Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
  • B01D53/1493—Selection of liquid materials for use as absorbents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
  • B01D53/1456—Removing acid components
  • B01D53/1475—Removing carbon dioxide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/34—Chemical or biological purification of waste gases
  • B01D53/46—Removing components of defined structure
  • B01D53/62—Carbon oxides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
  • B01D2252/20—Organic absorbents
  • B01D2252/202—Alcohols or their derivatives
  • B01D2252/2021—Methanol
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
  • B01D2252/20—Organic absorbents
  • B01D2252/204—Amines
  • B01D2252/20436—Cyclic amines
  • B01D2252/20447—Cyclic amines containing a piperazine-ring
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
  • B01D2252/20—Organic absorbents
  • B01D2252/204—Amines
  • B01D2252/20478—Alkanolamines
  • B01D2252/20484—Alkanolamines with one hydroxyl group
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
  • B01D2252/20—Organic absorbents
  • B01D2252/204—Amines
  • B01D2252/20478—Alkanolamines
  • B01D2252/20489—Alkanolamines with two or more hydroxyl groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
  • B01D2252/50—Combinations of absorbents
  • B01D2252/504—Mixtures of two or more absorbents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/50—Carbon oxides
  • B01D2257/504—Carbon dioxide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2258/00—Sources of waste gases
  • B01D2258/02—Other waste gases
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2258/00—Sources of waste gases
  • B01D2258/02—Other waste gases
  • B01D2258/0233—Other waste gases from cement factories
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2258/00—Sources of waste gases
  • B01D2258/02—Other waste gases
  • B01D2258/025—Other waste gases from metallurgy plants
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2258/00—Sources of waste gases
  • B01D2258/02—Other waste gases
  • B01D2258/0283—Flue gases
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B32/00—Carbon; Compounds thereof
  • C01B32/50—Carbon dioxide
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
  • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
  • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
  • C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
  • C07D487/08—Bridged systems
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
  • Y02C20/00—Capture or disposal of greenhouse gases
  • Y02C20/40—Capture or disposal of greenhouse gases of CO2
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

• the present invention relates to a carbon dioxide separation composition for selectively separating carbon dioxide from a carbon dioxide-containing mixed gas, and a method for separating carbon dioxide using the composition.
• the most common carbon dioxide absorber is an aqueous monoethanolamine solution.
• monoethanolamine is inexpensive and easily available industrially, it has a characteristic that carbon dioxide absorbed at a low temperature is not released unless it is heated to a high temperature of 120 ° C. or higher.
• the carbon dioxide emission temperature is set above the boiling point of water, a large amount of energy is required to recover carbon dioxide due to the high latent heat and specific heat of water.
• Patent Document 1 N-methyldiethanolamine
• the present invention has been made in view of the above problems, and an object of the present invention is to have excellent carbon dioxide emission efficiency (emission amount / absorption amount) and to prevent precipitation even if nitrogen oxides are mixed. It is an object of the present invention to provide a composition for carbon dioxide separation and a method for separating carbon dioxide.
• the present inventors have found that the carbon dioxide separation composition containing a specific amine compound has excellent carbon dioxide emission efficiency (emission amount / absorption amount). Moreover, they have found that precipitation is unlikely to occur even if nitrogen oxides are mixed in, and have completed the present invention.
• R 1 to R 3 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• R 15 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxymethyl group, a methoxyethoxymethyl group, or a 2-hydroxyethyl group.
• a composition for carbon dioxide separation which comprises at least one amine compound selected from the group consisting of amine compounds represented by.
• the mixing ratio of the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2) is 100 parts by weight of the amine compound represented by the general formula (1).
• a step of bringing a gas containing carbon dioxide into contact with the carbon dioxide separation composition according to any one of the above [1] to [7] to absorb carbon dioxide in the mixed gas is included.
• the composition for carbon dioxide separation of the present invention has a higher carbon dioxide emission efficiency (emission amount / absorption amount) than a conventionally known material, and carbon dioxide at a low temperature (low energy) as compared with a conventionally known material. It has the effect of enabling the recovery and separation of carbon gas and reducing the impact on the environment (high energy efficiency).
• composition for carbon dioxide separation of the present invention is characterized in that the carbon dioxide absorption rate per unit time is high and the emission rate per unit time is also high as compared with conventionally known materials, and a large amount of carbon dioxide is used. Has the effect of being able to absorb and separate the carbon dioxide at high speed. Therefore, the present invention is extremely useful industrially in that it can efficiently absorb and separate a large amount of carbon dioxide emitted in a large-scale thermal power generation or the like.
• the composition for carbon dioxide separation of the present invention has an effect that the risk of accumulation of solid matter and blockage of pipes in the carbon dioxide separation equipment can be reduced as compared with conventionally known materials.
• composition for carbon dioxide separation of the present invention contains at least one amine compound selected from the group consisting of the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2). It is a feature.
• At least one amine compound selected from the group consisting of the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2) plays a role of adsorbing and desorbing carbon dioxide. ..
• the present invention is characterized by containing at least one amine compound selected from the group consisting of the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2).
• the carbon dioxide separation composition may be a carbon dioxide separation composition containing an amine compound represented by the above general formula (1), or may be a carbon dioxide separation composition containing the above general formula (1).
• the composition for carbon dioxide separation containing the amine compound represented by 2) may be used, or a mixture of the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2).
• the composition for carbon dioxide separation may contain (containing both the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2)).
• the composition for carbon dioxide separation of the present invention is excellent in carbon dioxide separation performance, and is both an amine compound represented by the general formula (1) and an amine compound represented by the general formula (2). It is preferable that the compound contains.
• the composition for carbon dioxide separation of the present invention contains both the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2)
• the general formula (1) is used.
• the mixing ratio of the amine compound shown and the amine compound represented by the general formula (2) is not particularly limited, but the amine represented by the general formula (1) is excellent in terms of carbon dioxide separation performance.
• the amine compound represented by the general formula (2) is preferably mixed in an amount of 0.1 to 99.9 parts by weight, more preferably 1 to 90 parts by weight, based on 100 parts by weight of the compound. It is more preferably 1 to 75 parts by weight, further preferably 5 to 50 parts by weight, and particularly preferably 10 to 30 parts by weight.
• R 1 to R 3 in the above general formula (1) independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• the above-mentioned alkyl group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tertiary butyl group. be able to.
• R 1 is preferably a hydrogen atom, a methyl group, an ethyl group, or a butyl group, and is preferably a hydrogen atom or a methyl group, because it is excellent in carbon dioxide emission efficiency (emission amount / absorption amount). Is more preferable, and a hydrogen atom is further preferable.
• R 2 or R 3 is preferably a hydrogen atom, a methyl group, an ethyl group, or a butyl group independently in terms of excellent carbon dioxide emission efficiency (emission amount / absorption amount).
• Each independently is more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
• the amine compound represented by the above general formula (1) from the viewpoint of availability, the amine compound represented by the following formula, that is, 1- (2,3-dihydroxypropyl) -piperazine (the above general formula (1)).
• the amine compound represented by the above general formula (1) may be a commercially available compound or a compound synthesized by a known method, and is not particularly limited.
• the purity of the amine compound represented by the general formula (1) is not particularly limited, but is preferably 95% by weight or more, and 99% by weight or more is particularly preferable.
• the above 1- (2,3-dihydroxypropyl) -piperazine can be produced by reacting piperazine with 2,3-dihydroxychloropropane.
• R 10 , R 11 , R 12 , R 13 and R 14 in the above general formula (2) are independently hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, hydroxyl groups, and hydroxymethyl. Represents a group, a 2-hydroxyethyl group, or an alkoxy group having 1 to 4 carbon atoms.
• R 10 , R 11 , R 12 , R 13 and R 14 in the general formula (2) may correspond to the above definitions, and are not particularly limited, but are independent of each other.
• hydrogen atoms, methyl groups, ethyl groups, butyl groups, hydroxymethyl groups, or methoxy groups are preferably independent of each other in terms of excellent carbon dioxide emission efficiency.
• R 15 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxymethyl group, methoxyethoxymethyl group, or a 2-hydroxyethyl group.
• R 15 in the general formula (2) may be applicable to the above definition, is not particularly limited, for example, a hydrogen atom, a methyl group, an ethyl group, n- propyl group, an isopropyl group , Butyl group (n-butyl group, isobutyl group, sec-butyl group, tert-butyl group), methoxymethyl group, methoxyethoxymethyl group, or 2-hydroxyethyl group.
• a hydrogen atom, a methyl group, an ethyl group, a butyl group, a methoxymethyl group, a methoxyethoxymethyl group, or a 2-hydroxyethyl group is preferable in terms of excellent carbon dioxide emission efficiency.
• amine compound represented by the above general formula (2) examples include the following compounds (exemplified compounds 1 to 28), but the present invention is not limited thereto.
• R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are independent of each other in that they are excellent in carbon dioxide emission efficiency (emission amount / absorption amount). Therefore, it is preferably a hydrogen atom, a methyl group, an ethyl group, or a butyl group, and more preferably a hydrogen atom or a methyl group independently of each other.
• R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are more preferably hydrogen atoms from the viewpoint of availability.
• the amine compound represented by the above general formula (2) may be a commercially available compound or a compound synthesized by a known method, and is not particularly limited.
• the purity of the amine compound represented by the general formula (2) is not particularly limited, but is preferably 95% or more, and 99% or more is particularly preferable. If the purity is less than 95%, the amount of carbon dioxide absorbed may decrease.
• the amine compound represented by the general formula (2) is not particularly limited, but can be produced, for example, by a cyclization reaction of dihydroxyalkylpiperazines (for example, 2,3-dihydroxypropylpiperazine). (See, for example, Japanese Patent Application Laid-Open No. 2010-37325).
• composition for carbon dioxide separation of the present invention containing at least one amine compound selected from the group consisting of the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2).
• amine compound represented by the general formula (1) selected from the group consisting of the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2).
• It may contain at least one amine compound (A).
• the N atom content per unit weight of the carbon dioxide separation composition can be determined. It can be increased, and the effect of increasing the amount of carbon dioxide absorbed per unit weight of the carbon dioxide separation composition is expected.
• alkanolamines include ethanolamine, N-methylethanolamine, N, N-dimethylethanolamine, diethanolamine, N-methyldiethanolamine, and N- (2-aminoethyl) ethanolamine.
• alkanolamines include ethanolamine, N-methyldiethanolamine, N- (2-aminoethyl) ethanolamine, and 2- (2-aminoethoxy). ) It is preferable that it is at least one selected from the group consisting of ethanol.
• propylene diamines include 1,3-propanediamine, 3- (dimethylamino) propylamine, 3- (diethylamino) propylamine, 1,3-bis (dimethylamino) propane, and the like. And 1,3-bis (diethylamino) propane and the like.
• the propylene diamines are at least one selected from the group consisting of 1,3-propanediamine and 3- (dimethylamino) propylamine from the viewpoint of availability and production cost. Is preferable.
• piperazines include piperazine, 2-methylpiperazine, 1- (2-hydroxyethyl) -piperazine, 1- (2,3-dihydroxypropyl) -piperazine, 1- (2-). Hydroxyethyl) -4-methylpiperazine, 1- (2,3-dihydroxypropyl) -4-methylpiperazine, 1- (2,3-dihydroxypropyl) -4-ethylpiperazine, 1- (2,3-dihydroxypropyl) ) -4-propylpiperazine, 1- (2,3-dihydroxypropyl) -4-butylpiperazine, 1- (2-hydroxy-3-methoxypropyl) -piperazine, 1- (2-hydroxy-3-methoxypropyl) -4-Methylpiperazine, 1- (2-Hydroxy-3-methoxypropyl) -4-ethylpiperazine, 1- (2-Hydroxy-3-methoxypropyl) -4-propylpiperazine, 1-
• piperidines include piperidine, 2-methylpiperidin, 1- (2,3-dihydroxypropyl) -piperidin, 1- (2,3-dihydroxypropyl) -4-methylpiperidin, and the like.
• morpholins include morpholine, 2-methylmorpholine, 2,6-dimethylmorpholine, 1- (2,3-dihydroxypropyl) -morpholine, 1- (2-hydroxy-3-3). Examples thereof include methoxypropyl) -morpholine and 1- (2,3-dimethoxypropyl) -morpholine.
• pyrrolidines include pyrrolidine, 2-methylpyrrolidine, 2,5-dimethylpyrrolidine, 1- (2,3-dihydroxypropyl) -pyrrolidine, and 1- (2-hydroxy-3-3).
• examples thereof include methoxypropyl) -pyrrolidine, 1- (2,3-dimethoxypropyl) -pyrrolidine, 1,5-diazabicyclo [4.3.0] -5-nonen and the like.
• azepanes include azepane, 2-methylazepane, 2,7-dimethylazepane, 1,8-diazabicyclo [5.4.0] -7-undecene and the like.
• polyethylene polyamines include diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and hexaethyleneheptamine (HEHA). And polyethylene polyamine having 8 or more amino groups and the like.
• DETA diethylenetriamine
• TETA triethylenetetramine
• TEPA tetraethylenepentamine
• PEHA pentaethylenehexamine
• HEHA hexaethyleneheptamine
• TETA refers to a compound in which four amino groups are linearly or branchedly connected via an ethylene chain, but in the present invention, it also has four amino groups. Moreover, those having a piperazine ring structure are also included.
• Specific compound names of TETA include, for example, 1,4,7,10-tetraazadecane, N, N-bis (2-aminoethyl) -1,2-ethanediamine, 1- [2-[(. 2-Aminoethyl) Amino] Ethyl] -piperazine, 1,4-bis (2-aminoethyl) -piperazine and the like can be mentioned.
• TEPA refers to a compound in which five amino groups are linearly or branchedly connected via an ethylene chain, but in the present invention, it also has five amino groups and also has five amino groups. Those having a piperazine ring structure are also included.
• TEPA Specific compound names of TEPA include, for example, 1,4,7,10,13-pentaazatridecane, N, N, N'-tris (2-aminoethyl) -1,2-ethanediamine, 1 -[2- [2- [2-[(2-Aminoethyl) amino] ethyl] amino] ethyl] -piperazine, 1- [2- [bis (2-aminoethyl) amino] ethyl] -piperazine, bis [ 2- (1-Piperazineyl) ethyl] amine and the like can be mentioned.
• PEHA refers to a compound in which six amino groups are linearly or branchedly connected via an ethylene chain, but in the present invention, it also has six amino groups and also has six amino groups. Those having a piperazine ring structure are also included.
• PEHA Specific compound names of PEHA include, for example, 1,4,7,10,13,16-hexaazahexadecane, N, N, N', N'-tetrakis (2-aminoethyl) -1,2- Ethandiamine, N, N-bis (2-aminoethyl) -N'-[2-[(2-aminoethyl) amino] ethyl] -1,2-ethanediamine, 1- [2- [2- [2] -[2- [2-[(2-Aminoethyl) Amino] Ethyl] Amino] Ethyl] Amino] Ethyl] -Piperazine, 1- [2- [2- [2- [2- [Bis (2-Aminoethyl) Amino]] Ethyl] amino] ethyl] -piperazine, N, N'-bis [2- (1-piperazinyl) ethyl] -1,2-ethanedia
• HEHA refers to a compound in which seven amino groups are linearly or branchedly connected via an ethylene chain, but in the present invention, it also has seven amino groups and also has seven amino groups. Those having a piperazine ring structure are also included.
• HEHA Specific compound names of HEHA include, for example, 1,4,7,10,13,16,19-heptaazanonadecan, N- [2-[(2-aminoethyl) amino] ethyl] -N, N', N'-tris (2-aminoethyl) -1,2-ethanediamine, 1- [2- [2- [2- [2- [2- [2-[(2-aminoethyl) amino] Ethyl] Amino] Ethyl] Amino] Ethyl] Amino] Ethyl] Amino] Ethyl] -Piperazine, N- (2-aminoethyl) -N, N'-bis [2- (1-piperazinyl) ethyl] -1,2-ethanediamine, etc. Can be mentioned.
• polyethylene polyamine having 8 or more amino groups refers to a compound in which 8 or more amino groups are linearly or branchedly connected via an ethylene chain, but in the present invention, the amino is also used. Those having eight or more groups and having a piperazine ring structure are also included. Specific examples of the polyethylene polyamine having 8 or more amino groups include the trade name "Poly8" (manufactured by Tosoh Corporation), polyethyleneimine and the like.
• diethylenetriamine is one of the polyethylene polyamines from the viewpoint of availability and acquisition cost.
• alkanolamines, propylene diamines, piperazins, piperidines, morpholines, pyrrolidines, azepanes, or polyethylene polyamines may be commercially available or synthesized by a known method, and in particular. Not limited.
• the purity of alkanolamines, propylene diamines, piperazins, piperidines, morpholines, pyrrolidines, azepanes, or polyethylene polyamines is not particularly limited, but is preferably 95% by weight or more, preferably 99. More than% by weight is particularly preferable.
• the composition for carbon dioxide separation of the present invention comprises at least one amine compound selected from the group consisting of the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2), and alkanol.
• at least one amine compound (A) selected from the group consisting of amines, propylene diamines, piperazins, piperidines, morpholins, pyrrolidines, azepans, and polyethylene polyamines, their weights.
• the ratio is not particularly limited as long as the effect of the present invention is exhibited.
• the weight ratio is selected from the group consisting of the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2) from the viewpoint of increasing the amount of carbon dioxide absorbed per unit weight.
• the content of the amine compound (A) is preferably 0.1 to 99.9 parts by weight, more preferably 0.5 to 90 parts by weight, based on 100 parts by weight of at least one amine compound. It is more preferably to 75 parts by weight, further preferably 1 to 50 parts by weight, and particularly preferably 5 to 40 parts by weight.
• the composition for carbon dioxide separation of the present invention can be used as it is for the intended purpose, but from the viewpoint of operability, it is usually preferable to use it as a solution further containing a solvent.
• the solvent used in the carbon dioxide separation composition is not particularly limited, but is, for example, water, an alcohol compound, a polyol compound (although not particularly limited, for example, ethylene glycol, glycerin, or polyethylene. (Glycerol, etc.) and the like can be mentioned, and a mixture thereof may be used. Of these, water is preferable because it is excellent in efficiency of absorbing and separating carbon dioxide gas as bicarbonate.
• the composition for carbon dioxide separation of the present invention contains the above solvent (for example, water), the composition for carbon dioxide separation is excellent in operability with respect to the concentration of the solvent. It is preferably 20 to 95% by weight, more preferably 30 to 95% by weight, further preferably 30 to 85% by weight, and particularly preferably 40 to 75% by weight based on the total amount. ..
• the composition for carbon dioxide separation of the present invention has an amine compound represented by the above general formula (1) and an amine compound represented by the above general formula (2) in that it is excellent in deterioration durability against nitrogen oxides. It is preferable that the composition comprises only water and at least one amine compound selected from the group consisting of. At this time, the preferable range of the compound and the preferable range of the composition are as described above.
• a composition for carbon dioxide separation which comprises at least one amine compound selected from the group consisting of the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2).
• at least one amine compound selected from the group consisting of the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2) has a large absorption rate and amount of carbon dioxide.
• the amine compound is represented by the above general formula (1). That is, a composition for carbon dioxide separation characterized by containing the amine compound represented by the above general formula (1) is preferable.
• a preferable composition for carbon dioxide separation is prepared by dissolving the amine compound represented by the above general formula (1) in a solvent such as water.
• the amine compound represented by the general formula (1) plays a role of adsorbing and desorbing carbon dioxide. ..
• the definition, preferable range, production method and the like of the amine compound represented by the general formula (1) are described above. It is a street.
• the composition for carbon dioxide separation which comprises the amine compound represented by the general formula (1), is added to the amine compound represented by the general formula (1) to the extent that the effect of the present invention is exhibited.
• at least one amine compound (A') selected from the group consisting of alkanolamines, propylenediamines, and polyethylene polyamines may be contained.
• the definition of propylene diamines or polyethylene polyamines in the amine compound (A') and the preferable range are as described above.
• the definition and preferable range of alkanolamines in the amine compound (A') will be described later.
• the amine compound (A') does not include the amine compound represented by the general formula (1).
• the N atom content per unit weight of the carbon dioxide separation composition can be increased, and the N atom content per unit weight of the carbon dioxide separation composition can be increased. It is expected to have the effect of increasing the amount of carbon dioxide absorbed.
• examples of the alkanolamines include, for example, ethanolamine and N-methylethanol.
• R 10 , R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a hydroxymethyl group, a 2-hydroxyethyl group, or Represents an alkoxy group having 1 to 4 carbon atoms.
• R 15 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxymethyl group, a methoxyethoxymethyl group, or a 2-hydroxyethyl group.
• Examples thereof include amine compounds represented by.
• alkanolamines include ethanolamine, N-methyldiethanolamine, N- (2-aminoethyl) ethanolamine, and 2- (2-aminoethoxy). It is preferably at least one selected from the group consisting of ethanol and the amine compound represented by the above general formula (2).
• R 10 , R 11 , R 12 , R 13 and R 14 in the above general formula (2) may correspond to the above definitions and are not particularly limited, but are independent of each other, for example, hydrogen.
• hydrogen atoms, methyl groups, ethyl groups, butyl groups, hydroxymethyl groups, or methoxy groups are preferably independent of each other in terms of excellent carbon dioxide emission efficiency.
• R 15 in the general formula (2) may be applicable to the above definition, it is not particularly limited, for example, a hydrogen atom, a methyl group, an ethyl group, n- propyl group, isopropyl group, butyl Groups (n-butyl group, isobutyl group, sec-butyl group, tert-butyl group), methoxymethyl group, methoxyethoxymethyl group, or 2-hydroxyethyl group can be mentioned.
• a hydrogen atom, a methyl group, an ethyl group, a butyl group, a methoxymethyl group, a methoxyethoxymethyl group, or a 2-hydroxyethyl group is preferable in terms of excellent carbon dioxide emission efficiency.
• amine compound represented by the above general formula (2) examples include, for example, the following compounds (exemplified compounds 1 to 28), but the present invention is not limited thereto.
• the hydrogen atom and the methyl group are independent of each other in that they are excellent in carbon dioxide emission efficiency (emission amount / absorption amount). , Ethyl group, or butyl group, and more preferably hydrogen atom or methyl group, respectively.
• the R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are more preferably hydrogen atoms from the viewpoint of availability.
• alkanolamines, propylene diamines, or polyethylene polyamines may be commercially available or known. It may be synthesized by a method and is not particularly limited. The purity of alkanolamines, propylene diamines, or polyethylene polyamines is not particularly limited, but is preferably 95% by weight or more, and 99% by weight or more is particularly preferable.
• the composition for carbon dioxide separation which comprises the amine compound represented by the general formula (1), includes the amine compound represented by the general formula (1), alkanolamines, propylene diamines, and the like.
• their weight ratio is not particularly limited.
• the content of the amine compound (A') is 0.1 to 100 parts by weight of the amine compound represented by the general formula (1). It is preferably 99.9 parts by weight, more preferably 0.5 to 90 parts by weight, further preferably 1 to 75 parts by weight, still more preferably 1 to 50 parts by weight, and 5 parts. It is particularly preferably about 40 parts by weight.
• the carbon dioxide separation composition characterized by containing the amine compound represented by the above general formula (1) can be used as it is for the intended purpose, but from the viewpoint of operability, a solvent is usually used. It is preferable to use it as a solution further contained.
• the solvent used in the carbon dioxide separation composition is not particularly limited, but is, for example, water, an alcohol compound, a polyol compound (although not particularly limited, for example, ethylene glycol, glycerin, or polyethylene. (Glycerol, etc.) and the like can be mentioned, and a mixture thereof may be used.
• the concentration of the solvent is excellent in operability of the carbon dioxide separation composition characterized by containing the amine compound represented by the above general formula (1). It is preferably 20 to 95% by weight, more preferably 30 to 95% by weight, further preferably 30 to 85% by weight, and 40 to 75% by weight based on the total amount of the carbon dioxide separation composition. It is particularly preferable to be% by weight.
• a composition for carbon dioxide separation which comprises at least one amine compound selected from the group consisting of the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2).
• at least one amine compound selected from the group consisting of the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2) promotes the emission of carbon dioxide and the emission efficiency.
• the amine compound represented by the above general formula (2) is preferable in terms of increasing (carbon dioxide emission amount / carbon dioxide absorption amount). That is, a composition for carbon dioxide separation characterized by containing the amine compound represented by the above general formula (2) is preferable.
• a preferable composition for carbon dioxide separation is prepared by dissolving the amine compound represented by the above general formula (2) in a solvent such as water.
• a composition for carbon dioxide separation characterized by containing the amine compound represented by the above general formula (2) will be described below.
• the amine compound represented by the general formula (2) promotes the emission of carbon dioxide and the emission efficiency ( It plays a role in increasing the amount of carbon dioxide emitted / the amount of carbon dioxide absorbed.
• the definition, preferable range, production method and the like of the amine compound represented by the general formula (2) are described. As mentioned above.
• composition for carbon dioxide separation characterized by containing the amine compound represented by the general formula (2), in addition to the amine compound represented by the general formula (2), within the range in which the effect of the present invention is exhibited. Further, even if it contains at least one amine compound (A) selected from the group consisting of alkanolamines, propylenediamines, piperazins, piperidines, morpholins, pyrrolidines, azepans, and polyethylene polyamines. good.
• the definition of the amine compound (A) and the preferable range are as described above. In this case, the amine compound (A) does not include the amine compound represented by the general formula (2).
• the N atom content per unit weight of the carbon dioxide separation composition can be increased, and the carbon dioxide absorption amount per unit weight of the carbon dioxide separation composition can be increased. The effect of being able to do it is expected.
• the amine compound (A) which may be contained in the composition for carbon dioxide separation characterized by containing the amine compound represented by the general formula (2) may be a commercially available product or is known. It may be synthesized by the method of the above, and is not particularly limited.
• the purity of the amine compound (A) is not particularly limited, but is preferably 95% or more, and 99% or more is particularly preferable. If the purity is less than 95%, the amount of carbon dioxide absorbed may decrease.
• the weight fraction of the amine compound represented by (2) and the amine compound (A) is not particularly limited. From the viewpoint of increasing the amount of carbon dioxide absorbed per unit weight, the weight fraction of the amine compound represented by the general formula (2) (the total of the amine compound represented by the general formula (2) and the amine compound (A)) is calculated. (Assuming 100% by weight) is preferably 50 to 99.9% by weight, more preferably 80 to 99% by weight.
• the carbon dioxide separation composition characterized by containing the amine compound represented by the general formula (2) can be used as it is for the intended purpose, but from the viewpoint of operability, a solvent is further added. It can be used as an impregnated composition.
• the solvent used in the carbon dioxide separation composition is not particularly limited, but is, for example, water, an alcohol compound, or a polyol compound (although not particularly limited, for example, ethylene glycol, glycerin, or (Polyethylene glycol, etc.) and the like can be mentioned, and a mixture thereof may be used.
• the concentration of the solvent is excellent in operability of the carbon dioxide separation composition characterized by containing the amine compound represented by the above general formula (2). It is preferably 20 to 95% by weight, more preferably 30 to 95% by weight, further preferably 30 to 85% by weight, and 50 to 80% by weight based on the total amount of the carbon dioxide separation composition. It is particularly preferable to be% by weight.
• the method for separating carbon dioxide of the present invention has a step of bringing the above-mentioned composition for carbon dioxide separation into contact with a gas containing carbon dioxide and allowing the above-mentioned composition for carbon dioxide separation to absorb carbon dioxide in a highly selective manner. Characteristically, it may include a step of dissipating the absorbed carbon dioxide by heating and / or exposing the composition for carbon dioxide separation to a reduced pressure environment after being absorbed in this way.
• the method for separating carbon dioxide of the present invention there is no particular limitation on the method for bringing the gas containing carbon dioxide into contact with the above composition for carbon dioxide separation, and a known method can be used.
• Known methods include a bubbling method and a facing contact method using a packed column or a shelf column.
• the temperature at which the gas containing carbon dioxide is absorbed by the above-mentioned composition for carbon dioxide separation is not particularly limited, but is usually in the range of 0 ° C to 50 ° C. Can be mentioned.
• the temperature at which carbon dioxide is dissipated from the above-mentioned composition for carbon dioxide separation is not particularly limited, but is usually in the range of 60 to 150 ° C. However, from the viewpoint of energy saving, the temperature is preferably 100 ° C. or lower. Further, the above-mentioned composition for carbon dioxide separation can be used as a carbon dioxide absorbing / dissipating agent in a chemical absorption method for carbon dioxide.
• the chemical absorption method represents a method in which the above composition for carbon dioxide separation is brought into contact with a gas containing carbon dioxide to absorb carbon dioxide, and then the absorbed carbon dioxide is dissipated by increasing the temperature or reducing the pressure.
• the temperature at which carbon dioxide is dissipated is not particularly limited, but may be, for example, 60 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 90 ° C. or higher in terms of excellent emission efficiency. , 100 ° C. or higher is particularly preferable.
• the above-mentioned composition for carbon dioxide separation can also be used as a carbon dioxide absorbing / dissipating agent after being supported on a carrier.
• the carrier is not particularly limited, but for example, silica, alumina, magnesia, porous glass, activated carbon, polymethylmethacrylate-based porous resin, fibers, or the like can be used.
• the silica crystalline ones, non-crystalline (amorphous) ones, those having pores (for example, mesoporous silica) and the like are known.
• the silica that can be used is not particularly limited, and industrially distributed silica can be used, but silica having a large surface area is preferable.
• the supported amount of the carbon dioxide separation composition in the above carbon dioxide absorbing / dissipating agent is 5 to 70 weight with respect to 100 parts by weight of the carrier weight in that it is excellent in the amount of carbon dioxide absorbed and the carrying operation of the carbon dioxide separating composition.
• the amount is preferably 10 to 60 parts by weight, more preferably 10 to 60 parts by weight.
• the carbon dioxide absorbing / dissipating agent may further contain water.
• the above carbon dioxide absorption and dissipation agent can be applied to a carbon dioxide separation method widely known as a solid absorption method.
• a carbon dioxide absorbing / dissipating agent is brought into contact with a gas containing carbon dioxide, the carbon dioxide absorbing / dissipating agent absorbs carbon dioxide, and then the carbon dioxide absorbing / dissipating agent is heated or exposed to a reduced pressure environment.
• the temperature at which carbon dioxide is dissipated is not particularly limited, but may be, for example, 60 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 90 ° C. or higher in terms of excellent emission efficiency. , 100 ° C. or higher is particularly preferable.
• the above-mentioned gas containing carbon dioxide may be a pure carbon dioxide gas or a mixed gas containing carbon dioxide and other gases.
• the other gas is not particularly limited, and examples thereof include atmosphere, nitrogen, oxygen, hydrogen, argon, neon, helium, carbon monoxide, water vapor, methane, and nitrogen oxides.
• the mixed gas applicable to the carbon dioxide separation method of the present invention is not particularly limited as long as it is a mixed gas containing carbon dioxide, but in order to improve the separation performance between carbon dioxide and other gases, the carbon dioxide concentration. Is preferably 5% by volume or more, and more preferably 10% by volume or more.
• a cooling step, a heating step, a cleaning step, an extraction step, an ultrasonic treatment step, a distillation step, and other steps of treating with a chemical solution can be appropriately carried out.
• the method for separating carbon dioxide of the present invention is not particularly limited, but for example, separation of carbon dioxide (CO 2 ) from combustion exhaust gas generated in a thermal power plant, a steel plant, a cement factory, or the like, or steam reforming. It can be applied to the separation of carbon dioxide (CO 2 ) from the steam reformed gas obtained by the quality process.
• ⁇ Measurement method of carbon dioxide gas emission efficiency 100 g of the carbon dioxide absorbing solution (in a gas absorbing bottle having a capacity of 200 mL) prepared in the examples described later was adjusted to 40 ° C. in a water bath. A mixed gas (500 mL / min) of 100 mL / min carbon dioxide gas and 400 mL / min nitrogen gas was blown into this carbon dioxide absorbing solution for 1 hour while bubbling. The amount of carbon dioxide gas absorbed at this time (CO 2 absorption amount (L) for 1 hour) was measured using a gas flow meter and a carbon dioxide concentration meter. Using this 1-hour CO 2 absorption amount (L), the CO 2 absorption amount (L) per 1 kg of the carbon dioxide absorbing solution was calculated.
• this carbon dioxide absorbing solution was adjusted to 70 ° C. in a water bath. 500 mL / min of nitrogen gas was blown into this carbon dioxide absorbing solution for 2 hours while bubbling. The amount of carbon dioxide gas emitted at this time (CO 2 emission amount (L) for 2 hours) was measured using a gas flow meter and a carbon dioxide concentration meter. Using CO 2 emission amount of the 2 hours (L), it was calculated CO 2 emission amount per the carbon dioxide absorption solution 1kg of (L).
• PIP Piperazine (manufactured by Sigma-Aldrich)
• DHPP 1- (2,3-dihydroxypropyl) -piperazine (manufactured by Sigma-Aldrich)
• DABCOM 1,4-diazabicyclo [2,2,2] octane-2-methanol (manufactured by Tosoh Corporation)
• MDEA N-Methyldiethanolamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
• Example 1 70 g of pure water is added to 30 g of DHPP and mixed and stirred to prepare a carbon dioxide absorbing solution (100 g), which is placed in a 200 mL gas absorbing bottle to measure the emission efficiency of carbon dioxide gas and precipitate due to the influence of nitrogen oxides. It was confirmed whether or not an object was generated.
• the amount of CO 2 absorbed (L) per hour was 2.45 L in terms of standard conditions. That is, the amount of CO 2 absorbed (L) per 1 kg of carbon dioxide absorbing solution per hour was 24.5 L in terms of standard conditions.
• the amount of CO 2 emitted (L) for 2 hours was 1.24 L in terms of standard conditions. That is, the amount of CO 2 emitted (L) for 2 hours per 1 kg of carbon dioxide absorbing solution was 12.4 L in terms of standard conditions.
• Example 2 A carbon dioxide absorbing solution (100 g) was prepared by mixing and stirring 32.6 g of DHPP, 7.4 g of DABCOM, and 60 g of pure water. It was confirmed whether or not sediment was generated due to the influence. The evaluation results are shown in Table 1.
• Example 3 A carbon dioxide absorbing solution (100 g) was prepared by mixing and stirring 50.0 g of DHPP, 7.4 g of DABCOM, and 42.6 g of pure water. It was confirmed whether or not sediment was generated due to the influence of the substance. The evaluation results are shown in Table 1.
• Example 4 30 g of DABCOM and 70 g of pure water are mixed and stirred to prepare a carbon dioxide absorbing solution (100 g), and as in Example 1, the emission efficiency of carbon dioxide gas is measured and the presence or absence of precipitation due to the influence of nitrogen oxides is present. Was confirmed. The evaluation results are shown in Table 1.
• Example 5 A carbon dioxide absorbing solution (100 g) was prepared by mixing and stirring 36.7 g of DHPP, 8.3 g of DABCOM, and 55 g of pure water. It was confirmed whether or not sediment was generated due to the influence. The evaluation results are shown in Table 2.
• Example 6 28.6 g of DHPP, 6.4 g of DABCOM, and 65 g of pure water were mixed and stirred to prepare a carbon dioxide absorbing solution (100 g), and the emission efficiency of carbon dioxide gas was measured and nitrogen oxides were measured in the same manner as in Example 1. It was confirmed whether or not sediment was generated due to the influence. The evaluation results are shown in Table 2.
• Example 7 A carbon dioxide absorbing solution (100 g) was prepared by mixing and stirring 24.5 g of DHPP, 5.5 g of DABCOM, and 70 g of pure water. It was confirmed whether or not sediment was generated due to the influence. The evaluation results are shown in Table 2.
• Example 8 A carbon dioxide absorbing solution (100 g) was prepared by mixing and stirring 40.8 g of DHPP, 9.2 g of DABCOM, and 50 g of pure water. It was confirmed whether or not sediment was generated due to the influence. The evaluation results are shown in Table 2.
• Example 9 A carbon dioxide absorbent (100 g) was prepared by mixing and stirring 34.7 g of DHPP, 7.8 g of DABCOM, and 57.5 g of pure water. It was confirmed whether or not sediment was generated due to the influence of the substance. The evaluation results are shown in Table 2.
• Example 10 A carbon dioxide absorbent (100 g) was prepared by mixing and stirring 38.8 g of DHPP, 8.7 g of DABCOM, and 52.5 g of pure water. It was confirmed whether or not sediment was generated due to the influence of the substance. The evaluation results are shown in Table 2.
• the carbon dioxide separation composition of the present invention is superior in carbon dioxide emission efficiency (emission amount / absorption amount) to the conventionally known carbon dioxide separation composition, and nitrogen. It has the effect of making it difficult for precipitates to form even if oxides are mixed.
• composition of the present invention separates and purifies carbon dioxide from combustion exhaust gas generated in thermal power plants, steel plants, cement factories, etc., and separates carbon dioxide from steam reforming gas obtained by a steam reforming process. -Can be used for purification.

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