JP6694642B2 - Carbon dioxide absorption liquid and carbon dioxide separation and recovery method - Google Patents
Carbon dioxide absorption liquid and carbon dioxide separation and recovery method Download PDFInfo
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- JP6694642B2 JP6694642B2 JP2015238938A JP2015238938A JP6694642B2 JP 6694642 B2 JP6694642 B2 JP 6694642B2 JP 2015238938 A JP2015238938 A JP 2015238938A JP 2015238938 A JP2015238938 A JP 2015238938A JP 6694642 B2 JP6694642 B2 JP 6694642B2
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- carbon dioxide
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- unsubstituted
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 675
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 337
- 239000001569 carbon dioxide Substances 0.000 title claims description 330
- 238000010521 absorption reaction Methods 0.000 title claims description 119
- 239000007788 liquid Substances 0.000 title claims description 78
- 238000000034 method Methods 0.000 title claims description 34
- 238000011084 recovery Methods 0.000 title description 15
- 238000000926 separation method Methods 0.000 title description 13
- 239000002250 absorbent Substances 0.000 claims description 86
- 230000002745 absorbent Effects 0.000 claims description 86
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 82
- 150000001412 amines Chemical class 0.000 claims description 69
- -1 aliphatic phosphate ester Chemical class 0.000 claims description 67
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 57
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 56
- 239000002608 ionic liquid Substances 0.000 claims description 53
- 239000007789 gas Substances 0.000 claims description 41
- 239000001257 hydrogen Substances 0.000 claims description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims description 40
- 239000002904 solvent Substances 0.000 claims description 38
- 125000001424 substituent group Chemical group 0.000 claims description 27
- 150000001450 anions Chemical class 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910001868 water Inorganic materials 0.000 claims description 18
- 150000001768 cations Chemical class 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 125000001931 aliphatic group Chemical group 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 125000005328 phosphinyl group Chemical group [PH2](=O)* 0.000 claims description 11
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 11
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 10
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical group CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 claims description 10
- 230000008929 regeneration Effects 0.000 claims description 10
- 238000011069 regeneration method Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 150000003008 phosphonic acid esters Chemical class 0.000 claims description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 6
- 150000003672 ureas Chemical class 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 125000005496 phosphonium group Chemical group 0.000 claims description 4
- 230000001172 regenerating effect Effects 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 125000005600 alkyl phosphonate group Chemical group 0.000 claims description 2
- MVWDJLOUEUAWIE-UHFFFAOYSA-N O=C=O.O=C=O Chemical compound O=C=O.O=C=O MVWDJLOUEUAWIE-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 26
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 23
- 125000004433 nitrogen atom Chemical group N* 0.000 description 21
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 230000002378 acidificating effect Effects 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- YZBBUYKPTHDZHF-KNVGNIICSA-N (3R)-7,2'-dihydroxy-4'-methoxyisoflavanol Chemical compound OC1=CC(OC)=CC=C1[C@H]1C(O)C2=CC=C(O)C=C2OC1 YZBBUYKPTHDZHF-KNVGNIICSA-N 0.000 description 5
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 5
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 125000004437 phosphorous atom Chemical group 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methyl urea Chemical compound CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 2
- LZDSILRDTDCIQT-UHFFFAOYSA-N dinitrogen trioxide Chemical compound [O-][N+](=O)N=O LZDSILRDTDCIQT-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 150000004693 imidazolium salts Chemical group 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 229960001730 nitrous oxide Drugs 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 2
- HOMONHWYLOPSLL-UHFFFAOYSA-N tributyl(ethyl)phosphanium Chemical compound CCCC[P+](CC)(CCCC)CCCC HOMONHWYLOPSLL-UHFFFAOYSA-N 0.000 description 2
- YBBLOADPFWKNGS-UHFFFAOYSA-N 1,1-dimethylurea Chemical compound CN(C)C(N)=O YBBLOADPFWKNGS-UHFFFAOYSA-N 0.000 description 1
- KCUGPPHNMASOTE-UHFFFAOYSA-N 1,2,3-trimethylimidazol-1-ium Chemical compound CC=1N(C)C=C[N+]=1C KCUGPPHNMASOTE-UHFFFAOYSA-N 0.000 description 1
- XLJSMWDFUFADIA-UHFFFAOYSA-N 1,3-diethylimidazol-1-ium Chemical compound CCN1C=C[N+](CC)=C1 XLJSMWDFUFADIA-UHFFFAOYSA-N 0.000 description 1
- HVVRUQBMAZRKPJ-UHFFFAOYSA-N 1,3-dimethylimidazolium Chemical compound CN1C=C[N+](C)=C1 HVVRUQBMAZRKPJ-UHFFFAOYSA-N 0.000 description 1
- XUAXVBUVQVRIIQ-UHFFFAOYSA-N 1-butyl-2,3-dimethylimidazol-3-ium Chemical compound CCCCN1C=C[N+](C)=C1C XUAXVBUVQVRIIQ-UHFFFAOYSA-N 0.000 description 1
- ICIVTHOGIQHZRY-UHFFFAOYSA-N 1-butyl-3-methylimidazol-3-ium;cyanoiminomethylideneazanide Chemical compound [N-]=C=NC#N.CCCCN1C=C[N+](C)=C1 ICIVTHOGIQHZRY-UHFFFAOYSA-N 0.000 description 1
- PUHVBRXUKOGSBC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;methanesulfonate Chemical compound CS([O-])(=O)=O.CCCC[N+]=1C=CN(C)C=1 PUHVBRXUKOGSBC-UHFFFAOYSA-M 0.000 description 1
- IRGDPGYNHSIIJJ-UHFFFAOYSA-N 1-ethyl-2,3-dimethylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1C IRGDPGYNHSIIJJ-UHFFFAOYSA-N 0.000 description 1
- QLWOUBCORTYSPP-UHFFFAOYSA-N 1h-imidazol-1-ium;hydroxide Chemical compound O.C1=CNC=N1 QLWOUBCORTYSPP-UHFFFAOYSA-N 0.000 description 1
- HUEXNHSMABCRTH-UHFFFAOYSA-N 1h-imidazole Chemical compound C1=CNC=N1.C1=CNC=N1 HUEXNHSMABCRTH-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical compound CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- BCLSJHWBDUYDTR-UHFFFAOYSA-N 2-(propylamino)ethanol Chemical compound CCCNCCO BCLSJHWBDUYDTR-UHFFFAOYSA-N 0.000 description 1
- GFIWSSUBVYLTRF-UHFFFAOYSA-N 2-[2-(2-hydroxyethylamino)ethylamino]ethanol Chemical compound OCCNCCNCCO GFIWSSUBVYLTRF-UHFFFAOYSA-N 0.000 description 1
- RXFCIXRFAJRBSG-UHFFFAOYSA-N 3,2,3-tetramine Chemical compound NCCCNCCNCCCN RXFCIXRFAJRBSG-UHFFFAOYSA-N 0.000 description 1
- KRGXWTOLFOPIKV-UHFFFAOYSA-N 3-(methylamino)propan-1-ol Chemical compound CNCCCO KRGXWTOLFOPIKV-UHFFFAOYSA-N 0.000 description 1
- NYYVCPHBKQYINK-UHFFFAOYSA-O 3-ethyl-2-methyl-1h-imidazol-3-ium Chemical compound CCN1C=C[NH+]=C1C NYYVCPHBKQYINK-UHFFFAOYSA-O 0.000 description 1
- OZWKRRRMNRVSIN-UHFFFAOYSA-P 3-methyl-1H-imidazol-3-ium methyl phosphite Chemical compound P(OC)([O-])[O-].CN1C=[NH+]C=C1.CN1C=[NH+]C=C1 OZWKRRRMNRVSIN-UHFFFAOYSA-P 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- INDFXCHYORWHLQ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-butyl-3-methylimidazol-3-ium Chemical compound CCCCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F INDFXCHYORWHLQ-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- YLFBFPXKTIQSSY-UHFFFAOYSA-N dimethoxy(oxo)phosphanium Chemical compound CO[P+](=O)OC YLFBFPXKTIQSSY-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- WFPZPJSADLPSON-UHFFFAOYSA-N dinitrogen tetraoxide Chemical compound [O-][N+](=O)[N+]([O-])=O WFPZPJSADLPSON-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 125000005020 hydroxyalkenyl group Chemical group 0.000 description 1
- 125000005016 hydroxyalkynyl group Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229960003753 nitric oxide Drugs 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 235000013842 nitrous oxide Nutrition 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical compound O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XKFPGUWSSPXXMF-UHFFFAOYSA-N tributyl(methyl)phosphanium Chemical compound CCCC[P+](C)(CCCC)CCCC XKFPGUWSSPXXMF-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Gas Separation By Absorption (AREA)
- Carbon And Carbon Compounds (AREA)
Description
本発明は、二酸化炭素吸収液および二酸化炭素分離回収方法に関する。 The present invention relates to a carbon dioxide absorbent and a carbon dioxide separation and recovery method.
二酸化炭素や硫化水素などの酸性ガスの分離回収では、アミン化合物の水溶液を吸収液として用いた化学吸収法が実用化されている。この化学吸収法のプロセスでは、吸収塔において室温近傍で、酸性ガスを含む気体を吸収液に接触させて、酸性ガスを選択的に吸収液に化学的に吸収させ、酸性ガス濃度の低下した気体と酸性ガスを吸収した吸収液を分離し、再生塔において、その酸性ガスを吸収した吸収液を加熱して、酸性ガスを放散させて回収し、同時に吸収液を再生し、循環して用いる。 In the separation and recovery of acidic gases such as carbon dioxide and hydrogen sulfide, a chemical absorption method using an aqueous solution of an amine compound as an absorption liquid has been put into practical use. In the process of this chemical absorption method, a gas containing an acidic gas is brought into contact with the absorbing liquid in the vicinity of room temperature in an absorption tower to selectively chemically absorb the acidic gas into the absorbing liquid, thereby reducing the concentration of the acidic gas. And the absorption liquid that has absorbed the acidic gas are separated, and the absorption liquid that has absorbed the acidic gas is heated in the regeneration tower to diffuse and recover the acidic gas, and at the same time, the absorption liquid is regenerated and circulated for use.
しかし、従来のアミン水溶液を用いた二酸化炭素分離回収方法では、再生塔で二酸化炭素を回収して吸収液を再生するために吸収液を高温にする工程で消費エネルギーが著しく大きくなる。このような問題を解決するため様々な検討が行われている。 However, in the conventional carbon dioxide separation and recovery method using an aqueous amine solution, energy consumption is significantly increased in the step of raising the temperature of the absorption liquid in order to recover the absorption liquid by recovering carbon dioxide in the regeneration tower. Various studies have been made to solve such problems.
例えば特許文献１には、イオン液体およびアミン化合物を含む不純物除去混合物に流体を接触させて、二酸化炭素などの不純物ガスの量を低減する方法が記載されている。この特許文献１には、このイオン液体として、イミダゾリウム系のカチオンと、スルホネートやヘキサフルオロホスフェートなどのアニオンからなるイオン液体を用いること、４０℃で二酸化炭素を捕捉し１００℃で放出することが記載されている。 For example, Patent Document 1 describes a method of contacting a fluid with an impurity removal mixture containing an ionic liquid and an amine compound to reduce the amount of an impurity gas such as carbon dioxide. In Patent Document 1, an ionic liquid composed of an imidazolium-based cation and an anion such as sulfonate or hexafluorophosphate is used as the ionic liquid, and carbon dioxide is captured at 40 ° C. and released at 100 ° C. Have been described.
また、特許文献２には、ガス流からＣＯ２を分離する循環方法であって、アルカノールアミンＣＯ２吸収剤および非求核性の塩基を含む吸収剤にガス流を接触させる工程を含む方法が記載されている。この特許文献２には、更に、溶媒としてイオン液体を使用できる可能性があることが記載され、イオン液体のカチオンとしてイミダゾリウム、アニオンとしてアセテート、ハライド、チオシアネート、低級アルキル鎖カルボキシレ−トが例示されている。なお、特許文献２の実施例には、溶媒としてＤＭＳＯを用いたもののみが記載されている。 Further, Patent Document 2 discloses a circulation method for separating CO 2 from a gas stream, which includes a step of bringing the gas stream into contact with an alkanolamine CO 2 absorbent and an absorbent containing a non-nucleophilic base. Have been described. This Patent Document 2 further describes that an ionic liquid can be used as a solvent, and examples thereof include imidazolium as the cation of the ionic liquid, and acetate, halide, thiocyanate, and lower alkyl chain carboxylate as the anion. Has been done. In the examples of Patent Document 2, only those using DMSO as a solvent are described.
従来のアミン水溶液を用いた二酸化炭素分離回収方法の問題は、二酸化炭素の脱離（反応熱）の工程に高温が必要なこと、溶媒の水は比熱が大きく、昇温・冷却に過大なエネルギーを要すること、加熱に際して水の蒸発潜熱が余分に掛かることに由来する。また、特許文献１に記載の方法はアミン化合物１モル当たりの二酸化炭素吸収量が０．５モル程度と少なく、効率が低い。また、特許文献２には、イオン液体を使用した具体的な回収方法の開示がない。したがって、本発明の課題は、従来のアミン水溶液に比べて室温近傍での吸収量が高く、かつ高温での易脱性に優れ、蒸発損失が少なく、低比熱で、反応熱が小さく、回収する二酸化炭素当たりの二酸化炭素吸収液の再生に要するエネルギーを削減可能な二酸化炭素吸収液を提供することである。 The problems of the conventional carbon dioxide separation and recovery method using aqueous amine solution are that high temperature is required for the process of carbon dioxide desorption (reaction heat), and the water of solvent has a large specific heat, and excessive energy is required for heating and cooling. This is because the latent heat of vaporization of water is extra during heating. Further, the method described in Patent Document 1 has a low carbon dioxide absorption amount of about 0.5 mol per mol of the amine compound, and is low in efficiency. Further, Patent Document 2 does not disclose a specific recovery method using an ionic liquid. Therefore, an object of the present invention is to have a higher absorption amount in the vicinity of room temperature than the conventional amine aqueous solution, to be excellent in easy desorption at high temperature, to have a small evaporation loss, a low specific heat, a small reaction heat, and to be recovered. An object of the present invention is to provide a carbon dioxide absorbing liquid capable of reducing the energy required to regenerate the carbon dioxide absorbing liquid per carbon dioxide.
本発明者らは、前記課題を解決するため鋭意検討した結果、特定のイオン液体や、カルボニル基やホスフィニル基に電子供与性の窒素原子が結合した特定のアミド化合物は、水素結合性受容能力に富んでいること、窒素−水素結合を有するアミン化合物をそのような水素結合受容性溶媒中で用いると、従来のアミン水溶液に比べて室温近傍での二酸化炭素吸収量が高く、かつ高温での二酸化炭素易脱性に優れ、吸収液の蒸発損失が少なく、回収する単位二酸化炭素当たりの二酸化炭素吸収液の再生に要するエネルギーを削減できることを見出した。本発明者らは更に検討を行い、本発明を完成した。 As a result of intensive studies to solve the above problems, the present inventors have found that a specific ionic liquid or a specific amide compound having an electron-donating nitrogen atom bonded to a carbonyl group or a phosphinyl group has a hydrogen-bonding acceptability. When it is rich and the amine compound having a nitrogen-hydrogen bond is used in such a hydrogen bond-accepting solvent, it has a higher carbon dioxide absorption amount near room temperature than conventional amine aqueous solutions, and also has a high temperature. It has been found that carbon easily desorbs, the evaporation loss of the absorbing solution is small, and the energy required for regenerating the carbon dioxide absorbing solution per unit carbon dioxide to be recovered can be reduced. The present inventors conducted further studies and completed the present invention.
上記課題を解決するため本発明の二酸化炭素吸収液は、
式１で表される、窒素−水素結合を有する二酸化炭素化学吸収性アミンと、
水素結合受容性溶媒とを含み、
前記水素結合受容性溶媒は、アニオンが、式２、式３若しくは式４で表されるリン酸エステル若しくはリン酸、若しくは
式５で表されるホスホン酸エステル若しくはホスホン酸であるイオン液体である。
前記イオン液体のアニオンは、
式２、式３若しくは式４で表されるリン酸エステルのうち、Ｒ ３ 、Ｒ ４ 、Ｒ ５ 及びＲ ６ が、水素原子又は無置換若しくは置換基を有していてもよい脂肪族炭化水素基である、脂肪族リン酸エステル、又は、
式５で表されるホスホン酸エステルのうち、Ｒ ７ が、水素原子又は無置換若しくは置換基を有していてもよい脂肪族炭化水素基である、脂肪族ホスホン酸エステルであると好ましい。
In order to solve the above problems, the carbon dioxide absorbing solution of the present invention,
A carbon dioxide chemisorbable amine having a nitrogen-hydrogen bond, represented by Formula 1,
Including a hydrogen bond accepting solvent,
The hydrogen bond accepting solvents, anions of the formula 2, phosphoric acid esters or phosphoric acid represented by Formula 3 or Formula 4, or Ku Wakashi phosphonic acid ester of the formula 5 in the ionic liquid is a phosphonic acid is there.
The anion of the ionic liquid is
Among the phosphoric acid esters represented by Formula 2, Formula 3 or Formula 4, R 3 , R 4 , R 5 and R 6 are hydrogen atoms or an aliphatic hydrocarbon which may have an unsubstituted or substituted group. A group, an aliphatic phosphate ester, or
Among the phosphonate esters represented by formula 5, R 7 is preferably an aliphatic phosphonate ester, which is a hydrogen atom or an unsubstituted or optionally substituted aliphatic hydrocarbon group.
前記イオン液体のカチオンは、式１０で表されるイミダゾリウム類、式１１で表されるアンモニウム類、又は式１２で表されるホスホニウム類であると好ましい。
前記イオン液体のカチオンは、式１２で表されるホスホニウム類のうち、Ｒ ３４ 、Ｒ ３５ 、Ｒ ３６ 及びＲ ３７ が、水素原子又は無置換若しくは置換基を有していてもよい脂肪族炭化水素基である、脂肪族ホスホニウムであると好ましい。 The cation of the ionic liquid is an aliphatic hydrocarbon in which R 34 , R 35 , R 36, and R 37 in the phosphoniums represented by the formula 12 are hydrogen atoms or may be unsubstituted or have a substituent. it is a group, preferably a aliphatic phosphonium beam.
また、前記イオン液体のカチオンは式１０で表されるイミダゾリウム類であり、
前記イオン液体のアニオンは式２、式３若しくは式４で表されるリン酸エステルのうち、Ｒ ３ 、Ｒ ４ 、Ｒ ５ 及びＲ ６ が、水素原子又は無置換若しくは置換基を有していてもよいアルキル基である、アルキルリン酸エステル、又は、式５で表されるホスホン酸エステルのうち、Ｒ ７ が、水素原子又は無置換若しくは置換基を有していてもよいアルキル基である、アルキルホスホン酸エステルであると好ましい。
The cation of the ionic liquid is an imidazolium compound represented by formula 10 ,
In the anion of the ionic liquid , R 3 , R 4 , R 5 and R 6 in the phosphoric acid ester represented by Formula 2, Formula 3 or Formula 4 have a hydrogen atom or an unsubstituted or substituted group. also alkyl groups, alkyl phosphoric acid ester, or of phosphonic acid esters of the formula 5, R 7 is an alkyl group which may have a hydrogen atom or an unsubstituted or substituted, It is preferably an alkylphosphonate.
また、上記課題を解決するため本発明の二酸化炭素吸収液は、 Further, the carbon dioxide absorbent of the present invention for solving the above problems,
式１で表される、窒素−水素結合を有する二酸化炭素化学吸収性アミンと、 A carbon dioxide chemisorbable amine having a nitrogen-hydrogen bond, represented by Formula 1,
水素結合受容性溶媒とを含み、 Including a hydrogen bond accepting solvent,
前記水素結合受容性溶媒は、電子吸引基としてカルボニル基若しくはホスフィニル基を有する、式６、式７若しくは式８ The hydrogen bond accepting solvent has a carbonyl group or a phosphinyl group as an electron-withdrawing group, represented by Formula 6, Formula 7, or Formula 8
で表される、アミド化合物であり、 Is an amide compound represented by
水分含有量は１０質量％以下である。 The water content is 10% by mass or less.
前記アミド化合物は、式６で表される尿素誘導体であるであると好ましい。 The amide compound is preferably a urea derivative represented by Formula 6.
前記尿素誘導体は、Ｎ，Ｎ’−ジメチルプロピレン尿素又は１，３−ジメチル−２−イミダゾリジノンであると好ましい。 The urea derivative is preferably N, N'-dimethylpropyleneurea or 1,3-dimethyl-2-imidazolidinone.
前記二酸化炭素化学吸収性アミンは更に水酸基を有する炭化水素基を有すると好ましい。 It is preferable that the carbon dioxide chemically absorbing amine further has a hydrocarbon group having a hydroxyl group.
前記二酸化炭素化学吸収性アミンは、モノエタノールアミン又はジエタノールアミンであると好ましい。 The carbon dioxide chemically absorbing amine is preferably monoethanolamine or diethanolamine.
前記二酸化炭素化学吸収性アミンはモノエタノールアミンであると好ましい。 The carbon dioxide chemisorbable amine is preferably monoethanolamine.
前記二酸化炭素吸収液中の前記二酸化炭素化学吸収性アミンの濃度が１質量％以上５０質量％以下であると好ましい。 The concentration of the carbon dioxide chemically absorbing amine in the carbon dioxide absorbing liquid is preferably 1% by mass or more and 50% by mass or less.
水分含有量は１０質量％未満であると好ましい。 The water content is preferably less than 10% by mass.
本発明の二酸化炭素分離回収方法は、
前記二酸化炭素吸収液を二酸化炭素を含む混合ガスと５０℃以下で接触させることによって、二酸化炭素を前記二酸化炭素吸収液に吸収させて、前記混合ガスから二酸化炭素を選択的に分離する吸収工程、及び
前記の二酸化炭素を吸収した二酸化炭素吸収液を１２０℃以上に加熱することで吸収した二酸化炭素の９０％以上を放散させて回収し、前記二酸化炭素吸収液を再生する加熱再生工程を含む。
The carbon dioxide separation and recovery method of the present invention,
An absorption step of causing carbon dioxide to be absorbed by the carbon dioxide absorbent by bringing the carbon dioxide absorbent into contact with the mixed gas containing carbon dioxide at 50 ° C. or lower, and selectively separating carbon dioxide from the mixed gas; And heating and regenerating the carbon dioxide absorption liquid by heating the carbon dioxide absorption liquid that has absorbed the carbon dioxide to 120 ° C. or higher to diffuse and recover 90% or more of the absorbed carbon dioxide.
本発明の二酸化炭素吸収液は、従来のアミン水溶液に比べて室温近傍での二酸化炭素吸収量が多く、かつ高温での二酸化炭素易脱性に優れ、蒸発損失が少なく、低比熱で、反応熱が小さく、回収する二酸化炭素当たりの二酸化炭素吸収液の再生に要するエネルギーを削減可能である。 The carbon dioxide absorbing solution of the present invention has a large amount of carbon dioxide absorption near room temperature as compared with a conventional amine aqueous solution, and is excellent in carbon dioxide easy desorption at high temperature, has a small evaporation loss, has a low specific heat, and has a low reaction heat. Is small, and it is possible to reduce the energy required to regenerate the carbon dioxide absorbent per carbon dioxide to be recovered.
本発明の二酸化炭素吸収液は、二酸化炭素化学吸収性アミンと、水素結合受容性溶媒を含む。 The carbon dioxide absorbent of the present invention contains a carbon dioxide chemically absorbing amine and a hydrogen bond accepting solvent.
（二酸化炭素化学吸収性アミン）
本発明に係る二酸化炭素化学吸収性アミンは、式１で表され、窒素−水素結合を有する。
The carbon dioxide chemisorbable amine according to the present invention is represented by Formula 1 and has a nitrogen-hydrogen bond.
窒素−水素結合を有するアミンは、式１３−１に示すように二酸化炭素と反応してカルバメート塩を生成しうる。なお、生成したカルバメート塩と未反応のアミンとの間でプロトン移行が起こり（式１３−２）、二酸化炭素化学吸収性アミンと二酸化炭素との反応は化学量論的に２：１になることがある（式１３−３）。
このようにして、二酸化炭素化学吸収性アミンは２０℃程度の比較的低温で二酸化炭素を吸収する。二酸化炭素を吸収した二酸化炭素化学吸収性アミンは、１００℃や１５０℃といった高温にすると二酸化炭素を放出し、二酸化炭素化学吸収性アミンが再生される。 In this way, the carbon dioxide chemisorbable amine absorbs carbon dioxide at a relatively low temperature of about 20 ° C. The carbon dioxide chemically absorbing amine that has absorbed carbon dioxide releases carbon dioxide when the temperature is raised to a high temperature such as 100 ° C. or 150 ° C., and the carbon dioxide chemically absorbing amine is regenerated.
本発明に係る二酸化炭素化学吸収性アミンは、アンモニアの水素原子の１つ又は２つが炭化水素基で置換した、１級又は２級の窒素原子を有するアミンである。炭化水素基は、特に限定されないが、例えば、無置換又はハロゲン基、水酸基などの置換基を有するアルキル基、アルケニル基、アルキニル基が挙げられ、環状であっても非環状であってもよく、骨格にヘテロ原子を有していてもよい。また、本発明に係る二酸化炭素化学吸収性アミンは、一分子内に複数の窒素原子を有していても良い。この炭化水素基としては、脂肪族炭化水素基が好ましく、アルキル基がより好ましい。具体的には、メチル基、エチル基、プロピル基、ブチル基、ドデシル基、アリル基、ベンジル基、シアノメチル基、メトキシ基、エトキシ基などが挙げられる。本明細書では、一分子内に複数の窒素原子が存在し、それらの窒素原子が異なる級数であるときには、アミンの級数は、高い方の級数とする。例えば、一分子内に３級窒素原子（窒素原子に炭化水素基が３つ結合している）と２級窒素原子（窒素原子に炭化水素基が２つ結合し、水素原子が一つ結合している）を有する場合には、そのアミンは３級アミンとする。したがって、この例の場合には、水素−窒素結合を有する３級アミンである。窒素炭素二重結合は、炭化水素基が窒素原子に２つ結合しているとして級数を定める。 The carbon dioxide chemisorbable amine according to the present invention is an amine having a primary or secondary nitrogen atom in which one or two hydrogen atoms of ammonia are replaced with a hydrocarbon group. The hydrocarbon group is not particularly limited, and examples thereof include an unsubstituted or halogen group, an alkyl group having a substituent such as a hydroxyl group, an alkenyl group, and an alkynyl group, which may be cyclic or acyclic. The skeleton may have a hetero atom. Further, the carbon dioxide chemically absorbing amine according to the present invention may have a plurality of nitrogen atoms in one molecule. As this hydrocarbon group, an aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a dodecyl group, an allyl group, a benzyl group, a cyanomethyl group, a methoxy group and an ethoxy group. In this specification, when a plurality of nitrogen atoms are present in one molecule and the nitrogen atoms have different series, the series of amine is the higher series. For example, a tertiary nitrogen atom (having three hydrocarbon groups bonded to the nitrogen atom) and a secondary nitrogen atom (having two hydrocarbon groups bonded to the nitrogen atom and one hydrogen atom bonded to each other in one molecule) The amine is a tertiary amine. Therefore, in the case of this example, it is a tertiary amine having a hydrogen-nitrogen bond. The nitrogen-carbon double bond has a series defined as having two hydrocarbon groups bonded to the nitrogen atom.
本発明に係る二酸化炭素化学吸収性アミンの例としては、メチルアミン、エチルアミン、プロピルアミンなどの１級アルキルアミン；Ｎ，Ｎ−ジメチルアミン、Ｎ，Ｎ−ジエチルアミンなどの２級アルキルアミン；エチレンジアミン（ＥＤＡ）、ジエチレントリアミン（ＥＤＴＡ）、Ｎ−ヘキシルエチレンジアミン（ＨｅｘＥＤＡ）、ジエチレントリアミン（Ｈ２Ｎ（Ｃ２Ｈ４）ＨＮ（Ｃ２Ｈ４）ＮＨ２）、トリス（２−アミノエチル）アミン（Ｎ（Ｃ２Ｈ４ＮＨ２）３）、トリエチレンテトラミン（Ｈ２Ｎ（Ｃ２Ｈ４）ＨＮ（Ｃ２Ｈ４）ＨＮ（Ｃ２Ｈ４）ＮＨ２）、１，２−ビス（３−アミノプロピルアミノ）エタン（Ｈ２Ｎ（Ｃ３Ｈ６）ＨＮ（Ｃ２Ｈ４）ＨＮ（Ｃ３Ｈ６）ＮＨ２）などの２、３、４、又はそれ以上の窒素原子を有する多座のアミン；モルホリン、ピペラジン（ＰＺ）、１−（２−アミノエチル）ピペラジン（ＰＺ−（Ｃ２Ｈ４）ＮＨ２）などの環状アミン；アニリン、Ｎ−メチルアニリンなどの芳香族アミンが挙げられる。 Examples of the carbon dioxide chemically absorbing amine according to the present invention include primary alkylamines such as methylamine, ethylamine and propylamine; secondary alkylamines such as N, N-dimethylamine and N, N-diethylamine; ethylenediamine ( EDA), diethylenetriamine (EDTA), N-hexyl diamine (HexEDA), diethylenetriamine (H 2 N (C 2 H 4) HN (C 2 H 4) NH 2), tris (2-aminoethyl) amine (N (C 2 H 4 NH 2) 3) , triethylenetetramine (H 2 N (C 2 H 4) HN (C 2 H 4) HN (C 2 H 4) NH 2), 1,2- bis (3-aminopropyl amino) ethane (H 2 N (C 3 H 6) HN (C 2 H 4) HN (C 3 H 6) NH 2) polydentate amines having 2, 3, 4, or more nitrogen atoms, such as ; morpholine, piperazine (PZ), cyclic amines such as 1- (2-aminoethyl) piperazine (PZ- (C 2 H 4) NH 2); aniline, aromatic amines such as N- methylaniline.
本発明に係る二酸化炭素化学吸収性アミンは、窒素−水素結合を有するとともに、式１４又は式１５に示すように、水酸基を有する炭化水素基を有すると好ましい。
水酸基を有する炭化水素基は、特に限定されず、ヒドロキシアルキル基、ヒドロキシアルケニル基、ヒドロキシアルキニル基が挙げられ、更にハロゲン基などの置換基を有することもできる。水酸基を有する炭化水素基としては、ヒドロキシアルキル基が好ましい。ヒドロキシアルキル基を有するアミンは、アルカノールアミンとも呼ばれる。ヒドロキシアルキル基の例としては、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシ−ｉ−プロピル基、及びヒドロキシブチル基などが挙げられる。中でも、炭素数２又は３以上であると好ましく、ヒドロキシエチル基が特に好ましい。 The hydrocarbon group having a hydroxyl group is not particularly limited, and examples thereof include a hydroxyalkyl group, a hydroxyalkenyl group and a hydroxyalkynyl group, which may further have a substituent such as a halogen group. The hydrocarbon group having a hydroxyl group is preferably a hydroxyalkyl group. An amine having a hydroxyalkyl group is also called an alkanolamine. Examples of the hydroxyalkyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxy-i-propyl group, a hydroxybutyl group and the like. Among them, those having 2 or 3 or more carbon atoms are preferable, and a hydroxyethyl group is particularly preferable.
窒素−水素結合を有するとともに、水酸基を有する炭化水素基を有する、二酸化炭素化学吸収性アミンの具体例としては、モノエタノールアミン（ＭＥＡ）、モノプロパノールアミンなどの１級アミン；Ｎ−メチルエタノールアミン（ＭＭＥＡ）、２−（エチルアミノ）エタノール（ＥｔＮＨ（ＥｔＯＨ））、２−（プロピルアミノ）エタノール（ＰｒＮＨ（ＥｔＯＨ））、２−（ブチルアミノ）エタノール（ＢｕＮＨ（ＥｔＯＨ））、３−メチルアミノ−１−プロパノール（ＭｅＮＨ（ｎ−ＰｒＯＨ））、Ｎ−（２−ヒドロキシエチル）エチレンジアミン（Ｈ２Ｎ（Ｃ２Ｈ４）ＮＨＥｔＯＨ）、Ｎ−（２−ヒドロキシイソプロピル）エチレンジアミン（Ｈ２Ｎ（Ｃ２Ｈ４）ＮＨｉｓｏ−ＰｒＯＨ）、Ｎ，Ｎ’−ビス（２−ヒドロキシエチル）エチレンジアミン（ＥｔＯＨＮＨ（Ｃ２Ｈ４）ＮＨＥｔＯＨ）などの２級アミン；ジエタノールアミン（ＤＥＡ）、ジプロパノールアミンなどの水酸基を有する炭化水素基を２以上有する２級アミンなどが挙げられる。 Specific examples of the carbon dioxide chemically absorbing amine having a nitrogen-hydrogen bond and a hydrocarbon group having a hydroxyl group include primary amines such as monoethanolamine (MEA) and monopropanolamine; N-methylethanolamine. (MMEA), 2- (ethylamino) ethanol (EtNH (EtOH)), 2- (propylamino) ethanol (PrNH (EtOH)), 2- (butylamino) ethanol (BuNH (EtOH)), 3-methylamino 1-propanol (MeNH (n-PrOH)) , N- (2- hydroxyethyl) ethylenediamine (H 2 n (C 2 H 4) NHEtOH), N- (2- hydroxyisopropyl) ethylenediamine (H 2 n (C 2 H 4) NH iso -PrOH) , N, N'- bis (2-hydroxyethyl) ethylenediamine (EtOHNH (C 2 H 4) NHEtOH) 2 amines, such as; diethanolamine (DEA), a hydroxyl group, such as dipropanolamine And secondary amines having two or more hydrocarbon groups having
中でも、二酸化炭素吸収液として二酸化炭素分離回収の効率が高いなどの点で、水酸基を有する炭素数２以上の炭化水素基が窒素原子に結合した２級アミン又は１級アミンが好ましく、水酸基を有する炭素数２以上の炭化水素基が窒素原子に結合した２級アミンがより好ましい。より具体的には、ＭＥＡ、ＤＥＡ、ＭＭＥＡが好ましく、ＤＥＡがより好ましい。 Of these, secondary amines or primary amines having a hydroxyl group-containing hydrocarbon group having 2 or more carbon atoms bonded to a nitrogen atom are preferable, since they have a high efficiency of carbon dioxide separation and recovery as a carbon dioxide absorbing liquid, and have a hydroxyl group. A secondary amine in which a hydrocarbon group having 2 or more carbon atoms is bonded to a nitrogen atom is more preferable. More specifically, MEA, DEA and MMEA are preferable, and DEA is more preferable.
（水素結合受容性溶媒）
本発明に係る水素結合受容性溶媒は、アニオンが、リン酸、ホスホン酸、式２、式３、若しくは式４で表されるリン酸エステル、若しくは式５で表されるホスホン酸エステルであるイオン液体、又は電子吸引基としてカルボニル基若しくはホスフィニル基を有する、式６、式７、式８若しくは式９で表されるアミド化合物である。
The hydrogen bond-accepting solvent according to the present invention is an ion in which the anion is phosphoric acid, phosphonic acid, a phosphoric acid ester represented by Formula 2, Formula 3, or Formula 4, or a phosphonate ester represented by Formula 5. A liquid, or an amide compound represented by Formula 6, Formula 7, Formula 8 or Formula 9 having a carbonyl group or a phosphinyl group as an electron-withdrawing group.
これらのイオン液体及びアミド化合物は、水素結合受容性能力に富んでいる。これらを溶媒として、窒素−水素結合を有するアミンを用いると、従来のアミン水溶液に比べて室温近傍での二酸化炭素吸収量が高くかつ高温での易脱性に優れ、吸収液の蒸発損失が少なく、二酸化炭素吸収液の再生エネルギーを削減可能な低比熱で反応熱が小さい二酸化炭素吸収液が得られる。 These ionic liquids and amide compounds are rich in hydrogen bond accepting ability. When an amine having a nitrogen-hydrogen bond is used as a solvent for these, the carbon dioxide absorption amount is higher near room temperature than the conventional amine aqueous solution, the desorption property at high temperature is excellent, and the evaporation loss of the absorption liquid is small. Thus, a carbon dioxide absorbent having a low specific heat and a small reaction heat capable of reducing the regeneration energy of the carbon dioxide absorbent can be obtained.
（イオン液体）
本発明に係るイオン液体は、カチオンとアニオンからなり、１００℃、大気圧で液体の塩である。本発明に係るイオン液体は、特に室温（２５℃）で液体であると好ましい。すなわち、本発明に係るイオン液体の融点は、１００℃以下であれば特に限定されないが、５０℃未満であると好ましく、２５℃未満であるとより好ましく、１０℃未満であると特に好ましい。また、本発明に係るイオン液体の融点の下限は、特に限定されない。なお、イオン液体は融点以下でも過冷却となり液体状態をとることが多く、そのような液体状態を保持できれば融点が高くとも限定されない。また、イオン液体の融点はアミン類の混合により低下することがあり、二酸化炭素吸収液として利用できれば限定されない。
(Ionic liquid)
The ionic liquid according to the present invention is a salt that is composed of a cation and an anion and is liquid at 100 ° C. and atmospheric pressure. The ionic liquid according to the present invention is preferably liquid at room temperature (25 ° C.). That is, the melting point of the ionic liquid according to the present invention is not particularly limited as long as it is 100 ° C. or lower, but is preferably less than 50 ° C., more preferably less than 25 ° C., and particularly preferably less than 10 ° C. Moreover, the lower limit of the melting point of the ionic liquid according to the present invention is not particularly limited. It should be noted that the ionic liquid is often supercooled even at the melting point or lower and is in a liquid state. If the ionic liquid can maintain such a liquid state, it is not limited even if the melting point is high. Further, the melting point of the ionic liquid may be lowered by the mixing of amines, and is not limited as long as it can be used as a carbon dioxide absorbing liquid.
本発明に係るイオン液体を構成するアニオンは、リン酸、ホスホン酸、リン酸エステル又はホスホン酸エステルのアニオンである。 The anion constituting the ionic liquid according to the present invention is an anion of phosphoric acid, phosphonic acid, phosphoric acid ester or phosphonic acid ester.
リン酸エステルのアニオンは、リン酸（（ＨＯ）３Ｐ＝Ｏ）の水素原子の１つ又は２つが炭化水素基で置換された化合物のアニオンであり、式２、式３、又は式４で表される。リン酸エステルの炭化水素基は、特に限定されず、例えば二酸化炭素化学吸収性アミンの炭化水素基として例示したものが挙げられるが、脂肪族炭化水素基が好ましく、アルキル基がより好ましく、炭素数２以下のアルキル基が特に好ましい。より具体的には、リン酸エステルのアニオンとして、ジメチルホスホネート（（ＭｅＯ）２ＰＯＯ−）、ジエチルホスホネート（（ＥｔＯ）２ＰＯＯ−）が好ましい。 The anion of a phosphoric acid ester is an anion of a compound in which one or two hydrogen atoms of phosphoric acid ((HO) 3 P═O) are substituted with a hydrocarbon group, and is represented by Formula 2, Formula 3, or Formula 4. expressed. The hydrocarbon group of the phosphate ester is not particularly limited, and examples thereof include those exemplified as the hydrocarbon group of carbon dioxide chemically absorbable amine, but an aliphatic hydrocarbon group is preferable, an alkyl group is more preferable, and a carbon number is Alkyl groups of 2 or less are particularly preferred. More specifically, dimethylphosphonate ((MeO) 2 POO − ) and diethylphosphonate ((EtO) 2 POO − ) are preferable as the phosphate ester anion.
ホスホン酸エステルのアニオンは、ホスホン酸（Ｈ３ＰＯ４、（ＨＯ）２(Ｈ）Ｐ＝Ｏ）の水酸基の水素原子の１つが炭化水素基で置換されたアニオンであり、式５で表される。ホスホン酸エステルの炭化水素基は特に限定されず、例えば二酸化炭素化学吸収性アミンの炭化水素基として例示したものが挙げられるが、脂肪族炭化水素基が好ましく、アルキル基がより好ましく、炭素数２以下のアルキル基が特に好ましい。より具体的には、ホスホン酸エステルのアニオンとして、メチルホスファイト（（ＭｅＯ）ＨＰＯＯ−）が好ましい。 The anion of phosphonate is an anion in which one of the hydrogen atoms of the hydroxyl group of phosphonic acid (H 3 PO 4 , (HO) 2 (H) P═O) is substituted with a hydrocarbon group and is represented by Formula 5. It The hydrocarbon group of the phosphonate ester is not particularly limited, and examples thereof include those exemplified as the hydrocarbon group of carbon dioxide chemically absorbable amine, but an aliphatic hydrocarbon group is preferable, an alkyl group is more preferable, and a carbon number of 2 The following alkyl groups are particularly preferred. More specifically, as the anion of the phosphonate, methyl phosphite ((MeO) HPOO -) is preferred.
本発明に係るイオン液体において、カチオンは特に限定されないが、イミダゾリウム類、アンモニウム類、又はホスホニウム類であると好ましい。 In the ionic liquid according to the present invention, the cation is not particularly limited, but is preferably imidazolium, ammonium, or phosphonium.
イミダゾリウム類は、イミダゾール（１，３−ｄｉａｚａ−２，４−ｃｙｃｌｏｐｅｎｔａｄｉｅｎｅ）のカチオン又はイミダゾールの水素原子が炭化水素基に置換されている化合物のカチオンであり、例えば、式１０で表される。
イミダゾリウム類の炭化水素基は、特に限定されないが、例えば、無置換又はハロゲン基、水酸基などの置換基を有するアルキル基、アルケニル基、アルキニル基が挙げられ、環状であっても非環状であってもよく、骨格にヘテロ原子を有していてもよい。炭化水素基は、１つであっても２以上であってもよいが、１，３位の２つの窒素原子に炭化水素基を有していると好ましい。２以上の炭化水素基を有するときは、同一であっても異なっていてもよい。この炭化水素基は、特に限定されず、例えば二酸化炭素化学吸収性アミンの炭化水素基として例示したものが挙げられるが、メチル基、エチル基、プロピル基、ブチル基、ドデシル基、アリル基、ベンジル基、シアノメチル基、メトキシ基、エトキシ基が好ましく、脂肪族炭化水素基がより好ましい。より具体的には、イミダゾリウム類として、１，３−ジメチルイミダゾリウム（［ＭＭＩＭ］＋）、１，２，３−トリメチルイミダゾリウム（［ＭＭＭＩＭ］＋）、１−エチル−３−メチルイミダゾリウム（［ＥＭＩＭ］＋）、１−エチル−２，３−ジメチルイミダゾリウム（［ＥＭＭＩＭ］＋）、１，３−ジエチルイミダゾリウム（［ＥＥＩＭ］＋）、１，３−ジエチル−２−メチルイミダゾリウム（［ＥＭＥＩＭ］＋）、１−ブチル−３−メチルイミダゾリウム（［ＢＭＩＭ］＋）、１−ブチル−２，３−ジメチルイミダゾリウム（［ＢＭＭＩＭ］＋）が好ましい。 The hydrocarbon group of the imidazolium group is not particularly limited, and examples thereof include an alkyl group, an alkenyl group, and an alkynyl group which are unsubstituted or have a substituent such as a halogen group and a hydroxyl group, and are cyclic or acyclic. Or may have a hetero atom in the skeleton. Although the number of the hydrocarbon group may be one or two or more, it is preferable that the two nitrogen atoms at the 1st and 3rd positions have a hydrocarbon group. When it has two or more hydrocarbon groups, it may be the same or different. This hydrocarbon group is not particularly limited, and examples thereof include those exemplified as the hydrocarbon group of carbon dioxide chemically absorbable amine, and include methyl group, ethyl group, propyl group, butyl group, dodecyl group, allyl group, and benzyl group. A group, a cyanomethyl group, a methoxy group and an ethoxy group are preferable, and an aliphatic hydrocarbon group is more preferable. More specifically, as the imidazoliums, 1,3-dimethylimidazolium ([MMIM] + ), 1,2,3-trimethylimidazolium ([MMMIM] + ), 1-ethyl-3-methylimidazolium ([EMIM] +), 1- ethyl - 2, 3-dimethyl imidazolium ([EMMIM] +), 1,3- diethyl imidazolium ([EEIM] +), 1,3- di an ethyl-2-methyl Imidazolium ([EMEIM] + ), 1-butyl-3-methylimidazolium ([BMIM] + ) and 1-butyl-2,3-dimethylimidazolium ([BMMM] + ) are preferable.
アンモニウム類は、窒素原子に水素原子若しくは炭化水素基が結合したカチオンであり、式１１で表される。
ホスホニウム類は、リン原子に水素原子若しくは炭化水素基が結合したカチオンであり、式１２で表される。
ホスホニウム類の炭化水素基は、特に限定されないが、例えば、無置換又はハロゲン基、水酸基などの置換基を有するアルキル基、アルケニル基、アルキニル基が挙げられ、環状であっても非環状であってもよく、骨格にヘテロ原子を有していてもよい。この炭化水素基としては、脂肪族炭化水素基が好ましく、アルキル基がより好ましい。具体的には、メチル基、エチル基、プロピル基、ブチル基、ドデシル基、アリル基、ベンジル基、シアノメチル基、メトキシ基、エトキシ基などが挙げられる。置換基を、２以上有するときは、同一であっても異なってもよい。より具体的には、ホスホニウムとして、トリブチルメチルホスホニウム（［Ｐ１４４４］＋）、トリブチルヘキシルホスホニウム（Ｐ４４４６］＋）、テトラブチルホスホニウム（［Ｐ４４４４］＋）、トリブチルエチルホスホニウム（［Ｐ２４４４］＋）が好ましく、テトラブチルホスホニウム（［Ｐ４４４４］＋）、トリブチルエチルホスホニウム（［Ｐ２４４４］＋）がより好ましい。 The hydrocarbon group of the phosphoniums is not particularly limited, and examples thereof include an unsubstituted or halogen group, an alkyl group having a substituent such as a hydroxyl group, an alkenyl group, and an alkynyl group. Or may have a hetero atom in the skeleton. As this hydrocarbon group, an aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a dodecyl group, an allyl group, a benzyl group, a cyanomethyl group, a methoxy group and an ethoxy group. When having two or more substituents, they may be the same or different. More specifically, as phosphonium, tributylmethylphosphonium ([P 1444 ] + ), tributylhexylphosphonium (P 4446 ] + ), tetrabutylphosphonium ([P 4444 ] + ), tributylethylphosphonium ([P 2444 ] +). ) Is preferable, and tetrabutylphosphonium ([P 4444 ] + ) and tributylethylphosphonium ([P 2444 ] + ) are more preferable.
リン酸エステルのアニオン又はホスホン酸エステルのアニオンと、イミダゾリウム類、アンモニウム類、又はホスホニウム類との組み合わせは特に限定されないが、より具体的には、イオン液体として、［ＥＭＩＭ］［（ＭｅＯ）ＨＰＯＯ］、［ＭＭＩＭ］［（ＭｅＯ）ＨＰＯＯ］、［Ｐ４４４４］［（ＭｅＯ）ＨＰＯＯ］、［ＢＭＩＭ］［（ＭｅＯ）２ＰＯＯ］、［ＭＭＩＭ］［（ＭｅＯ）２ＰＯＯ］、［ＥＭＩＭ］［（ＥｔＯ）２ＰＯＯ］、［ＥＥＩＭ］［（ＥｔＯ）２ＰＯＯ］、［Ｐ２４４４］［（ＥｔＯ）２ＰＯＯ］が好ましい。これらのイオン液体は、水素結合性受容能力に優れ、二酸化炭素化学吸収性アミンの室温近傍での二酸化炭素吸収量を上げ、かつ高温での二酸化炭素易脱性を向上させる。 The combination of the anion of a phosphoric acid ester or the anion of a phosphonic acid ester and an imidazolium, ammonium, or phosphonium is not particularly limited, and more specifically, as an ionic liquid, [EMIM] [(MeO) HPOO ], [MMIM] [(MeO) HPOO], [P 4444 ] [(MeO) HPOO], [BMIM] [(MeO) 2 POO], [MMIM] [(MeO) 2 POO], [EMIM] [(( EtO) 2 POO], [EEIM] [(EtO) 2 POO], and [P 2444 ] [(EtO) 2 POO] are preferable. These ionic liquids have excellent hydrogen-bonding acceptability, increase the amount of carbon dioxide absorbed by a carbon dioxide chemically absorbing amine near room temperature, and improve the ease of carbon dioxide desorption at high temperatures.
カチオンがイミダゾリウム類でアニオンがホスホン酸エステルのときは、イオン液体は、例えば、アルキルイミダゾールのテトラヒドロフラン溶液に亜リン酸ジアルキルのテトラヒドロフラン溶液を等量滴下し、その後９０℃で数日間加熱還流することで得られる（式１６参照）。生成物をジエチルエーテルやジクロロメタンで分液後、エバポレーターや油回転式ポンプを用いて真空下で原料や溶媒、水分を除去することで、不純物を取り除くことができる。 When the cation is an imidazolium compound and the anion is a phosphonate ester, the ionic liquid should be, for example, an equal volume of a dialkyl phosphite tetrahydrofuran solution added dropwise to a tetrahydrofuran solution of alkylimidazole, and then heated under reflux at 90 ° C for several days. (See equation 16). Impurities can be removed by separating the product with diethyl ether or dichloromethane and then removing the raw material, solvent, and water under vacuum using an evaporator or an oil rotary pump.
カチオンがイミダゾリウム類、アンモニウム類、又はホスホニウム類で、アニオンがリン酸エステルのときは、イオン液体は、例えば、水酸化イミダゾリウム、水酸化アンモニウム、又は水酸化ホスホニウムの水溶液とリン酸類水溶液を等量滴下し、数時間撹拌して得られる。生成物をエバポレーターで脱水した後、ジエチルエーテルで分液後、エバポレーターや油回転式ポンプを用いて真空下で原料や溶媒、水分を除去することで、不純物を取り除くことができる。 When the cation is an imidazolium, ammonium, or phosphonium and the anion is a phosphoric ester, the ionic liquid is, for example, an aqueous solution of imidazolium hydroxide, ammonium hydroxide, or phosphonium hydroxide and an aqueous solution of phosphoric acid. It is obtained by dropping in a quantity and stirring for several hours. Impurities can be removed by dehydrating the product with an evaporator, separating it with diethyl ether, and then removing the raw material, solvent, and water under vacuum using an evaporator or an oil rotary pump.
カチオンがホスホニウム類で、アニオンがリン酸エステル又はホスホン酸エステルのときは、例えば、イオン液体は、ホスフィン化合物とアルキルハライドの求核反応によってホスホニウムハライドを得、その後アニオン交換して得られる。生成物をエバポレーターで脱水した後、ジエチルエーテルで分液後、エバポレーターや油回転式ポンプを用いて真空下で原料や溶媒、水分を除去して不純物を取り除く。 When the cation is a phosphonium compound and the anion is a phosphoric acid ester or a phosphonic acid ester, for example, an ionic liquid is obtained by nucleophilic reaction of a phosphine compound and an alkyl halide to obtain a phosphonium halide and then anion exchange. The product is dehydrated with an evaporator, separated with diethyl ether, and then the raw material, solvent, and water are removed under vacuum using an evaporator and an oil rotary pump to remove impurities.
（アミド化合物）
本発明に係るアミド化合物は、電子吸引基としてカルボニル基又はホスフィニル基を有する、式６、式７、式８、又は式９で表されるアミド化合物である。式６には、カルボニル基の炭素原子に２つの窒素原子が結合したアミド化合物が表されている。式７、式８、及び式９には、ホスフィニル基のリン原子に少なくとも１つの窒素原子が結合するアミド化合物が表されている。窒素原子は電子供与性であり、このようなアミド結合は、水素結合の受容能力に富んでおり、室温近傍での二酸化炭素化学吸収性アミンの二酸化炭素吸収量を増やし、かつ高温での二酸化炭素易脱性を向上させる。
(Amide compound)
The amide compound according to the present invention is an amide compound represented by Formula 6, Formula 7, Formula 8, or Formula 9 having a carbonyl group or a phosphinyl group as an electron-withdrawing group. Formula 6 represents an amide compound in which two nitrogen atoms are bonded to the carbon atom of the carbonyl group. Formulas 7, 8 and 9 represent amide compounds in which at least one nitrogen atom is bonded to the phosphorus atom of the phosphinyl group. The nitrogen atom has an electron donating property, and such an amide bond is rich in the ability to accept a hydrogen bond, increasing the carbon dioxide absorption amount of a carbon dioxide chemisorbing amine at room temperature and reducing the carbon dioxide at a high temperature. Improves ease of removal.
本発明に係るカルボニル基を有するアミド化合物は、式６に示すように、電子吸引基としてカルボニル基を有し、そのカルボニル基の炭素原子に２つの窒素原子が結合しているアミド化合物である。式６で表されるカルボニル基を有するアミド化合物としては、特に限定されないが、例えば尿素誘導体が挙げられる。尿素誘導体としては、尿素の窒素上の水素を炭化水素基で置換した化合物が挙げられる。式６で表されるアミド化合物の炭化水素基としては、例えば二酸化炭素化学吸収性アミンの炭化水素基として例示したものが挙げられるが、脂肪族炭化水素基が好ましく、互いに結合し環状であるとより好ましい。より具体的にはアミド化合物として、尿素、Ｎ−メチル尿素、Ｎ，Ｎ−ジメチル尿素、１，３−ジメチル−２−イミダゾリジノン（ＤＭＩ）、Ｎ，Ｎ’−ジメチルプロピレン尿素（ＤＭＰＵ）、テトラメチル尿素（ＴＭＵ）が好ましく、ＤＭＩやＤＭＰＵがより好ましい。 The amide compound having a carbonyl group according to the present invention is an amide compound having a carbonyl group as an electron-withdrawing group and two carbon atoms bonded to the carbon atom of the carbonyl group, as shown in Formula 6. The amide compound having a carbonyl group represented by Formula 6 is not particularly limited, and examples thereof include urea derivatives. Examples of the urea derivative include compounds in which hydrogen on the nitrogen of urea is replaced with a hydrocarbon group. Examples of the hydrocarbon group of the amide compound represented by Formula 6 include those exemplified as the hydrocarbon group of carbon dioxide chemically absorbable amine, but an aliphatic hydrocarbon group is preferable, and it is preferable that they are bonded to each other to form a ring. More preferable. More specifically, as the amide compound, urea, N-methylurea, N, N-dimethylurea, 1,3-dimethyl-2-imidazolidinone (DMI), N, N'-dimethylpropyleneurea (DMPU), Tetramethylurea (TMU) is preferable, and DMI and DMPU are more preferable.
本発明に係るホスフィニル基を有するアミド化合物は、式７、式８、又は式９で表される。式７で表されるアミド化合物は、ホスフィニル基のリン原子に１つの窒素原子と２つの水素原子又は炭化水素基が結合するアミド化合物である。式８で表されるアミド化合物は、ホスフィニル基のリン原子に２つの窒素原子と１つの水素原子又は炭化水素基が結合するアミド化合物である。式９で表されるアミド化合物は、ホスフィニル基のリン原子に３つの窒素原子が結合するリン酸トリアミドである。本発明に係るホスフィニル基を有するアミド化合物としては、特に限定されないが、リン酸トリアミドが好ましい。式７、式８又は式９で表されるアミド化合物の炭化水素基は特に限定されず、例えば二酸化炭素化学吸収性アミンの炭化水素基として例示したものが挙げられるが、脂肪族炭化水素基が好ましく、アルキル基がより好ましく、炭素数２以下のアルキル基が特に好ましい。より具体的には、リン酸トリアミドとして、ヘキサメチルリン酸トリアミド（ＨＭＰＡ）、トリス（Ｎ，Ｎ’−テトラメチレン）リン酸トリアミドが好ましく、ＨＭＰＡがより好ましい。 The amide compound having a phosphinyl group according to the present invention is represented by Formula 7, Formula 8, or Formula 9. The amide compound represented by Formula 7 is an amide compound in which one nitrogen atom and two hydrogen atoms or a hydrocarbon group are bonded to the phosphorus atom of the phosphinyl group. The amide compound represented by Formula 8 is an amide compound in which two nitrogen atoms and one hydrogen atom or a hydrocarbon group are bonded to the phosphorus atom of the phosphinyl group. The amide compound represented by Formula 9 is phosphoric acid triamide in which three nitrogen atoms are bonded to the phosphorus atom of the phosphinyl group. The amide compound having a phosphinyl group according to the present invention is not particularly limited, but phosphoric acid triamide is preferable. The hydrocarbon group of the amide compound represented by Formula 7, Formula 8 or Formula 9 is not particularly limited, and examples thereof include those exemplified as the hydrocarbon group of the carbon dioxide chemically absorbing amine, and the aliphatic hydrocarbon group is An alkyl group is more preferable, and an alkyl group having 2 or less carbon atoms is particularly preferable. More specifically, hexamethylphosphoric triamide (HMPA) and tris (N, N′-tetramethylene) phosphoric triamide are preferable as phosphoric acid triamide, and HMPA is more preferable.
（二酸化炭素吸収液）
本発明の二酸化炭素吸収液は、前述の二酸化炭素化学吸収性アミンと水素結合受容性溶媒を含む。本発明に用いる二酸化炭素化学吸収性アミン及び水素結合受容性溶媒は、通常、共に室温で液体であり、本発明の二酸化炭素吸収液は、二酸化炭素化学吸収性アミンと水素結合受容性溶媒と混合することによって得られる。
(Carbon dioxide absorbent)
The carbon dioxide absorbing liquid of the present invention contains the above-mentioned carbon dioxide chemically absorbing amine and a hydrogen bond accepting solvent. The carbon dioxide chemical-absorbing amine and the hydrogen bond-accepting solvent used in the present invention are usually both liquids at room temperature, and the carbon dioxide-absorbing liquid of the present invention is a mixture of the carbon dioxide chemical-absorbing amine and the hydrogen bond-accepting solvent. It is obtained by doing.
二酸化炭素化学吸収性アミンと水素結合受容性溶媒の組み合わせは特に限定されないが、ＭＥＡと、ＨＭＰＡ又はＤＥＡ；ＭＥＡと、ＤＭＰＵ又はＤＭＩ；ＭＥＡと、［ＥＭＩＭ］［（ＭｅＯ）ＨＰＯＯ］、［ＭＭＩＭ］［（ＭｅＯ）ＨＰＯＯ］、［Ｐ４４４４］［（ＭｅＯ）ＨＰＯＯ］、［ＢＭＩＭ］［（ＭｅＯ）２ＰＯＯ］、［ＭＭＩＭ］［（ＭｅＯ）２ＰＯＯ］、［ＥＭＩＭ］［（ＥｔＯ）２ＰＯＯ］、［ＥＥＩＭ］［（ＥｔＯ）２ＰＯＯ］、又は［Ｐ４４４４］［（ＥｔＯ）２ＰＯＯ］の組合せが好ましい。 The combination of the carbon dioxide chemisorbable amine and the hydrogen bond accepting solvent is not particularly limited, but MEA, HMPA or DEA; MEA, DMPU or DMI; MEA, [EMIM] [(MeO) HPOO], [MMIM]. [(MeO) HPOO], [ P 4444] [(MeO) HPOO], [BMIM] [(MeO) 2 POO], [MMIM] [(MeO) 2 POO], [EMIM] [(EtO) 2 POO] , [EEIM] [(EtO) 2 POO], or [P 4444 ] [(EtO) 2 POO] is preferred.
二酸化炭素吸収液中の二酸化炭素化学吸収性アミンと水素結合受容性溶媒の割合は特に限定されず、これらの種類によって適宜選択されるが、二酸化炭素化学吸収性アミン／（二酸化炭素化学吸収性アミン＋水素結合受容性溶媒）（質量比）で、好ましくは１／１００〜５０／１００、より好ましくは１０／１００〜４０／１００である。水素結合受容性溶媒がＨＭＰＡなどのアミド化合物である場合は特に、二酸化炭素吸収液中の二酸化炭素化学吸収性アミンの含有量で、１質量％以上５０質量％以下であると好ましく、１０質量％以上４０質量％以下であるとより好ましい。二酸化炭素化学吸収性アミンの比率がこの範囲にあると、室温近傍での二酸化炭素吸収量を上げ、かつ高温での二酸化炭素易脱性を向上できる。 The ratio of the carbon dioxide chemical-absorbing amine and the hydrogen bond-accepting solvent in the carbon dioxide-absorbing liquid is not particularly limited and may be appropriately selected depending on these types. + Hydrogen bond accepting solvent) (mass ratio), preferably 1/100 to 50/100, more preferably 10/100 to 40/100. Especially when the hydrogen bond accepting solvent is an amide compound such as HMPA, the content of the carbon dioxide chemically absorbing amine in the carbon dioxide absorbing liquid is preferably 1% by mass or more and 50% by mass or less, and 10% by mass is preferable. It is more preferably 40% by mass or less and 40% by mass or less. When the ratio of the carbon dioxide chemically absorbing amine is within this range, the carbon dioxide absorption amount near room temperature can be increased, and the carbon dioxide easiness of removal at high temperature can be improved.
本発明の二酸化炭素吸収液には、水を含むことができるが、１０質量％以下が好ましく、５質量％以下がより好ましく、３質量％以下が特に好ましい。 The carbon dioxide absorbent of the present invention may contain water, but is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less.
（二酸化炭素分離回収方法）
本発明の二酸化炭素吸収液は、二酸化炭素を含む混合ガスから、二酸化炭素ガスを分離回収できる。混合ガスは、二酸化炭素を含むガス状の混合物であれば、特に限定されず、その他の成分を含むことができる。その他の成分としては、二酸化炭素以外の酸性ガス、窒素ガス、酸素ガス、水、ばいじんなどが挙げられる。二酸化炭素以外の酸性ガスの例としては、硫化水素；一酸化硫黄、二酸化硫黄（亜硫酸ガス）、三酸化硫黄などの硫黄酸化物；一酸化窒素、二酸化窒素、亜酸化窒素（一酸化二窒素）、三酸化二窒素、四酸化二窒素、五酸化二窒素などの窒素酸化物；塩酸、硝酸、リン酸、硫酸などの無機酸類；カルボン酸、スルホン酸、炭酸などの有機酸類、が挙げられる。本発明の二酸化炭素吸収液は、混合ガスにその他の成分としての水が飽和量含まれていても二酸化炭素の回収性に影響が少ない。また、本発明の二酸化炭素吸収液は、混合ガスにその他の成分としてばいじんが含まれていても二酸化炭素の回収性に影響が少ない。
(Method of separating and collecting carbon dioxide)
The carbon dioxide absorbent of the present invention can separate and recover carbon dioxide gas from a mixed gas containing carbon dioxide. The mixed gas is not particularly limited as long as it is a gaseous mixture containing carbon dioxide, and may contain other components. Other components include acidic gases other than carbon dioxide, nitrogen gas, oxygen gas, water, dust and the like. Examples of acidic gases other than carbon dioxide include hydrogen sulfide; sulfur oxides such as sulfur monoxide, sulfur dioxide (sulfurous acid gas) and sulfur trioxide; nitric oxide, nitrogen dioxide, nitrous oxide (dinitrogen monoxide). , Nitrogen oxides such as dinitrogen trioxide, dinitrogen tetraoxide, and dinitrogen pentoxide; inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, and sulfuric acid; organic acids such as carboxylic acid, sulfonic acid, and carbonic acid. The carbon dioxide absorbent of the present invention has little effect on carbon dioxide recovery even if the mixed gas contains a saturated amount of water as another component. Further, the carbon dioxide absorbing liquid of the present invention has little influence on the carbon dioxide recoverability even if the mixed gas contains soot and dust as other components.
次に、本発明の二酸化炭素吸収液を用いた二酸化炭素分離回収方法について説明する。
本発明の二酸化炭素分離回収方法は、前述の二酸化炭素吸収液を二酸化炭素を含む混合ガスと接触させることによって、二酸化炭素を前記二酸化炭素吸収液に吸収させて、前記混合ガスから二酸化炭素を選択的に分離する吸収工程、及び前記の二酸化炭素を吸収した二酸化炭素吸収液を吸収工程より高温に加熱することで吸収した二酸化炭素を放散させて回収し、前記二酸化炭素吸収液を再生する加熱再生工程、を含む。本発明の二酸化炭素吸収液は、室温近傍での吸収量が高く、かつ高温での易脱性に優れ、蒸発損失が少なく、低比熱で、反応熱が小さいので、回収する二酸化炭素当たりの、二酸化炭素吸収液の再生に要するエネルギーを削減できる。
Next, a carbon dioxide separation and recovery method using the carbon dioxide absorbent of the present invention will be described.
The carbon dioxide separation and recovery method of the present invention, by contacting the carbon dioxide absorption liquid with a mixed gas containing carbon dioxide, allows the carbon dioxide absorption liquid to absorb carbon dioxide, and selects carbon dioxide from the mixed gas. The absorption step of separating the carbon dioxide and the carbon dioxide absorption solution that absorbs the carbon dioxide is heated to a higher temperature than the absorption step to dissipate and collect the absorbed carbon dioxide and regenerate the carbon dioxide absorption solution. The process is included. The carbon dioxide absorbent of the present invention has a high absorption amount in the vicinity of room temperature, and is excellent in easy desorption at high temperature, has a small evaporation loss, has a low specific heat, and has a small reaction heat, and therefore, per carbon dioxide to be recovered, The energy required to regenerate the carbon dioxide absorbent can be reduced.
吸収工程の二酸化炭素吸収液の温度は、下限が二酸化炭素吸収液が凝固しない限り特に限定されないが、６０℃以下が好ましく、４０℃以下が好ましく、室温近傍（２０℃±２０℃）が更に好ましく、１０℃以下が特に好ましい。吸収工程の二酸化炭素吸収液の温度が低いほど、二酸化炭素の吸収量が増加する傾向がある。本発明の二酸化炭素分離回収方法は、二酸化炭素を化学的に二酸化炭素吸収液に吸収させるので、吸収工程の圧力は、特に限定されないが、二酸化炭素の二酸化炭素吸収液への溶解性や、二酸化炭素吸収液の同伴による損失を防ぐなどの点で、通常、大気圧以上が好ましく、１ＭＰａ〜６ＭＰａなどの高圧条件でも利用することができる。 The temperature of the carbon dioxide absorbent in the absorption step is not particularly limited as long as the lower limit does not solidify the carbon dioxide absorbent, but is preferably 60 ° C. or lower, preferably 40 ° C. or lower, and more preferably around room temperature (20 ° C. ± 20 ° C.). A temperature of 10 ° C. or lower is particularly preferable. The lower the temperature of the carbon dioxide absorption liquid in the absorption step, the more the absorption amount of carbon dioxide tends to increase. In the carbon dioxide separation and recovery method of the present invention, since carbon dioxide is chemically absorbed in the carbon dioxide absorption liquid, the pressure of the absorption step is not particularly limited, but the solubility of carbon dioxide in the carbon dioxide absorption liquid and the carbon dioxide absorption From the viewpoint of preventing loss due to entrainment of the carbon absorbing liquid, the atmospheric pressure or higher is usually preferable, and the high pressure condition such as 1 MPa to 6 MPa can be used.
加熱再生工程の二酸化炭素吸収液の温度は、吸収工程の温度より高い限り特に限定されないが、好ましくは４０℃以上、より好ましくは８０℃以上、更に好ましくは１００℃以上、特に好ましくは１４０℃以上高くすることができる。温度差が大きいほど、吸収工程で吸収した二酸化炭素を高い割合で回収できる。より具体的な加熱再生工程の二酸化炭素吸収液の温度は、好ましくは５０℃以上、より好ましくは８０℃以上、更に好ましくは１２０℃以上、特に好ましくは１５０℃以上である。本発明の二酸化炭素吸収液は、高温で安定であり、蒸気圧が低いので、アミン水溶液に比べて高温にすることができる。加熱再生工程の二酸化炭素吸収液の温度の上限は特に限定されないが、好ましくは２００℃以下、より好ましくは１８０℃以下、更に好ましくは１６０℃以下である。本発明の二酸化炭素分離回収方法は、二酸化炭素を化学的に二酸化炭素吸収液から放散させて回収するので、加熱再生工程の圧力は、特に限定されないが、二酸化炭素の二酸化炭素吸収液からの放散性などの点で、吸収工程の圧力と同等又は低圧にすることが好ましく、吸収工程の圧力より高圧にすることもできる。 The temperature of the carbon dioxide absorbent in the heating regeneration step is not particularly limited as long as it is higher than the temperature in the absorption step, but is preferably 40 ° C or higher, more preferably 80 ° C or higher, further preferably 100 ° C or higher, particularly preferably 140 ° C or higher. Can be higher. The larger the temperature difference, the higher the ratio of the carbon dioxide absorbed in the absorption step can be recovered. The temperature of the carbon dioxide absorbent in the more specific heat regeneration step is preferably 50 ° C or higher, more preferably 80 ° C or higher, even more preferably 120 ° C or higher, and particularly preferably 150 ° C or higher. Since the carbon dioxide absorbent of the present invention is stable at high temperature and has a low vapor pressure, it can be heated to a higher temperature than an amine aqueous solution. The upper limit of the temperature of the carbon dioxide absorbent in the heating regeneration step is not particularly limited, but it is preferably 200 ° C or lower, more preferably 180 ° C or lower, still more preferably 160 ° C or lower. In the carbon dioxide separation and recovery method of the present invention, carbon dioxide is chemically released from the carbon dioxide absorption liquid to be recovered, so that the pressure in the heating regeneration step is not particularly limited, but the emission of carbon dioxide from the carbon dioxide absorption liquid is not limited. In terms of properties, it is preferable to make the pressure equal to or lower than the pressure in the absorption step, and it is also possible to make the pressure higher than the pressure in the absorption step.
本発明の二酸化炭素分離回収方法において、吸収工程で吸収した二酸化炭素を加熱再生工程で回収する割合は特に限定されないが、５０％以上回収することが好ましく、８０％以上回収することが好ましく、９０％以上回収することが好ましく、９５％以上回収することがより好ましい。本発明の二酸化炭素吸収液は、吸収工程と加熱再生工程における二酸化炭素吸収液の温度差を大きくすることができるの、高収率で二酸化炭素を回収できる。 In the carbon dioxide separation and recovery method of the present invention, the rate of recovering carbon dioxide absorbed in the absorption step in the heating and regeneration step is not particularly limited, but is preferably 50% or more, more preferably 80% or more, and 90 % Or more is preferable, and 95% or more is more preferable. Since the carbon dioxide absorbent of the present invention can increase the temperature difference between the carbon dioxide absorbent in the absorption step and the heating and regeneration step, carbon dioxide can be recovered in a high yield.
本発明の二酸化炭素分離回収方法において、混合ガスと二酸化炭素吸収液の接触方法は、二酸化炭素が二酸化炭素吸収液に化学的に吸収される限り、特に限定されない。例えば、二酸化炭素吸収液中に混合ガスをバブリングさせる方法、混合ガスに二酸化炭素吸収液をスプレーする方法、二酸化炭素吸収液を含浸又はゲル化させた材料と混合ガスを接触させる方法などが挙げられる。 In the method for separating and recovering carbon dioxide of the present invention, the method of contacting the mixed gas with the carbon dioxide absorbent is not particularly limited as long as carbon dioxide is chemically absorbed by the carbon dioxide absorbent. For example, a method of bubbling a mixed gas into a carbon dioxide absorbing liquid, a method of spraying a carbon dioxide absorbing liquid on the mixed gas, a method of contacting a mixed gas with a material impregnated or gelled with the carbon dioxide absorbing liquid, etc. ..
本発明の二酸化炭素分離回収方法において、二酸化炭素吸収液を再生する方法は、吸収した二酸化炭素が放散され、二酸化炭素吸収液が再生されるのであれば、特に限定されない。 In the carbon dioxide separation and recovery method of the present invention, the method for regenerating the carbon dioxide absorption liquid is not particularly limited as long as the absorbed carbon dioxide is diffused and the carbon dioxide absorption liquid is regenerated.
本発明の二酸化炭素吸収液およびそれを用いた二酸化炭素分離回収方法は、二酸化炭素の分離回収に優れているが、二酸化炭素以外の酸性ガスの分離回収に用いることも出来る。 The carbon dioxide absorbent of the present invention and the method for separating and recovering carbon dioxide using the same are excellent in separating and recovering carbon dioxide, but can also be used for separating and recovering acidic gas other than carbon dioxide.
（実施例）
以下、本発明を実施例に基づき説明するが、本発明はこれら実施例に限定されない。測定は、以下の測定方法を用いた。圧力は、特に断りのない限り絶対圧である。
（測定方法）
(Example)
Hereinafter, the present invention will be described based on examples, but the present invention is not limited to these examples. The following measurement method was used for the measurement. Pressures are absolute unless otherwise noted.
(Measuring method)
（１）二酸化炭素吸収量（常圧吹込型）
図１に示す、二酸化炭素吸収試験装置を用いて常圧で測定を行った。二酸化炭素吸収試験装置は、ガラス製の反応容器１１２に二酸化炭素を導入するための二酸化炭素のボンベ１０１、減圧弁１０２、流量計１０３、バルブ１０４、コイル状の熱交換器１０５、及びバルブ１０６、並びに、熱媒１０７を入れる恒温槽１０８、その恒温槽１０８内の熱媒１０７の温度を測定する白金測温体１０９を接続した抵抗表示器１１０、恒温槽１０８内の熱媒１０７の温度を一定に調節する冷却水循環装置１１１、反応容器１１２内に入れた回転子１１３を回転させるマグネチックスターラー１１４を備える。
反応容器１１２には、栓１１５、ガス導入管１１６、バルブ付き放出管１１７を取り付けることができる。バルブ１０６は、反応容器１１２に取り付けられたガス導入管１１６と接続できる。熱交換器１０５及び反応容器１１２は、恒温槽１０８の熱媒１０７に浸され、冷却水循環装置１１１で一定の温度に保たれる。反応容器１１２内には、回転子１１３が入れてあり、マグネチックスターラー１１４によって、反応容器１１２内の二酸化炭素吸収液を撹拌できる。熱媒１０７は、１０℃以上８０℃以下で測定する場合は水を用い、８０℃以上１５０℃以下で測定する場合にはオイルを用いる。
以下に、この二酸化炭素吸収試験装置を用いた、二酸化炭素吸収量測定手順を記載する。
１）窒素雰囲気下で、所定量（約１０ｃｃ）の二酸化炭素吸収液をガラス製の反応容器１１２に取り分け、反応容器１１２の口を栓１１５で封じる。反応容器全体の質量を分析天秤で計測し、これから風袋（反応容器１１２、回転子１１３及び栓１１５）の質量を差し引き、二酸化炭素吸収液の質量Ｗｔｏｔａｌを得る。
２）反応容器１１２にガス導入管１１６及び放出管１１７を取り付け、再度、質量を計測して反応容器全体の質量Ｗ２を得る。
３）反応容器１１２を恒温槽１０８に設置する。ガス導入管１１６をバルブ１０６に接続する。
４）恒温槽１０８の温度を４０℃に保ち、二酸化炭素を反応容器１１２に流通させ、二酸化炭素吸収液に二酸化炭素を吸収させる。一定時間（例えば６０分）毎に反応容器全体の質量を分析天秤で測定する。測定毎の質量変化が０．００１ｇ以下になった際の、反応容器全体の質量をＷ３とする。
５）二酸化炭素吸収液に吸収された二酸化炭素の質量ＷＣＯ２を下記式に基づき求める。
ＷＣＯ２＝Ｗ３−Ｗ２
また、二酸化炭素吸収液中の二酸化炭素化学吸収性アミン１モルあたりの二酸化炭素吸収量αＣＯ２を下記式に基づき決定する。
αＣＯ２＝（ＷＣＯ２／ＭＣＯ２）／（Ｗ１／Ｍｃｈｅｍ）
ここで上記式中、ＭＣＯ２は二酸化炭素のモル質量であり、Ｍｃｈｅｍは二酸化炭素化学吸収性アミンのモル質量であり、二酸化炭素化学吸収性アミンの質量Ｗ１は二酸化炭素吸収液の質量Ｗｔｏｔａｌに質量分率ｘ１を乗じて求めた。
６）恒温槽１０８の温度を適宜変更し、前記４）〜５）の操作と解析を行い、各温度における二酸化炭素吸収量を決定する。その後、４０℃で吸収された二酸化炭素の質量を再度計測し、再現性を確認する。
(1) Carbon dioxide absorption (normal pressure blowing type)
The measurement was performed at atmospheric pressure using the carbon dioxide absorption test apparatus shown in FIG. The carbon dioxide absorption test apparatus includes a carbon dioxide cylinder 101 for introducing carbon dioxide into a glass reaction vessel 112, a pressure reducing valve 102, a flow meter 103, a valve 104, a coiled heat exchanger 105, and a valve 106. In addition, a constant temperature bath 108 for containing the heat medium 107, a resistance indicator 110 connected to a platinum temperature measuring element 109 for measuring the temperature of the heat medium 107 in the constant temperature bath 108, and a constant temperature of the heat medium 107 in the constant temperature bath 108 The cooling water circulating device 111 for adjusting the temperature to the above and a magnetic stirrer 114 for rotating the rotor 113 placed in the reaction vessel 112 are provided.
A stopper 115, a gas introduction pipe 116, and a valved discharge pipe 117 can be attached to the reaction vessel 112. The valve 106 can be connected to a gas introduction pipe 116 attached to the reaction container 112. The heat exchanger 105 and the reaction vessel 112 are immersed in the heat medium 107 of the constant temperature bath 108 and kept at a constant temperature by the cooling water circulation device 111. A rotor 113 is placed in the reaction vessel 112, and the carbon dioxide absorbing solution in the reaction vessel 112 can be stirred by the magnetic stirrer 114. As the heat medium 107, water is used when measuring at 10 ° C. or higher and 80 ° C. or lower, and oil is used when measuring at 80 ° C. or higher and 150 ° C. or lower.
The procedure for measuring the amount of absorbed carbon dioxide using this carbon dioxide absorption test device is described below.
1) Under a nitrogen atmosphere, a predetermined amount (about 10 cc) of carbon dioxide absorption liquid is dispensed into a glass reaction container 112, and the mouth of the reaction container 112 is sealed with a stopper 115. The mass of the entire reaction container is measured with an analytical balance, and the mass of the tare (reaction container 112, rotor 113, and stopper 115) is subtracted from this to obtain the mass W total of the carbon dioxide absorbing liquid.
2) The gas introducing pipe 116 and the discharge pipe 117 are attached to the reaction container 112, and the mass is measured again to obtain the mass W 2 of the entire reaction container.
3) The reaction container 112 is installed in the constant temperature bath 108. The gas introduction pipe 116 is connected to the valve 106.
4) The temperature of the constant temperature bath 108 is maintained at 40 ° C., carbon dioxide is passed through the reaction vessel 112, and the carbon dioxide absorption liquid absorbs carbon dioxide. The mass of the entire reaction vessel is measured with an analytical balance at regular intervals (for example, 60 minutes). Let W 3 be the mass of the entire reaction container when the mass change for each measurement is 0.001 g or less.
5) The mass W CO2 of carbon dioxide absorbed in the carbon dioxide absorption liquid is calculated based on the following formula.
W CO2 = W 3 −W 2
Further, the carbon dioxide absorption amount α CO2 per mol of the carbon dioxide chemically absorbing amine in the carbon dioxide absorbing liquid is determined based on the following formula.
α CO2 = (W CO2 / M CO2 ) / (W 1 / M chem ).
Here, in the above formula, M CO2 is the molar mass of carbon dioxide, M chem is the molar mass of the carbon dioxide chemically absorbing amine, and the mass W 1 of the carbon dioxide chemically absorbing amine is the mass W of the carbon dioxide absorbing liquid. It was calculated by multiplying the total by the mass fraction x 1 .
6) The temperature of the constant temperature bath 108 is appropriately changed, and the operations and analyzes in 4) to 5) above are performed to determine the carbon dioxide absorption amount at each temperature. Then, the mass of carbon dioxide absorbed at 40 ° C. is measured again to confirm reproducibility.
（２）二酸化炭素吸収量（高圧密閉型セル）
前記（１）の常圧吹込型の測定方法において、特に溶媒の蒸気圧が高い場合に、溶媒が二酸化炭素ガスと同伴して反応容器から放出されて、二酸化炭素の吸収量が正確に測定できないことがある。比較例１のＭＥＡ／水からなる二酸化炭素吸収液は、水の蒸気圧が高いため、図２に示すように、反応容器１１２を耐圧容器である高圧セル（耐圧セル）２１５に代え、栓１１５、ガス導入管１１６、及び放出管１１７の代わりに、管の端部が液面に付かない長さのバルブ付きのガス導入管及び耐圧栓を用いて測定する。この二酸化炭素吸収試験装置（高圧密閉型セル）を用いた二酸化炭素吸収量測定手順は、質量変化を測定する前に、耐圧セルに接続したバルブ２１０を開放し、常圧において適当な時間静置することを除いて、前述した二酸化炭素吸収量装置（常圧吹込型）の手順と同じである。
(2) Carbon dioxide absorption (high-pressure closed cell)
In the atmospheric pressure blowing type measurement method of (1) above, particularly when the vapor pressure of the solvent is high, the solvent is discharged together with carbon dioxide gas from the reaction vessel, and the absorption amount of carbon dioxide cannot be accurately measured. Sometimes. Since the carbon dioxide absorbing liquid of MEA / water of Comparative Example 1 has a high vapor pressure of water, as shown in FIG. 2, the reaction vessel 112 is replaced with a high pressure cell (pressure cell) 215 which is a pressure vessel, and the stopper 115 is used. In place of the gas introduction pipe 116 and the discharge pipe 117, a gas introduction pipe with a valve and a pressure-resistant stopper whose length is such that the end of the pipe does not reach the liquid surface is used for the measurement. The procedure for measuring the amount of carbon dioxide absorption using this carbon dioxide absorption test device (high-pressure closed cell) is to open the valve 210 connected to the pressure-resistant cell before measuring the mass change, and leave it at normal pressure for an appropriate time. The procedure is the same as the procedure for the carbon dioxide absorption device (normal pressure blowing type) described above, except that this is done.
（実施例１：ＭＥＡ／［ＥＭＩＭ］［（ＭｅＯ）ＨＰＯＯ］）
二酸化炭素化学吸収性アミンとしてのエタノールアミン（ＭＥＡ、２−アミノエタノール、シグマアルドリッチ社製、純度≧９９．０％）０．６７ｇと、水素結合受容性溶媒としてのイオン液体１−エチル−３−メチルイミダゾリウム メチルホスファイト（［ＥＭＩＭ］［（ＭｅＯ）ＨＰＯＯ］、関東化学株式会社製、純度＞９７％）９．１５ｇを混合して二酸化炭素吸収液Ｅ１を得た（モル分率２０％）。二酸化炭素吸収液Ｅ１は、無色透明な均一相であった。図１に示す装置を用いて常圧で、二酸化炭素吸収液Ｅ１の二酸化炭素吸収量を測定した。結果を図３に示す。なお、１０℃以上８０℃以下の測定は、熱媒１０７として水を用い、８０℃以上１５０℃以下の測定は熱媒１０７としてオイルを用いた。また、高温側では、二酸化炭素吸収液Ｅ１の代わりに、ＭＥＡ ０．６１ｇと［ＥＭＩＭ］［（ＭｅＯ）ＨＰＯＯ］ ８．３５ｇを混合した二酸化炭素吸収液Ｅ１’（モル分率２０％）を用いて測定した。
(Example 1: MEA / [EMIM] [(MeO) HPOO])
0.67 g of ethanolamine (MEA, 2-aminoethanol, manufactured by Sigma-Aldrich, purity ≧ 99.0%) as a carbon dioxide chemically absorbing amine, and ionic liquid 1-ethyl-3- as a hydrogen bond accepting solvent. 9.15 g of methylimidazolium methylphosphite ([EMIM] [(MeO) HPOO], manufactured by Kanto Chemical Co., Inc., purity> 97%) was mixed to obtain a carbon dioxide absorbent E1 (molar fraction 20%). .. The carbon dioxide absorbent E1 was a colorless and transparent homogeneous phase. The carbon dioxide absorption amount of the carbon dioxide absorbent E1 was measured at normal pressure using the device shown in FIG. Results are shown in FIG. Water was used as the heat medium 107 for the measurement at 10 ° C or higher and 80 ° C or lower, and oil was used as the heat medium 107 for the measurement at 80 ° C or higher and 150 ° C or lower. Further, on the high temperature side, instead of the carbon dioxide absorbent E1, a carbon dioxide absorbent E1 ′ (molar fraction 20%) obtained by mixing 0.61 g of MEA and 8.35 g of [EMIM] [(MeO) HPOO] was used. Was measured.
（実施例２：ＭＥＡ／［ＢＭＩＭ］［（ＭｅＯ）２ＰＯＯ］）
ＭＥＡ ０．９４ｇと、水素結合受容性溶媒としてイオン液体［ＥＭＩＭ］［（ＭｅＯ）ＨＰＯＯ］の代わりに、イオン液体（［ＢＭＩＭ］［（ＭｅＯ）２ＰＯＯ］、Ｉｏｌｉｔｅｃ社製、純度＞９８％）１５．８７ｇを用いた以外は、実施例１と同様にして二酸化炭素吸収液Ｅ２を得た（モル分率２０％）。二酸化炭素吸収液Ｅ２は、わずかに黄色味を帯びた均一相であった。図１に示す装置を用いて常圧で、二酸化炭素吸収液Ｅ２二酸化炭素吸収量を測定した。結果を図３に示す。なお、１０℃以上８０℃以下の測定は、熱媒１０７として水を用い、８０℃以上１５０℃以下の測定は熱媒１０７としてオイルを用いた。
(Example 2: MEA / [BMIM] [ (MeO) 2 POO])
0.94 g of MEA and an ionic liquid [EMIM] [(MeO) HPOO] as a hydrogen bond accepting solvent ([BMIM] [(MeO) 2 POO], manufactured by Iolitec, purity> 98%) instead of the ionic liquid [EMIM] [(MeO) HPOO]. A carbon dioxide absorbent E2 was obtained in the same manner as in Example 1 except that 15.87 g was used (molar fraction 20%). The carbon dioxide absorbent E2 was a slightly yellowish homogeneous phase. The carbon dioxide absorption liquid E2 carbon dioxide absorption was measured at atmospheric pressure using the apparatus shown in FIG. Results are shown in FIG. Water was used as the heat medium 107 for the measurement at 10 ° C or higher and 80 ° C or lower, and oil was used as the heat medium 107 for the measurement at 80 ° C or higher and 150 ° C or lower.
（比較例１：ＭＥＡ／水）
ＭＥＡ ４．３７ｇと、イオン液体［ＥＭＩＭ］［（ＭｅＯ）ＨＰＯＯ］の代わりに溶媒として超純水５．１５ｇを用いた以外は実施例１と同様にして二酸化炭素吸収液Ｒ１を得た。図３に示す高圧密閉型セルを用いて、二酸化炭素吸収液Ｒ１の二酸化炭素吸収量を測定した。結果を図３に示す。二酸化炭素吸収液Ｒ１は、無色透明な均一相であった。
(Comparative Example 1: MEA / water)
A carbon dioxide absorbent R1 was obtained in the same manner as in Example 1 except that 4.37 g of MEA and 5.15 g of ultrapure water as a solvent were used instead of the ionic liquid [EMIM] [(MeO) HPOO]. The carbon dioxide absorption amount of the carbon dioxide absorption liquid R1 was measured using the high-pressure closed cell shown in FIG. Results are shown in FIG. The carbon dioxide absorbent R1 was a colorless and transparent homogeneous phase.
（比較例２：ＭＥＡ／［ＢＭＩＭ］［Ｔｆ２Ｎ］）
ＭＥＡ ０．５６ｇと、イオン液体［ＥＭＩＭ］［（ＭｅＯ）ＨＰＯＯ］の代わりにイオン液体１−ブチル−３−メチルイミダゾリウム ビス（トリフルオロメチルスルホニル）イミド（合成品、純度≧９９．０％、［ＢＭＩＭ］［Ｔｆ２Ｎ］） １５．３６ｇを用いた以外は実施例１と同様にして二酸化炭素吸収液Ｒ２を得た。二酸化炭素吸収液Ｒ２は、無色透明な均一相であった。図１に示す装置を用いて常圧で、二酸化炭素吸収液Ｒ２の二酸化炭素吸収量を測定した。結果を図３に示す。また、二酸化炭素吸収液Ｒ２の二酸化炭素吸収後の写真を図８に示す。二酸化炭素吸収後の二酸化炭素吸収液Ｒ２は、白濁した。
(Comparative Example 2: MEA / [BMIM] [Tf 2 N])
0.56 g of MEA and an ionic liquid 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (synthetic product, purity ≧ 99.0%, instead of the ionic liquid [EMIM] [(MeO) HPOO]] A carbon dioxide absorbent R2 was obtained in the same manner as in Example 1 except that 15.36 g of [BMIM] [Tf 2 N]) was used. The carbon dioxide absorbent R2 was a colorless and transparent homogeneous phase. The carbon dioxide absorption amount of the carbon dioxide absorbent R2 was measured at atmospheric pressure using the device shown in FIG. Results are shown in FIG. A photograph of the carbon dioxide absorbent R2 after carbon dioxide absorption is shown in FIG. The carbon dioxide absorbent R2 after absorbing carbon dioxide became cloudy.
（比較例３：ＭＥＡ／［ＢＭＩＭ］［ＢＦ４］）
ＭＥＡ ０．６６ｇと、イオン液体［ＥＭＩＭ］［（ＭｅＯ）ＨＰＯＯ］の代わりにイオン液体１−ブチル−３−メチルイミダゾリウム テトラフルオロボラート（関東化学社製、純度≧９５％、［ＢＭＩＭ］［ＢＦ４］） ９．７９ｇを用いた以外は実施例１と同様にして二酸化炭素吸収液Ｒ３を得た。二酸化炭素吸収液Ｒ３は、無色透明な均一相であった。図１に示す装置を用いて常圧で、二酸化炭素吸収液Ｒ３の二酸化炭素吸収量を測定した。結果を図３に示す。また、二酸化炭素吸収液Ｒ３の二酸化炭素吸収後の写真を図８に示す。二酸化炭素吸収後の二酸化炭素吸収液Ｒ３は、白濁し、液−液２相に分離した。
(Comparative Example 3: MEA / [BMIM] [ BF 4])
0.66 g of MEA and an ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (manufactured by Kanto Kagaku Co., purity ≧ 95%, [BMIM] [[BMIM] [, in place of the ionic liquid [EMIM] [(MeO) HPOO]. BF 4 ]) A carbon dioxide absorbent R3 was obtained in the same manner as in Example 1 except that 9.79 g was used. The carbon dioxide absorbent R3 was a colorless and transparent homogeneous phase. The carbon dioxide absorption amount of the carbon dioxide absorption liquid R3 was measured at atmospheric pressure using the device shown in FIG. Results are shown in FIG. A photograph of the carbon dioxide absorbent R3 after carbon dioxide absorption is shown in FIG. The carbon dioxide absorbent R3 after absorbing carbon dioxide became cloudy and separated into a liquid-liquid two phase.
（比較例４：ＭＥＡ／［ＢＭＩＭ］［ＰＦ６］）
ＭＥＡ ０．６２ｇと、イオン液体［ＥＭＩＭ］［（ＭｅＯ）ＨＰＯＯ］の代わりにイオン液体１−ブチル−３−メチルイミダゾリウム ヘキサフルオロホスファート（Ｌａｎｃａｓｔｅｒ社製、純度９９％、［ＢＭＩＭ］［ＰＦ６］） １１．６８ｇを用いた以外は実施例１と同様にして二酸化炭素吸収液Ｒ４を得た。二酸化炭素吸収液Ｒ４は、山吹色透明の均一相であった。図１に示す装置を用いて常圧で、二酸化炭素吸収液Ｒ４の二酸化炭素吸収量を測定した。結果を図３に示す。また、二酸化炭素吸収液Ｒ４の二酸化炭素吸収後の写真を図８に示す。二酸化炭素吸収後の二酸化炭素吸収液Ｒ４は、山吹色の液−液２相に分離した。
(Comparative Example 4: MEA / [BMIM] [PF 6 ])
0.62 g of MEA and an ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (manufactured by Lancaster, purity 99%, [BMIM] [PF 6 ] instead of the ionic liquid [EMIM] [(MeO) HPOO]. ]) A carbon dioxide absorbent R4 was obtained in the same manner as in Example 1 except that 11.68 g was used. The carbon dioxide absorbing solution R4 was a transparent phase with a bright yellow color. The carbon dioxide absorption amount of the carbon dioxide absorbent R4 was measured at atmospheric pressure using the device shown in FIG. Results are shown in FIG. A photograph of the carbon dioxide absorbent R4 after absorbing carbon dioxide is shown in FIG. The carbon dioxide absorption liquid R4 after carbon dioxide absorption was separated into a bright yellow liquid-liquid two phase.
（比較例５：ＭＥＡ／［ＢＭＩＭ］［Ｎ（ＣＮ）２］）
ＭＥＡ ０．８０ｇと、イオン液体［ＥＭＩＭ］［（ＭｅＯ）ＨＰＯＯ］の代わりにイオン液体１−ブチル−３−メチルイミダゾリウム ジシアナミド（Ｉｏｌｉｔｅｃ社製、純度≧９８％、［ＢＭＩＭ］［Ｎ（ＣＮ）２］） １０．７０ｇを用いた以外は実施例１と同様にして二酸化炭素吸収液Ｒ５を得た。二酸化炭素吸収液Ｒ５は、淡黄色透明な均一相であった。図１に示す装置を用いて常圧で、二酸化炭素吸収液Ｒ５の二酸化炭素吸収量を測定したが、測定値がばらついた。また、二酸化炭素吸収液Ｒ５の二酸化炭素吸収後の写真を図８に示す。二酸化炭素吸収後の二酸化炭素吸収液Ｒ５は、淡黄色透明な均一相であった。
(Comparative Example 5: MEA / [BMIM] [N (CN) 2 ])
MEA 0.80 g and ionic liquid 1-butyl-3-methylimidazolium dicyanamide (manufactured by Iolitec, purity ≧ 98%, [BMIM] [N (CN)] instead of ionic liquid [EMIM] [(MeO) HPOO]. 2 ]) A carbon dioxide absorbent R5 was obtained in the same manner as in Example 1 except that 10.70 g was used. The carbon dioxide absorbent R5 was a pale yellow transparent uniform phase. When the carbon dioxide absorption amount of the carbon dioxide absorption liquid R5 was measured using the apparatus shown in FIG. 1 at atmospheric pressure, the measured values varied. A photograph of the carbon dioxide absorbent R5 after carbon dioxide absorption is shown in FIG. The carbon dioxide absorbent R5 after absorbing carbon dioxide was a pale yellow transparent uniform phase.
（比較例６：ＭＥＡ／［ＢＭＩＭ］［ＭｅＳＯ３］）
ＭＥＡ ０．８５ｇと、イオン液体［ＥＭＩＭ］［（ＭｅＯ）ＨＰＯＯ］の代わりにイオン液体１−ブチル−３−メチルイミダゾリウム メタンスルホナート（Ｉｏｌｉｔｅｃ社製、純度９９％、［ＢＭＩＭ］［ＭｅＳＯ３］） １１．４８ｇを用いた以外は実施例１と同様にして二酸化炭素吸収液Ｒ６を得た。二酸化炭素吸収液Ｒ６は、わずかに黄色味を帯びた均一相であった。図１に示す装置を用いて常圧で、二酸化炭素吸収液Ｒ６の二酸化炭素吸収量を測定した。結果を図３に示す。二酸化炭素吸収後の二酸化炭素吸収液Ｒ６は、わずかに黄色味を帯びた均一相であった。
(Comparative Example 6: MEA / [BMIM] [MeSO 3 ])
MEA 0.85 g and ionic liquid 1-butyl-3-methylimidazolium methanesulfonate (manufactured by Iolitec, purity 99%, [BMIM] [MeSO 3 ]] instead of ionic liquid [EMIM] [(MeO) HPOO]. ) A carbon dioxide absorbent R6 was obtained in the same manner as in Example 1 except that 11.48 g was used. The carbon dioxide absorbent R6 was a slightly yellowish homogeneous phase. The carbon dioxide absorption amount of the carbon dioxide absorption liquid R6 was measured at atmospheric pressure using the device shown in FIG. Results are shown in FIG. The carbon dioxide absorbent R6 after absorbing carbon dioxide was a slightly yellowish homogeneous phase.
（実施例３〜８：ＭＥＡ／［ＭＭＩＭ］［（ＭｅＯ）ＨＰＯＯ］、［Ｐ４４４４］［（ＭｅＯ）ＨＰＯＯ］）、［ＭＭＩＭ］［（ＭｅＯ）２ＰＯＯ］、［ＥＭＩＭ］［（ＥｔＯ）２ＰＯＯ］、［ＥＥＩＭ］［（ＥｔＯ）２ＰＯＯ］、［Ｐ２４４４］［（ＥｔＯ）２ＨＰＯＯ］）
二酸化炭素化学吸収性アミンとしてのＭＥＡと、水素結合受容性溶媒としてのイオン液体［ＥＭＩＭ］［（ＭｅＯ）ＨＰＯＯ］の代わりに表１に示すイオン液体をそれぞれ混合し、二酸化炭素吸収液Ｅ３〜Ｅ８を得た（モル分率２０％）。図１に示す装置を用いて常圧で、二酸化炭素吸収液Ｅ３〜Ｅ８の二酸化炭素吸収量を測定した。結果を二酸化炭素吸収液Ｅ１、Ｅ２と共に図４に示す。
(Example 3~8: MEA / [MMIM] [ (MeO) HPOO], [P 4444] [(MeO) HPOO]), [MMIM] [(MeO) 2 POO], [EMIM] [(EtO) 2 POO], [EEIM] [(EtO) 2 POO], [P 2444 ] [(EtO) 2 HPOO])
Instead of the ionic liquid [EMIM] [(MeO) HPOO] as the hydrogen bond accepting solvent and MEA as the carbon dioxide chemically absorbing amine, the ionic liquids shown in Table 1 were mixed respectively, and the carbon dioxide absorbing liquids E3 to E8 were mixed. Was obtained (molar fraction 20%). The carbon dioxide absorption amounts of the carbon dioxide absorption liquids E3 to E8 were measured at atmospheric pressure using the device shown in FIG. The results are shown in FIG. 4 together with the carbon dioxide absorbents E1 and E2.
（実施例９〜１１：ＤＥＡ／［ＥＭＩＭ］［（ＭｅＯ）ＨＰＯＯ］）
水素結合受容性溶媒としてのイオン液体［ＥＭＩＭ］［（ＭｅＯ）ＨＰＯＯ］と、二酸化炭素化学吸収性アミンとしてエタノールアミンの代わりにジエタノールアミン（ＤＥＡ）を表２に示す量で用いた以外は、実施例１と同様にして二酸化炭素吸収液Ｅ９〜１１を得た（モル分率２０．０％、４５．７％、６６．２％）。二酸化炭素吸収液Ｅ９〜１１は、無色透明な均一相であった。図１に示す装置を用いて常圧で、二酸化炭素吸収液Ｅ９〜１１の二酸化炭素吸収量を測定した。結果を図５に示す。
(Examples 9 to 11: DEA / [EMIM] [(MeO) HPOO])
Example except that ionic liquid [EMIM] [(MeO) HPOO] as a hydrogen bond accepting solvent and diethanolamine (DEA) as a carbon dioxide chemisorbing amine were used in place of ethanolamine in the amounts shown in Table 2 Carbon dioxide absorbents E9 to 11 were obtained in the same manner as in 1 (molar fractions 20.0%, 45.7%, 66.2%). The carbon dioxide absorbents E9 to E11 were colorless and transparent homogeneous phases. Using the apparatus shown in FIG. 1, the carbon dioxide absorption amount of the carbon dioxide absorption liquids E9-11 was measured at normal pressure. Results are shown in FIG.
（比較例７：ＭＤＥＡ／［ＥＭＩＭ］［（ＭｅＯ）ＨＰＯＯ］）
二酸化炭素化学吸収性アミンとしてのエタノールアミンの代わりにＮ−メチルジエタノールアミン（ＭＤＥＡ、アルドリッチ社製、純度≧９９．０％）を１．５８ｇ用い、イオン液体［ＥＭＩＭ］［（ＭｅＯ）ＨＰＯＯ］を１０．９４ｇ用いた以外は、実施例１と同様にして二酸化炭素吸収液Ｒ７を得た（モル分率２０．０％）。二酸化炭素吸収液Ｒ７は、無色透明な均一相であった。図１に示す装置を用いて常圧で、二酸化炭素吸収液Ｒ７の二酸化炭素吸収量を測定した。結果を図５に示す。
(Comparative Example 7: MDEA / [EMIM] [(MeO) HPOO])
1.58 g of N-methyldiethanolamine (MDEA, manufactured by Aldrich Co., purity ≧ 99.0%) was used in place of ethanolamine as the carbon dioxide chemically absorbing amine, and the ionic liquid [EMIM] [(MeO) HPOO] was used as 10 A carbon dioxide absorption liquid R7 was obtained in the same manner as in Example 1 except that the amount of 0.94 g was used (molar fraction: 20.0%). The carbon dioxide absorbent R7 was a colorless and transparent homogeneous phase. The carbon dioxide absorption amount of the carbon dioxide absorption liquid R7 was measured at atmospheric pressure using the device shown in FIG. Results are shown in FIG.
（実施例１２：ＭＥＡ／ＤＭＰＵ）
二酸化炭素化学吸収性アミンとしてのエタノールアミン（ＭＥＡ、２−アミノエタノール、シグマアルドリッチ社製、純度≧９９．０％）１．０６ｇと、水素結合受容性溶媒としてのＮ，Ｎ’−ジメチルプロピレン尿素（ＤＭＰＵ、アルドリッチ社製、純度９８．０％）８．８５ｇを混合して二酸化炭素吸収液Ｅ１２を得た（モル分率２０％）。二酸化炭素吸収液Ｅ１２は、無色透明な均一相であった。図１に示す装置を用いて常圧で、二酸化炭素吸収液Ｅ１２の二酸化炭素吸収量を測定した。結果を図６に示す。
(Example 12: MEA / DMPU)
1.06 g of ethanolamine (MEA, 2-aminoethanol, manufactured by Sigma-Aldrich, purity ≧ 99.0%) as a carbon dioxide chemically absorbing amine, and N, N′-dimethylpropyleneurea as a hydrogen bond accepting solvent (DMPU, manufactured by Aldrich, purity 98.0%) was mixed with 8.85 g to obtain a carbon dioxide absorbent E12 (molar fraction 20%). The carbon dioxide absorbent E12 was a colorless and transparent homogeneous phase. The carbon dioxide absorption amount of the carbon dioxide absorbent E12 was measured at atmospheric pressure using the device shown in FIG. Results are shown in FIG.
（実施例１３：ＭＥＡ／ＤＭＩ）
ＭＥＡ １．１３ｇと、水素結合受容性溶媒としてのＤＭＰＵの代わりに１，３−ジメチル−２−イミダゾリジノン（ＤＭＩ、アルドリッチ社製、純度≧９９．０％）８．４３ｇを用いた以外は実施例１２と同様にして二酸化炭素吸収液Ｅ１３を得た（モル分率２０％）。二酸化炭素吸収液Ｅ１３は、無色透明な均一相であった。図１に示す装置を用いて常圧で、二酸化炭素吸収液Ｅ１３の二酸化炭素吸収量を測定した。結果を図６に示す。
(Example 13: MEA / DMI)
1.13 g of MEA and 8.43 g of 1,3-dimethyl-2-imidazolidinone (DMI, manufactured by Aldrich, purity ≧ 99.0%) instead of DMPU as a hydrogen bond accepting solvent were used. Carbon dioxide absorbent E13 was obtained in the same manner as in Example 12 (molar fraction 20%). The carbon dioxide absorbent E13 was a colorless and transparent homogeneous phase. The carbon dioxide absorption amount of the carbon dioxide absorbent E13 was measured at atmospheric pressure using the device shown in FIG. Results are shown in FIG.
（参考例１４：ＭＥＡ／ＨＭＰＡ）
ＭＥＡ ０．７０ｇと、水素結合受容性溶媒としてのＤＭＰＵの代わりにヘキサメチルリン酸トリアミド（アルドリッチ社製、純度９９．０％）８．１４ｇを混合して二酸化炭素吸収液Ｅ１４を得た（モル分率２０％、二酸化炭素化学吸収性アミン濃度１１質量％）。二酸化炭素吸収液Ｅ１４は、無色透明な均一相であった。図１に示す装置を用いて常圧で、二酸化炭素吸収液Ｅ１４の二酸化炭素吸収量を測定した。結果を図６に示す。なお、８０℃以上１５０℃以下の高温側では、二酸化炭素吸収液Ｅ１４の代わりに、ＭＥＡ ０．７７ｇとＨＭＰＡ ８．９１ｇを混合した二酸化炭素吸収液Ｅ１４’（モル分率２０％）を用いて測定した。
( Reference Example 14: MEA / HMPA)
0.70 g of MEA and 8.14 g of hexamethylphosphoric triamide (manufactured by Aldrich Co., purity 99.0%) instead of DMPU as a hydrogen bond-accepting solvent were mixed to obtain a carbon dioxide absorbent E14 (mol Fraction 20%, carbon dioxide chemical-absorbing amine concentration 11% by mass). The carbon dioxide absorbent E14 was a colorless and transparent homogeneous phase. The carbon dioxide absorption amount of the carbon dioxide absorbent E14 was measured at atmospheric pressure using the device shown in FIG. Results are shown in FIG. On the high temperature side of 80 ° C. or higher and 150 ° C. or lower, instead of the carbon dioxide absorption liquid E14, a carbon dioxide absorption liquid E14 ′ (mol fraction 20%) in which 0.77 g of MEA and 8.91 g of HMPA were mixed was used. It was measured.
（比較例８：ＭＥＡ／ｄｉｇｌｙｍｅ）
二酸化炭素化学吸収性アミンとしてのエタノールアミン（ＭＥＡ、２−アミノエタノール、シグマアルドリッチ社製、純度≧９９．０％）０．９１ｇと、溶媒としてのジグリム（ｄｉｇｌｙｍｅ、シグマアルドリッチ社製、純度≧９９．０％）７．９６ｇを混合して二酸化炭素吸収液Ｒ８を得た（モル分率２０％、二酸化炭素化学吸収性アミン濃度１１質量％）。二酸化炭素吸収液Ｒ８は、無色透明な均一相であった。図１に示す装置を用いて常圧で、二酸化炭素吸収液Ｒ８の二酸化炭素吸収量を測定した。結果を図６に示す。
(Comparative Example 8: MEA / diglyme)
0.91 g of ethanolamine (MEA, 2-aminoethanol, manufactured by Sigma-Aldrich, purity ≧ 99.0%) as a carbon dioxide chemically absorbing amine, and diglyme (diglyme, manufactured by Sigma-Aldrich, purity ≧ 99) as a solvent. (0.0%) 7.96 g was mixed to obtain a carbon dioxide absorption liquid R8 (molar fraction 20%, carbon dioxide chemically absorbing amine concentration 11% by mass). The carbon dioxide absorbent R8 was a colorless and transparent homogeneous phase. The carbon dioxide absorption amount of the carbon dioxide absorption liquid R8 was measured at atmospheric pressure using the device shown in FIG. Results are shown in FIG.
（参考例１５〜１７：ＤＥＡ／ＨＭＰＡ）
二酸化炭素化学吸収性アミンとしてジエタノールアミン（ＭＤＥＡ、アルドリッチ社製、純度≧９９．０％）１．４４ｇ、３．４４ｇ、又は６．７８ｇを用い、ヘキサメチルリン酸トリアミドの混合量を、それぞれ９．８３ｇ、８．０３ｇ、又は６．７８ｇに変えた以外は実施例１４と同様にして、二酸化炭素吸収液中の二酸化炭素化学吸収性アミンの濃度が１３質量％、３０質量％、又は５０質量％の二酸化炭素吸収液Ｅ１５〜１７を得た。得られた二酸化炭素吸収液Ｅ１５〜１７は、無色透明な均一相であった。図１に示す装置を用いて常圧で、二酸化炭素吸収液Ｅ１５〜１７の二酸化炭素吸収量を測定した。結果を図７に示す。
( Reference Examples 15 to 17: DEA / HMPA)
Diethanolamine (MDEA, manufactured by Aldrich Co., purity ≧ 99.0%) 1.44 g, 3.44 g, or 6.78 g was used as the carbon dioxide chemically absorbing amine, and the mixing amount of hexamethylphosphoric triamide was 9. The concentration of the carbon dioxide chemically absorbing amine in the carbon dioxide absorbent was 13% by mass, 30% by mass, or 50% by mass in the same manner as in Example 14 except that the amount was changed to 83 g, 8.03 g, or 6.78 g. Carbon dioxide absorption liquids E15 to E17 were obtained. The obtained carbon dioxide absorbents E15 to 17 were colorless and transparent homogeneous phases. The carbon dioxide absorption amount of the carbon dioxide absorbents E15 to 17 was measured at atmospheric pressure using the device shown in FIG. The results are shown in Fig. 7.
（比較例９：ＭＤＥＡ／ＨＭＰＡ）
エタノールアミンの代わりに、メチルジエタノールアミン（ＭＤＥＡ、アルドリッチ社製、純度≧９９．０％）１．３４ｇを用い、水素結合受容性溶媒としてヘキサメチルリン酸トリアミドを８．１０ｇ用いた以外は実施例１４と同様にして、二酸化炭素吸収液中の二酸化炭素化学吸収性アミンの濃度が１３質量％（モル分率２０％）の二酸化炭素吸収液Ｒ９を得た。得られた二酸化炭素吸収液Ｒ９は、無色透明な均一相であった。図１に示す装置を用いて常圧で、二酸化炭素吸収液Ｒ８の二酸化炭素吸収量を測定した。結果を図７に示す。
(Comparative Example 9: MDEA / HMPA)
Example 14 was repeated except that 1.34 g of methyldiethanolamine (MDEA, manufactured by Aldrich Co., purity ≧ 99.0%) was used in place of ethanolamine, and 8.10 g of hexamethylphosphoric triamide was used as a hydrogen bond-accepting solvent. In the same manner as described above, a carbon dioxide absorbent R9 having a carbon dioxide chemically absorbing amine concentration of 13% by mass (molar fraction 20%) in the carbon dioxide absorbent was obtained. The obtained carbon dioxide absorbent R9 was a colorless and transparent homogeneous phase. The carbon dioxide absorption amount of the carbon dioxide absorption liquid R8 was measured at atmospheric pressure using the device shown in FIG. The results are shown in Fig. 7.
本発明は、本発明の広義の精神と範囲を逸脱することなく、様々な実施の形態及び変形が可能とされるものである。また、上述した実施の形態は、この発明を説明するためのものであり、本発明の範囲を限定するものではない。すなわち、本発明の範囲は、実施の形態ではなく、特許請求の範囲によって示される。そして、特許請求の範囲内及びそれと同等の発明の意義の範囲内で施される様々な変形が、この発明の範囲内とみなされる。 The present invention allows various embodiments and modifications without departing from the broad spirit and scope of the present invention. Further, the above-described embodiments are for explaining the present invention and do not limit the scope of the present invention. That is, the scope of the present invention is shown not by the embodiments but by the scope of the claims. Various modifications made within the scope of the claims and within the scope of the meaning of the invention equivalent thereto are regarded as within the scope of the present invention.
１０１ 窒素又は二酸化炭素のボンベ
１０２ 減圧弁
１０３ 流量計
１０４ バルブ
１０５ 熱交換器
１０６ バルブ
１０７ 熱媒
１０８ 恒温槽
１０９ 白金測温体
１１０ 抵抗表示器
１１１ 冷却水循環装置
１１２ 反応容器
１１３ 回転子
１１４ マグネチックスターラー
１１５ 栓
１１６ ガス導入管
１１７ 放出管
２０１ 真空ポンプ
２０２ 真空計
２０３ 高圧セル部
２０４ ガスチャンバー部
２０５ 恒温槽
２０６、２０７、２０８、２０９、２１０ バルブ
２１１ サーミスター
２１２ 圧力計
２１３ 冷却水循環装置
２１４ 二酸化炭素ボンベ
２１５ 高圧セル
２１６ 撹拌子
２１７ スターラー
101 Nitrogen or carbon dioxide cylinder 102 Pressure reducing valve 103 Flow meter 104 Valve 105 Heat exchanger 106 Valve 107 Heat medium 108 Constant temperature bath 109 Platinum temperature measuring element 110 Resistance indicator 111 Cooling water circulation device 112 Reaction vessel 113 Rotor 114 Magnetic stirrer 115 stopper 116 gas introduction pipe 117 discharge pipe 201 vacuum pump 202 vacuum gauge 203 high pressure cell portion 204 gas chamber portion 205 constant temperature bath 206, 207, 208, 209, 210 valve 211 thermistor 212 pressure gauge 213 cooling water circulation device 214 carbon dioxide cylinder 215 High-pressure cell 216 Stirrer 217 Stirrer
Claims (14)
水素結合受容性溶媒とを含み、
前記水素結合受容性溶媒は、アニオンが、式２、式３若しくは式４で表されるリン酸エステル若しくはリン酸、若しくは
式５で表されるホスホン酸エステル若しくはホスホン酸であるイオン液体である、
二酸化炭素吸収液。 A carbon dioxide chemisorbable amine having a nitrogen-hydrogen bond, represented by Formula 1,
Including a hydrogen bond accepting solvent,
The hydrogen bond accepting solvents, anions of the formula 2, phosphoric acid esters or phosphoric acid represented by Formula 3 or Formula 4, or Ku Wakashi phosphonic acid ester of the formula 5 in the ionic liquid is a phosphonic acid is there,
Carbon dioxide absorption liquid.
式２、式３若しくは式４で表されるリン酸エステルのうち、Ｒ Of the phosphoric acid esters represented by Formula 2, Formula 3 or Formula 4, R ３Three 、Ｒ, R ４Four 、Ｒ, R ５5 及びＲAnd R ６6 が、水素原子又は無置換若しくは置換基を有していてもよい脂肪族炭化水素基である、脂肪族リン酸エステル、又は、Is a hydrogen atom or an aliphatic hydrocarbon group which may have an unsubstituted or a substituent, an aliphatic phosphate ester, or
式５で表されるホスホン酸エステルのうち、Ｒ Of the phosphonates represented by formula 5, R ７7 が、水素原子又は無置換若しくは置換基を有していてもよい脂肪族炭化水素基である、脂肪族ホスホン酸エステルである、請求項１に記載の二酸化炭素吸収液。The carbon dioxide absorbent according to claim 1, wherein is an aliphatic phosphonic acid ester, which is a hydrogen atom or an aliphatic hydrocarbon group which may be unsubstituted or may have a substituent.
請求項１又は２に記載の二酸化炭素吸収液。 The cation of the ionic liquid is an imidazolium represented by formula 10, an ammonium represented by formula 11, or a phosphonium represented by formula 12.
The carbon dioxide absorbent according to claim 1 or 2 .
前記イオン液体のアニオンは式２、式３若しくは式４で表されるリン酸エステルのうち、Ｒ ３ 、Ｒ ４ 、Ｒ ５ 及びＲ ６ が、水素原子又は無置換若しくは置換基を有していてもよいアルキル基である、アルキルリン酸エステル、又は、式５で表されるホスホン酸エステルのうち、Ｒ ７ が、水素原子又は無置換若しくは置換基を有していてもよいアルキル基である、アルキルホスホン酸エステルである、請求項３に記載の二酸化炭素吸収液。 The cation of the ionic liquid is an imidazolium compound represented by formula 10 ,
In the anion of the ionic liquid , R 3 , R 4 , R 5 and R 6 in the phosphoric acid ester represented by Formula 2, Formula 3 or Formula 4 have a hydrogen atom or an unsubstituted or substituted group. also alkyl groups, alkyl phosphoric acid ester, or of phosphonic acid esters of the formula 5, R 7 is an alkyl group which may have a hydrogen atom or an unsubstituted or substituted, The carbon dioxide absorbent according to claim 3 , which is an alkylphosphonate.
水素結合受容性溶媒とを含み、 Including a hydrogen bond accepting solvent,
前記水素結合受容性溶媒は、電子吸引基としてカルボニル基若しくはホスフィニル基を有する、式６、式７若しくは式８ The hydrogen bond accepting solvent has a carbonyl group or a phosphinyl group as an electron-withdrawing group, represented by Formula 6, Formula 7, or Formula 8
で表される、アミド化合物であり、 Is an amide compound represented by
水分含有量は１０質量％以下である、二酸化炭素吸収液。 Carbon dioxide absorption liquid whose water content is 10 mass% or less.
前記の二酸化炭素を吸収した二酸化炭素吸収液を１２０℃以上に加熱することで吸収した二酸化炭素の９０％以上を放散させて回収し、前記二酸化炭素吸収液を再生する加熱再生工程、を含む二酸化炭素分離回収方法。 By contacting the following mixed gas and 50 ° C. containing carbon dioxide carbon dioxide absorbing solution according to any one of claims 1 to 13 by absorbing carbon dioxide in the carbon dioxide absorbing solution, the mixed gas Absorption step of selectively separating carbon dioxide from the carbon dioxide, and by heating the carbon dioxide absorption liquid that has absorbed the carbon dioxide to 120 ° C. or higher, 90% or more of the absorbed carbon dioxide is diffused and recovered. A method for separating and recovering carbon dioxide, comprising a heating regeneration step of regenerating the carbon absorption liquid.
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