CN118176060A - Acid gas adsorbing material and acid gas adsorbing device - Google Patents
Acid gas adsorbing material and acid gas adsorbing device Download PDFInfo
- Publication number
- CN118176060A CN118176060A CN202280068883.2A CN202280068883A CN118176060A CN 118176060 A CN118176060 A CN 118176060A CN 202280068883 A CN202280068883 A CN 202280068883A CN 118176060 A CN118176060 A CN 118176060A
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- China
- Prior art keywords
- acid gas
- adsorbing material
- adsorption
- gas adsorbing
- polymer
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- 239000001569 carbon dioxide Substances 0.000 claims abstract description 90
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Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention provides an acid gas adsorbing material suitable for adsorbing and desorbing an acid gas under relatively mild conditions. The acid gas adsorbing material of the present invention contains a polymer P having an amino group. The density of nitrogen element in the acid gas adsorption material is more than 12.0mmol/g. When the adsorption test A1 was performed on the acid gas adsorbent, the adsorption amount A1 of carbon dioxide was 0.35mmol/g or more. When the desorption test B1 was carried out, the desorption amount B1 of carbon dioxide was 0.2mmol/g or more.
Description
Technical Field
The present invention relates to an acid gas adsorbing material and an acid gas adsorbing device.
Background
In recent years, in order to reduce the amount of carbon dioxide in the atmosphere, carbon dioxide recovery and storage (CCS: carbon capture and storage) and carbon dioxide recovery and utilization (CCU: carbon capture and utilization) have been studied. In CCS and CCU, carbon dioxide is sometimes recovered by separating carbon dioxide from the atmosphere.
As a method for separating an acid gas such as carbon dioxide from the atmosphere, an adsorption method has been developed in which the acid gas is adsorbed on an adsorbent to be separated. The adsorbent used in the adsorption method can adsorb acid gas by, for example, contact with the atmosphere.
Examples of the material of the adsorbent include amine compounds having a function of adsorbing an acid gas. As an example, patent document 1 discloses fibrillated cellulose having amino groups introduced therein as an adsorbent. Patent document 2 discloses an adsorbent obtained by introducing amino groups into the pores of a mesoporous material.
Prior art literature
Patent literature
Patent document 1: international publication No. 2017/009241
Patent document 2: U.S. Pat. No. 7767004 specification
Disclosure of Invention
Problems to be solved by the invention
There is a need for acid gas adsorbing materials suitable for adsorption and desorption of acid gases under relatively mild conditions.
Means for solving the problems
The present invention provides an acid gas adsorbing material comprising a polymer having an amino group,
The density of nitrogen element in the acid gas adsorption material is more than 12.0mmol/g,
When the following adsorption test A1 was carried out, the adsorption amount A1 of carbon dioxide was 0.35mmol/g or more,
When the following release test B1 was performed, the release amount B1 of carbon dioxide was 0.2mmol/g or more.
Adsorption test A1: the mixed gas composed of carbon dioxide, nitrogen and steam was continuously fed into the vessel containing the acid gas adsorbing material for 15 hours. Wherein the concentration of the carbon dioxide in the mixed gas is 400volppm, the temperature of the mixed gas is 23 ℃ and the humidity of the mixed gas is 50% RH.
Detachment test B1: the acid gas adsorbent after the adsorption test A1 was heated at 50 ℃ for 1.5 hours while the mixed gas was continuously fed into the vessel.
In addition, the present invention provides an acid gas adsorbing material, which is an acid gas adsorbing material comprising a polymer having an amino group,
The density of nitrogen element in the acid gas adsorption material is more than 12.0mmol/g,
The specific surface area of the acid gas adsorbing material is more than 0.5m 2/g,
The glass transition temperature of the polymer is 40 ℃ or lower.
The present invention also provides an acid gas adsorption apparatus comprising an adsorption unit having a gas inlet and a gas outlet,
The adsorption unit accommodates the acid gas adsorbent.
Effects of the invention
According to the present invention, an acid gas adsorbing material suitable for adsorbing and desorbing an acid gas under relatively mild conditions can be provided.
Drawings
FIG. 1 is a diagram for explaining a method of measuring the adsorption amount of carbon dioxide by an acid gas adsorbent.
Detailed Description
The acid gas adsorbing material according to claim 1 of the present invention is an acid gas adsorbing material comprising a polymer having an amino group,
The density of nitrogen element in the acid gas adsorption material is more than 12.0mmol/g,
When the following adsorption test A1 was carried out, the adsorption amount A1 of carbon dioxide was 0.35mmol/g or more,
When the following release test B1 was performed, the release amount B1 of carbon dioxide was 0.2mmol/g or more.
Adsorption test A1: the mixed gas composed of carbon dioxide, nitrogen and steam was continuously fed into the vessel containing the acid gas adsorbing material for 15 hours. Wherein the concentration of the carbon dioxide in the mixed gas is 400volppm, the temperature of the mixed gas is 23 ℃ and the humidity of the mixed gas is 50% RH.
Detachment test B1: the acid gas adsorbent after the adsorption test A1 was heated at 50 ℃ for 1.5 hours while the mixed gas was continuously fed into the vessel.
In the invention according to claim 2, for example, in the acid gas adsorbing material according to claim 1, the ratio of the separation amount b1 (mmol/g) to the adsorption amount a1 (mmol/g) is 50% or more.
In the invention according to claim 3, for example, in the acid gas adsorbing material according to claim 1 or 2, the carbon dioxide desorption amount B2 is 0.25mmol/g or more when the following desorption test B2 is performed.
Detachment test B2: the acid gas adsorbent subjected to the adsorption test A1 was heated at 65 ℃ for 1.5 hours while the mixed gas was continuously fed into the vessel.
In the 4 th aspect of the present invention, for example, in the acid gas adsorbing material according to the 3 rd aspect, the ratio of the separation amount b2 (mmol/g) to the adsorption amount a1 (mmol/g) is 70% or more.
In the invention according to claim 5, for example, in the acid gas adsorbing material according to any one of claims 1 to 4, when the following adsorption test A2 is performed, the carbon dioxide adsorption amount A2 is 0.05mmol/g or more.
Adsorption test A2: the mixed gas was continuously fed into the container for 1 hour.
In the 6 th aspect of the present invention, for example, in the acid gas adsorbing material according to any one of the 1 st to 5 th aspects, when the following adsorption test A3 is performed, the adsorption amount A3 of carbon dioxide is 0.1mmol/g or more.
Adsorption test A3: the mixed gas was continuously fed into the container for 4 hours.
In the 7 th aspect of the present invention, for example, in the acid gas adsorbing material according to any one of the 1 st to 6 th aspects, the glass transition temperature of the polymer is 40 ℃ or lower.
In the 8 th aspect of the present invention, for example, in the acid gas adsorbing material according to any one of the 1 st to 7 th aspects, the specific surface area is 0.5m 2/g or more.
The acid gas adsorbing material according to the 9 th aspect of the present invention is an acid gas adsorbing material comprising a polymer having an amino group,
The density of nitrogen element in the acid gas adsorption material is more than 12.0mmol/g,
The specific surface area of the acid gas adsorbing material is more than 0.5m 2/g,
The glass transition temperature of the polymer is 40 ℃ or lower.
In the 10 th aspect of the present invention, for example, when the acid gas adsorbing material according to any one of the 1 st to 9 th aspects is subjected to a heat treatment at 85 ℃ for 100 hours in an environment of 10% rh, the maintenance rate R1 of the amount of carbon dioxide that can be adsorbed (mmol/g) is 50% or more.
In the 11 th aspect of the present invention, for example, when the acid gas adsorbing material according to any one of the 1 st to 10 th aspects is subjected to a heat treatment at 85 ℃ for 100 hours in an environment of 85% rh, the maintenance rate R2 of the amount of carbon dioxide that can be adsorbed (mmol/g) is 50% or more.
In the 12 th aspect of the present invention, for example, the acid gas adsorbing material according to any one of the 1 st to 11 th aspects contains the polymer as a main component.
In the 13 th aspect of the present invention, for example, in the acid gas adsorbing material according to any one of the 1 st to 12 th aspects, the polymer is an amine polymer including a structural unit derived from an epoxy monomer.
In the 14 th aspect of the present invention, for example, in the acid gas adsorbing material according to the 13 th aspect, the amine polymer includes at least 1 kind selected from the group consisting of a polymer P1 of a monomer group including an amine monomer and an epoxy monomer, and a reactant P2 of a compound group including an amine prepolymer and an epoxy monomer.
In the 15 th aspect of the present invention, for example, in the acid gas adsorbing material according to the 14 th aspect, the weight average molecular weight of the amine prepolymer is 300 or more.
In the 16 th aspect of the present invention, for example, in the acid gas adsorbing material according to the 14 th or 15 th aspect, the amine prepolymer contains polyethyleneimine.
In the 17 th aspect of the present invention, for example, in the acid gas adsorbing material according to the 14 th aspect, the amine monomer includes an aliphatic amine.
In the 18 th aspect of the present invention, for example, in the acid gas adsorbing material according to any one of the 13 th to 17 th aspects, the epoxy equivalent of the epoxy monomer is 150g/eq.
In aspect 19 of the present invention, for example, in the acid gas adsorbing material according to any one of aspects 13 to 18, the epoxy monomer includes a polyfunctional epoxy compound having an ether group.
In the 20 th aspect of the present invention, for example, the acid gas adsorbing material according to any one of the 1 st to 19 th aspects has a porous structure.
An acid gas adsorption apparatus according to claim 21 of the present invention includes an adsorption unit having a gas inlet and a gas outlet,
The adsorption unit houses an acid gas adsorption material according to any one of aspects 1 to 20.
The details of the present invention will be described below, but the following description is not intended to limit the present invention to the specific embodiments.
The acid gas adsorbing material of the present embodiment contains a polymer P having an amino group. The density d of nitrogen element in the acid gas adsorption material is more than 12.0mmol/g.
The density d of nitrogen element in the acid gas adsorbing material is preferably 12.2mmol/g or more, and may be 12.5mmol/g or more, 13.0mmol/g or more, 13.5mmol/g or more, 14.0mmol/g or more, 14.5mmol/g or more, 15.0mmol/g or more, 15.5mmol/g or more, 16.0mmol/g or more, 16.5mmol/g or more, 17.0mmol/g or more, and further may be 17.5mmol/g or more. The greater the density d of nitrogen element, the greater the adsorption amount of acid gas by the acid gas adsorbent and the rate of adsorption of acid gas. The upper limit of the density d of the nitrogen element is not particularly limited, and may be, for example, 30mmol/g or 20mmol/g. In the present specification, the density d of the nitrogen element in the acid gas adsorbing material means the amount of the nitrogen element substance contained in 1g of the acid gas adsorbing material. When all nitrogen elements contained in the acid gas adsorbing material are derived from amino groups, the density d of nitrogen elements may be regarded as the density of amino groups in the acid gas adsorbing material.
The density d of nitrogen element can be measured by the following method. First, the weight ratio w (wt%) of nitrogen element contained in the acid gas adsorbing material was measured using a commercially available CHN element analyzer. The density d of the nitrogen element can be calculated from the following formula based on the obtained result.
Density d (mmol/g) = (weight ratio w (wt%) ×1000)/(atomic weight of nitrogen×100)
In the acid gas adsorbent according to the present embodiment, when the following adsorption test A1 is performed, the adsorption amount A1 of carbon dioxide is 0.35mmol/g or more. In the case where the following release test B1 was performed, the release amount B1 of carbon dioxide was 0.2mmol/g or more.
Adsorption test A1: the mixed gas G composed of carbon dioxide, nitrogen and steam was continuously fed into the vessel containing the acid gas adsorbent for 15 hours. Wherein the concentration of carbon dioxide in the mixed gas G was 400volppm, the temperature of the mixed gas G was 23℃and the humidity was 50% RH.
Detachment test B1: the acid gas adsorbing material after the adsorption test A1 was heated at 50 ℃ for 1.5 hours while continuously feeding the mixed gas G into the above-mentioned vessel.
(Adsorption test and separation test)
Details of the adsorption test A1 and the detachment test B1 are described below. The adsorption test A1 and the desorption test B1 can be measured using, for example, the measuring apparatus 10 shown in fig. 1. The measurement device 10 includes a1 st tank 30 and a 2 nd tank 31. As an example, tank 1 stores nitrogen in a dry state, and tank 2 stores a mixed gas of nitrogen in a dry state and carbon dioxide in a dry state. The concentration of carbon dioxide in the mixed gas in the 2 nd tank 31 is, for example, 5vol%.
The measurement device 10 further includes a1 st container 40 containing water 70, and a1 st path 60 for feeding nitrogen from the 1 st tank 30 to the 1 st container 40. The 1 st path 60 has one end connected to the gas outlet of the 1 st tank 30 and the other end disposed in the water 70 of the 1 st container 40. The nitrogen delivered from tank 130 to tank 140 is humidified by contact with water 70. In the 1 st path 60, a mass flow controller 35 for adjusting the flow rate of nitrogen to be sent from the 1 st tank 30 to the 1 st vessel 40 is provided.
The measurement device 10 further includes a 2 nd vessel 41, a 2 nd path 62, and a bypass path 61. The 2 nd path 62 connects the 1 st container 40 with the 2 nd container 41. The nitrogen humidified by being sent to the 1 st container 40 is sent to the 2 nd container 41 through the 2 nd path 62. The bypass path 61 branches from the 1 st path 60 at a position between the 1 st tank 30 and the mass flow controller 35, and is connected to the 2 nd path 62. A part of the nitrogen supplied from the 1 st tank 30 flows into the bypass path 61, and is supplied to the 2 nd tank 41 through the 2 nd path 62. In the bypass path 61, a mass flow controller 36 for adjusting the flow rate of nitrogen delivered from the 1 st tank 30 to the bypass path 61 is disposed.
The measurement device 10 further includes a 3 rd path 63 for conveying the mixed gas from the 2 nd tank 31 to the 2 nd path 62. The 3 rd path 63 has one end connected to the gas outlet of the 2 nd tank 31 and the other end connected to the 2 nd path 62. In the 3 rd path 63, a mass flow controller 37 for adjusting the flow rate of the mixed gas sent from the 2 nd tank 31 to the 2 nd path 62 is provided. The mixed gas fed to the 2 nd path 62 is fed to the 2 nd container 41 through the 2 nd path 62.
The measurement device 10 further includes a 3 rd vessel 42 and a 4 th path 64. The 3 rd container 42 accommodates water 71 and the adsorbing portion 21 disposed in the water 71. In the 3 rd vessel 42, the temperature of the water 71 was maintained at 23 ℃. The adsorption section 21 has a gas inlet 22 and a gas outlet 23. The adsorption unit 21 functions as a container for storing an acid gas adsorbent therein. The adsorption unit 21 is configured so that the water 71 does not enter inside. Typically, the adsorbing portion 21 is a tube made of a hydrophobic resin, for example, a fluororesin such as tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA). As an example, the inner diameter of the tube as the adsorbing portion 21 is 4mm and the outer diameter is 6mm. The adsorption unit 21 is configured to be detachable from the measurement device 10.
The measurement apparatus 10 may also be used as an acid gas adsorption apparatus including the adsorption unit 21. In another aspect, the present invention provides an acid gas adsorbing device 20 comprising an adsorbing portion 21 having a gas inlet 22 and a gas outlet 23, wherein the adsorbing portion 21 houses an acid gas adsorbing material.
Path 4 connects vessel 2 41 with vessel 3 42. In detail, the 4 th path 64 is connected to the gas inlet 22 of the adsorption unit 21 in the 3 rd vessel 42. In the 4 th path 64, a1 st concentration meter 50 for measuring the concentration of carbon dioxide in the gas supplied to the adsorption unit 21 is disposed. As the 1 st concentration meter 50, for example, a CO 2/H2 O gas analyzer manufactured by LI-COR, or LI-850-3 can be used.
The measurement device 10 further includes a 5 th path 65 connected to the gas outlet 23 of the adsorption unit 21 for discharging the gas from the adsorption unit 21 to the outside of the measurement device 10. In the 5 th path 65, a back pressure valve 55 and a2 nd concentration meter 51 are disposed. The back pressure valve 55 can be used to adjust the pressure in the adsorption unit 21 to a constant value. The 2 nd concentration meter 51 can measure the concentration of carbon dioxide in the gas discharged from the adsorption unit 21. As the 2 nd concentration meter 51, for example, a CO 2/H2 O gas analyzer manufactured by LI-COR, or LI-850-3 can be used.
Each path of the measuring device 10 is constituted by a pipe made of metal or resin, for example.
[ Pretreatment ]
First, an acid gas adsorbent is prepared and dried. As the acid gas adsorbing material, an acid gas adsorbing material before the heat resistance test and the wet heat resistance test described later was used. The drying treatment may be performed, for example, by subjecting the acid gas adsorbing material to a treatment at 60 ℃ for 2 hours or more under a vacuum atmosphere. Next, the acid gas adsorbent after the drying treatment is filled into the adsorbent 21 in a drying chamber having a dew point of about-60 ℃. The weight of the acid gas adsorbing material charged into the adsorbing portion 21 is, for example, 50mg. Next, the 4 th path 64 and the 5 th path 65 are connected to both ends of the adsorbing portion 21, and the adsorbing portion 21 is immersed in the water 71 in the 3rd container 42.
Next, the 1 st path 60, the 2 nd path 62, the bypass path 61, and the 3 rd path 63 of the measuring apparatus 10 supply the nitrogen from the 1 st tank 30 and the mixed gas from the 2 nd tank 31 to the 2 nd vessel 41. In the 2 nd vessel 41, these gases are mixed to obtain a mixed gas G composed of carbon dioxide, nitrogen and water vapor. In the 2 nd vessel 41, the concentration of carbon dioxide in the mixed gas G was adjusted to 400volppm. The temperature of the mixed gas G was 23℃and the humidity was 50% RH. The mixed gas G is supplied to the adsorption unit 21 through the 4 th path 64 at a flow rate sufficient for the weight of the acid gas adsorbent, for example, 300mL/min for 50mg of the acid gas adsorbent. In the adsorption portion 21, the pressure of the mixed gas G can be regulated to, for example, 107kPa by the back pressure valve 55.
Next, the mixed gas G was supplied to the adsorption unit 21, and the adsorption unit 21 was taken out of the 3 rd vessel 42, and immersed in a hot water bath (not shown) at 80 ℃ for 2 hours or more. The immersion of the adsorption unit 21 in the hot water bath is performed until the concentration of carbon dioxide measured by the 1 st concentration meter 50 is substantially the same as the concentration of carbon dioxide measured by the 2 nd concentration meter 51. Thus, the pretreatment is completed for the acid gas adsorbing material in the adsorbing portion 21.
[ Adsorption test ]
Next, the mixed gas G is supplied to the adsorption unit 21, and the adsorption unit 21 is taken out of the hot water bath and immersed in the water 71 in the 3 rd vessel 42. Thus, the adsorption test of carbon dioxide with respect to the acid gas adsorbent in the adsorption unit 21 (adsorption test A1) was started. The adsorption test was performed until 15 hours elapsed from the start. Specifically, the mixed gas G was continuously fed to the adsorption unit 21 for 15 hours. In the case of performing the 15-hour adsorption test, it is generally considered that the adsorption of carbon dioxide by the acid gas adsorbent is balanced.
In the adsorption test A1, the amount M1 of the carbon dioxide adsorbed by the acid gas adsorbent was measured from the beginning to 15 hours. The amount of the substance of carbon dioxide adsorbed by the acid gas adsorbing material can be calculated from the result of measuring the difference between the concentration of carbon dioxide measured by the 1 st concentration meter 50 and the concentration of carbon dioxide measured by the 2 nd concentration meter 51 over time. Based on the amount M1 of the substance, the amount of the substance of carbon dioxide adsorbed by 1g of the acid gas adsorbent within 15 hours was calculated, and the calculated value thus obtained was determined as the adsorption amount a1.
[ Detachment test ]
Next, the mixed gas G is continuously supplied to the adsorption unit 21, and the adsorption unit 21 is taken out of the 3 rd vessel 42, and the adsorption unit 21 is immersed in a hot water bath (not shown) at 50 ℃. Thus, the carbon dioxide desorption test (desorption test B1) was started for the acid gas adsorbent in the adsorption unit 21. The detachment test was performed until 1.5 hours passed from the start.
In the desorption test B1, the amount M2 of carbon dioxide desorbed from the acid gas adsorbing material 1.5 hours from the start was measured. The amount of the carbon dioxide desorbed from the acid gas adsorbing material can be calculated from the result of measuring the difference between the concentration of carbon dioxide measured by the 1 st concentration meter 50 and the concentration of carbon dioxide measured by the 2 nd concentration meter 51 over time. Based on the amount M2 of the substance, the amount of the substance of carbon dioxide desorbed from 1g of the acid gas adsorbing material in 1.5 hours was calculated, and the calculated value was determined as the desorption amount b1.
[ Adsorption amount and separation amount ]
In the acid gas adsorbent of the present embodiment, the adsorption amount A1 of carbon dioxide in the case of carrying out the adsorption test A1 is preferably 0.4mmol/g or more, but may be 0.5mmol/g or more, 0.8mmol/g or more, 1.0mmol/g or more, 1.3mmol/g or more, 1.5mmol/g or more, 1.8mmol/g or more, 2.0mmol/g or more, 2.1mmol/g or more, 2.2mmol/g or more, and further may be 2.3mmol/g or more. The upper limit of the adsorption amount a1 of carbon dioxide is not particularly limited, and is, for example, 10mmol/g.
In the acid gas adsorbing material of the present embodiment, the carbon dioxide release amount B1 in the case where the release test B1 is performed is preferably 0.25mmol/g or more, but may be 0.3mmol/g or more, 0.5mmol/g or more, 0.8mmol/g or more, 1.0mmol/g or more, 1.3mmol/g or more, 1.5mmol/g or more, and further may be 1.8mmol/g or more. The upper limit of the carbon dioxide release amount b1 is not particularly limited, but is, for example, 10mmol/g.
The ratio of the amount of separation b1 (mmol/g) to the amount of adsorption a1 (mmol/g) (separation rate at 50 ℃) is, for example, 40% or more, 45% or more, 50% or more, 60% or more, 70% or more, 80% or more, and 90% or more. The upper limit of the 50℃release rate is not particularly limited, but is, for example, 99%.
Viewed from another aspect the present invention provides an acid gas adsorbing material, which is an acid gas adsorbing material comprising a polymer P having amino groups,
The density of nitrogen element in the acid gas adsorption material is more than 12.0mmol/g,
When the adsorption test A1 was carried out, the adsorption amount A1 of carbon dioxide was 0.35mmol/g or more,
When the above-mentioned desorption test B1 was performed, the ratio of the desorption amount B1 (mmol/g) of carbon dioxide to the adsorption amount a1 (mmol/g) (desorption rate at 50 ℃) was 40% or more.
In the acid gas adsorbing material, the 50 ℃ release rate may satisfy the ranges exemplified above, and particularly may be 50% or more.
In the acid gas adsorbing material of the present embodiment, the carbon dioxide desorption amount B2 is preferably 0.25mmol/g or more when the following desorption test B2 is performed.
Detachment test B2: the acid gas adsorbent subjected to the adsorption test A1 was heated at 65 ℃ for 1.5 hours while continuously feeding the mixed gas G to a vessel (the adsorption unit 21) containing the acid gas adsorbent.
The detachment test B2 can be performed by the same method as the detachment test B1 described above, except that the adsorption portion 21 is immersed in a hot water bath at 65 ℃. The amount of carbon dioxide released in the case of the release test B2 is preferably 0.3mmol/g or more, but may be 0.5mmol/g or more, 0.8mmol/g or more, 1.0mmol/g or more, 1.3mmol/g or more, 1.5mmol/g or more, 1.8mmol/g or more, 2.0mmol/g or more, 2.1mmol/g or more, and further may be 2.2mmol/g or more. The upper limit of the carbon dioxide release amount b2 is not particularly limited, but is, for example, 10mmol/g.
The ratio of the amount of separation b2 (mmol/g) to the amount of adsorption a1 (mmol/g) (separation rate at 65 ℃) is, for example, 40% or more, 45% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 95% or more, 96% or more, and 97% or more, or 100% or more.
In the acid gas adsorbing material of the present embodiment, when the following adsorption test A2 is performed, the adsorption amount A2 of carbon dioxide is preferably 0.05mmol/g or more. The adsorption amount a2 can be used as an index of the rate of adsorption of the acid gas. That is, the greater the adsorption amount a2, the greater the rate at which the acid gas adsorbent adsorbs the acid gas can be said to be.
Adsorption test A2: the mixed gas G was continuously fed into a vessel (the above-mentioned adsorption unit 21) containing an acid gas adsorbent for 1 hour.
The adsorption test A2 was performed by the same method as the adsorption test A1 described above, except that the test time was changed from 15 hours to 1 hour. The adsorption amount A2 of carbon dioxide in the case of carrying out the adsorption test A2 is preferably 0.1mmol/g or more, but may be 0.2mmol/g or more, 0.3mmol/g or more, 0.4mmol/g or more, 0.5mmol/g or more, 0.6mmol/g or more, 0.7mmol/g or more, 0.8mmol/g or more, and further may be 0.9mmol/g or more. The upper limit of the adsorption amount a2 of carbon dioxide is not particularly limited, but is, for example, 5mmol/g.
In the acid gas adsorbing material of the present embodiment, the adsorption amount A3 of carbon dioxide is preferably 0.1mmol/g or more when the following adsorption test A3 is performed. The adsorption amount a3 may be used as an index of the rate of adsorption of the acid gas. That is, the greater the adsorption amount a3, the greater the rate at which the acid gas adsorbent adsorbs the acid gas can be said to be.
Adsorption test A3: the mixed gas G was continuously fed into a vessel (the above-mentioned adsorption unit 21) containing an acid gas adsorbent for 4 hours.
The adsorption test A3 was performed by the same method as the adsorption test A1 described above, except that the test time was changed from 15 hours to 4 hours. The adsorption amount A3 of carbon dioxide in the case of carrying out the adsorption test A3 is preferably 0.3mmol/g or more, but may be 0.5mmol/g or more, 0.8mmol/g or more, 1.0mmol/g or more, 1.3mmol/g or more, 1.5mmol/g or more, 1.7mmol/g or more, and further may be 1.8mmol/g or more. The upper limit of the adsorption amount a3 of carbon dioxide is not particularly limited, but is, for example, 5mmol/g.
(Heat resistance test)
The acid gas adsorbing material of the present embodiment is preferably high in heat resistance. The heat resistance of the acid gas adsorbing material can be evaluated, for example, by conducting a heat resistance test on the acid gas adsorbing material. The heat resistance test can be performed by, for example, subjecting the acid gas adsorbing material to a heat treatment at 85℃and 10% RH for 100 hours. As an example, when the acid gas adsorbing material is subjected to heat treatment for 100 hours at 85 ℃ under 10% rh, the maintenance rate R1 of the amount of carbon dioxide adsorbable (mmol/g) may be, for example, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 85% or more, 90% or more, 92% or more, 94% or more, 95% or more, or 96% or more. The higher the retention rate R1, the higher the heat resistance of the acid gas adsorbing material. It can be said that the acid gas adsorbing material having high heat resistance has high durability when used for a long period of time. The upper limit of the maintenance ratio R1 is not particularly limited, but is, for example, 99%.
In detail, the maintenance rate R1 can be determined by the following method. First, an acid gas adsorbing material is placed in a glass container (for example, laboran screw vial manufactured by AS ONE company) in a drying chamber having a dew point of about-60 ℃. Next, the glass container was set in a constant temperature and humidity machine (for example, PSL-2J manufactured by ESPEC Co., ltd.) and subjected to a heat treatment at 85℃and 10% RH for 100 hours in air. Then, the acid gas adsorbing material after the heat treatment is set in a vacuum dryer (for example, VOS-310C manufactured by eyla corporation) in a drying chamber, and the treatment is performed at 60 ℃ for 2 hours or more under a vacuum atmosphere. The adsorption amount a4 of carbon dioxide when the adsorption test A1 was performed on the treated acid gas adsorbent was measured. The maintenance rate R1 can be calculated from the following formula based on the obtained adsorption amount a4 and the adsorption amount A1 of carbon dioxide when the adsorption test A1 is performed on the acid gas adsorbent before the heat resistance test.
Maintenance ratio R1 (%) =adsorption amount a4 (mmol/g)/(adsorption amount a1 (mmol/g) ×100)
The adsorption amount a4 of carbon dioxide may be, for example, 0.35mmol/g or more, 0.4mmol/g or more, 0.5mmol/g or more, 0.8mmol/g or more, 1.0mmol/g or more, 1.3mmol/g or more, 1.5mmol/g or more, 1.8mmol/g or more, and further 2.0mmol/g or more. The upper limit of the adsorption amount a4 of carbon dioxide is not particularly limited, and is, for example, 10mmol/g.
(Test for moist Heat resistance)
The acid gas adsorbent of the present embodiment is preferably high in wet heat resistance. The wet heat resistance of the acid gas adsorbing material can be evaluated by, for example, performing a wet heat resistance test on the acid gas adsorbing material. The wet heat resistance test can be performed by, for example, subjecting the acid gas adsorbing material to a heat treatment at 85 ℃ for 100 hours in an environment of 85% rh. As an example, when the acid gas adsorbing material is subjected to heat treatment for 100 hours at 85 ℃ in an environment of 85% rh, the maintenance rate R2 of the amount of carbon dioxide adsorbable (mmol/g) may be, for example, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 85% or more, 90% or more, 95% or more, or 96% or more. The higher the retention rate R2, the higher the wet heat resistance of the acid gas adsorbent. It can be said that the acid gas adsorbing material having high wet heat resistance has high durability when used for a long period of time. The upper limit of the maintenance ratio R2 is not particularly limited, but is, for example, 99%.
In detail, the maintenance rate R2 can be determined by the following method. First, an acid gas adsorbing material is placed in a glass container (for example, laboran screw vial manufactured by AS ONE company) in a drying chamber having a dew point of about-60 ℃. Next, the glass container was set in a constant temperature and humidity machine (for example, PSL-2J manufactured by ESPEC Co., ltd.) and subjected to a heat treatment at 85℃and 85% RH for 100 hours in air. Then, the acid gas adsorbing material after the heat treatment is set in a vacuum dryer (for example, VOS-310C manufactured by eyla corporation) in a drying chamber, and the treatment is performed at 60 ℃ for 2 hours or more under a vacuum atmosphere. The adsorption amount a5 of carbon dioxide when the adsorption test A1 was performed on the treated acid gas adsorbent was measured. The maintenance rate R2 can be calculated from the following equation based on the obtained adsorption amount a5 and the adsorption amount A1 of carbon dioxide when the adsorption test A1 is performed on the acid gas adsorbent before the wet heat resistance test.
Maintenance ratio R2 (%) =adsorption amount a5 (mmol/g)/(adsorption amount a1 (mmol/g) ×100)
The adsorption amount a5 of carbon dioxide may be, for example, 0.35mmol/g or more, 0.4mmol/g or more, 0.5mmol/g or more, 0.8mmol/g or more, 1.0mmol/g or more, 1.3mmol/g or more, 1.5mmol/g or more, 1.8mmol/g or more, 2.0mmol/g or more, or further 2.1mmol/g or more. The upper limit of the adsorption amount a5 of carbon dioxide is not particularly limited, and is, for example, 10mmol/g.
(Polymer)
In the acid gas adsorbing material, the polymer P has a function of adsorbing an acid gas due to an amino group. The polymer P contains, for example, at least 1 selected from the group consisting of primary amino groups, secondary amino groups, and tertiary amino groups as amino groups. From the viewpoint of the adsorptivity of the acid gas, the polymer P preferably contains at least 1 selected from the group consisting of primary amino groups and secondary amino groups, and particularly preferably contains secondary amino groups. In other words, the amino group of the polymer P preferably contains a secondary amino group. If the polymer P having a secondary amino group is used, the adsorbed acid gas tends to be easily desorbed. That is, when the polymer P having a secondary amino group is used, the regeneration treatment of the acid gas adsorbing material can be performed under relatively mild conditions. The polymer P may or may not contain a tertiary amino group.
The weight ratio of nitrogen element in the polymer P is, for example, 5wt% or more, preferably 10wt% or more. The higher the weight ratio, the more the adsorptivity of the acid gas in the acid gas adsorbing material tends to be improved. The upper limit of the weight ratio of nitrogen element in the polymer P is not particularly limited, and is, for example, 30wt%. When all nitrogen elements contained in the polymer P are derived from amino groups, the weight ratio of the nitrogen elements can be regarded as the weight ratio of the amino groups in the polymer P.
The density of nitrogen element in the polymer P is, for example, more than 12.0mmol/g, preferably 12.2mmol/g or more, but may be 12.5mmol/g or more, 13.0mmol/g or more, 13.5mmol/g or more, 14.0mmol/g or more, 14.5mmol/g or more, 15.0mmol/g or more, and further may be 15.5mmol/g or more. The upper limit of the density of nitrogen element is not particularly limited, and may be, for example, 30mmol/g or 20mmol/g. In the present specification, the density of the nitrogen element in the polymer P means the amount of the nitrogen element contained in 1g of the polymer P, and can be measured by the same method as the density d of the nitrogen element in the acid gas adsorbing material described above, for example. In the case where all nitrogen elements contained in the polymer P are derived from amino groups, the density of the nitrogen elements can be regarded as the density of the amino groups in the polymer P.
The polymer P may also contain other functional groups than amino groups. Examples of the other functional group include a hydroxyl group, an ether group, an ester group, and an amide group. The polymer P preferably contains ether groups as further functional groups.
The polymer P is, for example, an amine polymer comprising structural units U1 from an epoxy monomer. The amine polymer includes, for example, at least 1 selected from the group consisting of a polymer P1 of a monomer group including an amine monomer and an epoxy monomer, and a reactant P2 of a compound group including an amine prepolymer and an epoxy monomer, preferably the reactant P2. The reactant P2 tends to have high heat resistance and moist heat resistance as well as high density of nitrogen element. Specific examples of the reactant P2 are those obtained by crosslinking an amine prepolymer with an epoxy monomer (crosslinked product).
As described above, the monomer group for forming the polymer P1 includes the amine monomer and the epoxy monomer, and is preferably composed of only these monomers. That is, the polymer P1 is preferably a polymer of an amine monomer and an epoxy monomer.
Amine monomers are monomers containing at least 1 amino group, for example, containing at least 1 primary amino group. The number of primary amino groups contained in the amine monomer is preferably 2 or more, but may be 3 or more, or may be 4 or more. The upper limit of the number of primary amino groups is not particularly limited, and is, for example, 10. The amine monomer may or may not contain a secondary amino group or a tertiary amino group in addition to the primary amino group. The ratio of the number of primary amino groups to the total number of amino groups in the amine monomer is not particularly limited, and is, for example, 10% or more, preferably 20% or more, more preferably 30% or more, and may be 40% or more. The upper limit of the ratio is not particularly limited, and may be, for example, 80% or 60%.
The molecular weight of the amine monomer is, for example, 50 or more, preferably 100 or more, and more preferably 150 or more. The greater the molecular weight of the amine monomer, the greater the density of nitrogen element in the polymer P1 can be easily adjusted. The upper limit of the molecular weight of the amine monomer is not particularly limited, and is, for example, less than 1000, preferably 500 or less, and may be 300 or less. The amine equivalent of the amine monomer is, for example, 10g/eq. Or more, preferably 20g/eq. Or more, more preferably 30g/eq. Or more. The greater the amine equivalent of the amine monomer, the greater the density of nitrogen element in the polymer P1 can be easily adjusted. The upper limit of the amine equivalent of the amine monomer is not particularly limited, and is, for example, 150g/eq. Or less, preferably 100g/eq. Or less, or 50g/eq. Or less. In the present specification, the term "amine equivalent" means the mass of the amine monomer relative to 1 equivalent of active hydrogen of the primary amino group contained in the amine monomer.
Examples of the amine monomer include aliphatic amines such as ethylamine, ethylenediamine, 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, 1, 7-heptanediamine, 1, 8-octanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, iminodipropylamine, bis (hexamethylenetriamine, 1,3, 6-trisaminomethylhexane, tris (2-aminoethyl) amine, N' -bis (3-aminopropyl) ethylenediamine, polymethylenediamine, trimethylhexamethylenediamine, and polyetherdiamine; and alicyclic amines such as isophoronediamine, menthanediamine, piperazine, N-aminoethylpiperazine, 3, 9-bis (3-aminopropyl) 2,4,8, 10-tetraoxaspiro (5, 5) undecane adducts, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, and modified products thereof. The amine monomer preferably comprises an aliphatic amine, especially triethylenetetramine (TETA). The amine monomer may be used alone or in combination of 2 or more.
The epoxy monomer is a monomer containing at least 1 epoxy group. The number of epoxy groups contained in the epoxy monomer is preferably 2 or more, but may be 3 or more, or may be 4 or more. The more the number of epoxy groups is, the more the crosslinking points in the epoxy monomer are increased, and the denser the crosslinked structure in the polymer P1, whereby the heat resistance and the moist heat resistance tend to be improved. The upper limit of the number of epoxy groups contained in the epoxy monomer is not particularly limited, and is, for example, 10.
The molecular weight of the epoxy monomer is not particularly limited, and is, for example, less than 1000, preferably 500 or less. The epoxy equivalent of the epoxy monomer is not particularly limited, and is, for example, 150g/eq. Or less, preferably 100g/eq. Or less. The density of nitrogen element in the polymer P1 tends to increase as the epoxy equivalent of the epoxy monomer is smaller. The lower limit of the epoxy equivalent of the epoxy monomer is not particularly limited, and is, for example, 50g/eq. The epoxy equivalent means the mass of an epoxy monomer containing 1 equivalent of an epoxy group.
Examples of the epoxy monomer include monofunctional epoxy compounds such as n-butyl glycidyl ether, higher alcohol glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, tolyl glycidyl ether, p-sec-butylphenyl glycidyl ether, and t-butylphenyl glycidyl ether; diepoxy alkanes such as 1, 5-hexadiene diepoxide, 1, 7-octadiene diepoxide, 1, 9-decadiene diepoxide; polyfunctional epoxy compounds having an ether group such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether; polyfunctional epoxy compounds having an amino group such as N, N' -tetraglycidyl m-xylylenediamine and 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane.
The epoxy monomer may be an aromatic epoxy resin, a non-aromatic epoxy resin, or the like, as the case may be. Examples of the aromatic epoxy resin include a polyphenyl epoxy resin (polyphenyl-based epoxy resin), an epoxy resin containing a fluorene ring, an epoxy resin containing triglycidyl isocyanurate, and an epoxy resin containing a heteroaromatic ring (for example, a triazine ring). Examples of the polyphenyl epoxy resin include bisphenol a type epoxy resin, brominated bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, stilbene type epoxy resin, biphenyl type epoxy resin, bisphenol a Novolac type epoxy resin, cresol Novolac type epoxy resin, diaminodiphenylmethane type epoxy resin, and tetra (hydroxyphenyl) ethyl epoxy resin. Examples of the non-aromatic epoxy resin include aliphatic glycidyl ether type epoxy resins, aliphatic glycidyl ester type epoxy resins, alicyclic glycidyl ether type epoxy resins, alicyclic glycidyl amine type epoxy resins, and alicyclic glycidyl ester type epoxy resins.
The epoxy monomer may be used alone or in combination of 2 or more. In the case of using a monofunctional epoxy compound, it is preferable to use the monofunctional epoxy compound in combination with another epoxy monomer having 2 or more epoxy groups. The monofunctional epoxy compound can also be used as a reactive diluent for adjusting the viscosity of the monomer set used to form the polymer P1.
The epoxy monomer preferably contains a polyfunctional epoxy compound having an ether group such as ethylene glycol diglycidyl ether (EDE) and pentaerythritol tetraglycidyl ether (PETG). The EDE and PETG have small epoxy equivalent, and the glass transition temperature Tg of the polymer P can be easily lowered. These epoxy compounds also tend to be low in cost. The epoxy monomer may contain a polyfunctional epoxy compound having an amino group such as N, N' -tetraglycidyl m-xylylenediamine, 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane, or the like, together with or in place of the polyfunctional epoxy compound having an ether group.
The amine prepolymers used to form reactant P2 comprise, for example, at least 1 amino group, in particular a primary amino group. The number of primary amino groups contained in the amine prepolymer is preferably 2 or more, but may be 3 or more, or may be 4 or more. The upper limit of the number of primary amino groups is not particularly limited, and is, for example, 100. The amine prepolymer may contain secondary amino groups in addition to primary amino groups, tertiary amino groups. The ratio of the number of primary amino groups to the total number of amino groups in the amine prepolymer is not particularly limited, and is, for example, 10% or more, preferably 20% or more, more preferably 30% or more, and may be 40% or more. The higher the ratio, the more the crosslinking points in the amine prepolymer are increased, and the crosslinked structure in the reactant P2 becomes dense, and thus the heat resistance and moist heat resistance tend to be improved. The upper limit of the ratio is not particularly limited, and may be, for example, 80% or 60%.
The weight average molecular weight of the amine prepolymer is not particularly limited, and may be, for example, 200 or more, 300 or more, 500 or more, 1000 or more, and 1500 or more. Amine prepolymers with large weight average molecular weights tend to be highly safe in handling. In addition, when an amine prepolymer having a large weight average molecular weight is used, the density of nitrogen element in the reactant P2 tends to increase. The upper limit of the weight average molecular weight of the amine prepolymer is not particularly limited, and is, for example, 5000. The amine equivalent of the amine prepolymer is, for example, 10g/eq. Or more, preferably 20g/eq. Or more, more preferably 30g/eq. Or more. The upper limit of the amine equivalent of the amine prepolymer is not particularly limited, and may be, for example, 200g/eq. Or less, 150g/eq. Or less, or 100g/eq. Or less. The number of structural units (polymerization degree) contained in the amine prepolymer is not particularly limited, and is, for example, 5 to 100.
Examples of the amine prepolymer include aliphatic polyamines such as polyethyleneimine and polyalkylenepolyamine; amino group-containing (meth) acrylic polymers such as amino ethylated acrylic polymers; aliphatic polyamidoamine (ALIPH ATIC polyamideamines) formed by the reaction of a polyamine with a dimer acid, and the like. The amine prepolymer preferably comprises an aliphatic polyamine, in particular Polyethylenimine (PEI). The amine prepolymer may be used alone or in combination of 2 or more.
Amine prepolymers, particularly PEI, tend to be safer to handle than amine monomers. As an example, the amine prepolymer may not be a hazardous material in the fire control law, or may not be a target substance in the poison and highly toxic substance banning law. The amine prepolymer may also be a substance that is negative as a result of a mutagenicity test (Ames test). The amine prepolymer may also be a substance that results from a skin irritation test (a single irritation test using rabbit skin) as a mild or moderate irritant.
Examples of the epoxy monomer used to form the reactant P2 include the epoxy monomers described above for the polymer P1.
As described above, the polymer P as an amine polymer contains the structural unit U1 derived from an epoxy monomer. In the case where the polymer P is the polymer P1, the polymer P further comprises a structural unit U2 derived from an amine monomer. The content of the structural unit U1 in the polymer P, particularly the polymer P1, is, for example, 20wt% to 70wt%. The content of the structural unit U2 in the polymer P, particularly the polymer P1, is, for example, 30wt% or more, preferably 50wt% or more. The upper limit of the content of the structural unit U2 is not particularly limited, but is, for example, 80wt%.
The glass transition temperature Tg of the polymer P is not particularly limited, and is, for example, 40 ℃ or less, preferably 30 ℃ or less, more preferably 20 ℃ or less, further preferably 15 ℃ or less, and may be 10 ℃ or less, or may be 5 ℃ or less, or may be 0 ℃ or less. When the glass transition temperature Tg of the polymer P is low to this extent, the acid gas adsorbing material tends to adsorb acid gas at a high rate. The lower limit value of the glass transition temperature Tg of the polymer P is, for example, -100 ℃, preferably-50 ℃, more preferably-10 ℃ from the viewpoint of sufficiently securing the adsorptivity of the acid gas in the acid gas adsorbing material and the viewpoint of heat resistance. In the present specification, the glass transition temperature Tg means a glass transition temperature according to JIS K7121:1987, the intermediate point glass transition temperature (T mg). The polymer P generally belongs to a thermosetting resin. The polymer P is solid at, for example, 25℃and preferably in the range of 25℃to 80 ℃.
The weight average molecular weight of the polymer P is not particularly limited, and is, for example, 500 or more, preferably 1000 or more, more preferably 10000 or more, and still more preferably 100000 or more. The upper limit of the weight average molecular weight of the polymer P is 10000000, for example.
The acid gas adsorbing material contains, for example, a polymer P as a main component. In the present specification, the "main component" means a component contained in the acid gas adsorbing material at the largest weight ratio. The content of the polymer P in the acid gas adsorbing material is, for example, 50wt% or more, preferably 70wt% or more, more preferably 90wt% or more, or 95wt% or more, or 99wt% or more. The acid gas adsorbing material may consist essentially of only polymer P. The higher the content of the polymer P, the more the adsorptivity of the acid gas in the acid gas adsorbing material tends to be improved.
The acid gas adsorbing material may be substantially composed of only the polymer P, but may further contain other components than the polymer P. Examples of the other components include a reaction accelerator, a plasticizer, a pigment, a dye, an anti-aging agent, a conductive material, an antistatic agent, an ultraviolet absorber, a flame retardant, an antioxidant, and the like. The reaction accelerator is used, for example, in the synthesis of the polymer P. Examples of the reaction accelerator include tertiary amines such as triethylamine and tributylamine; imidazoles such as 2-phenol-4-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenol-4, 5-dihydroxyimidazole. These reaction promoters are capable of promoting reactions, for example, for the synthesis of the polymer P1.
The weight ratio of nitrogen element in the acid gas adsorbing material is, for example, 5wt% or more, preferably 10wt% or more. The higher the weight ratio, the more the adsorptivity of the acid gas in the acid gas adsorbing material tends to be improved. The upper limit of the weight ratio of nitrogen element in the acid gas adsorbing material is not particularly limited, and is, for example, 30wt%. When all nitrogen elements contained in the acid gas adsorbent are derived from amino groups, the weight ratio of nitrogen elements described above can be regarded as the weight ratio of amino groups in the acid gas adsorbent.
The shape of the acid gas adsorbing material is not particularly limited, and may be, for example, a block shape, a sheet shape, a particle shape, or the like. In the present specification, the particle shape includes a sphere shape, an ellipsoid shape, a scale shape, a fiber shape, and the like.
The acid gas adsorbing material may have a porous structure. As an example, the acid gas adsorbing material may be provided with a porous body S containing the polymer P. Typically, the porous body S is composed of only the polymer P. The porous body S has a block shape, a sheet shape, a particle shape, or the like. The acid gas adsorbing material may or may not include a porous resin sheet as the porous body S. The acid gas adsorbing material may not include a member other than the porous body S, for example, a carrier for carrying the polymer P. In the case where the acid gas adsorbing material does not include a carrier or the like, the shape of the acid gas adsorbing material tends to be easily adjusted by cutting.
The porous body S has, for example, a three-dimensional network skeleton composed of the polymer P. In the porous body S, for example, the three-dimensional network skeleton described above extends continuously. The pores included in the porous body S are, for example, continuous pores formed continuously in three dimensions. The porous body S may have individual pores or may have penetrating pores penetrating the porous body S.
The specific surface area of the acid gas adsorbing material (porous body S) is not particularly limited, and may be, for example, 0.5m 2/g or more, 1.0m 2/g or more, 2.0m 2/g or more, 3.0m 2/g or more, 4.0m 2/g or more, 5.0m 2/g or more, 6.0m 2/g or more, 7.0m 2/g or more, 8.0m 2/g or more, and further 9.0m 2/g or more. There is a tendency to: the greater the specific surface area of the acid gas adsorbing material, the greater the rate of adsorption of the acid gas in the acid gas adsorbing material. The upper limit of the specific surface area of the acid gas adsorbing material is not particularly limited, but is, for example, 100m 2/g. The specific surface area of the acid gas adsorbing material is BET (Brunauer-Emmett-Teller) specific surface area obtained by nitrogen adsorption. The specific surface area of the acid gas adsorbing material can be determined by the method according to JIS Z8830:2013 is measured by a predetermined method.
Viewed from another aspect the present invention provides an acid gas adsorbing material, which is an acid gas adsorbing material comprising a polymer P having amino groups,
The density d of nitrogen element in the acid gas adsorption material is more than 12.0mmol/g,
The specific surface area of the acid gas adsorption material is more than 0.5m 2/g,
The glass transition temperature of the polymer P is 40 ℃ or lower.
The acid gas adsorbent has, for example, the adsorption characteristics and the desorption characteristics described above for carbon dioxide. As an example, the acid gas adsorbing material may be subjected to the ranges exemplified above, such as adsorption amounts a1 to a3, desorption amounts b1 to b2, a 50 ℃ desorption rate, and a 65 ℃ desorption rate, which are measured by the above-described methods.
The pore volume of the acid gas adsorbing material (porous body S) is not particularly limited, and may be, for example, 0.1cm 3/g or more, 0.2cm 3/g or more, 0.3cm 3/g or more, 0.5cm 3/g or more, 1.0cm 3/g or more, or 2.0cm 3/g or more. The upper limit of the pore volume of the acid gas adsorbing material is not particularly limited, and may be, for example, 5.0cm 3/g, 4.0cm 3/g, or 3.0cm 3/g. The pore volume of the acid gas adsorbing material can be measured by mercury porosimetry. The mercury porosimetry is performed under an initial pressure of 21kPa using a commercially available pore-distribution analyzer (for example, AUTOPORE V9620 manufactured by Micromeritics).
The average pore diameter of the acid gas adsorbing material (porous body S) is not particularly limited, and may be, for example, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, or 0.5 μm or more. The upper limit of the average pore diameter of the acid gas adsorbing material is not particularly limited, and is, for example, 50. Mu.m. In the present specification, the average pore diameter of the acid gas adsorbing material means a median particle diameter measured by mercury intrusion. The mercury porosimetry is performed under an initial pressure of 21kPa using a commercially available pore-distribution analyzer (for example, AUTOPORE V9620 manufactured by Micromeritics).
When the acid gas adsorbent is in the form of particles, the average particle diameter of the acid gas adsorbent is not particularly limited, and is, for example, 0.5 μm or more, preferably 1 μm or more, or may be 10 μm or more, or may be 20 μm or more, or may be 30 μm or more. The average particle diameter of the acid gas adsorbing material may be 200 μm or less, 100 μm or less, or less than 75 μm. In the present specification, the average particle diameter of the acid gas adsorbing material means a particle diameter (d 50) corresponding to 50% by volume accumulation in a particle size distribution measured by a laser diffraction type particle size meter or the like.
(Method for producing acid gas adsorbing Material)
The method for producing the acid gas adsorbing material according to the present embodiment includes, for example, a step of reacting a compound group including an amine monomer, an amine prepolymer, and an epoxy monomer to form the polymer P. The group of compounds is, for example, a group of monomers comprising amine monomers and epoxy monomers. Wherein the group of compounds may also comprise amine prepolymers in place of or in addition to the amine monomers.
The compound group may contain only the epoxy monomer E1 containing 2 epoxy groups, or may contain the epoxy monomer E2 containing 3 or more, for example, 4 epoxy groups in place of the epoxy monomer E1 or together with the epoxy monomer E1. When the compound group includes the epoxy monomers E1 and E2, the weight ratio E1/E2 of the epoxy monomer E2 to the epoxy monomer E1 is not particularly limited, and is, for example, 4/6 to 8/2.
In the case of producing the polymer P, the compounding ratio of the epoxy monomer to the amine monomer or the amine prepolymer is preferably set such that the ratio E/a of the equivalent (E) of the epoxy group contained in the epoxy monomer to the equivalent (a) of the active hydrogen of the primary amino group contained in the amine monomer or the amine prepolymer is, for example, 1 or less, preferably 0.9 or less, more preferably 0.5 or less. The density d of nitrogen element in the acid gas adsorbing material tends to increase as the ratio E/a is smaller. The lower limit of the ratio E/A is not particularly limited, and is, for example, 0.1.
The reaction of the group of compounds is, for example, a polymerization reaction of an amine monomer with an epoxy monomer. Wherein the reaction of the group of compounds may also be a crosslinking reaction of an amine prepolymer based on epoxy monomers. In the reaction of the compound group, the amino group of the amine monomer or amine prepolymer reacts with the epoxy group of the epoxy monomer. The reaction of the group of compounds may be performed by applying energy to the group of compounds. The energy applied to the group of compounds is preferably thermal energy. As an example, the reaction of the compound set may be performed by heating the compound set at a temperature of 40℃to 100 ℃. The energy applied to the compound group may be light energy.
The acid gas adsorbing material having a porous structure can be produced, for example, by the following method. First, the compound set described above was mixed with a pore-forming agent to prepare a mixed solution. The porogen is, for example, a solvent capable of dissolving the monomer or prepolymer contained in the compound group and further capable of causing reaction-induced phase separation after the compound group has reacted. Specific examples of the pore-forming agent include cellosolves such as methyl cellosolve and ethyl cellosolve, esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, glycols such as polyethylene glycol, polypropylene glycol and polyoxyalkylene glycol, and ethers such as polyoxyethylene monomethyl ether and polyoxyethylene dimethyl ether. Specific examples of polyoxyalkylene glycol include poly (1, 2-butanediol) -6-propanediol, polyoxypropylene diglycerol ether, and the like. The pore-forming agent may be ethyl acetate, N-Dimethylformamide (DMF), polar solvents such as acetonitrile, ethanol and isopropanol, nonpolar solvents such as toluene, or a mixed solvent thereof. The porogen may be used alone or in combination of 2 or more.
To the mixed solution, other components than the compound group may be further added. Examples of the other component include the reaction accelerator described above.
Next, the compound group is reacted in the mixed solution. As an example, the compound group is reacted by filling the mixed solution into a mold and then performing a heat treatment. Thereby, a cured body containing the polymer P and the porogen is obtained. In the cured body, the polymer P is phase-separated from the porogen, thereby forming a co-continuous structure.
Next, the porogen is extracted from the solidified body and removed. Thus, an acid gas adsorbing material having a porous structure can be obtained. The extraction of the porogen may be performed, for example, by immersing the cured body in a solvent. As the solvent, water, an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, an aliphatic alcohol solvent, an ester solvent, an ether solvent, a halogen-containing organic solvent, and the like can be used. Examples of the aliphatic hydrocarbon solvent include n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, isooctane, petroleum ether, and petroleum essence (benzine). Examples of the aromatic hydrocarbon solvent include toluene, xylene, mesitylene, benzene, and the like. Examples of the aliphatic alcohol solvent include methanol, ethanol, isopropanol, butanol, cyclohexanol, ethylene glycol, propylene glycol monomethyl ether, diethylene glycol, and the like. The ester solvent includes ethyl acetate and the like. Examples of the ether solvent include diethyl ether, diisopropyl ether, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, anisole, and the like. Examples of the halogen-containing organic solvent include methylene chloride, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, and the like. These solvents may be used singly or in combination of 2 or more.
In the production of a cured product, the greater the reaction rate of the compound group, the finer the pore-forming agent tends to be dispersed in the cured product. By removing the pore-forming agent from the solidified body in which the pore-forming agent is finely dispersed, an acid gas adsorbing material having a large specific surface area can be produced. The reaction rate of the compound group varies depending on, for example, the kind of monomer, prepolymer, compounding ratio, and the like contained in the compound group. As an example, in the case of using an epoxy monomer E2 containing 3 or more, for example, 4 epoxy groups, the case of using a polyethyleneimine having a large weight average molecular weight as an amine prepolymer, or the like, the reaction rate of the compound group tends to be large.
(Use of acid gas adsorbing Material)
The acid gas adsorbing material of the present embodiment can adsorb acid gas. Examples of the acid gas include carbon dioxide, hydrogen sulfide, carbonyl sulfide, sulfur oxides (SOx), hydrogen cyanide, and nitrogen oxides (NOx), and carbon dioxide is preferable.
The acid gas adsorbing material can be used by the following method, for example. First, a mixed gas containing an acid gas is brought into contact with an acid gas adsorbing material. The mixed gas contains, for example, other gases than the acid gas. Examples of the other gas include nonpolar gases such as hydrogen and nitrogen, and inert gases such as helium, and nitrogen is preferable. The mixed gas is typically atmospheric air. The mixed gas may be waste gas of chemical plant equipment or thermal power generation.
The temperature of the mixed gas is, for example, room temperature (23 ℃). The concentration of the acid gas in the mixed gas is not particularly limited, and may be, for example, 0.01vol% (100 volppm) or more, preferably 0.04vol% (400 volppm) or more, or 1.0vol% or more in the standard state (0 ℃ C., 101 kPa). The upper limit of the concentration of carbon dioxide in the mixed gas is not particularly limited, and is, for example, 10vol% in a standard state. Typically, the pressure of the mixed gas is equal to the atmospheric pressure in the environment in which the acid gas adsorbing material is used. However, the mixed gas contacting the acid gas adsorbing material may be pressurized.
The acid gas adsorbing material in contact with the mixed gas adsorbs the acid gas contained in the mixed gas. The operation of bringing the mixed gas into contact with the acid gas adsorbing material is performed, for example, until the adsorption of the acid gas by the acid gas adsorbing material reaches equilibrium.
Next, the acid gas adsorbing material to which the acid gas is adsorbed is subjected to a regeneration treatment. The regeneration treatment may be performed by heating the acid gas adsorbing material, for example. The heating temperature of the acid gas adsorbing material is, for example, 50 to 80 ℃. The acid gas adsorbing material may be heated under a reduced pressure atmosphere or a vacuum atmosphere. By heating the acid gas adsorbing material, the acid gas is desorbed from the acid gas adsorbing material. Thereby, the acid gas adsorbent is regenerated, and the acid gas adsorbent can be reused. Acid gases, especially carbon dioxide, desorbed from the acid gas adsorbing material can be used as synthesis raw materials for chemicals, dry ice. The acid gas adsorption operation by the acid gas adsorbent and the regeneration treatment of the acid gas adsorbent can be performed using the measurement apparatus 10 (acid gas adsorbent) described above.
Examples
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited thereto.
Example 1
First, 1.73g of poly (1, 2-butanediol) -6-propanediol (manufactured by Nitro oil Co., ltd., UNIOL (registered trademark) PB-500) and 0.43g of polyoxypropylene diglycerol ether (manufactured by Nitro oil Co., ltd., UNILUB (registered trademark) DGP-700) were added to a 6mL screw vial (manufactured by AS ONE Co., ltd.). To the obtained mixed solution, 0.74g of ethylene glycol diglycidyl ether (manufactured by NAGASE CHEM tex, EX-810) and 0.74g of pentaerythritol tetraglycidyl ether (manufactured by sho-am electric company, shofree (registered trademark) PETG) were dissolved, to prepare a mixed solution of an epoxy monomer and a porogen.
Next, 1.56g of polyethyleneimine (Epom in SP-003, manufactured by Japanese catalyst Co., ltd.) was added to the mixture, to thereby prepare a mixture of an epoxy monomer, an amine prepolymer and a porogen. In this mixed solution, the ratio E/A of the equivalent (E) of the epoxy group contained in the epoxy monomer to the equivalent (A) of the active hydrogen of the primary amino group contained in the amine prepolymer was 0.5.
Next, the intensity of the bench oscillator (Angel Vibrator Digital Hz) was set to 5, and the mixture was oscillated for 2 minutes. Next, the mixture was allowed to stand in a constant temperature bath at 80 ℃ for 2 hours, thereby solidifying the mixture. Thus, a block-shaped cured body containing the polymer P having an amino group was obtained. The cured product was taken out of the screw vial and cut into about 3mm square. Next, the operation of immersing the cured body in ethyl acetate at 60 ℃ for 1 hour was repeated 2 times to perform liquid exchange. Thus, the porogen is removed from the cured body, and a porous body comprising the polymer P is formed. The porous body was dried at 60℃for 1 hour and further dried under vacuum for 2 hours, whereby the acid gas adsorbing material of example 1 was obtained.
Examples 2 to 11
Acid gas adsorbing materials of examples 2 to 11 were obtained in the same manner as in example 1, except that the types and the blending amounts of the raw materials were changed as shown in table 1.
Comparative example 1
First, 2.63g of polypropylene glycol (manufactured by ADEKA, ADEKA POLYETHER P-400) and 0.36g of polyethylene glycol (manufactured by Sigma-Aldrich, average molecular weight 200) were added to a 6mL screw vial (manufactured by AS ONE). 1.58g of bisphenol A type epoxy resin (JER g, JER, manufactured by Mitsubishi chemical corporation) was dissolved in the obtained mixed solution, to thereby prepare a mixed solution of an epoxy prepolymer and a porogen.
Next, 0.60g of triethylenetetramine was added to the mixed solution, thereby preparing a mixed solution of an epoxy prepolymer, an amine monomer and a porogen. In this mixed solution, the ratio E/A of the equivalent (E) of the epoxy group contained in the epoxy prepolymer to the equivalent (A) of the active hydrogen of the primary amino group contained in the amine monomer was 0.5.
Next, the intensity of the bench oscillator (Angel Vibrator Digital Hz) was set to 5, and the mixture was oscillated for 2 minutes. Next, the mixture was allowed to stand in a constant temperature bath at 80 ℃ for 4 hours, thereby solidifying the mixture. Thus, a block-shaped cured body containing the polymer P having an amino group was obtained. The cured product was taken out of the screw vial and cut into about 3mm square. Next, the operation of immersing the cured body in isopropyl alcohol at 60 ℃ for 1 hour was repeated 2 times to perform liquid replacement. Further, the operation of immersing the cured body in ultrapure water at 60℃for 1 hour was repeated 2 times so as to perform liquid exchange. Next, the cured body was immersed in methanol at room temperature for 1 hour. The cured product was air-dried at room temperature for 12 hours, and further vacuum-dried at 60℃for 8 hours, whereby the acid gas adsorbing material of comparative example 1 was obtained.
Comparative examples 2 to 3
Acid gas adsorbing materials of comparative examples 2 to 3 were obtained in the same manner as in comparative example 1 except that the types and the blending amounts of the raw materials were changed as shown in table 1.
[ Density of Nitrogen element ]
The density d of nitrogen element in the produced acid gas adsorbing material was measured by the method described above. As a CHN element analyzer, vario EL III manufactured by Elementar was used.
[ Specific surface area ]
The produced acid gas adsorbing material was produced by a method according to JIS Z8830:2013, the specific surface area was measured by a predetermined method. For the measurement, a specific surface area measuring device (trade name "BERSORP-mini", manufactured by MicrotracBEL Co., ltd.) was used.
[ Glass transition temperature Tg ]
The glass transition temperature Tg of the polymer contained in the produced acid gas adsorbing material was measured by the following method. First, about 5mg of the acid gas adsorbing material was set in a differential scanning calorimeter (DSC 2500, manufactured by TA Instruments). With this apparatus, the temperature was increased from 30℃to 200℃at a heating rate of 10℃per minute under a nitrogen atmosphere, and the temperature was maintained for 1 minute. Then, the mixture was cooled to-50℃at a cooling rate of 10℃per minute, and after the mixture was kept at that temperature for 1 minute, the mixture was further heated to 200℃at a heating rate of 10℃per minute. In the DSC curve at the time of the 2 nd temperature rise, the 1 st base line before occurrence of the change in specific heat, the 2 nd base line after occurrence of the change in specific heat, and a tangent line passing through a point having the largest gradient among the curved portions formed by the change in specific heat are determined. The intermediate temperatures of the intersection point of the 1 st base line and the tangential line and the intersection point of the 2 nd base line and the tangential line are determined as the glass transition temperature Tg.
[ Adsorption amount of carbon dioxide ]
The adsorption amounts a1 to a3 and the desorption amounts b1 to b2 of the produced acid gas adsorbing materials were measured by the above-described methods. Based on the results, the ratio of the desorption amount b1 (mmol/g) to the adsorption amount a1 (mmol/g) (desorption rate at 50 ℃) and the ratio of the desorption amount b2 (mmol/g) to the adsorption amount a1 (mmol/g) (desorption rate at 65 ℃) were calculated.
[ Heat resistance test ]
The produced acid gas adsorbent was subjected to a heat resistance test by the method described above, and the carbon dioxide adsorption amount a4 was measured. Further, the ratio (maintenance ratio R1) of the adsorption amount a4 (mmol/g) to the adsorption amount a1 (mmol/g) was calculated.
[ Test for resistance to moist Heat ]
The wet heat resistance test was performed on the produced acid gas adsorbent by the method described above, and the adsorption amount a5 of carbon dioxide was measured. Further, the ratio (maintenance ratio R2) of the adsorption amount a5 (mmol/g) to the adsorption amount a1 (mmol/g) was calculated.
TABLE 1
In table 1, the epoxy monomer and the epoxy prepolymer are simply expressed as epoxy compounds. The amine monomer and the amine prepolymer are simply referred to as amine compounds.
The abbreviations in table 1 are as follows.
EDE: ethylene glycol diglycidyl ether (manufactured by Nagase Chemtex corporation, EX-810)
JER828: bisphenol A type epoxy resin (JER 828 manufactured by Mitsubishi chemical corporation)
PETG: pentaerythritol tetraglycidyl Ether (Shofree (registered trademark) PETG manufactured by Showa electric company)
T-C:1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane (manufactured by Mitsubishi GAS CHEMICAL Company, TETRAD-C)
T-X: n, N, N ', N' -tetraglycidyl m-xylylenediamine (manufactured by Mitsubishi GAS CHEMICAL Company, TETRAD-X)
PEI300: polyethyleneimine (Epomin SP-003, manufactured by Japanese catalyst Co., ltd., weight average molecular weight of about 300)
PEI1200: polyethyleneimine (Epomin SP-012, manufactured by Japanese catalyst Co., ltd., weight average molecular weight of about 1200)
PEI1800: polyethyleneimine (Epomin SP-018, manufactured by Japanese catalyst Co., ltd., weight average molecular weight of about 1800)
TETA: triethylenetetramine (manufactured by TOSOH Co., ltd.)
PB-500: poly (1, 2-butanediol) -6-propanediol (manufactured by Nipple Co., ltd., UNIOL (registered trademark) PB-500)
P-400: polypropylene glycol (manufactured by ADEKA company ADEKA POLYETHER P-400)
DGP-700: polyoxypropylene diglycerol ether (UNILUB (registered trademark) DGP-700 manufactured by Nitro oil Co., ltd.)
PB-700: copolymers of butanediol and propylene glycol (UNIOL (registered trademark) PB-700 manufactured by Nitro oil Co., ltd.)
PEG: polyethylene glycol (Sigma-Aldrich Co., ltd., average molecular weight of 200)
The indicators of the safety in handling of the amine compounds used in examples and comparative examples are shown in table 2 below.
TABLE 2
TABLE 3
As is clear from table 3, the density d of nitrogen element in the acid gas adsorbing material of example was large, and the adsorption amount a1 and the desorption amount b1 were also large. The acid gas adsorbing material of the example is said to be suitable for adsorption and desorption of acid gas under relatively mild conditions.
Industrial applicability
The acid gas adsorbent according to the present embodiment can adsorb carbon dioxide in the atmosphere, for example.
Claims (21)
1. An acid gas adsorbing material comprising a polymer having an amino group,
The density of nitrogen element in the acid gas adsorption material is more than 12.0mmol/g,
When the following adsorption test A1 was carried out, the adsorption amount A1 of carbon dioxide was 0.35mmol/g or more,
When the following release test B1 was carried out, the release amount B1 of carbon dioxide was 0.2mmol/g or more,
Adsorption test A1: continuously conveying a mixed gas consisting of carbon dioxide, nitrogen and steam into a container containing the acid gas adsorption material for 15 hours; wherein the concentration of the carbon dioxide in the mixed gas is 400volppm, the temperature of the mixed gas is 23 ℃ and the humidity is 50% rh;
Detachment test B1: the acid gas adsorbent after the adsorption test A1 was heated at 50 ℃ for 1.5 hours while the mixed gas was continuously fed into the vessel.
2. The acid gas adsorbing material as set forth in claim 1, wherein a ratio of the desorption amount b1 (mmol/g) to the adsorption amount a1 (mmol/g) is 50% or more.
3. The acid gas adsorbing material according to claim 1, wherein the carbon dioxide desorption amount B2 is 0.25mmol/g or more when the following desorption test B2 is performed,
Detachment test B2: the acid gas adsorbent subjected to the adsorption test A1 was heated at 65 ℃ for 1.5 hours while the mixed gas was continuously fed into the vessel.
4. The acid gas adsorbing material as set forth in claim 3, wherein a ratio of the desorption amount b2 (mmol/g) to the adsorption amount a1 (mmol/g) is 70% or more.
5. The acid gas adsorbing material according to claim 1, wherein the adsorption amount A2 of carbon dioxide is 0.05mmol/g or more when the following adsorption test A2 is performed,
Adsorption test A2: the mixed gas was continuously fed into the container for 1 hour.
6. The acidic gas adsorbing material according to claim 1, wherein the adsorption amount A3 of carbon dioxide is 0.1mmol/g or more when the following adsorption test A3 is performed,
Adsorption test A3: the mixed gas was continuously fed into the container for 4 hours.
7. The acid gas adsorbing material as set forth in claim 1, wherein the polymer has a glass transition temperature of 40 ℃ or less.
8. The acid gas adsorbing material as set forth in claim 1, which has a specific surface area of 0.5m 2/g or more.
9. An acid gas adsorbing material comprising a polymer having an amino group,
The density of nitrogen element in the acid gas adsorption material is more than 12.0mmol/g,
The specific surface area of the acid gas adsorption material is more than 0.5m 2/g,
The glass transition temperature of the polymer is below 40 ℃.
10. The acid gas adsorbing material according to claim 1 or 9, wherein the maintenance ratio R1 of the amount of carbon dioxide (mmol/g) that can be adsorbed is 50% or more when the acid gas adsorbing material is subjected to heat treatment at 85 ℃ for 100 hours in an atmosphere of 10% RH.
11. The acid gas adsorbing material according to claim 1 or 9, wherein the maintenance ratio R2 of the amount of carbon dioxide (mmol/g) that can be adsorbed is 50% or more when the acid gas adsorbing material is subjected to heat treatment at 85 ℃ for 100 hours in an environment of 85% RH.
12. The acid gas adsorbing material as set forth in claim 1 or 9, which comprises the polymer as a main component.
13. The acid gas adsorbing material of claim 1 or 9 wherein the polymer is an amine polymer comprising structural units from an epoxy monomer.
14. The acid gas adsorbing material as set forth in claim 13, wherein the amine polymer comprises at least 1 selected from the group consisting of polymer P1 of a monomer group comprising an amine monomer and an epoxy monomer, and reactant P2 of a compound group comprising an amine prepolymer and an epoxy monomer.
15. The acid gas adsorbing material as set forth in claim 14, wherein the amine prepolymer has a weight average molecular weight of 300 or more.
16. The acid gas adsorbing material of claim 14 wherein the amine prepolymer comprises polyethylenimine.
17. The acid gas adsorbing material of claim 14 wherein the amine monomer comprises an aliphatic amine.
18. The acid gas adsorbing material as set forth in claim 13, wherein the epoxy monomer has an epoxy equivalent weight of 150g/eq.
19. The acid gas adsorbing material as set forth in claim 13, wherein the epoxy monomer comprises a multifunctional epoxy compound having an ether group.
20. The acid gas adsorbing material as set forth in claim 1 or 9, which has a porous structure.
21. An acid gas adsorption device comprising an adsorption unit having a gas inlet and a gas outlet,
The adsorption unit houses the acid gas adsorption material according to claim 1 or 9.
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| PCT/JP2022/035487 WO2023063051A1 (en) | 2021-10-15 | 2022-09-22 | Acidic gas adsorbent and acidic gas adsorption device |
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