CN118159358A - Acid gas adsorbing material, structure provided with acid gas adsorbing material, acid gas adsorbing device, acid gas recovery device, method for producing acid gas adsorbing material, and sheet-like structure - Google Patents
Acid gas adsorbing material, structure provided with acid gas adsorbing material, acid gas adsorbing device, acid gas recovery device, method for producing acid gas adsorbing material, and sheet-like structure Download PDFInfo
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- CN118159358A CN118159358A CN202280068560.3A CN202280068560A CN118159358A CN 118159358 A CN118159358 A CN 118159358A CN 202280068560 A CN202280068560 A CN 202280068560A CN 118159358 A CN118159358 A CN 118159358A
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- China
- Prior art keywords
- acid gas
- adsorbing material
- gas adsorbing
- polymer
- porous sheet
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Abstract
The present invention provides novel acid gas adsorbing materials suitable for adsorbing acid gases. The acid gas adsorbing material 10 of the present invention includes a porous sheet 1 containing a polymer P. The polymer P has amino groups. The porous sheet 1 has a three-dimensional network skeleton composed of the polymer P. The structure 15 of the present invention includes the acid gas adsorbing material 10 and the ventilation passage 14. The acid gas adsorption apparatus 200 of the present invention includes an adsorption unit 221 having a gas inlet 222 and a gas outlet 223. The adsorption unit 221 houses the acid gas adsorbent 10.
Description
Technical Field
The present invention relates to an acid gas adsorbing material, a structure provided with the acid gas adsorbing material, an acid gas adsorbing device, an acid gas recovering device, a method for producing the acid gas adsorbing material, and a sheet-like structure.
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.
For example, patent document 1 discloses an adsorbent obtained by coating a substrate with an amine compound. Specifically, in patent document 1, porous particles of alumina are supported on a matrix, and amine compounds are filled in pores of the porous particles.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2014-533195
Disclosure of Invention
Problems to be solved by the invention
There is a need for new acid gas adsorbing materials suitable for adsorbing acid gases.
Means for solving the problems
The present invention provides an acid gas adsorbing material comprising a porous sheet comprising a polymer,
The aforementioned polymers have an amino group and,
The porous sheet has a three-dimensional network skeleton composed of the polymer.
The present invention also provides a structure comprising:
the above-mentioned acid gas adsorbing material; and
Ventilation path.
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.
The present invention also provides an acid gas recovery device comprising:
the above-mentioned acid gas adsorbing material; and
The path of the medium is such that,
In the separation operation for separating the acid gas adsorbed by the acid gas adsorbing material from the acid gas adsorbing material, a heat medium for heating the acid gas adsorbing material passes through the medium path.
The present invention also provides a method for producing an acid gas adsorbing material comprising a porous sheet, the method comprising the steps of:
A step (I) of curing a mixed solution containing a compound group containing an amine monomer and a porogen to obtain a cured product; and
And (II) removing the porogen from the sheet-like cured product to obtain the porous sheet.
The present invention also provides a sheet-like structure comprising:
a porous sheet comprising a polymer; and
A support body for supporting the porous sheet,
The aforementioned polymers have an amino group and,
The porous sheet has a three-dimensional network skeleton composed of the polymer.
Effects of the invention
According to the present invention, a novel acid gas adsorbing material suitable for adsorbing an acid gas can be provided.
Drawings
Fig. 1 is a cross-sectional view schematically showing an acid gas adsorbing material according to an embodiment of the present invention.
FIG. 2A is a view for explaining a method for producing an acid gas adsorbing material.
FIG. 2B is a view for explaining a method for producing an acid gas adsorbing material.
FIG. 3 is a diagram for explaining a method of measuring the adsorption amount of carbon dioxide by the acid gas adsorbent.
Fig. 4 is a cross-sectional view schematically showing a modification of the acid gas adsorbing material.
Fig. 5A is a perspective view schematically showing an example of a structure body including an acid gas adsorbing material.
Fig. 5B is a perspective view schematically showing a modification of the structure provided with the acid gas adsorbing material.
Fig. 5C is a perspective view schematically showing another modification of the structure provided with the acid gas adsorbing material.
Fig. 6A is a perspective view schematically showing an example of the acid gas recovery apparatus.
FIG. 6B is a cross-sectional view schematically showing a modified example of the acid gas recovery device.
FIG. 7 is a Scanning Electron Microscope (SEM) image of a cross section of the porous sheet produced in example 1.
FIG. 8 is a graph showing the results of measuring the carbon dioxide adsorption amount with respect to the acid gas adsorbing materials of example 1 and comparative examples 1 to 3.
FIG. 9 is a graph showing the results of measuring the carbon dioxide adsorption amount with respect to the acid gas adsorbing materials of example 2 and comparative examples 4 to 6.
Detailed Description
The acid gas adsorbing material according to claim 1 of the present invention comprises a porous sheet comprising a polymer,
The aforementioned polymers have an amino group and,
The porous sheet has a three-dimensional network skeleton composed of the polymer.
In the invention according to claim 2, for example, in the acid gas adsorbing material according to claim 1, the porous sheet includes continuous pores formed continuously in three dimensions.
In the invention according to claim 3, for example, in the acid gas adsorbing material according to claim 1 or 2, the porous sheet contains the polymer as a main component.
In the 4 th aspect of the present invention, for example, in the acid gas adsorbing material according to any one of the 1 st to 3 rd aspects, the amino group includes a secondary amino group.
In the invention according to claim 5, for example, in the acid gas adsorbing material according to any one of claims 1 to 4, the polymer is an epoxy polymer including a structural unit derived from an amine monomer.
In the invention according to claim 6, for example, in the acid gas adsorbing material according to any one of claims 1 to 5, the glass transition temperature of the polymer is 40 ℃ or lower.
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 specific surface area of the porous sheet is 1.0m 2/g or more.
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 porosity of the porous sheet is 20% or more.
In the 9 th aspect of the present invention, for example, the acid gas adsorbing material according to any one of the 1 st to 8 th aspects further comprises a support body for supporting the porous sheet.
In the 10 th aspect of the present invention, for example, the adsorption amount of carbon dioxide when the acid gas adsorbent according to any one of the 1 st to 9 th aspects is contacted with a mixed gas composed of carbon dioxide, nitrogen and water vapor for 15 hours is 0.1mmol/cm 3 or more.
Wherein the concentration of the carbon dioxide in the mixed gas is 400volppm, the temperature of the mixed gas is 20 ℃ and the humidity of the mixed gas is 50% RH.
In the 11 th aspect of the present invention, for example, the acid gas adsorbing material according to any one of the 1 st to 10 th aspects has a flat plate shape or a corrugated shape.
A structure according to claim 12 of the present invention includes:
the acid gas adsorbing material according to any one of aspects 1 to 11; and
Ventilation path.
An acid gas adsorption apparatus according to claim 13 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 11.
An acid gas recovery device according to claim 14 of the present invention includes:
the acid gas adsorbing material according to any one of aspects 1 to 11; and
The path of the medium is such that,
In the separation operation for separating the acid gas adsorbed by the acid gas adsorbing material from the acid gas adsorbing material, a heat medium for heating the acid gas adsorbing material passes through the medium path.
In a 15 th aspect of the present invention, for example, in the acid gas recovery apparatus according to the 14 th aspect, the medium path penetrates the acid gas adsorbing material in a thickness direction of the acid gas adsorbing material.
In a 16 th aspect of the present invention, for example, the acid gas recovery apparatus according to the 14 th aspect is provided with 2 pieces of the acid gas adsorbing material, and the medium path is formed between 2 pieces of the acid gas adsorbing material.
In a 17 th aspect of the present invention, for example, in the acid gas recovery device according to any one of the 14 th to 16 th aspects, a cooling medium that cools the acid gas adsorbing material is passed through the medium path after the disengaging operation.
The method for producing an acid gas adsorbing material according to claim 18 of the present invention is a method for producing an acid gas adsorbing material comprising a porous sheet, comprising the steps of:
A step (I) of curing a mixed solution containing a compound group containing an amine monomer and a porogen to obtain a cured product; and
And (II) removing the porogen from the sheet-like cured product to obtain the porous sheet.
In the 19 th aspect of the present invention, for example, in the step (I) of the production method according to the 18 th aspect, the mixed solution is applied to a support, and the obtained coating film is cured, whereby the sheet-shaped cured body is obtained.
A sheet-like structure according to claim 20 of the present invention includes:
a porous sheet comprising a polymer; and
A support body for supporting the porous sheet,
The aforementioned polymers have an amino group and,
The porous sheet has a three-dimensional network skeleton composed of the polymer.
The acid gas adsorbing material according to claim 21 of the present invention comprises a porous resin sheet containing a polymer,
The aforementioned polymer has an amino group.
A sheet-like structure according to claim 22 of the present invention includes:
a porous resin sheet containing a polymer; and
A support body for supporting the porous resin sheet,
The aforementioned polymer has an amino group.
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.
< Embodiment of acid gas adsorbing Material >
As shown in fig. 1, the acid gas adsorbing material 10 of the present embodiment includes a porous sheet 1 including a polymer P, and for example, a support 2. The porous sheet 1 is a porous resin sheet containing the polymer P. The polymer P has an amino group, and has a function of adsorbing an acid gas due to the amino group.
The porous sheet 1 has a three-dimensional network skeleton composed of the polymer P. Specifically, the porous sheet 1 has a porous structure including pores derived from a three-dimensional network skeleton. The pores from the three-dimensional network skeleton have a size that can be observed when observed at a magnification of 5000 times using a Scanning Electron Microscope (SEM), for example. The diameter (average pore diameter) of the pores is preferably 0.1 μm or more and 5 μm or less, more preferably 3 μm or less. When the pore diameter is 0.1 μm or more, the gas diffusivity in the porous sheet 1 tends to be sufficiently ensured. When the pore diameter is 5 μm or less, the three-dimensional network skeleton in the porous sheet 1 is not excessively thickened even at a moderate porosity, and the decrease in the diffusion rate of the acid gas into the polymer P is easily suppressed.
In another aspect, the present invention provides an acid gas adsorbing material 10 comprising a porous sheet 1, wherein the porous sheet 1 has a porous structure including pores derived from a three-dimensional network skeleton,
The three-dimensional network skeleton includes a polymer P having amino groups.
The support 2 supports the porous sheet 1 and is in direct contact with the porous sheet 1. The acid gas adsorbing material 10 provided with the support 2 is suitable for the applications of the components of an acid gas recovery device described later. The acid gas adsorbing material 10 may or may not further include a fixing mechanism for fixing the porous sheet 1 and the support 2. Specific examples of the fixing means include an adhesive, and more specifically, an adhesive sheet containing an adhesive. In the present specification, the term "adhesive" is used as a term including an adhesive (pressure-SENSITIVE ADHESIVE).
The acid gas adsorbing material 10 may be constituted by only the porous sheet material 1 without the support 2. That is, the acid gas adsorbing material 10 may be a self-supporting film (single-layer film) of the porous sheet 1.
Typically, the acid gas adsorbing material 10 is a sheet-like structure. The acid gas adsorbing material 10 as a sheet-like structure has, for example, a flat plate shape or a corrugated shape.
Viewed from another aspect, the present invention provides a sheet-like structure comprising:
a porous sheet 1 containing a polymer P; and
A support body 2 for supporting the porous sheet 1,
The polymer P has an amino group which is,
The porous sheet 1 has a three-dimensional network skeleton composed of the polymer P.
In another aspect, the present invention provides a sheet-like structure comprising:
A porous sheet 1 having a porous structure including pores derived from a three-dimensional network skeleton; and
A support body 2 for supporting the porous sheet 1,
The three-dimensional network skeleton described above contains a polymer P having amino groups.
(Porous sheet)
In the porous sheet 1, the polymer P contains, for example, at least 1 kind selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group as an amino group. 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 10 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 10 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 amino groups in the polymer P is, for example, 1mmol/g or more, preferably 5mmol/g or more, and more preferably 10mmol/g or more. The upper limit of the density of the amino group is not particularly limited, and is, for example, 30mmol/g. In the present specification, the density of amino groups in the polymer P refers to the amount of amino groups contained in 1g of 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 is, for example, an epoxy polymer comprising structural units U1 from amine monomers. The epoxy polymer is, 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 monomer and an epoxy prepolymer, and preferably the polymer P1. Specific examples of the reactant P2 are those obtained by crosslinking an epoxy prepolymer with an amine 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 may be, for example, 30 or 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 molecular weight of the amine monomer is not particularly limited, and is, for example, less than 5000, preferably 3000 or less, and may be 1000 or less, or 500 or less.
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, iminodipropylamine, bis (hexamethylenetriamine), 1,3, 6-trisaminomethylhexane, tris (2-aminoethyl) amine, N' -bis (3-aminopropyl) ethylenediamine, polymethylenediamine, trimethylhexamethylenediamine, polyetherdiamine, and polyethyleneimine; 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 may also be an aliphatic polyamidoamine (ALIPHATIC POLYAMIDEAMINE) comprising polyamines and dimer acids, as the case may be. The amine monomer is preferably 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 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.
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; ether group-containing polyfunctional epoxy compounds 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; amino group-containing polyfunctional epoxy compounds such as N, N, N ', N' -tetraglycidyl m-xylylenediamine and 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane. The epoxy monomer is preferably an ether group-containing polyfunctional epoxy compound such as ethylene glycol diglycidyl ether (EDE) or pentaerythritol tetraglycidyl ether (PETG). 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.
Examples of the amine monomer used for forming the reactant P2 include the amine monomers described above for the polymer P1.
The epoxy prepolymer contains, for example, at least 1 epoxy group. The number of epoxy groups contained in the epoxy 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 epoxy groups contained in the epoxy prepolymer is not particularly limited, and is, for example, 100. The weight average molecular weight of the epoxy prepolymer is not particularly limited, and is, for example, 1000 to 50000.
Examples of the epoxy prepolymer include aromatic epoxy resins and non-aromatic epoxy resins. 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 prepolymers may be used singly or in combination of 2 or more.
As described above, the polymer P as an epoxy polymer contains the structural unit U1 derived from an amine monomer. In the case where the polymer P is the polymer P1, the polymer P further contains a structural unit U2 derived from an epoxy monomer. The content of the structural unit U1 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 U1 is not particularly limited, but is, for example, 80wt%. The content of the structural unit U2 in the polymer P, particularly the polymer P1, is, for example, 20wt% to 70wt%.
In the case of producing the polymer P, the compounding ratio of the amine monomer to the epoxy monomer or the epoxy prepolymer is preferably set such that the ratio of the equivalent of the epoxy group contained in the epoxy monomer or the epoxy prepolymer to the equivalent of the active hydrogen of the primary amino group contained in the amine monomer becomes, for example, 1 or less, preferably 0.9 or less, more preferably 0.5 or less.
The glass transition temperature Tg of the polymer P is not particularly limited, and is, for example, 40 ℃ or lower, preferably 30 ℃ or lower, more preferably 20 ℃ or lower, and still more preferably 15 ℃ or lower. When the glass transition temperature Tg of the polymer P is low to this extent, the regeneration treatment of the acid gas adsorbing material 10 can be performed under relatively mild conditions, for example, by a heat treatment at a low temperature. 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 10 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 porous sheet 1 contains, for example, a polymer P as a main component. In the present specification, the "main component" refers to a component contained in the porous sheet 1 at the largest weight ratio. The content of the polymer P in the porous sheet 1 is, for example, 50wt% or more, preferably 70wt% or more, more preferably 90wt% or more, or 95wt% or more, or 99wt% or more. The porous sheet 1 may be substantially composed of only the polymer P. The higher the content of the polymer P, the more the adsorptivity of the acid gas in the acid gas adsorbing material 10 tends to be improved.
The porous sheet 1 may be substantially composed of only the polymer P, but may further include other materials than the polymer P. Examples of the other materials include reaction accelerators, plasticizers, fillers, pigments, dyes, anti-aging agents, conductive materials, antistatic agents, ultraviolet absorbers, flame retardants, antioxidants, and the like. The porous sheet 1 preferably does not contain porous particles such as alumina, and a binder for binding the porous particles to each other is other materials.
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.
Examples of the filler include fibers and fiber structures including fibers. Examples of the fibers include glass fibers; natural fibers such as wood pulp, cotton, hemp (e.g., manila hemp); chemical fibers (synthetic fibers) such as polyester fibers, rayon, vinylon, acetate fibers, polyvinyl alcohol (P VA) fibers, polyamide fibers, polyolefin fibers, and polyurethane fibers. The fibrous structure may be a woven fabric, a nonwoven fabric, or paper. A specific example of the fibrous structure is cellophane. When the porous sheet 1 contains a fibrous structure as a filler, the dimensional change of the porous sheet 1 tends to be suppressed during the use of the acid gas adsorbing material 10 or the like.
In the case where the porous sheet 1 includes a fibrous structure as a filler, the three-dimensional network skeleton including the polymer P and the fibrous structure may be present in the porous sheet 1 independently of each other. In this case, the porous structure of the porous sheet 1 has, for example, pores derived from the three-dimensional network skeleton including the polymer P and pores derived from the fibrous structure. In this case, it can be considered that the three-dimensional network skeleton including the polymer P and the fibrous structure are combined in the porous sheet 1.
From the viewpoint of suppressing the change in the size of the porous sheet 1, the fiber structure as the filler is preferably large in tensile strength. As an example, the tensile strength S TD of the fiber structure measured in the following test 1 is preferably 1MPa or more.
Test 1: the fiber structure was cut into test pieces having a width of 10mm and a length of 100 mm. At this time, the longitudinal direction of the test piece was aligned with the TD direction (TRANSVERSE DIRECTION ) of the fiber structure. The test piece was set in a tensile tester, and tensile test was performed under conditions of a distance between chucks of 20mm and a tensile speed of 100 mm/min. The tensile strength S TD at 3% elongation of the test piece was determined.
In the tensile test described above, the test force applied to the test piece (test force when the test piece is elongated by 3% in N/10 mm) was measured at a point in time when the distance between chucks was increased by 0.6mm after the start of the test. The tensile strength S TD can be calculated from the following formula based on the value of the test force (N/10 mm) obtained and the thickness (μm) of the fiber structure. The tensile test was performed in an atmosphere at 25 ℃.
Tensile strength S TD (MPa) =test force (N/10 mm)/(thickness (μm)/100)
The tensile strength S TD of the fiber structure is more preferably 2MPa or more, but may be 3MPa or more, 4MPa or more, 5MPa or more, 6MPa or more, 7MPa or more, and further 8MPa or more. The upper limit of the tensile strength S TD is not particularly limited, and is, for example, 30MPa.
In the fiber structure, the tensile strength S MD measured by the same method as in the above-described test 1 is preferably 1MPa or more, except that the longitudinal direction of the test piece is aligned with the MD direction (machine direction, mechanical direction) of the fiber structure. The tensile strength S MD is more preferably 2MPa or more, but may be 5MPa or more, 8MPa or more, 10MPa or more, 11MPa or more, and further 12MPa or more. The upper limit of the tensile strength S MD is not particularly limited, and is, for example, 30MPa.
The density d of the nitrogen element in the porous sheet 1 is not particularly limited, and is, for example, 1mmol/g or more, preferably 5mmol/g or more, and more preferably 10mmol/g or more. The upper limit of the density d of nitrogen element is not particularly limited, but is, for example, 30mmol/g. When all of the nitrogen elements contained in the porous sheet 1 are derived from amino groups, the density d of the nitrogen element can be regarded as the density of the amino groups in the porous sheet 1.
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 porous sheet 1 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)
The amount of the amino group per unit volume of the porous sheet 1 may be, for example, 4.0mmol/cm 3 or more, 4.3mmol/cm 3 or more, 4.5mmol/cm 3 or more, 5.0mmol/cm 3 or more, 6.0mmol/cm 3 or more, 7.0mmol/cm 3 or more, or 8.0mmol/cm 3 or more. The upper limit of the amount of the amino group is not particularly limited, and is, for example, 20mmol/cm 3.
The weight ratio of nitrogen element in the porous sheet 1 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 10 tends to be improved. The upper limit of the weight ratio of nitrogen element in the porous sheet 1 is not particularly limited, and is, for example, 30wt%. When all of the nitrogen elements contained in the porous sheet 1 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 porous sheet 1.
As described above, the porous sheet 1 has a three-dimensional network skeleton composed of the polymer P. The three-dimensional network skeleton may contain, for example, the polymer P as a main component, or may substantially contain only the polymer P. The three-dimensional network skeleton may also contain other components than the polymer P. In the porous sheet 1, for example, the three-dimensional network skeleton described above extends continuously. The pores included in the porous sheet 1 are, for example, continuous pores formed continuously in three dimensions. In other words, the porous sheet 1 includes continuous pores formed continuously in three dimensions, for example. The porous sheet 1 may have individual pores or may have through-holes penetrating the porous sheet 1. The porous sheet 1 preferably does not have fibers including the polymer P, for example, and is preferably not a nonwoven fabric including the fibers. That is, in the present embodiment, the porous sheet 1 does not include, for example, a nonwoven fabric having fibers including the polymer P.
The thickness of the porous sheet 1 is not particularly limited, and is, for example, 1000 μm or less, preferably 500 μm or less, and more preferably 300 μm or less. As will be described later, the smaller the thickness of the porous sheet 1, the larger the cross-sectional area of the ventilation path of a structure, particularly a honeycomb structure, produced using the acid gas adsorbing material 10, for example, can be adjusted. The structure having a large cross-sectional area of the ventilation path is suitable for reducing pressure loss caused by contact with an acid gas or the like. In the present embodiment, the porous sheet 1 tends to have a relatively large amount of the amino group per unit volume. When the porous sheet 1 is used, the acid gas tends to be sufficiently adsorbed even when the thickness of the sheet 1 is small. The lower limit of the thickness of the porous sheet 1 is not particularly limited, and is, for example, 10 μm.
The specific surface area of the porous sheet 1 is not particularly limited, but is, for example, 0.1m 2/g or more, preferably 1.0m 2/g or more, and more preferably 2.0m 2/g or more. The upper limit of the specific surface area of the porous sheet 1 is not particularly limited, and is, for example, 10m 2/g. The specific surface area of the porous sheet 1 is a BET (Brunauer-Emmett-Teller) specific surface area obtained by nitrogen adsorption. The BET specific surface area can be determined by following JIS Z8830:2013 is measured by a predetermined method.
The porosity of the porous sheet 1 is, for example, 20% or more, preferably 30% or more, and more preferably 40% or more. The upper limit of the porosity of the porous sheet 1 is not particularly limited, and may be, for example, 80% or 60%. The porosity of the porous sheet 1 can be calculated from the following formula based on the volume V (cm 3), the weight W (g), and the true density D (g/cm 3) of the porous sheet 1. The true density D is the specific gravity of the material constituting the porous sheet 1.
Void ratio (%) =100× (V- (W/D))/V
In the porous sheet 1, it is preferable that the dimensional change is suppressed when the acid gas adsorbing material 10 is used, particularly when the acid gas adsorbing material 10 is in contact with water. The porous sheet 1 in which the dimensional change is suppressed tends to be less likely to fall off from the support 2, the acid gas recovery apparatus, and the like during use of the acid gas adsorbing material 10 or the like. The porous sheet 1 is also less likely to be deformed during use of the acid gas adsorbing material 10 or the like, and is less likely to cause obstruction of gas passage by deformation. As described above, the porous sheet 1 including the fiber structure as the filler tends to suppress the change in size during use of the acid gas adsorbing material 10 or the like.
As an example, the dimensional change rate R TD of the porous sheet 1 measured in the following test 2 is preferably 5% or less.
Test 2: the porous sheet 1 was cut into test pieces 30mm in the longitudinal direction and 20mm in the transverse direction. At this time, the longitudinal direction of the test piece was aligned with the MD direction of the porous sheet 1 (MD direction of the fibrous structure in the case of containing the fibrous structure), and the transverse direction of the test piece was aligned with the TD direction of the porous sheet 1 (TD direction of the fibrous structure in the case of containing the fibrous structure). The test pieces were dried under vacuum at 60℃for 2 hours. The test piece was placed in a drying chamber having a dew point of about-60 ℃. The dimensions of the test piece were measured in a drying chamber, and the obtained value was regarded as the dimensions of the test piece in a dry state. Next, an immersion test was performed in which the test piece was immersed in pure water at 22 ℃ for 2 hours. The dimensions of the test piece after the immersion test were measured, and the obtained value was regarded as the dimensions of the test piece in the water-absorbing state. The dimensional change rate R TD (%) was calculated from the length L TD1 (mm) in the transverse direction of the test piece in the dry state and the length L TD2 (mm) in the transverse direction of the test piece in the water-absorbing state.
The dimensional change rate R TD (%) can be calculated from the following formula.
Dimensional change rate R TD＝100×|LTD2-LTD1|/LTD1
The dimensional change rate R TD of the porous sheet 1 is more preferably 4% or less, but may be 3% or less, 2% or less, 1% or less, and further may be 0.5% or less. The lower limit of the dimensional change rate R TD is not particularly limited, and is, for example, 0.01%.
The dimensional change rate R MD of the porous sheet 1 measured in the above test 2 is also preferably 5% or less. The dimensional change rate R MD can be calculated from the following equation based on the longitudinal length L MD1 (mm) of the test piece in the dry state and the longitudinal length L MD2 (mm) of the test piece in the water-absorbing state.
Dimensional change rate R MD＝100×|LMD2-LMD1|/LMD1
The dimensional change rate R MD of the porous sheet 1 is more preferably 4% or less, but may be 3% or less, 2% or less, and further may be 1% or less. The lower limit of the dimensional change rate R MD is not particularly limited, and is, for example, 0.01%.
(Support)
The material of the support 2 is not particularly limited, and examples thereof include ceramics such as cordierite, alumina, cordierite- α alumina, silicon nitride, zircon mullite, spodumene, alumina-silica magnesia, zircon silicate, sillimanite, magnesium silicate, zirconium, petalite, aluminosilicate; metals such as aluminum, titanium, copper, stainless steel, fe-Cr alloy, cr-Al-Fe alloy, etc.; silicone resins, polyolefins, polyesters, polyurethanes, polycarbonates, polyetheretherketones, polyphenylene oxides, polyethersulfones, melamine, polyamides, poly (meth) acrylates, polystyrene, poly (meth) acrylonitrile, polyimides, polyfurfurol, phenol furfuryl alcohol, melamine formaldehyde, resorcinol formaldehyde, cresol formaldehyde, phenol formaldehyde, polyvinyl alcohol dialdehyde, polycyanurates, poly (meth) acrylamides, epoxy resins, agarose, cellulose and like resins. The material of the support 2 is preferably a material that is excellent in thermal conductivity and durability and is not easily degraded by the generation of rust, hydrolysis, or the like when in contact with water.
The support 2 may or may not have a porous structure. Examples of the support 2 having a porous structure include paper, nonwoven fabric, foam, and mesh. Examples of the support 2 having no porous structure include a non-porous sheet and a foil. The support 2 is preferably an aluminum sheet, paper, nonwoven fabric, or the like, from the viewpoint that the acid gas adsorbing material 10 having a corrugated shape can be easily produced.
The support 2 may be a support functioning as a planar heater, or may be a planar thermoelectric heater or a peltier element.
The thickness of the support 2 is not particularly limited, and is, for example, 1 μm to 100 μm. The support 2 may be thinner than the porous sheet 1.
(Method for producing acid gas adsorbing Material)
The method for producing the acid gas adsorbing material 10 includes, for example, the following steps: a step (I) of curing a mixed solution L containing a compound group containing an amine monomer and a porogen to obtain a cured body B; and (II) removing the porogen from the sheet-like solidified body B to obtain the porous sheet 1.
In step (I), the compound group is typically a monomer group including an amine monomer and an epoxy monomer. Wherein the group of compounds may also comprise epoxy prepolymers in place of or in addition to the epoxy monomers.
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 L, other components than the compound group and the porogen may be further added. Examples of the other component include the reaction accelerator described above.
In the step (I), the polymer P is formed by reacting the compound group. Thus, the mixed liquid L is cured to obtain a cured body B. Typically, the reaction of the compound set is 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 epoxy prepolymer based on amine monomers. In the reaction of the compound group, the amino group of the amine monomer reacts with the epoxy group of the epoxy monomer or the epoxy prepolymer. The reaction of the compound group can be performed by applying energy to the mixed solution L. The energy applied to the mixed liquid L is preferably thermal energy. As an example, the reaction of the compound group may be performed by heating the mixed solution L at a temperature of 40 to 100 ℃. The energy applied to the mixed liquid L may be light energy.
The cured body B contains a polymer P and a pore-forming agent. In the cured body B, the polymer P is phase-separated from the porogen, thereby forming a co-continuous structure. The shape of the cured body B obtained in the step (I) is typically a sheet. The sheet-like cured body B can be produced, for example, by applying the mixed liquid L to the support 2 (typically, the support 2 having no porous structure) and curing the obtained coating film. The method of applying the mixed liquid L is not particularly limited, and roll coating, spin coating, dip coating, and the like can be used.
The sheet-like cured body B may be produced by bringing a sheet-like base material other than the support 2 into contact with the mixed liquid L and then curing the mixed liquid L. As the substrate, for example, a release liner or a fibrous structure can be used. The substrate may be a laminate comprising a release liner and a fibrous structure. When a fiber structure is used as a base material, the mixed liquid L is brought into contact with the fiber structure, whereby the mixed liquid L tends to penetrate into the fiber structure. By curing the mixed liquid L in a state where the mixed liquid L is immersed in the inside of the fiber structure, a cured body containing the fiber structure as a filler can be obtained.
The shape of the cured body B obtained in the step (I) may be not sheet-like, but may be block-like, particularly cylindrical or columnar. The block-shaped cured body B can be produced, for example, by curing the mixed liquid L filled in the mold in the step (I). In this case, the vicinity of the surface of the block-shaped cured body B may be cut to a predetermined thickness, thereby obtaining a sheet-shaped cured body B used in the step (II). As an example, when the cured body B is cylindrical or columnar, the sheet-shaped cured body B may be produced by cutting the vicinity of the surface of the cured body B while rotating the cured body B about the cylindrical or columnar axis.
In the step (II), the method for removing the porogen from the sheet-like solidified body B is not particularly limited. For example, the porogen may be extracted from the cured body B by immersing the cured body B in a solvent. As the solvent for extracting the porogen, water, an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, an aliphatic alcohol solvent, an ether solvent, a halogen-containing organic solvent, an ester 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. 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. The ester solvent includes ethyl acetate and the like. These solvents may be used singly or in combination of 2 or more.
In the step (II), the porogen is removed from the sheet-like solidified material B, whereby the porous sheet 1 having a flat plate shape can be obtained, for example. As an example, when the solidified material B is produced by applying the mixed liquid L to the support 2, the pore-forming agent is removed from the solidified material B, whereby the sheet-like acid gas adsorbing material 10 including the porous sheet 1 and the support 2 can be obtained. The self-supporting film of the porous sheet 1 may be produced by a method using a substrate other than the support 2, or the like, and the self-supporting film may be used as the acid gas adsorbing material 10. A self-supporting film of the porous sheet 1 may be produced, and the self-supporting film may be fixed to the support 2 by using a fixing means such as an adhesive sheet, and the obtained product may be used as the acid gas adsorbing material 10.
The acid gas adsorbing material 10 manufactured by the above-described method generally has a flat plate shape. The acid gas adsorbing material 10 having a flat plate shape may be further corrugated. Thus, the acid gas adsorbing material 10 having a corrugated shape can be obtained.
As one example, the acid gas adsorbing material 10 may be manufactured using the manufacturing apparatus 100 shown in FIG. 2A. Fig. 2A shows a schematic structure of the manufacturing apparatus 100. The manufacturing apparatus 100 includes: a drawing roller 45 for drawing the support body 2; a winding roller 49 for winding the produced acid gas adsorbing material 10; and a plurality of guide rollers 46, 47 and 48 located between the draw-out roller 45 and the winding roller 49. In the manufacturing apparatus 100, the support body 2 is conveyed from the drawing roller 45 to the winding roller 49. The manufacturing apparatus 100 further includes a mixed liquid ejecting section 20, a 1 st heating section 30, an extracting section 40, and a 2 nd heating section 35, which are sequentially arranged in the conveyance direction of the support 2. In the manufacturing apparatus 100, a substrate other than the support 2 may be used instead of the support 2.
The mixed liquid discharge portion 20 includes a1 st supply portion 21, a2 nd supply portion 22, a mixing portion 23, and a discharge port 24. The 1 st supply section 21 can convey the 1 st raw material 5 to the mixing section 23. The 2 nd supply section 22 can convey the 2 nd raw material 6 to the mixing section 23. As an example, 1 st raw material 5 contains an amine monomer, and 2 nd raw material 6 contains an epoxy monomer and/or an epoxy prepolymer. At least one selected from the group consisting of 1 st raw material 5 and 2 nd raw material 6 contains a porogen. In the mixing section 23, the 1 st raw material 5 and the 2 nd raw material 6 are mixed to prepare a mixed solution L.
The mixed liquid L prepared in the mixing section 23 is discharged to the outside of the mixed liquid discharge section 20 through the discharge port 24. For example, the mixed liquid discharge section 20 is located near the guide roller 46, and can apply the mixed liquid L to the support 2 conveyed from the drawing roller 45 to the guide roller 46. Thereby, the coating film 7 can be formed on the support 2. The coating film 7 is transported to the 1 st heating section 30 together with the support 2 by a guide roller 47.
The 1 st heating unit 30 includes a heater 31 for heating the coating film 7. The coating film 7 is heated by moving in the 1 st heating unit 30. Thereby, the coating film 7 is cured to form a sheet-like cured body 8. The solidified body 8 is conveyed to the extracting section 40 together with the support body 2.
The extraction unit 40 houses a solvent 41 for extracting the porogen from the solidified body 8. In the extraction unit 40, the solidified body 8 is immersed in a solvent 41. Thus, the porogen is removed from the cured body 8, thereby forming the porous sheet 1. The porous sheet 1 is conveyed to the 2 nd heating portion 35 together with the support 2.
The 2 nd heating unit 35 includes a heater 36 for drying the porous sheet 1 conveyed from the extracting unit 40. The porous sheet 1 is heated by moving in the 2 nd heating portion 35. Thus, the porous sheet 1 is dried, and the sheet-like acid gas adsorbing material 10 including the porous sheet 1 and the support 2 is obtained. The acid gas adsorbing material 10 passes through the guide roller 48 and is wound by the winding roller 49.
The apparatus 100 for producing the acid gas adsorbing material 10 is not limited to the apparatus shown in fig. 2A. Fig. 2B shows a schematic configuration of the manufacturing apparatus 110 according to a modification. As shown in fig. 2B, the manufacturing apparatus 110 does not include the extracting section 40 and the 2 nd heating section 35. The configuration of the manufacturing apparatus 110 is the same as that of the manufacturing apparatus 100 except for the above. Therefore, elements common to these manufacturing apparatuses 100 and 110 may be denoted by the same reference numerals, and their descriptions may be omitted. The following descriptions of the embodiments are applicable to each other as long as they are not technically contradictory. Further, the embodiments may be combined with each other as long as there is no technical contradiction.
In the manufacturing apparatus 110, the solidified material 8 formed in the 1 st heating section 30 passes through the guide roller 48 together with the support 2 and is wound by the winding roller 49. Thereby, a wound body of the cured body 8 and the support body 2 is obtained. The coiled body is immersed in a solvent, and the pore-forming agent is extracted from the solidified body 8, whereby the sheet-like acid gas adsorbing material 10 can be obtained.
(Adsorption amount of carbon dioxide based on acid gas adsorbing Material)
The acid gas adsorbing material 10 of the present embodiment tends to have high adsorptivity for acid gas such as carbon dioxide. As an example, when the acid gas adsorbent 10 is brought into contact with the mixed gas G composed of carbon dioxide, nitrogen and water vapor for 15 hours, the adsorption amount a of carbon dioxide is, for example, 0.1mmol/cm 3 or more, preferably 0.3mmol/cm 3 or more, more preferably 0.5mmol/cm 3 or more, still more preferably 0.7mmol/cm 3 or more, particularly preferably 0.8mmol/cm 3 or more, and particularly preferably 1.0mmol/cm 3 or more. The upper limit of the adsorption amount a of carbon dioxide is not particularly limited, and is, for example, 10mmol/cm 3.
[ Method for measuring carbon dioxide adsorption amount ]
Hereinafter, a method for measuring the carbon dioxide adsorption amount a will be described. The adsorption amount a can be measured, for example, using the measuring apparatus 200 shown in fig. 3. The measurement device 200 includes a1 st tank 230 and a 2 nd tank 231. As an example, the 1 st tank 230 stores nitrogen in a dry state, and the 2 nd tank 231 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 231 is, for example, 5vol%.
The measurement device 200 further includes a1 st container 240 containing water 270, and a1 st path 260 for transporting nitrogen from the 1 st tank 230 to the 1 st container 240. The 1 st path 260 has one end connected to the gas outlet of the 1 st tank 230 and the other end disposed in the water 270 of the 1 st container 240. The nitrogen delivered from tank 1 230 to tank 1240 is humidified by contact with water 270. In the 1 st path 260, a mass flow controller 235 for adjusting the flow rate of nitrogen delivered from the 1 st tank 230 to the 1 st vessel 240 is provided.
The measurement apparatus 200 further includes a2 nd vessel 241, a2 nd path 262, and a bypass path 261. Path 2 connects vessel 1 240 with vessel 2 241. The nitrogen supplied to the 1 st vessel 240 and humidified is supplied to the 2 nd vessel 241 through the 2 nd path 262. The bypass path 261 branches from the 1 st path 260 at a position between the 1 st tank 230 and the mass flow controller 235, and is connected to the 2 nd path 262. A part of the nitrogen supplied from the 1 st tank 230 flows into the bypass path 261, and is supplied to the 2 nd vessel 241 through the 2 nd path 262. In the bypass path 261, a mass flow controller 236 for adjusting the flow rate of nitrogen delivered from the 1 st tank 230 to the bypass path 261 is arranged.
The measurement apparatus 200 further includes a 3 rd path 263 for conveying the mixed gas from the 2 nd tank 231 to the 2 nd path 262. The 3 rd path 263 has one end connected to the gas outlet of the 2 nd tank 231 and the other end connected to the 2 nd path 262. In the 3 rd path 263, a mass flow controller 237 for adjusting the flow rate of the mixed gas sent from the 2 nd tank 231 to the 2 nd path 262 is provided. The mixed gas supplied to the 2 nd path 262 is supplied to the 2 nd vessel 241 through the 2 nd path 262.
The measurement apparatus 200 further includes a 3 rd container 242 and a 4 th path 264. The 3 rd vessel 242 accommodates the water 271 and the adsorbing portion 221 disposed in the water 271. In vessel 3, 242, the temperature of water 271 is maintained at 20 ℃. The adsorption part 221 has a gas inlet 222 and a gas outlet 223. The adsorption unit 221 houses the acid gas adsorbent 10 therein. The suction unit 221 is configured so that the water 271 does not enter inside. Typically, the adsorbing portion 221 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 221 is 4mm and the outer diameter is 6mm. The adsorption unit 221 is configured to be detachable from the measurement device 200.
The measurement apparatus 200 may also be used as an acid gas adsorption apparatus including the adsorption unit 221. In another aspect, the present invention provides an acid gas adsorbing device 200 that includes an adsorbing portion 221 having a gas inlet 222 and a gas outlet 223, wherein the adsorbing portion 221 houses an acid gas adsorbing material 10. The adsorption unit 221 of the acid gas adsorption apparatus 200 may house a structure described later including the acid gas adsorbent 10.
The 4 th path 264 connects the 2 nd container 241 with the 3 rd container 242. Specifically, the 4 th path 264 is connected to the gas inlet 222 of the adsorbing portion 221 in the 3 rd vessel 242. In the 4 th path 264, a1 st concentration meter 250 for measuring the concentration of carbon dioxide in the gas supplied to the adsorption unit 221 is disposed. As the 1 st concentration meter 250, for example, a CO 2/H2 O gas analyzer manufactured by LI-COR, or LI-850-3 can be used.
The measurement apparatus 200 further includes a 5 th path 265 connected to the gas outlet 223 of the adsorption unit 221 and configured to discharge the gas from the adsorption unit 221 to the outside of the measurement apparatus 200. In the 5 th passage 265, a back pressure valve 255 and a 2 nd concentration meter 251 are disposed. The back pressure valve 255 can be used to adjust the pressure in the adsorption unit 221 to a constant value. The 2 nd concentration meter 251 can measure the concentration of carbon dioxide in the gas discharged from the adsorption unit 221. As the 2 nd concentration meter 251, 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 apparatus 200 is constituted by a pipe made of metal or resin, for example.
[ Pretreatment ]
In the method for measuring the adsorption amount a, first, the acid gas adsorbent 10 is dried. The drying treatment may be performed, for example, by subjecting the acid gas adsorbing material 10 to a treatment at 60 ℃ for 2 hours or more under a vacuum atmosphere. Next, the acid gas adsorbing material 10 after the drying treatment is filled into the adsorbing portion 221 in a drying chamber having a dew point of about-60 ℃. At this time, the acid gas adsorbing material 10 is measured in size in advance, and the volume of the acid gas adsorbing material 10 is determined. The weight of the acid gas adsorbing material 10 charged into the adsorbing portion 221 is, for example, 50mg. Next, the 4 th passage 264 and the 5 th passage 265 are connected to both ends of the adsorbing portion 221, and the adsorbing portion 221 is immersed in the water 271 of the 3 rd container 242.
Next, the 1 st path 260, the 2 nd path 262, the bypass path 261, and the 3 rd path 263 of the measuring apparatus 200 supply the nitrogen from the 1 st tank 230 and the mixed gas from the 2 nd tank 231 to the 2 nd vessel 241. In the 2 nd vessel 241, these gases are mixed to obtain a mixed gas G composed of carbon dioxide, nitrogen and water vapor. In the 2 nd vessel 241, the concentration of carbon dioxide in the mixed gas G was adjusted to 400volppm. The temperature of the mixed gas G was 20℃and the humidity was 50% RH. The mixed gas G is supplied to the adsorption unit 221 through the 4 th passage 264 at a flow rate sufficient for the weight of the acid gas adsorbent 10, for example, 300mL/min for 50mg of the acid gas adsorbent 10. In the adsorption unit 221, the pressure of the mixed gas G can be adjusted to 107kPa by the back pressure valve 255.
Next, the mixed gas G is supplied to the adsorbing portion 221, and the adsorbing portion 221 is taken out from the 3 rd vessel 242, and the adsorbing portion 221 is immersed in a hot water bath (not shown) at 80 ℃ for 2 hours or more. The immersion of the adsorption unit 221 in the hot water bath proceeds until the concentration of carbon dioxide measured by the 1 st concentration meter 250 is substantially the same as the concentration of carbon dioxide measured by the 2 nd concentration meter 251. Thus, the pretreatment is completed for the acid gas adsorbing material 10 in the adsorbing portion 221.
[ Adsorption test ]
Next, the mixed gas G is supplied to the adsorbing portion 221, and the adsorbing portion 221 is taken out of the hot water bath and immersed in the water 271 in the 3 rd vessel 242. Thus, the adsorption test was started for the acid gas adsorbent 10 in the adsorption unit 221. The adsorption test was performed until 15 hours elapsed from the start. In the case of performing the 15-hour adsorption test, it is generally considered that the adsorption of carbon dioxide by the acid gas adsorbing material 10 is balanced.
In the adsorption test, the amount M of the carbon dioxide adsorbed by the acid gas adsorbent 10 was measured from the start to 15 hours. The amount M of the carbon dioxide adsorbed by the acid gas adsorbing material 10 can be calculated from the result of measuring the difference between the concentration of carbon dioxide measured by the 1 st concentration meter 250 and the concentration of carbon dioxide measured by the 2 nd concentration meter 251 over time. Based on the amount M of the substance, the amount of the substance of carbon dioxide adsorbed by the acid gas adsorbing material 10 of 1cm 3 in 15 hours was calculated, and the calculated value was determined as the adsorption amount a.
As described above, in the conventional adsorbent, for example, the pores of the porous particles supported on the substrate are filled with the amine compound. In such an adsorbent, since porous particles and a binder for binding the porous particles to each other are required, it is difficult to adjust the amount of the amino group substance per unit volume of the adsorbent to be large. In the conventional adsorbent, if the amount of amine compound to be charged is increased in order to increase the amount of amino groups per unit volume, the porous particles may be clogged with holes, and the adsorption performance for acid gas may be adversely lowered. In contrast, in the acid gas adsorbing material 10 of the present embodiment, by using the porous sheet 1 having the three-dimensional network skeleton composed of the polymer P, the amount of the amino group substance per unit volume can be easily increased while maintaining the pores of the porous sheet 1. The acid gas adsorbent 10 of the present embodiment is said to have a tendency to have high adsorption performance for acid gas, and is suitable for adsorption of acid gas.
(Use of acid gas adsorbing Material)
The acid gas adsorbing material 10 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 10 can be used by the following method, for example. First, a mixed gas containing an acid gas is brought into contact with the acid gas adsorbing material 10. 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 10 is used. However, the mixed gas contacting the acid gas adsorbing material 10 may be pressurized.
The acid gas adsorbing material 10 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 10 is performed, for example, until the adsorption of the acid gas by the acid gas adsorbing material 10 reaches equilibrium.
Next, the acid gas adsorbing material 10 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 10, for example. The heating temperature of the acid gas adsorbing material 10 is, for example, 50 to 80 ℃. The acid gas adsorbing material 10 may be heated under a reduced pressure atmosphere or a vacuum atmosphere. By heating the acid gas adsorbing material 10, the acid gas is desorbed from the acid gas adsorbing material 10. Thereby, the acid gas adsorbing material 10 is regenerated, and the acid gas adsorbing material 10 can be reused. Acid gases, particularly carbon dioxide, that are stripped from the acid gas adsorbing material 10 can be used as a synthetic raw material for chemicals, dry ice. The acid gas adsorption operation by the acid gas adsorbent 10 and the regeneration treatment of the acid gas adsorbent 10 can be performed using the measurement apparatus 200 (acid gas adsorption apparatus) described above and an acid gas recovery apparatus described below.
< Modification of acid gas adsorbing Material >
The acid gas adsorbing material 10 may include a plurality of porous sheets 1. The acid gas adsorbing material 11 shown in fig. 4 includes 2 porous sheets 1A and 1B. The structure of the acid gas adsorbing material 11 is the same as that of the acid gas adsorbing material 10, except for this.
In the acid gas adsorbing material 11, the support 2 is located between the 2 porous sheets 1A and 1B, and is directly in contact with each of the porous sheets 1A and 1B. The composition and structure of the porous sheet 1A may be the same as or different from those of the porous sheet 1B.
< Embodiment of Structure >
As shown in fig. 5A, the structure 15 of the present embodiment includes the acid gas adsorbing material 10 and the ventilation path 14. Instead of the acid gas adsorbing material 10, the acid gas adsorbing material 11 shown in fig. 4 may be used. Typically, the structure 15 is a honeycomb structure having a plurality of ventilation paths 14 extending in the same direction.
In the structure 15, the acid gas adsorbing material 10 preferably includes a porous sheet 1 and a support 2. In the acid gas adsorbing material 10, the porous sheet 1 may contain a fibrous structure as a filler. The acid gas adsorbing material 10 included in the structure 15 may be a self-supporting film of the porous sheet 1.
The structure 15 includes, for example, an adsorbent unit U formed by stacking an acid gas adsorbent 10A having a corrugated shape and an acid gas adsorbent 10B having a flat plate shape. In the acid gas adsorbing material 10A, the plurality of mountain portions 12 and the plurality of valley portions 13 are alternately arranged. A ventilation path 14 is formed between the mountain portion 12 or the valley portion 13 of the acid gas adsorbing material 10A and the acid gas adsorbing material 10B. In the present embodiment, the direction x is a direction (wave direction) in which the plurality of mountain portions 12 and the plurality of valley portions 13 of the acid gas adsorbing material 10A are alternately arranged. The direction y is the stacking direction of the acid gas adsorbing materials 10A and 10B in the adsorbing material unit U. The direction z is a direction orthogonal to the directions x and y, respectively, and is a direction in which the ventilation path 14 extends.
The structure 15 includes, for example, a plurality of adsorbing material units U. The number of the adsorbing material units U in the structure 15 is not particularly limited, and is, for example, 2 to 100. In the structure 15, the plurality of adsorbing material units U are stacked in the direction y so that the plurality of acid gas adsorbing materials 10A and the plurality of acid gas adsorbing materials 10B are alternately arranged. Since a plurality of adsorbing material units U are stacked, the structure body 15 has a block shape.
The ventilation path 14 is a through hole penetrating the structure 15 in the direction z. The ventilation path 14 is surrounded by the acid gas adsorbing materials 10A and 10B. In the structure 15, the acid gas moves in the direction z through the ventilation path 14, and is efficiently adsorbed by the acid gas adsorbing materials 10A and 10B.
In the structure 15, the smaller the thickness of the porous sheet 1 in the acid gas adsorbing materials 10A and 10B is, the larger the cross-sectional area of the ventilation path 14 can be adjusted. The structure 15 having a large cross-sectional area of the ventilation path 14 is suitable for reducing pressure loss generated when it comes into contact with an acid gas or the like. By using the structure 15 with reduced pressure loss, the power of a fan for moving the acid gas, for example, can be reduced. Since the amount of the substance of the amino group per unit volume of the acid gas adsorbing material 10 tends to be relatively large, the acid gas tends to be sufficiently adsorbed even when the thickness of the porous sheet 1 is small.
< Modification of Structure >
The shape of the structure 15 including the acid gas adsorbing material 10 is not limited to the shape shown in fig. 5A. The structure 16 shown in fig. 5B has a shape in which 1 adsorbing material unit U is wound around the center tube 50. Except for this, the structure 16 has the same structure as the structure 15.
The structure 16 has a cylindrical shape. In the structure 16, the plurality of mountain portions 12 and the plurality of valley portions 13 of the acid gas adsorbing material 10A are alternately arranged along the circumferential direction of the structure 16. The ventilation path 14 formed between the mountain portion 12 or the valley portion 13 of the acid gas adsorbing material 10A and the acid gas adsorbing material 10B penetrates the structure 16 in the direction in which the center pipe 50 extends. In the structure 16, the acid gas passes through the ventilation path 14, moves in the direction in which the center tube 50 extends, and is efficiently adsorbed by the acid gas adsorbing materials 10A and 10B.
< Other modification of Structure >
The structure may not include the acid gas adsorbing material 10A having a corrugated shape, or may be a honeycomb structure such as the structures 15 and 16. The structure 17 shown in fig. 5C includes only the acid gas adsorbing material 10B having a flat plate shape as the acid gas adsorbing material 10. Specifically, the structure 17 includes a plurality of acid gas adsorbing materials 10B, and the plurality of acid gas adsorbing materials 10B are arranged with gaps therebetween. The gaps between the 2 acid gas adsorbing materials 10B function as ventilation paths 14.
The structure 17 may further include a fixing member 55 for fixing the plurality of acid gas adsorbing materials 10B to ensure the ventilation path 14. The fixing member 55 is, for example, a rod (rod). As an example, through holes penetrating the acid gas adsorbing materials 10B in the thickness direction are formed in each of the plurality of acid gas adsorbing materials 10B, and the rods as the fixing members 55 are inserted into the through holes of the respective acid gas adsorbing materials 10B, whereby the plurality of acid gas adsorbing materials 10B are fixed. The rod as the fixing member 55 may be a bolt having a male screw portion formed on a side surface thereof. In this case, the bolts and nuts can be screwed at positions between the 2 acid gas adsorbing materials 10B, whereby the ventilation path 14 can be ensured more reliably. In this example, the nut functions as a spacer.
In the example of fig. 5C, each of the plurality of acid gas adsorbing materials 10B has a rectangular shape in plan view, and through holes are formed near four corners thereof. The acid gas adsorbing material 10C further includes 4 fixing members 55,4 and 55 inserted into 4 through holes formed in the four corners of the acid gas adsorbing material 10B. The number, positions, and number of the fixing members 55 formed in the through holes of the acid gas adsorbing material 10B are not limited to the example of fig. 5C.
In the structure 17, the acid gas moves in the ventilation path 14 between the 2 acid gas adsorbing materials 10B, and is efficiently adsorbed by the 2 acid gas adsorbing materials 10B.
< Embodiment of acid gas recovery device >
As shown in fig. 6A, the acid gas recovery apparatus 300 of the present embodiment includes the acid gas adsorbing material 10 and the medium path 60. Instead of the acid gas adsorbing material 10, the acid gas adsorbing material 11 shown in fig. 4 may be used. In the acid gas recovery apparatus 300, the heat medium 61 that heats the acid gas adsorbing material 10 passes through the medium path 60 during the disengaging operation that causes the acid gas adsorbed by the acid gas adsorbing material 10 to be disengaged from the acid gas adsorbing material 10.
In the acid gas recovery apparatus 300, the acid gas adsorbing material 10 preferably includes a porous sheet 1 and a support 2. In the acid gas adsorbing material 10, the porous sheet 1 may contain a fibrous structure as a filler. The acid gas adsorbing material 10 included in the acid gas recovery apparatus 300 may be a self-supporting film of the porous sheet material 1.
The acid gas recovery apparatus 300 includes, for example, a plurality of acid gas adsorbing materials 10. The plurality of acid gas adsorbing materials 10 may be arranged with gaps therebetween, and the gaps between 2 acid gas adsorbing materials 10 may also function as ventilation paths 14. In the acid gas recovery apparatus 300, the configurations of the acid gas adsorbing material 10 and the ventilation passage 14 may be the same as those described above for the structures 15 to 17.
In the acid gas recovery device 300, the medium path 60 is constituted by a pipe made of a metal such as copper, for example, or more specifically, a heat pipe. In the acid gas recovery apparatus 300, the medium path 60 penetrates the acid gas adsorbing material 10 in the thickness direction of the acid gas adsorbing material 10, for example. Specifically, in the acid gas adsorbing material 10, through holes penetrating the acid gas adsorbing material 10 in the thickness direction are formed, and the medium path 60 is inserted into the through holes of the acid gas adsorbing material 10. Typically, the acid gas recovery device 300 has the same structure as a fin-tube heat exchanger including heat transfer fins and heat transfer tubes penetrating the heat transfer fins.
The medium path 60 has a U-shape and can be inserted into 2 through holes formed in the acid gas adsorbing material 10. The number of through holes formed in the acid gas adsorbing material 10 and the number of medium paths 60 are not limited to the number shown in fig. 6A. For example, 4 or more through holes may be formed in the acid gas adsorbing material 10, and 2 or more medium paths 60 having a U-shape may be inserted into the through holes of the acid gas adsorbing material 10.
As described above, the medium path 60 functions as a path for the heat medium 61 that heats the acid gas adsorbing material 10 during the disengaging operation. The medium path 60 may be used as a path for a cooling medium for cooling the acid gas adsorbing material 10 after the disengaging operation. That is, the medium path 60 may serve as both the path of the heat medium 61 and the path of the cooling medium.
The acid gas recovery apparatus 300 further includes a housing (not shown) that houses the acid gas adsorbing material 10 and the medium path 60. The housing has, for example, a mixed gas inlet for delivering a mixed gas containing an acid gas to the interior of the housing. The housing may further have a desorption gas outlet for discharging the desorption gas desorbed from the acid gas adsorbing material 10 to the outside of the housing at the time of the desorption operation, and a purge gas inlet for feeding a purge gas to the inside of the housing. In the case, the mixed gas inlet may also serve as the purge gas inlet. The housing may have a medium inlet for feeding the heat medium 61 and the cooling medium to the medium path 60, and a medium outlet for discharging the heat medium 61 and the cooling medium from the medium path 60.
[ Method of operating acid gas recovery device ]
The acid gas recovery apparatus 300 repeats, for example, an adsorption operation for adsorbing the acid gas to the acid gas adsorbent 10 and a desorption operation for desorbing the acid gas adsorbed by the acid gas adsorbent 10 from the acid gas adsorbent 10. By performing the adsorption operation and the desorption operation using the acid gas recovery device 300, the acid gas can be recovered.
(Adsorption operation)
The adsorption operation of the acid gas recovery apparatus 300 can be performed, for example, as follows. First, a mixed gas containing an acid gas is fed into the interior of the housing through the mixed gas inlet. The mixed gas may be the above mixed gas. The mixed gas moves, for example, in the ventilation path 14 while being in contact with the acid gas adsorbing material 10. Thereby, the acid gas adsorbent 10 adsorbs the acid gas contained in the mixed gas. The adsorption operation is performed, for example, until the adsorption of the acid gas by the acid gas adsorbent 10 reaches equilibrium.
(Off operation)
The disengagement operation of the acid gas recovery apparatus 300 can be performed, for example, as follows. First, the purge gas is delivered to the inside of the housing through the above-described purge gas inlet, and the purge gas is discharged to the outside of the housing from the release gas outlet. By this operation, the mixed gas remaining in the interior of the housing can be discharged to the outside of the housing, and the interior of the housing can be filled with the purge gas. As the purge gas, for example, a vapor gas or a gas containing an acid gas such as carbon dioxide at a high concentration can be used. The operation of depressurizing the interior of the housing may be performed in place of or in addition to the operation of supplying the purge gas to the interior of the housing. The depressurizing operation may be performed by means of a depressurizing device or the like connected to the disengaging gas outlet of the housing, for example.
Next, the heat medium 61 is fed to the medium path 60 in a state where the purge gas is supplied to the inside of the casing. As the heat medium 61, warm water, high-temperature gas, or the like can be used. Specific examples of the gas contained in the high-temperature gas are freon, carbon dioxide, air, water vapor, and the like. The heat medium 61 may be prepared using, for example, waste heat, a heat pump, self-heating regeneration, or the like.
By feeding the heat medium 61 to the medium path 60, heat exchange between the heat medium 61 and the acid gas adsorbing material 10 occurs via the medium path 60, and the acid gas adsorbing material 10 is heated. The heating temperature of the acid gas adsorbing material 10 is, for example, 50 to 80 ℃. Thereby, the acid gas is desorbed from the acid gas adsorbing material 10. The stripping gas stripped from the acid gas adsorption material 10 is discharged from a stripping gas outlet together with the purge gas. Thereby, the acid gas can be recovered. In the case where the purge gas contains water vapor, the purge gas discharged from the purge gas outlet may be cooled to condense the water vapor, thereby removing the water vapor. The heat medium 61 is not necessarily required to be used for heating the acid gas adsorbing material 10. For example, when the support 2 functions as a planar heater, the acid gas adsorbing material 10 can be heated by energizing the support 2.
The acid gas recovery device 300 is configured such that the heat medium 61 does not come into direct contact with the off gas during the off operation. According to the acid gas recovery apparatus 300, the acid gas can be efficiently recovered. The recovered acid gases, especially carbon dioxide, can be used as synthesis feedstock for chemicals, dry ice.
(Preparation for operation)
The acid gas recovery device 300 may perform a preparatory operation for performing the adsorption operation after the disengagement operation. The preparation operation can be performed as follows, for example. First, the supply of the purge gas to the inside of the housing is stopped, and the heat medium 61 is discharged from the medium path 60. Next, the cooling medium is delivered to the medium path 60. As the cooling medium, an antifreeze or the like can be used. Heat exchange between the cooling medium and the acid gas adsorbing material 10 occurs via the medium path 60, and the acid gas adsorbing material 10 is cooled. The acid gas adsorbing material 10 is cooled to, for example, normal temperature (25 ℃). After cooling of the acid gas adsorbing material 10, the cooling medium is discharged from the medium path 60, thereby completing the preparation for the adsorption operation.
< Modification example of acid gas recovery apparatus >
The acid gas recovery device is not limited to the acid gas recovery device shown in fig. 6A. For example, in the acid gas recovery apparatus 310 shown in fig. 6B, the medium path 60 is formed between 2 acid gas adsorbing materials 10. Specifically, in the acid gas recovery apparatus 310, among the plurality of voids formed between the plurality of acid gas adsorbing materials 10, a part of the voids functions as the medium path 60, and the remaining voids function as the ventilation path 14. The medium paths 60 and the ventilation paths 14 are alternately arranged along the arrangement direction of the plurality of acid gas adsorbing materials 10. Typically, the acid gas recovery device 310 has the same structure as a plate heat exchanger formed by stacking a plurality of heat transfer plates.
In the acid gas recovery apparatus 310, the acid gas adsorbing material 10 preferably includes a porous sheet 1 and a support 2. In the acid gas recovery device 310, for example, the porous sheet 1 provided in the acid gas adsorbing material 10 faces the ventilation passage 14, and the support 2 faces the medium passage 60. In the acid gas recovery device 310, the separator 65 is disposed in the ventilation path 14, and a separator (not shown) is also disposed in the medium path 60. These spacers are constructed in the following manner: the ventilation path 14 and the medium path 60 are ensured, and an appropriate fluid is introduced into each path, thereby further preventing leakage of the fluid to other paths. In fig. 6B, the ventilation path 14 may be configured as follows: the mixed gas is taken into the ventilation path 14 from the external space by being connected to the external space of the acid gas recovery device 310 at a position far from the paper surface and near the front of the paper surface. In addition, a member may be arranged to block the connection between the ventilation path 14 and the external space during the disengagement operation of the acid gas recovery apparatus 310.
The acid gas recovery apparatus 310 further includes a restraining member 70 that restrains the plurality of acid gas adsorbing materials 10. The restraining member 70 includes, for example, a pair of plate members 71a and 71b, a rod 72, and a fixing member 73. The plate members 71a and 71b are arranged along the arrangement direction of the plurality of acid gas adsorbing materials 10, sandwiching the plurality of acid gas adsorbing materials 10. According to the plate members 71a and 71b, pressure can be applied to the plurality of acid gas adsorbing materials 10 in the arrangement direction. The plate members 71a and 71b may be provided with a release gas outlet, a purge gas inlet, a medium outlet, and the like described above with respect to the acid gas recovery device 310.
Through holes are formed in the plate members 71a and 71b, respectively, and the rod 72 is inserted into the through holes of the plate members 71a and 71 b. The rod 72 may be a bolt having a male screw portion formed on a side surface thereof. The fixing member 73 fixes, for example, 1 of the plate members 71a and 71b and the rod 72 to each other. Typically, the fixing member 73 is a nut having an internal thread portion that can be screwed with the rod 72. The constraining member 70 has a fixing member 73a that fixes the plate member 71a and the rod 72 to each other, and a fixing member 73b that fixes the plate member 71b and the rod 72 to each other.
In the example of fig. 6B, 2 bars 72 are fixed by fixing members 73, respectively. The number of bars 72 and the like are not limited to the example of fig. 6B.
The acid gas recovery device 310 may perform the same operation method as described above for the acid gas recovery device 300. In the acid gas recovery apparatus 310, the medium path 60 is formed between 2 acid gas adsorbing materials 10. According to this configuration, the heat medium passes through the medium passage 60 during the disengaging operation, and thus the entire acid gas adsorbing material 10 can be heated uniformly.
Unlike the acid gas recovery device 300, the acid gas recovery device 310 is configured such that the ventilation path 14 does not interfere with the medium path 60. Therefore, the acid gas recovery device 310 tends to have a small pressure loss due to the passage of the mixed gas through the ventilation path 14 during the adsorption operation.
Compared to the acid gas recovery apparatus 300, the acid gas recovery apparatus 310 is easier to remove the acid gas adsorbing material 10 and other components. Replacement of the acid gas adsorbing material 10 is easily performed by removing the acid gas adsorbing material 10 from the acid gas recovery apparatus 310. Further, by removing each component of the acid gas recovery apparatus 310, maintenance such as washing operation can be easily performed on each component.
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, 5.22g of poly (1, 2-butanediol) -6-propanediol (manufactured by Nitro oil Co., ltd., UNIOL (registered trademark) PB-500) and 5.22g of polyoxypropylene diglycerol ether (manufactured by Nitro oil Co., ltd., UNILUB (registered trademark) DGP-700) were added to a 50mL Laboran-screw vial (manufactured by AS ONE Co., ltd.). To the obtained mixture was dissolved 2.55g of ethylene glycol diglycidyl ether (EX-810, manufactured by Nagase Chemtex corporation) and 3.83g of pentaerythritol tetraglycidyl ether (Shofree (registered trademark) PETG, manufactured by sho-o electric company), whereby a mixture of an epoxy monomer and a porogen was prepared.
Next, 6.57g of triethylenetetramine (manufactured by TOSOH Co.) was added to the mixed solution, to thereby prepare a mixed solution of an epoxy monomer, 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 monomer to the equivalent (A) of the active hydrogen of the primary amino group contained in the amine monomer was 0.4.
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 mixed liquid was applied to an aluminum sheet having a thickness of 20 μm using an applicator having a gap of 350 μm. The obtained coating film was allowed to stand in a dryer at 120℃for 30 minutes, thereby curing it. Thus, a sheet-like cured body containing the polymer P having an amino group was obtained. The procedure of immersing the cured body in ethyl acetate at 60℃for 30 minutes was repeated 2 times to perform liquid exchange. Thus, the porogen is removed from the cured body, thereby forming a porous sheet. Next, the acid gas adsorbing material (self-supporting film of porous sheet) of example 1 was obtained by drying at 60 ℃ for 30 minutes in a dryer to remove the aluminum sheet. In example 1, the porous sheet had a three-dimensional network skeleton composed of the polymer P.
In example 1, the porous sheet had a thickness of 215. Mu.m, a weight per unit area of 13.03mg/cm 2, and a void fraction of 45% calculated from the true density of the polymer P or the like. The density of amino groups in the polymer P, calculated from the compounding ratio of the monomers, was 13.87mmol/g. The amount of the amino group-containing substance per unit volume of the porous sheet was 8.39mmol/cm 3.
Example 2
First, a mixed solution of the epoxy monomer, the amine monomer and the porogen was prepared in the same manner as in example 1, except that the blending amounts of the epoxy monomer, the amine monomer and the porogen were changed as shown in table 1. 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 applied to a cellophane (PHN-50 GC, manufactured by Oji F-Tex Co.) having a thickness of 250 μm using an applicator having a gap of 500. Mu.m. At this time, the mixed solution is immersed in the cellophane. The cellophane impregnated with the mixed solution was allowed to stand in a dryer at 120℃for 30 minutes, whereby the mixed solution was cured. Thus, a sheet-like cured body containing the polymer P having an amino group and cellophane as a filler was obtained. The procedure of immersing the cured body in ethyl acetate at 60℃for 30 minutes was repeated 2 times to perform liquid exchange. Thus, the porogen is removed from the cured body, thereby forming a porous sheet. Next, the acid gas adsorbing material (self-supporting film of the porous sheet) of example 2 containing cellophane as a filler was obtained by drying in a dryer at 60 ℃ for 30 minutes. In example 2, the porous sheet had a three-dimensional network skeleton composed of the polymer P.
In example 2, the weight per unit area of the acid gas adsorbing material (porous sheet) was 15.8mg/cm 2. The value (10.8 mg/cm 2) obtained by subtracting the unit area weight (5.0 mg/cm 2) of the cellophane from the unit area weight (15.8 mg/cm 2) of the acid gas adsorbing material can be regarded as the unit area weight of the three-dimensional network skeleton composed of the polymer P. The theoretical thickness of the three-dimensional network skeleton calculated from the true density of the polymer P (1.1 g/cm 3) and the void fraction of the three-dimensional network skeleton (45%) was 179. Mu.m. The density of amino groups in the polymer P, calculated from the compounding ratio of the monomers, was 12.38mmol/g. The amount of amino groups per unit volume of the three-dimensional network skeleton contained in the porous sheet was 7.49mmol/cm 3. The amount of the amino group substance per unit volume of the porous sheet was 5.27mmol/cm 3.
Examples 3 to 6
Acid gas adsorbing materials (self-supporting films of porous sheets) of examples 3 to 6 were obtained in the same manner as in example 2, except that the fiber structures shown in table 1 were used instead of cellophane. In each of examples 3 to 6, the porous sheet had a three-dimensional network skeleton composed of the polymer P.
Comparative example 1
First, 3.00g of porous silica (SUNSPERA H-52 manufactured by AGC Si-Tech Co., ltd.) having a pore volume of 1.5mL/g, a specific surface area of 700m 2/g, a pore diameter of 10nm and a true density of 2.2g/mL was prepared, and 60g of methanol (manufactured by FUJIFILM Wako Pure Chemical Corporation Co., ltd., superfine) was immersed for 1 night to prepare a dispersion. Next, as amine monomers, 0.447g of triethylenetetramine (TETA, manufactured by Sigma-Aldrich Co., ltd.) was prepared, and as epoxy monomers, 0.174g of ethylene glycol diglycidyl ether (manufactured by EX-810,Nagase Chemtex Co., ltd.) and 0.261g of pentaerythritol tetraglycidyl ether (manufactured by Showa electrician Co., ltd., shofree (registered trademark) PETG) were prepared. 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 was 0.4.
Next, these monomers are added to the above dispersion. Thus, the compound groups (TETA, EX-810, and PETG) invade the inside of the pores of the porous body, and the compound groups contact the surfaces of the pores of the porous body. Next, the dispersion was heated at a temperature of 60 ℃ under a reduced pressure atmosphere using a rotary evaporator. Thereby, the reaction of the compound group is performed, and the solvent contained in the dispersion liquid is distilled off. Next, the porous body was heated at a temperature of 80 ℃ under a vacuum atmosphere, thereby performing a drying treatment of the porous body. Thus, the acid gas adsorbing material of comparative example 1 in which the polymer P was supported on the porous body was obtained. In the acid gas adsorbing material of comparative example 1, the three-dimensional network skeleton described above for the examples was not present.
Comparative examples 2 to 6
The acid gas adsorbing materials of comparative examples 2 to 6 were obtained in the same manner as in comparative example 1 except that the amounts of the epoxy monomer and the amine monomer were changed as shown in table 1. In the acid gas adsorbing materials of comparative examples 2 to 6, the three-dimensional network skeleton described above for examples was not present.
[ Cross-sectional view of porous sheet ]
The porous sheet produced in example 1 was observed for its cross section by a Scanning Electron Microscope (SEM). The SEM image obtained is shown in fig. 7. As can be seen from fig. 7, the porous sheet has a three-dimensional network skeleton composed of the polymer P.
BET specific surface area
The BET specific surface area by nitrogen adsorption was measured for the acid gas adsorbing materials produced in examples 1 to 2 and comparative examples 1 to 6. As the BET specific surface area, a specific surface area measuring apparatus (trade name "BELSORP-mini", manufactured by MicrotracBEL corporation) was used by following JIS Z8830:2013 is measured by a predetermined method.
[ Glass transition temperature Tg ]
The glass transition temperature Tg of the polymer P contained in the acid gas adsorbing materials produced in examples and comparative examples was measured by the following method. First, a polymer having the same composition as the polymer P contained in the acid gas adsorbing material is synthesized. About 5mg of the polymer was set in a differential scanning calorimeter (DS C2500, 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.
[ True Density ]
The true densities of the polymers P contained in the acid gas adsorbing materials produced in the examples and comparative examples were determined by the following methods. First, a mixed solution containing an epoxy monomer and an amine monomer was prepared in the same blending amount as the mixed solution used in examples and comparative examples. Next, the intensity of the bench oscillator (Angel Vibrator Digital Hz) was set to 5, and the mixture was oscillated for 2 minutes. The mixed solution was poured into a PFA plate having an inner diameter of 75mm, and left to stand in a desiccator at 120 ℃ for 30 minutes, whereby the mixed solution was solidified. Thereby, a cured body containing the polymer P having an amino group is obtained. The procedure of immersing the cured body in ethyl acetate at 60℃for 30 minutes was repeated 2 times to perform liquid exchange, and the monomers remaining in the cured body were removed. Then, the resultant was dried in a dryer at 60℃for 30 minutes, thereby obtaining a cured product of the polymer P. The cured product was obtained by using an electron densitometer (EW-300SG,Alfa Mirage Co.) in accordance with JIS K7112:1999 (method for measuring density and specific gravity of non-foamed Plastic) the density was measured, and the measured value obtained was regarded as the true density of the polymer P.
[ Amount of amino substance per unit volume ]
The amounts of the substances per unit volume of the amino groups of the acid gas adsorbing materials of comparative examples 1 to 6 were determined by the following methods. First, an acid gas adsorbing material was set in a simultaneous thermal analysis DSC/TGA apparatus (DSC 6500, manufactured by TA Instruments Co.). With this apparatus, the temperature was raised from 30℃to 100℃at a heating rate of 10℃per minute under a nitrogen atmosphere, and the temperature was maintained for 40 minutes (operation 1). Thereby, water contained in the acid gas adsorbing material is removed. Then, the temperature was raised from 100℃to 800℃at a heating rate of 10℃per minute, and the mixture was kept at that temperature for 5 minutes (operation 2). Thereby, the polymer P is removed from the acid gas adsorbing material.
Next, the ratio (weight maintenance ratio W1 (%)) of the weight (g) of the acid gas adsorbing material after the above operation 1 was performed to the weight (g) of the acid gas adsorbing material before the apparatus, and the ratio (weight maintenance ratio W2 (%)) of the weight (g) of the acid gas adsorbing material after the above operation 2 was performed to the weight (g) of the acid gas adsorbing material before the apparatus were determined. The weight maintenance ratios W1 and W2 were used to calculate the ratio F of the weight (g) of the polymer P to the weight (g) of the acid gas adsorbing material from the following formula.
Ratio f=1- (1/W1) ×w2
Next, the volume a (mL) per 1g of the porous body, the weight B (g) of the polymer P relative to 1g of the porous body, the density C (g/mL) of the composite particles composed of the porous body and the polymer P, and the density D of the amino groups in the composite particles were calculated from the following formulas, respectively.
Volume a (mL) =pore volume per 1g of porous body (mL) +weight of porous body (g)/true density of porous body (g/mL)
Weight B (g) =ratio F/(1-ratio F) ×weight of porous body (g)
Density C (g/mL) = (weight of porous body (g) +weight B (g))/volume a (mL) of composite particles
Density of amino groups D (mmol/g) =density of amino groups in polymer P (mmol/g) than f×f
Further, the amount E of the substance per unit volume of the amino group of the acid gas adsorbing material was calculated from the following formula. In the following formula, the packing ratio of the composite particles was a value (0.74) assuming that the composite particles were densely packed in the acid gas adsorbing material.
Quantity of substance E (mmol/cm 3) =density of composite particles C (g/mL) ×packing fraction of composite particles×density of amino groups in composite particles D (mmol/g)
TABLE 1
TABLE 2
(1) Ratio F of weight of Polymer P to weight of acid gas adsorbing Material
((2) Density C of composite particles composed of porous body and Polymer P)
((3) Amount of amino group substance per unit volume of acid gas adsorbing Material)
Amount of amino group substance per unit volume of three-dimensional network skeleton contained in porous sheet material
The abbreviations in table 1 are as follows.
EX-810: ethylene glycol diglycidyl ether (Nagase Chemtex Co., ltd., EX-810)
PETG: pentaerythritol tetraglycidyl Ether (Shofree (registered trademark) PETG manufactured by Showa electric company)
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)
DGP-700: polyoxypropylene diglycerol ether (UNILUB (registered trademark) DGP-700 manufactured by Nitro oil Co., ltd.)
PHN-50GC: cellophane (pulp-containing nonwoven fabric) (PHN-50 GC manufactured by Oji F-Tex Co., ltd.)
MP-22: pulp-containing nonwoven fabric (Nippon PAPER PAPYLIA Co., ltd., MP-22)
PY120-01: synthetic fiber nonwoven fabric (PY 120-01 manufactured by Abo paper Co., ltd.)
PY120-32: synthetic fiber nonwoven fabric (PY 120-32 manufactured by Abo paper Co., ltd.)
120H-PB: pulp-containing nonwoven fabric (Nippon PAPER PAPYLIA Co., ltd., 120H-PB base paper)
[ Adsorption amount of carbon dioxide ]
The adsorption amount of carbon dioxide was measured by the method described above for the acid gas adsorbing materials of example 1 and comparative examples 1 to 3. In this case, in example 1, a sample obtained by cutting the acid gas adsorbing material so that the area of the main surface becomes 4.72cm 2 was used as a measurement sample. In comparative examples 1 to 3, measurement samples obtained by adjusting the weight so as to have the same volume as the measurement sample used in example 1 were used. The weights of the measurement samples of comparative examples 1 to 3 were 49mg, 64mg and 76mg, respectively. The weight of the measurement sample in comparative examples 1 to 3, which was the same volume as the measurement sample used in example 1, was calculated from the following formula using the density C (g/mL) of the composite particles composed of the porous body and the polymer P and the packing ratio of the composite particles. In the following formula, the packing ratio of the composite particles is a value (0.74) assuming that the composite particles are densely packed in the acid gas adsorbing material.
Weight (mg) of measurement sample of comparative example=volume (cm 3) x density C (g/mL) x packing ratio of composite particles of measurement sample of example 1
Fig. 8 shows the measurement results of the adsorption amount of carbon dioxide in example 1 and comparative examples 1 to 3. Fig. 8 is a graph showing a relationship between a time after starting an adsorption test and an adsorption amount of carbon dioxide by the acid gas adsorbent. From fig. 8, it was confirmed that the adsorption amount of carbon dioxide was saturated and stabilized for a predetermined period of time. As is clear from fig. 8, the adsorption amount of carbon dioxide per unit volume of the acid gas adsorbent of example 1 is larger than that of comparative examples 1 to 3, and is suitable for adsorption of acid gas. The adsorption amount a of carbon dioxide when the acid gas adsorbent of example 1 was brought into contact with the above-mentioned mixed gas G for 15 hours was 1.45mmol/cm 3.
The adsorption amount of carbon dioxide was measured by the above method for the acid gas adsorbing materials of example 2 and comparative examples 4 to 6. In this case, in example 2, a sample obtained by cutting the acid gas adsorbing material so that the area of the main surface becomes 5.76cm 2 was used as a measurement sample. In comparative examples 4 to 6, measurement samples obtained by adjusting the weight so as to have the same volume as the measurement sample used in example 2 were used. The weights of the measurement samples of comparative examples 4 to 6 were 50mg, 60mg and 72mg, respectively. The weights of the measurement samples of comparative examples 4 to 6, which were the same volume as the measurement sample used in example 2, were calculated by the same method as described above for comparative examples 1 to 3.
Fig. 9 shows the measurement results of the adsorption amount of carbon dioxide in example 2 and comparative examples 4 to 6. Fig. 9 is a graph showing a relationship between a time after starting an adsorption test and an adsorption amount of carbon dioxide by the acid gas adsorbent. From fig. 9, it was confirmed that the adsorption amount of carbon dioxide was saturated and stabilized for a predetermined period of time. As is clear from fig. 9, the adsorption amount of carbon dioxide per unit volume of the acid gas adsorbent of example 2 is larger than that of comparative examples 4 to 6, and is suitable for adsorption of acid gas. The adsorption amount a of carbon dioxide when the acid gas adsorbent of example 2 was brought into contact with the above-mentioned mixed gas G for 15 hours was 1.27mmol/cm 3.
From the above results, it is clear that the acid gas adsorbing materials of examples 1 and 2 having the porous sheet material having the three-dimensional network skeleton including the polymer P have a larger adsorption amount of carbon dioxide than the comparative example, and are suitable for adsorption of acid gas. The acid gas adsorbing materials of other examples 3 to 6 had the same structure as in example 2, except for the type of the fiber structure used as the filler. Therefore, it is estimated that the acid gas adsorbing materials of examples 3 to 6 have the same adsorption performance for acid gas such as carbon dioxide as in example 2.
The acid gas adsorbing material of the example is suitable for maintaining the adsorption performance of the acid gas and adjusting the thickness of the porous sheet to be small because the amount of the substance per unit volume of the amino group is relatively large. When a porous sheet having a small thickness is used, for example, the cross-sectional area of the ventilation path of a structure made of an acid gas adsorbing material, particularly a honeycomb structure, can be adjusted to be large. The structure having a large cross-sectional area of the ventilation path is suitable for reducing pressure loss caused by contact with an acid gas or the like. As described above, it can be said that the acid gas adsorbing material of the embodiment is suitable for reducing the pressure loss generated in the structure provided with the acid gas adsorbing material.
Calculation example 1
Next, it is assumed that an acidic gas adsorbing material is produced using a sheet-like structure formed by aggregation of porous alumina particles. Specifically, it is assumed that the polymer P produced in example 1 is filled in the pores of the porous particles in the sheet-like structure, and an acid gas adsorbing material is produced. The amount of the substance per unit volume of the amino group of the acid gas adsorbing material was calculated by the following method. In the following calculation, additives such as binders generally required for conventional acid gas adsorbing materials are not considered.
First, the porous particles were assumed to have a pore volume of 1.25mL/g, a specific surface area of 175m 2/g, a pore diameter of 20nm, and a true density of 3.8g/mL. The ratio F of the weight of the polymer P to the weight of the acid gas adsorbing material (weight of the polymer P (g)/(weight of the polymer P (g) +weight of the porous particles (g))) was assumed to be 0.39.
The volume A per 1g of porous particles was calculated to be 1.51mL by the following formula.
Volume a (mL) =pore volume per 1g porous particle (mL) +weight of porous particle (g)/true density of porous particle (g/mL)
＝1.25+1/3.8＝1.51(mL)
In the acid gas adsorbing material, the weight B of the polymer P relative to 1g of the porous particles was calculated to be 0.639g from the following formula.
Weight B (g) =weight ratio F of polymer P/(weight ratio F of 1-polymer P) ×weight of porous particles (g)
＝0.39/(1-0.39)×1＝0.639(g)
The density C of the composite particles composed of the porous particles and the polymer P was calculated to be 1.08g/mL by the following formula.
Density C (g/mL) of composite particles= (weight of porous particles (g) +weight of polymer P B (g))/volume a (mL) per 1g of porous particles
＝(1+0.639)/1.51＝1.08(g/mL)
The density D of amino groups in the composite particles was calculated to be 5.4mmol/g from the following formula.
Density of amino groups D (mmol/g) =weight ratio F of polymer p×density of amino groups in polymer P (mmol/g)
＝0.39×13.87＝5.4(mmol/g)
In calculation example 1, the amount E of the substance of the amino group per unit volume of the acid gas adsorbing material was calculated to be 4.34mmol/cm 3 from the following formula. In the following formula, the packing ratio of the composite particles was a value (0.74) assuming that the composite particles were densely packed in the acid gas adsorbing material.
Amount of amino group substance E (mmol/cm 3) =density of composite particles C (g/mL) ×filling ratio of composite particles×density of amino group in composite particles D (mmol/g)
＝1.08×0.74×5.4＝4.34(mmol/cm3)
The amount of carbon dioxide adsorbable by the acid gas adsorbing material of example 1 was calculated to be 0.75mmol/cm 3 at maximum based on the amount of amino group, E. From the results, it is understood that the acid gas adsorbing materials of examples 1 and 2 have higher adsorption performance for acid gas such as carbon dioxide than the acid gas adsorbing material of example 1.
[ Tensile Strength of fiber Structure ]
The fiber structures used in examples 2 to 6 were measured for tensile strength S TD and S MD by the methods described above. As a tensile tester, AUTOGRAPH equipment (A GS-50NX, manufactured by Shimadzu corporation) was used. Table 3 also shows the test force when the test piece was elongated by 3% together with the tensile strengths S TD and S MD.
[ Dimensional Change Rate ]
The dimensional change rates R TD and R MD of the porous sheets produced in examples 2 to 6 were measured by the above-described method.
TABLE 3
As is clear from table 3, the tensile strength of the fibrous structure as the filler tends to be higher, and the dimensional change rate of the porous sheet tends to be lower. In particular, in examples 2 to 5 in which the tensile strength S TD of the fiber structure was 2MPa or more, the dimensional change rate R TD of the porous sheet was a sufficiently low value. From the above results, it is estimated that the porous sheets of examples 2 to 6, in particular examples 2 to 5, are less likely to fall off from the support, the acid gas recovery device, and the like during the use thereof or the like. In addition, it is also estimated that these porous sheets are less likely to be deformed during use or the like, and that the gas passage is less likely to be blocked by the deformation.
Industrial applicability
The acid gas adsorbent according to the present embodiment can adsorb carbon dioxide in the atmosphere, for example.
Claims (20)
1. An acid gas adsorbing material comprising a porous sheet comprising a polymer,
The polymer has an amino group and is provided with a hydroxyl group,
The porous sheet has a three-dimensional network skeleton composed of the polymer.
2. The acid gas adsorbing material as set forth in claim 1, wherein the porous sheet material contains continuous pores formed continuously in a three-dimensional shape.
3. The acid gas adsorbing material as set forth in claim 1, wherein the porous sheet contains the polymer as a main component.
4. The acid gas adsorbing material as set forth in claim 1, wherein said amino groups comprise secondary amino groups.
5. The acid gas adsorbing material of claim 1 wherein the polymer is an epoxy polymer comprising structural units from an amine monomer.
6. The acid gas adsorbing material as set forth in claim 1, wherein the polymer has a glass transition temperature of 40 ℃ or less.
7. The acid gas adsorbing material as set forth in claim 1, wherein the porous sheet has a specific surface area of 1.0m 2/g or more.
8. The acid gas adsorbing material as set forth in claim 1, wherein the porous sheet has a void ratio of 20% or more.
9. The acid gas adsorbing material according to claim 1, further comprising a support body that supports the porous sheet.
10. The acidic gas adsorbing material according to claim 1, wherein the amount of carbon dioxide adsorbed by the acidic gas adsorbing material when the acidic gas adsorbing material is contacted with a mixed gas comprising carbon dioxide, nitrogen and water vapor for 15 hours is 0.1mmol/cm 3 or more,
Wherein the concentration of the carbon dioxide in the mixed gas is 400volppm, the temperature of the mixed gas is 20 ℃ and the humidity is 50% rh.
11. The acid gas adsorbing material as set forth in claim 1, which has a flat plate shape or a corrugated shape.
12. A structure is provided with:
The acid gas adsorbing material of any one of claims 1 to 11; and
Ventilation path.
13. 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 any one of claims 1 to 11.
14. An acid gas recovery device is provided with:
The acid gas adsorbing material of any one of claims 1 to 11; and
The path of the medium is such that,
During a desorption operation for desorbing the acid gas adsorbed by the acid gas adsorbing material from the acid gas adsorbing material, a heat medium for heating the acid gas adsorbing material passes through the medium path.
15. The acid gas recovery apparatus of claim 14, wherein the media path extends through the acid gas adsorbing material in a thickness direction of the acid gas adsorbing material.
16. An acid gas recovery apparatus according to claim 14, comprising 2 of said acid gas adsorbing materials,
The media path is formed between 2 of the acid gas adsorbing materials.
17. The acid gas recovery apparatus of claim 14, wherein a cooling medium that cools the acid gas adsorbing material passes through the medium path after the disengaging operation.
18. A method for producing an acid gas adsorbing material comprising a porous sheet, the method comprising the steps of:
A step (I) of curing a mixed solution containing a compound group containing an amine monomer and a porogen to obtain a cured product; and
And (II) removing the porogen from the sheet-like cured body to obtain the porous sheet.
19. The production method according to claim 18, wherein in the step (I), the mixed solution is applied to a support, and the obtained coating film is cured, whereby the sheet-shaped cured body is obtained.
20. A sheet-like structure is provided with:
a porous sheet comprising a polymer; and
A support body for supporting the porous sheet,
The polymer has an amino group and is provided with a hydroxyl group,
The porous sheet has a three-dimensional network skeleton composed of the polymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-169443 | 2021-10-15 | ||
| JP2022-148614 | 2022-09-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118159358A true CN118159358A (en) | 2024-06-07 |
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