WO2023182173A1

WO2023182173A1 - Carbon dioxide isolator, method for isolating or recovering carbon dioxide, and method for producing carbon dioxide isolator

Info

Publication number: WO2023182173A1
Application number: PCT/JP2023/010423
Authority: WO
Inventors: ティクェンブ; フィローズアラムチョウドリー; 克則余語; 利紀村岡
Original assignee: 公益財団法人地球環境産業技術研究機構
Priority date: 2022-03-25
Filing date: 2023-03-16
Publication date: 2023-09-28
Also published as: JP2023143289A

Abstract

This carbon dioxide isolator includes polyamine. The polyamine includes a propyl polyamine component having a hydrogen atom or a functional group that bonds to a nitrogen atom and having three or more propyl groups which bond to respective nitrogen atoms within a molecule. At least one of the propyl groups is a hydroxypropyl group having a hydroxy group, and the hydroxypropyl group bonds to a nitrogen atom that constitutes a tertiary amine. The hydroxy group bonds to a secondary carbon atom. At least two of the propyl groups are unsubstituted isopropyl groups which do not have a hydroxy group.

Description

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

The present invention relates to a carbon dioxide separation material, a method for separating or recovering carbon dioxide, and a method for manufacturing a carbon dioxide separation material.

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

Patent Document 2 proposes a method for preparing alkylalkanolamines that involves the reaction of a carbonyl compound and a hydroxyalkylamine in the presence of hydrogen and a catalyst.

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

US Pat. No. 5,001,202 proposes a renewable solid sorbent for adsorbing carbon dioxide from gas mixtures containing air, comprising a modified polyamine and a solid support. Modified polyamines are reaction products of amines and epoxides.

International Publication No. 2014/208712 Special Publication No. 2012-530771 (Patent No. 5678050) US Patent No. 10654025 US Published Patent No. 2019/0168185

As mentioned above, multiple materials for adsorbing carbon dioxide have been developed, but there is a need to reduce manufacturing costs and further improve performance. For example, it is desired to increase the resistance to oxidative deterioration of a carbon dioxide separation material in which a polyamine is supported on a support, and to suppress the decrease due to volatilization of the polyamine. This is because the carbon dioxide separation material is expected to be used in an oxygen-containing atmosphere (particularly air) at a temperature of, for example, about 60°C.

One aspect of the present invention includes a polyamine, the polyamine having a hydrogen atom or a functional group bonded to a nitrogen atom, and a propyl polyamine component having three or more propyl groups bonded to different nitrogen atoms in the molecule. at least one of the propyl groups is a hydroxypropyl group having a hydroxy group, the hydroxypropyl group is bonded to a nitrogen atom constituting a tertiary amine, and the hydroxy group is bonded to a secondary carbon atom. and the two or more propyl groups are unsubstituted isopropyl groups having no hydroxy group.

Another aspect of the present invention includes a first step of bringing a gas to be treated into contact with the carbon dioxide separation material to absorb carbon dioxide, and a step of bringing carbon dioxide from the carbon dioxide separation material that has absorbed carbon dioxide in the first step. A method for separating or recovering carbon dioxide, the second step comprising: (A) placing the carbon dioxide separation material under reduced pressure conditions and desorbing carbon dioxide; (pressure swing method), (B) a step of contacting the carbon dioxide separation material with at least one of water vapor and an inert gas (preferably a gas not containing carbon dioxide) and desorbing carbon dioxide, and (C) the step of desorbing the carbon dioxide. The present invention relates to a method for separating or recovering carbon dioxide, which includes any one or more of the steps of heating a carbon separation material and desorbing carbon dioxide (temperature swing method).

Yet another aspect of the present invention includes the steps of: preparing a polyamine; and contacting the polyamine with a support to obtain a polyamine carrier comprising the polyamine and the support supporting the polyamine. The polyamine includes a propyl polyamine component having a hydrogen atom or a functional group bonded to a nitrogen atom and three or more propyl groups bonded to different nitrogen atoms in the molecule, and at least one of the propyl The group is a hydroxypropyl group having a hydroxy group, the hydroxypropyl group is bonded to a nitrogen atom constituting a tertiary amine, the hydroxy group is bonded to a secondary carbon atom, and two or more of the The propyl group is an unsubstituted isopropyl group having no hydroxy group, and relates to a method for producing a carbon dioxide separation material.

The polyamine according to the present disclosure allows easy control of reactants in the reaction produced, and the carbon dioxide separation material supporting this polyamine has high resistance to oxidative deterioration, suppresses reduction due to volatilization of the polyamine, and absorbs carbon dioxide. Excellent detachability. Therefore, it is possible to provide a carbon dioxide separation material with low cost and high performance. Further, by using the carbon dioxide separation material according to the present disclosure, carbon dioxide can be separated or recovered with high efficiency.

While the novel features of the invention are set forth in the appended claims, the invention is further understood by the following detailed description, taken together with the drawings, both as to structure and content, as well as other objects and features of the invention. It will be well understood.

FIG. 3 is a diagram showing adsorption/desorption behavior of carbon dioxide by fresh polyamine carriers of Examples 2 and 4 and Comparative Examples 1 and 2. FIG. 3 is a diagram showing adsorption/desorption behavior of carbon dioxide by the polyamine carriers of Examples 2 and 4 and Comparative Examples 1 and 2 after heating in air at 100° C. for 42 hours. FIG. 2 is a diagram comparing and showing adsorption/desorption behavior of carbon dioxide by the polyamine support before and after heating in air at 100° C. for 42 hours in Examples 2 and 4 and Comparative Examples 1 and 2. FIG. 3 is a diagram showing the adsorption/desorption behavior of carbon dioxide by the fresh polyamine carrier of Example 4. FIG. 3 is a diagram showing the adsorption/desorption behavior of carbon dioxide by the polyamine support after heating in air at 100° C. for 42 hours in Example 4.

Hereinafter, a carbon dioxide separation material according to an embodiment of the present invention will be described, but the carbon dioxide separation material is not limited to the following embodiments. In the following description, specific numerical values and materials may be illustrated, but other numerical values and materials may be applied as long as the effects of the present disclosure can be obtained. In this specification, the expression "numerical value A to numerical value B" includes numerical value A and numerical value B, and can be read as "more than or equal to numerical value A and less than or equal to numerical value B." In the following explanation, when lower and upper limits of numerical values related to specific physical properties or conditions are illustrated, any of the illustrated lower limits and any of the illustrated upper limits can be arbitrarily combined as long as the lower limit is not greater than the upper limit. . When a plurality of materials are exemplified, one type may be selected from them and used alone, or two or more types may be used in combination.

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

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

However, at least one propyl group is a hydroxypropyl group having a hydroxy group. The hydroxypropyl group is bonded to the nitrogen atom that constitutes the tertiary amine. In hydroxypropyl groups, the hydroxy group is attached to a secondary carbon atom. That is, the hydroxypropyl group is a 2-hydroxy-n-propyl group (-CH ₂ CH(OH)CH ₃ ). Furthermore, the two or more propyl groups are unsubstituted isopropyl groups (-CH(CH ₃ )CH ₃ ) having no hydroxy group. By introducing the unsubstituted isopropyl group, the chemical bond between N and CO ₂ becomes loose, and CO ₂ can be eliminated with less energy (for example, at low temperature). Hereinafter, such a propyl polyamine component will also be referred to as a "PO-IP-polyamine component."

Here, when simply referring to "propyl group", "propyl group" is used as a general term for both "hydroxypropyl group" having a hydroxy group and "unsubstituted propyl group (especially isopropyl group)" not having a hydroxy group. .

Hereinafter, the propyl group bonded to the nitrogen atom is also referred to as "propyl group N." The PO-IP-polyamine component contains three or more nitrogen atoms within the molecule. In the PO-IP-polyamine component, among the three or more propyl groups N in the molecule, at least one is a hydroxypropyl group, and two or more are unsubstituted isopropyl groups.

In the PO-IP-polyamine component, two or more of the three or more nitrogen atoms are each bonded to a hydrogen atom. All but one of the plurality of nitrogen atoms may each be bonded to a hydrogen atom.

A nitrogen atom that bonds with a hydrogen atom may form a secondary amino group that bonds with one hydrogen atom, or may form a primary amino group that bonds with two hydrogen atoms.

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

The polyamine component having no hydroxypropyl groups and only unsubstituted isopropyl groups may be a polyamine in which the hydroxypropyl groups of the PO-IP-polyamine component are replaced with hydrogen atoms. Hereinafter, such a propyl polyamine component will also be referred to as an "IP-polyamine component."

The PO-IP-polyamine component may have a linear structure, a branched structure, or a ring structure containing a nitrogen atom. Among them, a PO-IP-polyamine component with a linear structure is preferable because it has many CO ₂ adsorption sites.

A carbon dioxide separation material supporting a propyl polyamine component as a mixture containing a PO-IP-polyamine component and an IP-polyamine component as essential components has particularly excellent stability. Specifically, it has high resistance to oxidative deterioration, suppresses decrease in polyamine due to volatilization, and has high carbon dioxide adsorption/desorption performance.

Among the propyl polyamine components, the PO-IP-polyamine component is thought to play a major role in increasing the stability of the carbon dioxide separation material. This is because a polyamine containing a PO-IP-polyamine component and an IP-polyamine component has much higher resistance to oxidative deterioration than a polyamine containing only an IP-polyamine component, has a lower vapor pressure, and suppresses volatilization. Such carbon dioxide separation materials are suitable for long-term use.

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

The propyl group N can be bonded to a nitrogen atom constituting a secondary amine or a nitrogen atom constituting a tertiary amine, but an unsubstituted isopropyl group constitutes a secondary amine because it increases the ability to eliminate carbon dioxide. It is desirable that it be bonded to a nitrogen atom. On the other hand, the hydroxypropyl group can be bonded to the nitrogen atom constituting the tertiary amine. The hydroxypropyl group is desirably bonded to a nitrogen atom constituting the tertiary amine that is present at a location other than the terminal end of the polyamine molecule.

It is desirable that the unsubstituted isopropyl group is bonded to the end of the polyamine molecule. For example, in the case of a polyamine molecule with a linear structure, isopropyl groups may be bonded to two ends. In the case of a polyamine molecule having a branched structure, isopropyl groups may be bonded to the ends of all branched chains.

The isopropyl group bonded to the nitrogen atom constituting the secondary amine may be formed, for example, by reacting the starting material of the isopropyl group N with a primary amino group. As a starting material for the isopropyl group, for example, acetone can be used.

The hydroxypropyl group bonded to the nitrogen atom constituting the tertiary amine may be formed, for example, by a reaction between a starting material for the hydroxypropyl group and a secondary amino group. As a starting material for the hydroxypropyl group, for example, propylene oxide can be used.

The PO-IP polyamine component is, for example, a polyamine having two or more primary amino groups (-NH ₂ groups) and an -NH- group that is commercially available or obtained by a known method. After introducing an isopropyl group, it can be produced by introducing one or more hydroxypropyl groups into the secondary amino group of the polyamine.

A method for introducing an isopropyl group includes a method of reacting a -NH ₂ group with a starting material for isopropyl group N such as acetone. A method for introducing a hydroxypropyl group includes a method of reacting an -NH group with a starting material for a hydroxypropyl group such as propylene oxide. At this time, by controlling the molar ratio of polyamine and propylene oxide, a mixture of PO-IP-polyamine component and IP-polyamine can be obtained with any composition.

Specifically, a platinum oxide catalyst and anhydrous ethanol are placed in a reaction container such as a flask, and the inside of the reaction container is replaced with hydrogen. Then, hydrogen is added until the pressure reaches 100 kPa to 150 kPa, and the mixture is stirred for a predetermined period of time. Give back. Next, a polyamine having primary amino groups (-NH ₂ groups) and -NH- groups, acetone, and anhydrous ethanol are placed in a reaction vessel containing the reduced catalyst, and the inside of the reaction vessel is replaced with hydrogen. After that, hydrogen is added until the pressure becomes about 200 kPa to 350 kPa, and then the mixture is stirred while supplying hydrogen until there is no pressure drop. At this time, acetone and NH ₂ react, water is dehydrated, and the N=C bond formed is hydrogenated. After filtering the solution to remove the catalyst, ethanol is removed under reduced pressure, and the resulting colorless liquid is further dried under vacuum to obtain the IP-polyamine component. In the reaction between acetone and a primary amino group (first reaction), an unsubstituted isopropyl group is formed.

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

Acetone reacts preferentially with primary amino groups to generate nitrogen atoms that constitute secondary amines having NH groups. That is, the isopropyl group preferentially bonds to the nitrogen atom constituting the secondary amine. Therefore, it is easy to control the reactants in the first reaction, and more NH groups that adsorb and desorb carbon dioxide can be secured.

Below, a PO-IP-polyamine component (hereinafter referred to as "PO- The structure of an example of IP-TEPA (referred to as "IP-TEPA") is shown below.

PO-IP-TEPA can be obtained, for example, by the process shown in the scheme below. First, tetraethylenepentamine (TEPA) is reacted with two molecules of acetone per molecule of TEPA to add two isopropyl groups to TEPA. The isopropylated TEPA obtained at this time is also referred to as "IP-TEPA." Thereafter, one molecule of propylene oxide or less per molecule of IP-TEPA is reacted to add a hydroxypropyl group. For example, by setting the amount of propylene oxide to be reacted with 1 mol or less (for example, 0.5 mol or less) per 1 mol of IP-TEPA, PO-IP-TEPA and IP- Mixtures with TEPA can be obtained.

Like PO-IP-TEPA, the PO-IP-polyamine component consists of two isopropyl groups bonded to nitrogen atoms constituting separate secondary amines and a hydroxypropyl group bonded to nitrogen atoms constituting a tertiary amine, respectively. It may have. In the hydroxypropyl group, the hydroxyl group is bonded to a secondary carbon atom.

Hereinafter, the polyamine component IP produced by reacting 0.25 mol (or 0.5 mol) of propylene oxide per 1 mol of IP-TEPA will be referred to as "0.25PO-IP-TEPA" ("0.50PO-IP-TEPA"). ”).

Note that the vapor pressure of IP-TEPA at 60°C is 1.80 kPa, but the vapor pressure of 0.5PO-IP-TEPA is reduced to 1.47 kPa.

Next, as another example of the PO-IP-polyamine component, a polyamine component (hereinafter referred to as , referred to as "PO-IP-PEHA"). Here, too, by setting the amount of propylene oxide to be reacted with 1 mol or less of IP-PEPA to be 1 mol or less (for example, 0.5 mol or less), PO-IP-PEHA and IP that does not have a hydroxypropyl group and have only an unsubstituted isopropyl group - A mixture with PEHA can be obtained.

Next, as yet another example of the PO-IP-polyamine component, a polyamine component produced by reacting hexaethyleneheptamine (HEHA), which is a backbone amine, with 2 mol of acetone and 1 mol of propylene oxide per 1 mol of HEHA. (hereinafter referred to as "PO-IP-HEHA"). Here, too, by setting the amount of propylene oxide to be reacted with 1 mol or less of IP-HEHA to be 1 mol or less (for example, 0.5 mol or less), PO-IP-HEHA and IP that does not have a hydroxypropyl group and only have an unsubstituted isopropyl group - A mixture with HEHA can be obtained.

The structure of the PO-IP polyamine component (polyamine molecule) is preferably a structure having two or more NH groups and one or more alkylene groups interposed between nitrogen atoms. The number of NH groups contained in one polyamine molecule is preferably as large as possible from the viewpoint of increasing carbon dioxide adsorption ability, and the number of NH groups contained in one polyamine molecule is preferably 2 or more and 50 or less, and 3 or more and 30 or less. is more desirable. On the other hand, in consideration of the handleability of the polyamine molecule, the number of NH groups contained in one polyamine molecule is preferably 3 or more and 20 or less, more preferably 4 or more and 10 or less, and even more preferably 4 or more and 7 or less.

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

Specifically, the PO-IP-polyamine component has the general formula (1):

It may have a skeleton represented by However, R in formula (1) represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylamino group having 1 to 6 carbon atoms, A represents an alkylene group having 2 to 6 carbon atoms, and m represents an integer of 2 to 50, multiple R's may be the same or different, at least one R is a hydrogen atom or an alkylamino group having 1 to 6 carbon atoms, and there are multiple R's. A may be the same or different.

The PO-IP-polyamine component has, for example, general formula (2):

It can be expressed as

In formula (2), R ^A represents R ⁶ or a group: -A-NR ⁶ R ⁷ , R ^B represents R ⁸ or a group: -A-NR ⁸ R ⁹ , and A has a carbon number of 2. ~6 alkylene group, n represents an integer of 1 to 5 (for example, 2 or more), and p and q each independently represent 0 or 1.

A plurality of A's may be the same or different, and when there are a plurality of A's, ^R5 's may be the same or different.

R ¹ , R ² , R ⁷ and R ⁹ represent an unsubstituted isopropyl group, R ³ , R ⁴ , R ⁶ and R ⁸ represent a hydrogen atom, and at least one of R ⁵ (preferably two or less, More preferably, one) represents the hydroxypropyl group, and the remainder of R ⁵ represents a hydrogen atom.

Examples of the backbone amine of the polyamine include at least one selected from the group consisting of monopolymers of ethyleneimine, propyleneimine, 2-ethylaziridine, 2-propylaziridine, and 2-butylaziridine, and copolymers of at least two of these. . Here, the monopolymer and copolymer include oligomers having a polymerized number of molecules of 10 or less (for example, 7 or less). For example, from the group consisting of tetraethylenepentamine, spermine, N,N,N',N'-tetrakis(3-aminopropyl)-1,4-butanediamine, pentaethylenehexamine, hexaethyleneheptamine and triethylenetetramine. At least one selected type is mentioned. The backbone amine of a polyamine refers to a polyamine having a primary amino group that is reacted with the starting material of the isopropyl group when producing the isopropyl group bonded to the nitrogen atom constituting the secondary amine.

Specific examples of the IP-polyamine component that is a raw material for the PO-IP-polyamine component include diisopropylated tetraethylenepentamine, diisopropylated spermine, diisopropylated pentaethylenehexamine, diisopropylated hexaethyleneheptamine, diisopropylated triethylenetetramine, etc. diisopropylated polyamines; tetraisopropylated polyamines such as tetraisopropylated N,N,N',N'-tetrakis(3-aminopropyl)-1,4-butanediamine; more specifically, 1,11-bis(isopropylamino)-3,6,9-triazaundecane, N,N'-bis(3-(isopropylamino)propyl)-1,4-butanediamine, N,N,N', N'-tetrakis(3-(isopropylamino)propyl)-1,4-butanediamine, 1,14-bis(isopropylamino)-3,6,9,12-tetraazatetradecane, 1,17-bis(isopropyl) Examples include amino)-3,6,9,12,15-pentaazaheptadecane and 1,8-bis(isopropylamino)-3,6-diazaoctane.

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

The boiling point of polyamine (especially propyl polyamine component) at 760 mmHg is 320°C or higher. In this case, the carbon dioxide separation material containing polyamine can be stably used even at high temperatures (for example, about 60° C.). If the polyamine has a boiling point of 320° C. or higher at 760 mmHg, the state in which the polyamine is supported on the support can be maintained even if the boiling point is lowered by reduced pressure (for example, about 0.2 Pa). Therefore, by using these polyamines, the operating temperature can be set higher than room temperature, and carbon dioxide can be efficiently desorbed.

<Support>
The support may be any material as long as it can support a polyamine (particularly a propyl polyamine component) and can withstand the conditions for separating and recovering carbon dioxide. For example, ceramics, porous materials, carbon materials, resin materials, etc. can be used. Specifically, silica, polymethyl methacrylate, alumina, silica alumina, clay minerals, magnesia, zirconia, zeolite, zeolite related compounds, natural minerals, waste solids, activated carbon, carbon molecular sieves, etc. can be mentioned. One type of support may be used alone, or two or more types may be used in combination.

As the support, a commercially available product may be used as is, or a support synthesized by a known method may be used. Commercially available products include mesostructured silica MSU-F manufactured by Sigma-Aldrich, SIPERNAT (registered trademark) 50S manufactured by Evonik, and CARiACT (registered trademark) Q10, Q30, Q50 manufactured by Fuji Silysia Chemical Co., Ltd.

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

The specific surface area and pore volume can be measured, for example, using a constant volume method using a specific surface area/pore size distribution measuring device (ASAP2420: manufactured by Shimadzu Corporation). As a more specific gas adsorption measurement method using a specific surface area/pore size distribution measuring device, for example, a sample is pretreated by heating and evacuation, and approximately 0.1 g of the measurement sample is weighed into a sample tube. Thereafter, the sample was heated to 40° C., evacuated for 6 hours, cooled to room temperature, and the mass of the sample was measured. For measurements, set the liquid nitrogen temperature and specify the pressure range. The specific surface area, pore volume, and pore diameter can be calculated by analyzing the obtained nitrogen adsorption isotherm.

<Polyamine carrier>
A polyamine carrier is a support in which a polyamine is supported. The polyamine carrier includes a polyamine (particularly a propyl polyamine component) and a support supporting the polyamine.

The polyamine support can be produced by a manufacturing method that includes a step of preparing a polyamine and a step of obtaining the polyamine support. In the step of obtaining a polyamine carrier, a polyamine may be brought into contact with a support to produce a support supporting the polyamine.

The polyamine carrier can be produced, for example, by mixing a support into a solution of a polyamine (particularly a propyl polyamine component), stirring at room temperature, and then distilling off the solvent (for example, water, alcohol). Examples of the method for distilling off the solvent include a method of reducing the pressure while heating with an evaporator or the like.

By supporting a polyamine (particularly a propyl polyamine component) on a support, it is possible to apply it to pressure swing methods and temperature swing methods, which cannot be applied to aqueous carbon dioxide separation materials. The pressure swing method includes a step of placing a carbon dioxide separation material under reduced pressure conditions and desorbing carbon dioxide. The temperature swing method includes a step of heating a carbon dioxide separation material to desorb carbon dioxide.

<Carbon dioxide separation material>
The carbon dioxide separation material includes, for example, a polyamine carrier and a binder that granulates the polyamine carrier. That is, the carbon dioxide separation material may include a polyamine support in the form of granules using a binder. By granulating the polyamine carrier using a binder, vibration resistance and abrasion resistance can be imparted, and further, stability in water can be improved.

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

Commercially available binders include Snowtech 30 and AS-200 manufactured by Nissan Chemical Co., Ltd., Polyflon PTFE D-210C manufactured by Daikin Industries, Ltd., NEOVISCO MC RM4000 manufactured by Sansho Co., Ltd., and AQ manufactured by Toray Industries, Inc. Nylon P-70, Denacol EX-421 manufactured by Nagase ChemteX Corporation, etc. can be used.

The content of the binder in the carbon dioxide separation material is not particularly limited as long as it can be granulated, but it is preferably a small amount in order to prevent a decrease in the polyamine content.

The average particle diameter of the granules when granulated using a binder is preferably 0.1 mm to 2.0 mm from the viewpoint of reducing pressure loss when gas is supplied to the adsorbent packed bed.

The content of polyamine (especially propyl polyamine component) contained in the carbon dioxide separation material is not particularly limited, but from the viewpoint of efficiently separating and recovering carbon dioxide, it is preferably 15% by mass or more, and 20% by mass or more. Particularly preferred. The content of polyamine may be, for example, 70% by mass or less.

<Method of separating or recovering carbon dioxide>
The target of the carbon dioxide separation (recovery) method is gas containing carbon dioxide. Gases containing carbon dioxide are used, for example, in thermal power plants that use coal, heavy oil, natural gas, etc. as fuel, blast furnaces in steel plants that reduce iron oxide with coke, and steel plants that burn carbon in pig iron to make steel. Converters, boilers in various manufacturing plants, kilns in cement factories, etc., and even exhaust gas emitted from transportation equipment such as automobiles, ships, and aircraft that use gasoline, heavy oil, light oil, etc. as fuel may be used. Gas containing carbon dioxide may be emitted from human breathing or energy conversion of equipment in closed spaces such as indoor spaces such as submarine research vessels, space stations, buildings, and offices. good. Alternatively, carbon dioxide in the atmosphere may be used.

The carbon dioxide separation or recovery method according to the present disclosure is characterized by using a carbon dioxide separation material.

The carbon dioxide separation (recovery) method includes a first step in which the gas to be treated is brought into contact with a carbon dioxide separation material to absorb carbon dioxide, and a second step in which carbon dioxide is removed from the carbon dioxide separation material that has absorbed carbon dioxide in the first step. A second step of desorption is included.

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

The gas to be treated in the first step may contain water vapor. Since the carbon dioxide separation material has excellent adsorption properties for carbon dioxide even if the gas to be treated contains water vapor, the dehumidification operation can be omitted.

The method for desorbing carbon dioxide in the second step includes (A) placing the carbon dioxide separation material under reduced pressure conditions and desorbing carbon dioxide (pressure swing method), (B) applying water vapor to the carbon dioxide separation material. and a step of contacting at least one of an inert gas (preferably a gas not containing carbon dioxide (or a gas with a low carbon dioxide content)) to desorb carbon dioxide, and (C) heating the carbon dioxide separation material. , a method including a step of desorbing carbon dioxide (temperature swing method), and the like.

In the method including step (A), it is preferable to lower the pressure to about 0.2 Pa in terms of the amount of carbon dioxide desorbed and the stability of the carbon dioxide separation material. The carbon dioxide separation material or the container containing it may be heated during the pressure reduction. When heating, the temperature is desirably up to about 60° C., and in this case, it is preferable to lower the pressure to about 0.5 Pa. The method including step (A) is suitable when the gas to be treated has a temperature of 20 to 60° C. and a carbon dioxide partial pressure of 100 kPa or less.

In the method including step (B), for example, by bringing an inert gas, water vapor, a gas not containing carbon dioxide, etc. into contact with the carbon dioxide separation material, the partial pressure of carbon dioxide can be lowered and carbon dioxide can be desorbed. can. The gas to be brought into contact with the carbon dioxide separation material may be any gas as long as the carbon dioxide separation material is stable in the gas, preferably an inert gas such as argon, nitrogen, water vapor, etc., and more preferably reduced pressure water vapor.

In the method including step (C), carbon dioxide can be desorbed by increasing the temperature above that during carbon dioxide absorption. In this case, the temperature during carbon dioxide absorption may be, for example, 10 to 40°C, and the temperature during carbon dioxide desorption may be, for example, about 60°C.

[Example]
Next, the present disclosure will be described in detail using examples, but the present invention is not limited to the following examples. In addition, the supported amount of polyamine (mass%) is expressed as a percentage of the mass of polyamine relative to the mass of carbon dioxide separation material (polyamine carrier) excluding carbon dioxide (here, the total amount of polyamine and support percentage of polyamine).

The following equipment was used to measure the physicochemical properties of the synthesized polyamine.
Liquid chromatograph mass spectrometer (LC-MS): Alliance LC/MS system manufactured by Nippon Waters Co., Ltd.

In the following, descriptions such as "xPO" such as "xPO-IP-TEPA" indicate that the number of moles of propylene oxide reacted with 1 mol of the skeleton amine (TEPA in this example) is x mol. For example, a description such as "0.25PO" such as "0.25PO-IP-TEPA" indicates that the number of moles of propylene oxide reacted with 1 mol of the skeleton amine is 0.25 mol.

In addition, "IP" such as "0.25PO-IP-TEPA" means that the two primary amino groups of the backbone amine are isopropylated to form diisopropylamine (in other words, the reaction per molecule and The number of moles of acetone produced is 2 mol).

In addition, for example, "(29)/Q30" described in "0.25PO-IP-TEPA(29)/Q30" etc. has a polyamine component content of 29% by mass and a polyamine support. Indicates that the body is Q30.

《Example 1》
<Synthesis of IP-polyamine component>
Synthesis of diisopropylated tetraethylenepentamine (also known as 1,11-diisopropylamino-3,6,9-triazaundecane) (IP-TEPA)

Put 2 g of platinum oxide catalyst and 100 ml of commercially available anhydrous ethanol into a 1 L flask, replace the inside of the flask with hydrogen, then add hydrogen until the pressure reaches 150 kPa, stir at 500 rpm for 15 to 20 minutes, and reduce the platinum oxide catalyst. did.

Next, a catalyst containing 189.31 g (1.0 mol) of tetraethylenepentamine (TEPA), 121.97 g (2.1 mol) of acetone (CH ₃ -CO-CH ₃ ), and 150 ml of absolute ethanol was added. into a flask.

After replacing the inside of the flask with hydrogen, hydrogen was added until the pressure reached approximately 200 kPa, and the pressure decreased as the theoretical amount of hydrogen (2 mol) was absorbed.Then, the solution was stirred for 10 hours until it was confirmed that there was no absorption.

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

<Synthesis of PO-IP-polyamine component>
0.5 mole of propylene oxide per mole of IP-TEPA was mixed dropwise and the mixture was stirred at room temperature for 12 hours, then warmed to 60° C. and held for an additional 2 hours. Water was removed from the obtained liquid under reduced pressure and further vacuum dried to obtain 0.5PO-IP-TEPA.

<Preparation of carbon dioxide separation material (polyamine carrier)>
A predetermined amount of 0.5PO-IP-TEPA was weighed and dissolved in 20 g of methanol (manufactured by Wako Pure Chemical Industries, Ltd.; special grade) weighed into a 300 cm ³ eggplant flask.

Thereafter, a separately weighed predetermined amount of support Q30 (CARiACT Q30 manufactured by Fuji Silysia Chemical Co., Ltd.; specific surface area 100 m ² /g, average pore diameter 30 nm, pore volume 0.9 mL/g) was placed in an eggplant flask, and the mixture was heated at room temperature. After stirring for 2 hours, the methanol solvent was removed by heating it to 40°C with a rotary evaporator (manufactured by EYELA; N-1000) and reducing the pressure in the system until the pressure became 0.03 MPa. A polyamine carrier (0.5PO-IP-TEPA(25)/Q30) containing 25% by mass of 0.5PO-IP-TEPA was obtained.

Removal of the methanol solvent was determined by weighing the total weight of the flask and reagents in advance, and was considered complete when a mass loss of 20 g, which corresponds to the methanol solvent, was confirmed. The prepared polyamine carrier was stored in an eggplant flask with a stopper in a desiccator until it was used for evaluation tests.

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

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

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

《Example 5》
<Synthesis of IP-polyamine>
Synthesis of 1,10-diisopropylamino-4,7-diazadecane (IP-DEDP)

A flask containing the reduced catalyst was charged with 174.29 g (1.0 mol) of 1,10-amino-4,7-diazadecane (DEDP) as a backbone amine, and 121.97 g (1.0 mol) of acetone was added as a starting material for the isopropyl group. IP-DEDP was obtained in the same manner as in Example 1, except that 2.1 mol) was added (yield: 95%).

<Synthesis of PO-IP-polyamine component>
0.25PO-IP-DEDP was obtained in the same manner as in Example 1, except that 1 mole of IP-DEDP was reacted with 0.25 mole of propylene oxide (yield: 95%). Further, in the same manner as in Example 1, a polyamine carrier (0.25PO-IP-DEDP(29)/Q30) containing 29% by mass of 0.25PO-IP-DEDP was obtained.

《Example 6》
<Synthesis of IP-polyamine>
Same as Example 1, except that 1.0 mol of pentaethylenehexamine (PEHA) was added as the backbone amine and 2.1 mol of acetone was added as the starting material for the isopropyl group to the flask containing the reduced catalyst. IP-PEHA was obtained (yield 95%).

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

《Example 7》
<Synthesis of IP-polyamine>
Same as Example 1, except that 1.0 mol of hexaethyleneheptamine (HEHA) was added as the backbone amine and 2.1 mol of acetone was added as the starting material for the isopropyl group into the flask containing the reduced catalyst. , IP-HEHA was obtained (yield 95%).

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

《Comparative example 1》
TEPA (skeletal amine) was directly supported on Q30 at a content of 29% by mass to obtain a polyamine support (TEPA(29)/Q30).

《Comparative example 2》
IP-TEPA was directly supported on Q30 at a content of 29% by mass to obtain a polyamine support (IP-TEPA(29)/Q30).

《Comparative example 3》
DEDP (skeletal amine) was directly supported on Q30 at a content of 29% by mass to obtain a polyamine support (DEDP(29)/Q30).

《Comparative example 4》
IP-DEDP was directly supported on Q30 at a content of 29% by mass to obtain a polyamine support (IP-DEDP(29)/Q30).

《Comparative example 5》
PEHA (skeletal amine) was directly supported on Q30 at a content of 29% by mass to obtain a polyamine support (PEHA(29)/Q30).

《Comparative example 6》
IP-PEHA was directly supported on Q30 at a content of 29% by mass to obtain a polyamine support (IP-PEHA(29)/Q30).

《Comparative Example 7》
HEHA (skeletal amine) was directly supported on Q30 at a content of 29% by mass to obtain a polyamine support (HEHA(29)/Q30).

《Comparative Example 8》
IP-HEHA was directly supported on Q30 at a content of 29% by mass to obtain a polyamine support (IP-HEHA(29)/Q30).

Table 1 summarizes the composition of the polyamine carrier of each Example and Comparative Example.

<Evaluation test 1>
Regarding the polyamine carriers of Examples and Comparative Examples, the absorption amount of carbon dioxide at each pressure at a predetermined temperature was measured using a breakthrough curve measurement device (manufactured by GL Sciences, Inc.).

Approximately 1 g of a measurement sample was weighed into a sample tube, and the sample was pretreated by flowing argon at 80°C for 6 hours, and then the sample temperature was maintained at 60°C. Carbon dioxide was flowed through the sample tube at a partial pressure of 13 kPa, and the outlet gas composition was measured using a gas chromatograph. The absorption amount was determined from the integration of the time from the start of CO ₂ absorption to saturation and the outlet gas concentration.

The amount of carbon dioxide desorbed (recovered) was determined from the integration of the time from switching the flowing gas to argon until no carbon dioxide was detected in the exit gas and the exit gas concentration.

The amount of carbon dioxide absorbed by the polyamine carriers obtained in Example 4 and Comparative Examples 1 and 2 and the amount desorbed (recovered) under reduced pressure were measured. Table 2 shows the results.

Hereinafter, the unit of carbon dioxide absorption amount in the table is the absorption amount (mol) per 1 kg of polyamine carrier. In addition, the amount of absorption (mol/kg) shown in (A) indicates the amount of absorption at 60°C and 13 kPa of a fresh sample, and the amount of desorption (recovery) shown in (B) is the amount of absorption by flowing argon gas. This is the amount of desorption (recovery) at 60°C.

<Evaluation test 2>
For the polyamine carriers of Examples and Comparative Examples, the equilibrium absorption amount of carbon dioxide at each pressure at a predetermined temperature was measured by a constant volume method. ChemiSorb HTP manufactured by Micromeritics was used as a measuring device. The measurement methods in Evaluation Tests 2 to 4 are as follows unless otherwise specified. Approximately 0.1 g of a measurement sample was weighed into a sample tube, and the sample was pretreated by flowing helium at 80°C for 6 hours, and then the sample temperature was maintained at 40°C. Carbon dioxide was introduced little by little into the sample tube, a pressure range up to 100 kPa was specified, and the relationship between the partial pressure of carbon dioxide and the absorption amount at each measurement temperature was obtained. The equilibrium absorption amount at 13 kPa was read from the obtained isotherm.

Oxidative degradation of the polyamine support was performed using a packed bed reactor. 1.0 g of the polyamine carrier was packed in a quartz tube, pretreated by flowing nitrogen at 100°C for 3 hours, and then subjected to deterioration treatment by flowing simulated air (21% O ₂ - N ₂ balance) at 100°C for 42 hours. did. Thereafter, carbon dioxide was introduced at 40° C. by the same method as above, and an isotherm was obtained. The amount of carbon dioxide absorbed was measured as the equilibrium absorption amount at 13 kPa.

The amount of carbon dioxide absorbed by the fresh polyamine carriers obtained in Examples 1 to 7 and Comparative Examples 1 to 8 and the polyamine carriers after deterioration treatment, and the carbon dioxide absorption amount of the polyamine carriers after deterioration relative to the fresh polyamine carriers. The absorption retention rate (Retention) was measured. Table 3 shows the results.

Further, FIGS. 1 to 3 show the results of fresh samples and samples after deterioration treatment of Examples 2 and 4 and Comparative Examples 1 and 2. In FIGS. 1 and 2, the horizontal axis (Absolute pressure) corresponds to the absolute pressure or partial pressure of CO ₂ , and the vertical axis (CO ₂ adsorbed) indicates the amount of CO ₂ absorbed. FIG. 3 is a bar graph showing the results of FIGS. 1 and 2 together.

<Evaluation test 3>
The absorption amount at 100 kPa was read from the isotherm obtained in the same manner as in Evaluation Test 2, and was taken as the absorption amount of carbon dioxide.

The isotherm of the polyamine support that was degraded in the same manner as in Evaluation Test 2 was obtained in the same manner as in Evaluation Test 2. The amount of carbon dioxide absorbed was measured at 100 kPa.

The amount of carbon dioxide absorbed by the fresh polyamine carriers obtained in Examples 1 to 7 and Comparative Examples 1 to 8 and the polyamine carriers after deterioration treatment, and the carbon dioxide absorption amount of the polyamine carriers after deterioration relative to the fresh polyamine carriers. The absorption retention rate (Retention) was measured. Table 4 shows the results.

<Evaluation test 4>
After Evaluation Test 2, the samples of the fresh polyamine carrier and the degraded polyamine carrier of Example 4 were evacuated for 20 minutes, and then carbon dioxide was introduced at 40°C by the same method as Evaluation Test 2. Then, the isotherm was measured. The amount of carbon dioxide absorbed was measured at 100 kPa.

Further, FIGS. 4 and 5 show the results of fresh samples and samples after deterioration treatment. In each figure, the horizontal axis (Absolute pressure) corresponds to the absolute pressure or partial pressure of CO ₂ , and the vertical axis (CO ₂ adsorbed) indicates the amount of CO ₂ absorbed. Table 5 shows the results.

<Evaluation test 5: Examination of the influence of water vapor>
Since the polyamine support is used under conditions where carbon dioxide is separated from a mixed gas containing water vapor in addition to carbon dioxide, the influence of water vapor was investigated. The amount of carbon dioxide absorbed under humidified conditions was measured using a breakthrough curve measuring device (manufactured by GL Sciences, Inc.).

Approximately 1 g of the fresh polyamine support of Example 4 and Example 7 was weighed into a sample tube, and after pretreatment for drying and degassing by flowing argon at 80°C for 6 hours, the sample temperature was maintained at 60°C. did. Next, a H ₂ O/Ar mixed gas was flowed to cause the polyamine support to absorb water.

After water absorption reached saturation, carbon dioxide was flowed at a partial pressure of 13 kPa, and at the same time, the outlet gas composition was measured using a gas chromatograph to obtain a breakthrough curve.

After the amount of carbon dioxide absorbed reached saturation, argon was flowed and the outlet gas composition was measured using a gas chromatograph. In this measurement, instead of depressurizing with a vacuum pump, argon gas was flowed to lower the partial pressure of carbon dioxide in the system and remove carbon dioxide.

The amount of absorption was determined from the integration of the time from the start of absorption until reaching saturation and the outlet concentration. The amount of desorption was determined from the integration of the time from the time of switching to argon gas until no carbon dioxide was detected in the outlet gas and the outlet concentration. Table 6 shows the results. For evaluation under dry conditions, the amount of carbon dioxide absorbed was measured at 60°C and 13 kPa, and the amount desorbed was measured at 60°C.

The carbon dioxide separation material according to the present disclosure increases the amount of carbon dioxide absorbed and can separate and recover a large amount of carbon dioxide in a short time under reduced pressure, so it is efficient, practical, and suitable for reuse. In addition, the carbon dioxide separation material according to the present disclosure can separate and recover carbon dioxide using either the pressure swing method or the temperature swing method in the carbon dioxide absorption and desorption process, and can be used in various usage environments. It is possible to select appropriate carbon dioxide absorption and desorption steps. In addition, the carbon dioxide separation material according to the present disclosure has high resistance to oxidative deterioration and is less likely to be reduced due to volatilization of polyamine. Furthermore, even when water vapor coexists, the performance of absorption, desorption, and reabsorption does not deteriorate, and a dehumidification process is not required, making it possible to construct an energy-saving system and reduce costs by downsizing the device.

Although the invention has been described in terms of presently preferred embodiments, such disclosure is not to be construed as a limitation. Various modifications and alterations will no doubt become apparent to those skilled in the art to which this invention pertains after reading the above disclosure. It is, therefore, intended that the appended claims be construed as covering all changes and modifications without departing from the true spirit and scope of the invention.

Claims

Contains polyamines,
The polyamine includes a propyl polyamine component having a hydrogen atom or a functional group bonded to a nitrogen atom and three or more propyl groups bonded to different nitrogen atoms in the molecule,
At least one of the propyl groups is a hydroxypropyl group having a hydroxy group,
The hydroxypropyl group is bonded to a nitrogen atom constituting a tertiary amine,
the hydroxy group is bonded to a secondary carbon atom,
A carbon dioxide separation material, wherein the two or more propyl groups are unsubstituted isopropyl groups having no hydroxy group.
The carbon dioxide separation material according to claim 1, wherein the unsubstituted isopropyl group is bonded to a nitrogen atom that constitutes a secondary amine.
The carbon dioxide separation material according to claim 1 or 2, wherein the propyl polyamine component has two or more NH groups and one or more alkylene groups interposed between nitrogen atoms.
The propyl polyamine component has the general formula (1):

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

In formula (2),
R A represents R 6 or a group: -A-NR 6 R 7 ;
R B represents R 8 or a group: -A-NR 8 R 9 ;
A represents an alkylene group having 2 to 6 carbon atoms,
n represents an integer from 1 to 5,
p and q each independently represent 0 or 1,
Multiple A's may be the same or different,
When there are multiple R 5 's, they may be the same or different,
R 1 , R 2 , R 7 and R 9 represent the unsubstituted isopropyl group, R 3 , R 4 , R 6 and R 8 represent a hydrogen atom,
The carbon dioxide separation material according to claim 4, wherein at least one of R 5 represents the hydroxypropyl group, and the remaining R 5 represent hydrogen atoms.
The carbon dioxide separation material according to any one of claims 1 to 5, wherein the polyamine has a boiling point of 320°C or higher at 760 mmHg.
The backbone amine of the polyamine is at least one selected from the group consisting of monopolymers of ethyleneimine, propyleneimine, 2-ethylaziridine, 2-propylaziridine and 2-butylaziridine, and copolymers of at least two of these. The carbon dioxide separation material according to any one of claims 1 to 6.
The backbone amine of the polyamine is tetraethylenepentamine, spermine, N,N,N',N'-tetrakis(3-aminopropyl)-1,4-butanediamine, pentaethylenehexamine, hexaethyleneheptamine, and triethylene. The carbon dioxide separation material according to any one of claims 1 to 7, which is at least one member selected from the group consisting of tetramine.
The carbon dioxide separation material includes a polyamine carrier,
The carbon dioxide separation material according to any one of claims 1 to 8, wherein the polyamine carrier includes the polyamine and a support supporting the polyamine.
The support is at least one selected from the group consisting of silica, polymethyl methacrylate, alumina, silica alumina, clay minerals, magnesia, zirconia, zeolites, zeolite analogs, natural minerals, waste solids, activated carbon, and carbon molecular sieves. The carbon dioxide separation material according to claim 9, which is a seed.
Claim 9 or 9, wherein the support has a specific surface area (BET) of 50 m 2 /g or more and 1000 m 2 /g or less, and a pore volume of 0.1 cm 3 /g to 2.3 cm 3 /g. 10. Carbon dioxide separation material according to 10.
The carbon dioxide separation material according to any one of claims 9 to 11, comprising the polyamine carrier and a binder for granulating the polyamine carrier.
The carbon dioxide separation material according to claim 12, wherein the binder is at least one selected from the group consisting of silica, alumina, silica alumina, clay minerals, fluororesins, cellulose derivatives, and epoxy resins.
A first step of bringing the gas to be treated into contact with the carbon dioxide separation material according to any one of claims 1 to 13 and absorbing carbon dioxide, and the carbon dioxide separation that absorbed carbon dioxide in the first step. a second step of desorbing carbon dioxide from the material;
A method for separating or recovering carbon dioxide containing
The second step is (A) a step of placing the carbon dioxide separation material under reduced pressure conditions and desorbing carbon dioxide (pressure swing method);
(B) a step of contacting the carbon dioxide separation material with at least one of water vapor and an inert gas to desorb carbon dioxide, and (C) a step of heating the carbon dioxide separation material to desorb carbon dioxide ( temperature swing method)
A method for separating or recovering carbon dioxide, including one or more of the following.
The method for separating or recovering carbon dioxide according to claim 14, wherein the gas to be treated is a gas having a temperature of 20 to 60°C and a partial pressure of carbon dioxide of 100 kPa or less.
a step of preparing a polyamine;
contacting the polyamine with a support to obtain a polyamine carrier containing the polyamine and the support supporting the polyamine;
Equipped with
The polyamine includes a propyl polyamine component having a hydrogen atom or a functional group bonded to a nitrogen atom and three or more propyl groups bonded to different nitrogen atoms in the molecule,
At least one of the propyl groups is a hydroxypropyl group having a hydroxy group,
The hydroxypropyl group is bonded to a nitrogen atom constituting a tertiary amine,
the hydroxy group is bonded to a secondary carbon atom,
A method for producing a carbon dioxide separation material, wherein the two or more propyl groups are unsubstituted isopropyl groups having no hydroxy group.