO suspension was used, and the exhaust gas was discharged. The concentration of carbon dioxide was measured. The results are shown in FIG. The results of Example 18 are also shown in FIG. 28.

As is clear from FIG. 28, the concentration of carbon dioxide in the exhaust gas showed the same tendency as in the case of Example 18. For example, about 10 minutes after the start of the heat treatment, the concentration of the carbon dioxide became maximum, and then the concentration of the carbon dioxide decreased. However, the maximum value of the carbon dioxide concentration was higher in Example 23 than in Example 18, which was presumed to be the effect of using the base catalyst.

The amount of carbon dioxide released 120 minutes after the start of the heat treatment was 1.11 mmol. The corrected emission rate of carbon dioxide when the amino group was limited, which was calculated using this emission amount, was determined to be 100%. The carbon dioxide emission rate without correction, which was calculated using the above-mentioned carbon dioxide absorption amount and emission amount, was 87%.
By this step, in the DMSO suspension, the white solid was finally disappeared, and the DMSO solution was regenerated.

[Example 24]
<< Manufacture of carbon dioxide absorption / release agent >>
The carbon dioxide absorbing / releasing agent was produced in the same manner as in Example 18.

As is clear from FIG. 29, the concentration of carbon dioxide in the exhaust gas showed the same tendency as in the case of Example 18. The concentration of carbon dioxide in the exhaust gas eventually became about 1% by volume, and carbon dioxide was not removed. The amount of carbon dioxide absorbed by the DMSO solution (carbon dioxide absorbing / releasing agent) was calculated to be 1.25 mmol from the start of the inflow of carbon dioxide to about 240 minutes later. It was determined that the corrected absorption rate of carbon dioxide when the amino group was limited, which was calculated using this absorption amount and the amount of isophorone diamine used, was 100%. The absorption rate of carbon dioxide was 63% when the amino group was not limited and the correction was not performed.
By this step, the DMSO solution became a DMSO suspension.

<Carbon dioxide release>
Next, the DMSO suspension was heat-treated at 30 ° C. for 90 minutes while flowing nitrogen gas from the outside of the test tube into the DMSO suspension inside the test tube at a flow rate of 50 mL / min and bubbling. (Step (B), Step (B1)), the gas inside the test tube was discharged to the outside of the test tube from the gas outlet of the three-way cock. Then, using FT-IR, the concentration of carbon dioxide in the exhaust gas was measured.
Next, the DMSO suspension was heat-treated at 40 ° C. for 90 minutes (step (B), step (B1)), and the concentration of carbon dioxide in the exhaust gas was measured in the same manner.
Next, the DMSO suspension was heat-treated at 50 ° C. for 90 minutes (step (B), step (B1)), and the concentration of carbon dioxide in the exhaust gas was measured in the same manner.
Next, the DMSO suspension was heat-treated at 60 ° C. for 90 minutes (step (B), step (B1)), and the concentration of carbon dioxide in the exhaust gas was measured in the same manner.
The above results are shown in FIG.

As is clear from FIG. 30, the concentration of carbon dioxide in the exhaust gas rapidly increases to the maximum and then decreases after the heat treatment temperature is changed to 30 ° C, 40 ° C, 50 ° C and 60 ° C. bottom. Then, by performing the heat treatment at 60 ° C., the concentration of carbon dioxide finally became 0% by volume. That is, it was shown that the release of carbon dioxide from the carbon dioxide absorption / release agent (the isophorone diamine derivative) was completed by the heat treatment at 60 ° C.

The amount of carbon dioxide released after the start of the heat treatment (ie, the carbon dioxide released by the end of all heat treatment at 30-90 ° C.) was 1.40 mmol. The corrected emission rate of carbon dioxide when the amino group is limited, which is calculated using this emission amount, and the carbon dioxide when no correction is performed, which is calculated using the above-mentioned absorption amount and emission amount of carbon dioxide. The release rate of carbon dioxide was determined to be 100%.
By this step, in the DMSO suspension, the white solid was finally disappeared, and the DMSO solution was regenerated.

[Example 25]
<< Manufacture of carbon dioxide absorption / release agent >>
The carbon dioxide absorbing / releasing agent was produced in the same manner as in Example 18.

As is clear from FIG. 31, the concentration of carbon dioxide in the exhaust gas showed the same tendency as in the case of Example 18. The concentration of carbon dioxide in the exhaust gas eventually became about 1% by volume, and carbon dioxide was not removed. The amount of carbon dioxide absorbed by the DMSO solution (carbon dioxide absorbing / releasing agent) was calculated to be 1.20 mmol from the start of the inflow of carbon dioxide to about 240 minutes later. It was determined that the corrected absorption rate of carbon dioxide when the amino group was limited, which was calculated using this absorption amount and the amount of isophorone diamine used, was 100%. The absorption rate of carbon dioxide was 60% when the amino group was not limited and the correction was not performed.
By this step, the DMSO solution became a DMSO suspension.

<Carbon dioxide release>
Next, steps (B) (step (B1)) were performed in the same manner as in Example 18 except that the temperature of the heat treatment was changed to 100 ° C. instead of 60 ° C., and carbon dioxide in the exhaust gas was used. The concentration of carbon dioxide was measured. The results are shown in FIG.

As is clear from FIG. 32, about 10 minutes after the start of the heat treatment, the concentration of the carbon dioxide becomes maximum, and then the concentration of the carbon dioxide decreases sharply, and about 19 minutes after the start of the heat treatment. The concentration of carbon dioxide was almost 0% by volume. The concentration of carbon dioxide at the maximum exceeded the upper limit of detection, 6% by volume. From these results, in this example, carbon dioxide was released more rapidly from the DMSO suspension (carbon dioxide absorbing / releasing agent) than in the case of Example 18 (when the temperature of the heat treatment was 60 ° C.). I was able to confirm that.
By this step, in the DMSO suspension, the white solid was finally disappeared, and the DMSO solution was regenerated.

[Example 26]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing isophorone diamine and dimethyl sulfoxide (DMSO), a DMSO solution of isophorone diamine having a concentration of isophorone diamine of 0.07 M was prepared, and this was used as a carbon dioxide absorption / release agent.

<< Absorption of carbon dioxide >>
A DMSO solution (15 mL) of the isophorone diamine obtained above was placed in a test tube, and the same apparatus as in Example 1 was assembled.
Then, using the above device at room temperature, a mixed gas containing 1% by volume of carbon dioxide and 99% by volume of nitrogen was added to the test tube at a flow rate of 20 mL / min (0.54 mmol / h of carbon dioxide). From the outside, the gas inside the test tube is flowed into the DMSO solution inside the test tube for bubbling (steps (a) and (a1)), and the gas inside the test tube is discharged from the gas outlet of the three-way cock to the test tube. It was discharged to the outside. Then, the amount of carbon dioxide absorbed by the DMSO solution (that is, the carbon dioxide absorption / release agent) was calculated by the same method as in the case of Example 1, and the carbon dioxide removal efficiency (absorption efficiency) was calculated. The results are shown in FIG.

As time passed from the start of the inflow of carbon dioxide, a reaction product of isophorone diamine and carbon dioxide was generated as a white solid in the DMSO solution. As described above, the DMSO solution became a DMSO suspension.
As is clear from FIG. 33, the carbon dioxide removal efficiency gradually decreases immediately after the start of the inflow of carbon dioxide, and the decrease in the carbon dioxide removal efficiency becomes larger about 120 minutes after the start of the inflow of carbon dioxide. Approximately 200 minutes after the start of carbon inflow, carbon dioxide was no longer removed.
It was confirmed by analysis by ¹³ C-NMR that the obtained reaction product was (3-aminomethyl-3,5,5-trimethylcyclohexyl) carbamic acid.

[Example 27]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing isophorone diamine and dimethyl sulfoxide (DMSO), a DMSO solution of isophorone diamine having a concentration of isophorone diamine of 0.1 M was prepared, and this was used as a carbon dioxide absorption / release agent.

<< Absorption of carbon dioxide >>
Step (a) (step (a1)) was performed in the same manner as in Example 26 except that the carbon dioxide absorption / release agent obtained above was used, and the DMSO solution (that is, the carbon dioxide absorption / release agent) was used. ) Was calculated, and the carbon dioxide removal efficiency (absorption efficiency) was calculated. The results are shown in FIG.

As time passed from the start of the inflow of carbon dioxide, a reaction product of isophorone diamine and carbon dioxide was generated as a white solid in the DMSO solution. As described above, the DMSO solution became a DMSO suspension.
As is clear from FIG. 33, the carbon dioxide removal efficiency gradually decreases immediately after the start of the inflow of carbon dioxide, and the decrease in the carbon dioxide removal efficiency becomes larger about 100 minutes after the start of the inflow of carbon dioxide. Approximately 180 minutes after the start of carbon inflow, carbon dioxide was no longer removed. However, from about 140 minutes after the start of inflow of carbon dioxide, especially from about 40 minutes to about 140 minutes, the efficiency of removing carbon dioxide was clearly higher in this example than in the case of Example 26. rice field.
It was confirmed by analysis by ¹³ C-NMR that the obtained reaction product was (3-aminomethyl-3,5,5-trimethylcyclohexyl) carbamic acid.

[Example 28]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing isophorone diamine and dimethyl sulfoxide (DMSO), a DMSO solution of isophorone diamine having a concentration of isophorone diamine of 0.2 M was prepared, and this was used as a carbon dioxide absorption / release agent.

As time passed from the start of the inflow of carbon dioxide, a reaction product of isophorone diamine and carbon dioxide was generated as a white solid in the DMSO solution. As described above, the DMSO solution became a DMSO suspension.
As is clear from FIG. 33, immediately after the start of the inflow of carbon dioxide, the carbon dioxide removal efficiency was close to 100%, and the DMSO solution absorbed carbon dioxide with high efficiency. Approximately 120 minutes after the start of inflow of carbon dioxide, a sharp decrease in carbon dioxide removal efficiency begins, and about 85 minutes after the start of inflow of carbon dioxide, the decrease in carbon dioxide removal efficiency becomes gradual and the inflow of carbon dioxide starts. After about 175 minutes, carbon dioxide was no longer removed. From about 135 minutes after the start of inflow of carbon dioxide, especially from about 40 minutes to about 135 minutes, the carbon dioxide removal efficiency of this example is clearer than that of Examples 26 and 27. It was expensive.
It was confirmed by analysis by ¹³ C-NMR that the obtained reaction product was (3-aminomethyl-3,5,5-trimethylcyclohexyl) carbamic acid.

[Example 29]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing cyclohexylamine and dimethyl sulfoxide (DMSO), a DMSO solution of cyclohexylamine having a concentration of cyclohexylamine of 0.07 M was prepared, and this was used as a carbon dioxide absorption / release agent.

<< Absorption of carbon dioxide >>
The DMSO solution (15 mL) of cyclohexylamine obtained above was placed in a test tube, and the same apparatus as in Example 1 was assembled.
Then, using the above device at room temperature, a mixed gas containing 1% by volume of carbon dioxide and 99% by volume of nitrogen was added to the test tube at a flow rate of 20 mL / min (0.54 mmol / h of carbon dioxide). From the outside, the gas inside the test tube was flowed into the DMSO solution inside the test tube for bubbling (step (a)), and the gas inside the test tube was discharged to the outside of the test tube from the gas discharge port of the three-way cock. .. Then, the amount of carbon dioxide absorbed by the DMSO solution (that is, the carbon dioxide absorption / release agent) was calculated by the same method as in the case of Example 1, and the carbon dioxide removal efficiency (absorption efficiency) was calculated. The results are shown in FIG.

Unlike the case of Example 26, no solid substance was formed in the DMSO solution even after a lapse of time from the start of the inflow of carbon dioxide.
As is clear from FIG. 34, the efficiency of removing carbon dioxide decreased with the passage of time immediately after the start of the inflow of carbon dioxide, and the carbon dioxide was not removed about 150 minutes after the start of the inflow of carbon dioxide.
It was confirmed by analysis by ¹³ C-NMR that the obtained reaction product was N-cyclohexylcarbamic acid.

[Example 30]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing cyclohexylamine and dimethyl sulfoxide (DMSO), a DMSO solution of cyclohexylamine having a concentration of cyclohexylamine of 0.1 M was prepared, and this was used as a carbon dioxide absorption / release agent.

<< Absorption of carbon dioxide >>
Except for the fact that the carbon dioxide absorbing / releasing agent obtained above was used, the step (a) was carried out in the same manner as in Example 29, and the carbon dioxide was absorbed by the DMSO solution (that is, the carbon dioxide absorbing / releasing agent). The amount was calculated, and the carbon dioxide removal efficiency (absorption efficiency) was calculated. The results are shown in FIG.

As in the case of Example 29, no solid substance was formed in the DMSO solution even after a lapse of time from the start of the inflow of carbon dioxide.
As is clear from FIG. 34, the efficiency of removing carbon dioxide decreased with the passage of time immediately after the start of the inflow of carbon dioxide, and the carbon dioxide was not removed about 170 minutes after the start of the inflow of carbon dioxide. In this example, after the start of the inflow of carbon dioxide, the carbon dioxide removal efficiency was about the same as in the case of Example 29.
It was confirmed by analysis by ¹³ C-NMR that the obtained reaction product was N-cyclohexylcarbamic acid.

[Example 31]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing cyclohexylamine and dimethyl sulfoxide (DMSO), a DMSO solution of cyclohexylamine having a cyclohexylamine concentration of 0.2 M was prepared, and this was used as a carbon dioxide absorption / release agent.

As in the case of Example 29, no solid substance was formed in the DMSO solution even after a lapse of time from the start of the inflow of carbon dioxide.
As is clear from FIG. 34, the efficiency of removing carbon dioxide decreased with the passage of time immediately after the start of the inflow of carbon dioxide, and the carbon dioxide was not removed about 170 minutes after the start of the inflow of carbon dioxide. In this example, after the start of the inflow of carbon dioxide, the carbon dioxide removal efficiency was about the same as in the cases of Examples 29 to 30.
It was confirmed by analysis by ¹³ C-NMR that the obtained reaction product was N-cyclohexylcarbamic acid.

[Example 32]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing cyclohexylamine and dimethyl sulfoxide (DMSO), a DMSO solution of cyclohexylamine having a concentration of cyclohexylamine of 1 M was prepared, and this was used as a carbon dioxide absorption / release agent.

<< Absorption of carbon dioxide >>
Step (a) (step (a1)) was performed in the same manner as in Example 29, except that the carbon dioxide absorption / release agent obtained above was used, and the DMSO solution (that is, the carbon dioxide absorption / release agent) was used. ) Was calculated, and the carbon dioxide removal efficiency (absorption efficiency) was calculated. The results are shown in FIG.

In this example, unlike the cases of Examples 29 to 31, a reaction product of cyclohexylamine and carbon dioxide is generated as a white solid in the DMSO solution as time elapses from the start of inflow of carbon dioxide. rice field. As described above, the DMSO solution became a DMSO suspension.
As is clear from FIG. 34, the carbon dioxide removal efficiency gradually decreases immediately after the start of the inflow of carbon dioxide, and the decrease in the carbon dioxide removal efficiency becomes larger about 45 minutes after the start of the inflow of carbon dioxide. Approximately 100 minutes after the start of carbon inflow, carbon dioxide was no longer removed. However, from the start of the inflow of carbon dioxide to about 50 minutes later, the efficiency of removing carbon dioxide was clearly higher in this example than in the cases of Examples 29 to 31. In this example, the consumption rate of the compound (1) at the time of removing carbon dioxide was faster than that in the cases of Examples 29 to 31.
It was confirmed by analysis by ¹³ C-NMR that the obtained reaction product was N-cyclohexylcarbamic acid.

From the results of Examples 29 to 32, in the step (a), the concentration of the compound (1) in the liquid carbon dioxide absorption / release agent is increased to absorb and release the reaction product of the compound (1) and carbon dioxide. It was confirmed that the carbon dioxide removal efficiency can be significantly improved by precipitating in the agent.

[Example 33]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing cyclohexylamine and dimethyl sulfoxide (DMSO), a DMSO solution of cyclohexylamine having a cyclohexylamine concentration of 0.4 M was prepared, and this was used as a carbon dioxide absorption / release agent.

<< Absorption of carbon dioxide >>
Step (a) (step (a1)) was performed in the same manner as in Example 29, except that the carbon dioxide absorption / release agent obtained above was used, and the DMSO solution (that is, the carbon dioxide absorption / release agent) was used. ) Was calculated, and the carbon dioxide removal efficiency (absorption efficiency) was calculated. The results are shown in FIG. 35 together with the results of Examples 28 and 31.

In this example, unlike the case of Example 31, a reaction product of cyclohexylamine and carbon dioxide was generated as a white solid in the DMSO solution as time passed from the start of inflow of carbon dioxide. As described above, the DMSO solution became a DMSO suspension.
As is clear from FIG. 35, the carbon dioxide removal efficiency gradually decreases immediately after the start of the inflow of carbon dioxide, and the decrease in the carbon dioxide removal efficiency becomes larger about 100 minutes after the start of the inflow of carbon dioxide. Approximately 220 minutes after the start of carbon inflow, carbon dioxide was no longer removed. However, after the start of the inflow of carbon dioxide, especially after about 20 minutes, the efficiency of removing carbon dioxide was clearly higher in this example than in the case of Example 31.
It was confirmed by analysis by ¹³ C-NMR that the obtained reaction product was N-cyclohexylcarbamic acid.

From the results of Examples 31 and 33, in step (a), the concentration of compound (1) in the liquid carbon dioxide sink was increased, and the reaction product of compound (1) and carbon dioxide was converted to carbon dioxide. It was confirmed that the efficiency of carbon dioxide removal can be improved by precipitating in the absorption / release agent.

[Example 34]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing 1,4-cyclohexanediamine and dimethyl sulfoxide (DMSO), a DMSO solution of 1,4-cyclohexanediamine having a concentration of 1,4-cyclohexanediamine of 0.2 M was prepared, and this was used as carbon dioxide. It was used as an absorption / release agent.

<< Absorption of carbon dioxide >>
Step (a) (step (a1)) was performed in the same manner as in Example 26 except that the carbon dioxide absorption / release agent obtained above was used, and the DMSO solution (that is, the carbon dioxide absorption / release agent) was used. ) Was calculated, and the carbon dioxide removal efficiency (absorption efficiency) was calculated. The results are shown in FIG. 36 together with the results of Example 28.

As time passed from the start of the inflow of carbon dioxide, a reaction product of 1,4-cyclohexanediamine and carbon dioxide was generated as a white solid in the DMSO solution. As described above, the DMSO solution became a DMSO suspension.
As is clear from FIG. 36, in this example, unlike the case of Example 28, the carbon dioxide removal efficiency gradually decreases immediately after the start of the inflow of carbon dioxide, and about 120 minutes from the start of the inflow of carbon dioxide. Later, the decrease in carbon dioxide removal efficiency became larger, and carbon dioxide was not removed 200 minutes after the start of carbon dioxide inflow.
It was confirmed by analysis by ¹³ C-NMR that the obtained reaction product was mainly (4-aminocyclohexyl) carbamic acid.

[Example 35]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing 1,2-cyclohexanediamine and dimethyl sulfoxide (DMSO), a DMSO solution of 1,2-cyclohexanediamine having a concentration of 1,2-cyclohexanediamine of 0.2 M was prepared, and this was used as carbon dioxide. It was used as an absorption / release agent.

As time passed from the start of the inflow of carbon dioxide, a reaction product of 1,2-cyclohexanediamine and carbon dioxide was generated as a white solid in the DMSO solution. As described above, the DMSO solution became a DMSO suspension.
As is clear from FIG. 36, in this example, as in the case of Example 34, the carbon dioxide removal efficiency gradually decreases immediately after the start of the inflow of carbon dioxide, and about 100 minutes from the start of the inflow of carbon dioxide. Later, the decrease in carbon dioxide removal efficiency became larger, and carbon dioxide was not removed 200 minutes after the start of carbon dioxide inflow.
It was confirmed by analysis by ¹³ C-NMR that the obtained reaction product was mainly (2-aminocyclohexyl) carbamic acid.

From the comparison between Examples 33 and Examples 35 to 36, in the step (a), the reaction between the compound (1) and carbon dioxide when the number of amino groups in one molecule of the compound (1) is large. It was confirmed that the substance was easily deposited.

[Example 36]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing isophorone diamine and water, an aqueous solution of isophorone diamine having a concentration of isophorone diamine of 0.2 M was prepared, and this was used as a carbon dioxide absorption / release agent.

<< Absorption of carbon dioxide >>
Step (a) (step (a1)) is performed in the same manner as in Example 26 except that the carbon dioxide absorption / release agent obtained above is used, and the aqueous solution (that is, the carbon dioxide absorption / release agent) is performed. The amount of carbon dioxide absorbed was calculated, and the carbon dioxide removal efficiency (absorption efficiency) was calculated. The results are shown in FIG. 37 together with the results of Example 28.

As time passed from the start of the inflow of carbon dioxide, a reaction product of isophorone diamine and carbon dioxide was generated as a white solid in the aqueous solution. As described above, the aqueous solution became an aqueous suspension.
As is clear from FIG. 37, in this example, as in the case of Example 28, the carbon dioxide removal efficiency is close to 100% immediately after the start of the inflow of carbon dioxide, and the aqueous solution is highly efficient in producing carbon dioxide. I was absorbing. Approximately 140 minutes after the start of the inflow of carbon dioxide, the efficiency of removing carbon dioxide began to drop sharply, and about 250 minutes after the start of the inflow of carbon dioxide, carbon dioxide was not removed. When the amount of carbon dioxide absorbed by the aqueous solution (carbon dioxide absorbing / releasing agent) up to this point was calculated, it was 1.3 mol per 1 mol of isophorone diamine, which was the target reactant ((3-aminomethyl-3). , 5,5-trimethylcyclohexyl) carbamic acid) was obtained, and a part of dicarbamic acid produced by reacting with carbon dioxide with two amino groups in one molecule of isophoronediamine was also obtained. ..

[Example 37]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing isophorone diamine and DMF, a DMF solution of isophorone diamine having a concentration of isophorone diamine of 0.2 M was prepared, and this was used as a carbon dioxide absorption / release agent.

<< Absorption of carbon dioxide >>
Step (a) (step (a1)) was performed in the same manner as in Example 26 except that the carbon dioxide absorption / release agent obtained above was used, and the DMF solution (that is, the carbon dioxide absorption / release agent) was used. ) Was calculated, and the carbon dioxide removal efficiency (absorption efficiency) was calculated. The results are shown in FIG. 37.

As time passed from the start of the inflow of carbon dioxide, a reaction product of isophorone diamine and carbon dioxide was generated as a white solid in the DMF solution. As described above, the DMF solution became a DMF suspension.
As is clear from FIG. 37, in this example, unlike the cases of Examples 28 and 36, the carbon dioxide removal efficiency gradually decreases immediately after the start of the inflow of carbon dioxide, and about from the start of the inflow of carbon dioxide. After 150 minutes, the decrease in carbon dioxide removal efficiency became larger, and about 210 minutes after the start of the inflow of carbon dioxide, carbon dioxide was not removed.
It was confirmed by analysis by ¹³ C-NMR that the obtained reaction product was (3-aminomethyl-3,5,5-trimethylcyclohexyl) carbamic acid.

[Example 38]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing isophorone diamine and toluene, a toluene solution of isophorone diamine having a concentration of isophorone diamine of 0.2 M was prepared, and this was used as a carbon dioxide absorption / release agent.

<< Absorption of carbon dioxide >>
Step (a) (step (a1)) was performed in the same manner as in Example 26 except that the carbon dioxide absorption / release agent obtained above was used, and the toluene solution (that is, the carbon dioxide absorption / release agent) was used. ) Was calculated, and the carbon dioxide removal efficiency (absorption efficiency) was calculated. The results are shown in FIG. 37.

As time passed from the start of the inflow of carbon dioxide, a reaction product of isophorone diamine and carbon dioxide was generated as a white solid in the toluene solution. As described above, the toluene solution became a toluene suspension.
As is clear from FIG. 37, in this example, as in the case of Example 37, the carbon dioxide removal efficiency gradually decreases immediately after the start of the inflow of carbon dioxide, and about 100 minutes from the start of the inflow of carbon dioxide. Later, the decrease in carbon dioxide removal efficiency became larger, and about 200 minutes after the start of the inflow of carbon dioxide, carbon dioxide was not removed.
It was confirmed by analysis by ¹³ C-NMR that the obtained reaction product was (3-aminomethyl-3,5,5-trimethylcyclohexyl) carbamic acid.

[Example 39]
<< Manufacture of carbon dioxide absorption / release agent >>
By mixing isophorone diamine and methanol, a methanol solution of isophorone diamine having a concentration of isophorone diamine of 0.2 M was prepared, and this was used as a carbon dioxide absorption / release agent.

<< Absorption of carbon dioxide >>
Step (a) (step (a1)) was performed in the same manner as in Example 26 except that the carbon dioxide absorption / release agent obtained above was used, and the methanol solution (that is, the carbon dioxide absorption / release agent) was used. ) Was calculated, and the carbon dioxide removal efficiency (absorption efficiency) was calculated. The results are shown in FIG. 37.

After a while from the start of the inflow of carbon dioxide, a reaction product of isophorone diamine and carbon dioxide was formed as a white solid in the methanol solution. As described above, the methanol solution became a methanol suspension.
As is clear from FIG. 37, in this example, unlike the cases of Examples 28 and 36 to 38, the carbon dioxide removal efficiency is almost consistently lower than that of these Examples immediately after the start of the inflow of carbon dioxide. About 160 minutes after the start of the inflow of carbon dioxide, carbon dioxide was not removed.

In the steps (a) of Examples 28 and 36 to 39, the time from the start of inflow of carbon dioxide to the start of precipitation of the reaction product (white solid substance) of isophorone diamine and carbon dioxide is 35 minutes (Example). 28), 75 minutes (Example 36), 20 minutes (Example 37), 10 minutes (Example 38), and 130 minutes (Example 39). That is, it was confirmed that the carbon dioxide removal efficiency can be adjusted by adjusting the type of the solvent in the carbon dioxide absorbing / releasing agent.

The present invention can be used in all fields of carbon dioxide fixation and carbon dioxide recovery.

Claims

It ’s a method of recovering carbon dioxide.
The method for recovering carbon dioxide is the following general formula (1).

(In the formula, m is 0 or 1; R 1 and R 2 are independently an alkyl group, an alkoxy group, a carboxy group, an alkyloxycarbonyl group, a formyl group, an alkylcarbonyl group, an alkylthio group and a sulfo group, respectively. It is an alkyloxysulfonyl group, a nitro group, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group may have a substituent; p 1 and p 2 are independently 1 or 2, respectively. Yes; if m is 0, q 1 is an integer from 0 to 11, where p 1 + q 1 is less than or equal to 12, and if m is 1, q 1 is an integer from 0 to 10. However, when p 1 + q 1 is 11 or less, q 2 is an integer of 0 to 10, and q 1 is an integer of 2 or more, two or more R 1s may be the same or different from each other. Well, when q 2 is an integer of 2 or more, two or more R 2s may be the same or different from each other, q 1 is an integer of 2 or more, and two or more R 1s are. In the case of the alkyl group which may have a substituent, the two or more R 1s may be bonded to each other to form a ring, and q 2 is an integer of 2 or more. Moreover, when two or more R 2s are the alkyl groups which may have a substituent, the two or more R 2s may be bonded to each other to form a ring.)
By allowing a liquid carbon dioxide absorbing / releasing agent containing the compound represented by the above to absorb carbon dioxide, the reaction product of the compound represented by the general formula (1) and the carbon dioxide is formed into the liquid. Step (A1) of precipitating in the carbon dioxide absorption / release agent of
Step (B1) of absorbing the carbon dioxide and releasing the carbon dioxide from the liquid carbon dioxide absorbing / releasing agent by heat-treating the liquid carbon dioxide absorbing / releasing agent after the reactant is precipitated (B1). A method for recovering carbon dioxide (where m is 0, p 1 is 2, and two amino groups with p 1 are arranged in meta positions with each other. Excluding carbon dioxide recovery methods).
The method for recovering carbon dioxide according to claim 1, wherein the step (B1) is performed in the coexistence of a base catalyst.
It ’s a method of recovering carbon dioxide.
The method for recovering carbon dioxide is the following general formula (1).

(In the formula, m is 0 or 1; R 1 and R 2 are independently an alkyl group, an alkoxy group, a carboxy group, an alkyloxycarbonyl group, a formyl group, an alkylcarbonyl group, an alkylthio group and a sulfo group, respectively. It is an alkyloxysulfonyl group, a nitro group, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group may have a substituent; p 1 and p 2 are independently 1 or 2, respectively. Yes; if m is 0, q 1 is an integer from 0 to 11, where p 1 + q 1 is 12 or less, and if m is 1, q 1 is an integer from 0 to 10. However, when p 1 + q 1 is 11 or less, q 2 is an integer of 0 to 10, and q 1 is an integer of 2 or more, two or more R 1s may be the same or different from each other. Well, when q 2 is an integer of 2 or more, two or more R 2s may be the same or different from each other, q 1 is an integer of 2 or more, and two or more R 1s are. In the case of the alkyl group which may have a substituent, the two or more R 1s may be bonded to each other to form a ring, and q 2 is an integer of 2 or more. Moreover, when two or more R 2s are the alkyl groups which may have a substituent, the two or more R 2s may be bonded to each other to form a ring.)
The step (A) of allowing a carbon dioxide absorbing / releasing agent containing the compound represented by the above to absorb carbon dioxide, and
It comprises a step (B2) of releasing the carbon dioxide from the carbon dioxide absorbing / releasing agent by heat-treating the carbon dioxide absorbing / releasing agent after absorbing the carbon dioxide in the coexistence of a base catalyst. Carbon dioxide recovery method (However, carbon dioxide recovery method when m is 0, p 1 is 2, and two amino groups with p 1 are arranged at the meta positions of each other. except for).
The compound represented by the general formula (1) is the following general formula (11A), (12A) or (11B).

(In the formula, R 11 , R 12 , R 13 and R 21 are independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a carboxy group and an alkyloxy having 2 to 11 carbon atoms, respectively. Carbonyl group, formyl group, alkylcarbonyl group with 2 to 11 carbon atoms, alkylthio group with 1 to 10 carbon atoms, sulfo group, alkyloxysulfonyl group with 1 to 10 carbon atoms, nitro group, hydroxyl group, thiol group, cyano group or It is a halogen atom and the alkyl group may have an amino group as the substituent; q 11 and q 12 are independently integers of 0 to 6 and q 11 is an integer of 2 or more. In some cases, the two or more R 11s may be the same or different from each other, and if q 12 is an integer of two or more, the two or more R 12s may be the same or different from each other. When q 11 is an integer of 2 or more and 2 or more R 11s are the alkyl groups which may have an amino group as the substituent, the two or more R 11s are mutual. The alkyl group may be bonded to to form a ring, q 12 may be an integer of 2 or more, and R 12 of 2 or more may have an amino group as the substituent. In some cases, the two or more R 12s may be coupled to each other to form a ring; q 13 and q 21 are independently integers from 0 to 4, and q 13 is 2 or more. If the integers of, the two or more R 13s may be the same or different from each other, and if q 21 is an integer of two or more, the two or more R 21s may be the same or different from each other. Also, when q 13 is an integer of 2 or more and 2 or more R 13 are the alkyl groups which may have an amino group as the substituent, the two or more Rs may be used. 13 may be bonded to each other to form a ring, q 21 may be an integer of 2 or more, and 2 or more R 21 may have an amino group as the substituent. When it is a group, the two or more R 21s may be bonded to each other to form a ring.)
The method for recovering carbon dioxide according to any one of claims 1 to 3, which is a compound represented by (however, in the above general formula (12A), it is directly bonded to the carbon atom constituting the cyclohexane ring skeleton. Except for the method of recovering carbon dioxide when the two amino groups are located at the meta positions of each other).
The compound represented by the general formula (11A), (12A) or (11B) is the following general formula (111A), (121A), (122A) or (111B).

(In the formula, R 111 , R 121 , R 122 , R 131 and R 211 are independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms and an alkyloxy group having 2 to 6 carbon atoms, respectively. It is a carbonyl group, a formyl group, an alkylcarbonyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 5 carbon atoms, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group has an amino group as the substituent. Independently, q 111 , q 121 and q 122 are integers of 0 to 4, and when q 111 is an integer of 2 or more, the two or more R 111s are the same as each other. However, if q 121 is an integer of 2 or more, the two or more R 121s may be the same or different from each other, and if q 122 is an integer of 2 or more, 2 or more. The number of R 122s may be the same or different from each other, q 111 may be an integer of 2 or more, and two or more R 111s may have an amino group as the substituent. When is, the two or more R 111s may be coupled to each other to form a ring, q 121 is an integer of 2 or more, and two or more R 121s are the substituents. In the case of the alkyl group which may have an amino group, the two or more R 121s may be bonded to each other to form a ring, and q 122 is an integer of 2 or more. In addition, when the two or more R 122s are the alkyl groups which may have an amino group as the substituent, the two or more R 122s are bonded to each other to form a ring. May; q 131 and q 211 are independently integers of 0 to 2, and if q 131 is 2, the two R 131s may be the same or different from each other, q 211 . When is 2, the two R 211s may be the same or different from each other, even if q 131 is 2 and the two R 131s have an amino group as the substituent. In the case of a good alkyl group, the two R 131s may be bonded to each other to form a ring, q 211 is 2, and the two R 211s are the substituents. The compound represented by the above-mentioned alkyl group which may have an amino group, the two R 211s may be bonded to each other to form a ring). 4. The method for recovering carbon dioxide according to 4.
The method for recovering carbon dioxide according to any one of claims 1 to 5, wherein the steps (A1) and (B1), or the steps (A) and (B2) are repeated two or more times.
It ’s a method of absorbing carbon dioxide.
The method for absorbing carbon dioxide is the following general formula (1).

(In the formula, m is 0 or 1; R 1 and R 2 are independently an alkyl group, an alkoxy group, a carboxy group, an alkyloxycarbonyl group, a formyl group, an alkylcarbonyl group, an alkylthio group and a sulfo group, respectively. It is an alkyloxysulfonyl group, a nitro group, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group may have a substituent; p 1 and p 2 are independently 1 or 2, respectively. Yes; if m is 0, q 1 is an integer from 0 to 11, where p 1 + q 1 is 12 or less, and if m is 1, q 1 is an integer from 0 to 10. However, when p 1 + q 1 is 11 or less, q 2 is an integer of 0 to 10, and q 1 is an integer of 2 or more, two or more R 1s may be the same or different from each other. Well, when q 2 is an integer of 2 or more, two or more R 2s may be the same or different from each other, q 1 is an integer of 2 or more, and two or more R 1s are. In the case of the alkyl group which may have a substituent, the two or more R 1s may be bonded to each other to form a ring, and q 2 is an integer of 2 or more. Moreover, when two or more R 2s are the alkyl groups which may have a substituent, the two or more R 2s may be bonded to each other to form a ring.)
By allowing a liquid carbon dioxide absorbing / releasing agent containing the compound represented by the above to absorb carbon dioxide, the reaction product of the compound represented by the general formula (1) and the carbon dioxide is formed into the liquid. A method for absorbing carbon dioxide having a step (a1) of precipitating in the carbon dioxide absorbing / releasing agent (where m is 0, p 1 is 2 and p 1 is attached to the two amino groups. Except for the method of absorbing carbon dioxide when they are placed in meta positions with each other).
It ’s a method of releasing carbon dioxide.
The method for releasing carbon dioxide is the following general formula (1).

(In the formula, m is 0 or 1; R 1 and R 2 are independently an alkyl group, an alkoxy group, a carboxy group, an alkyloxycarbonyl group, a formyl group, an alkylcarbonyl group, an alkylthio group and a sulfo group, respectively. It is an alkyloxysulfonyl group, a nitro group, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group may have a substituent; p 1 and p 2 are independently 1 or 2, respectively. Yes; if m is 0, q 1 is an integer from 0 to 11, where p 1 + q 1 is 12 or less, and if m is 1, q 1 is an integer from 0 to 10. However, when p 1 + q 1 is 11 or less, q 2 is an integer of 0 to 10, and q 1 is an integer of 2 or more, two or more R 1s may be the same or different from each other. Well, when q 2 is an integer of 2 or more, two or more R 2s may be the same or different from each other, q 1 is an integer of 2 or more, and two or more R 1s are. In the case of the alkyl group which may have a substituent, the two or more R 1s may be bonded to each other to form a ring, and q 2 is an integer of 2 or more. Moreover, when two or more R 2s are the alkyl groups which may have a substituent, the two or more R 2s may be bonded to each other to form a ring.)
By heat-treating a liquid carbon dioxide-releasing agent containing a reaction product of a compound represented by A method for releasing carbon dioxide, which comprises a step (b1) of releasing carbon dioxide.
It ’s a method of releasing carbon dioxide.
The method for releasing carbon dioxide is the following general formula (1).

(In the formula, m is 0 or 1; R 1 and R 2 are independently an alkyl group, an alkoxy group, a carboxy group, an alkyloxycarbonyl group, a formyl group, an alkylcarbonyl group, an alkylthio group and a sulfo group, respectively. It is an alkyloxysulfonyl group, a nitro group, a hydroxyl group, a thiol group, a cyano group or a halogen atom, and the alkyl group may have a substituent; p 1 and p 2 are independently 1 or 2, respectively. Yes; if m is 0, q 1 is an integer from 0 to 11, where p 1 + q 1 is 12 or less, and if m is 1, q 1 is an integer from 0 to 10. However, when p 1 + q 1 is 11 or less, q 2 is an integer of 0 to 10, and q 1 is an integer of 2 or more, two or more R 1s may be the same or different from each other. Well, when q 2 is an integer of 2 or more, two or more R 2s may be the same or different from each other, q 1 is an integer of 2 or more, and two or more R 1s are. In the case of the alkyl group which may have a substituent, the two or more R 1s may be bonded to each other to form a ring, and q 2 is an integer of 2 or more. Moreover, when two or more R 2s are the alkyl groups which may have a substituent, the two or more R 2s may be bonded to each other to form a ring.)
A step of releasing the carbon dioxide from the carbon dioxide releasing agent by heat-treating the carbon dioxide releasing agent containing a reaction product of the compound represented by (b2) and carbon dioxide in the coexistence of a base catalyst (b2). ), A method of releasing carbon dioxide.