ES2299373B1 - AMINO ACID CYCLALQUIL FOR THE ELIMINATION OF CARBON DIOXIDE FROM GAS MIXTURES. - Google Patents
AMINO ACID CYCLALQUIL FOR THE ELIMINATION OF CARBON DIOXIDE FROM GAS MIXTURES. Download PDFInfo
- Publication number
- ES2299373B1 ES2299373B1 ES200602545A ES200602545A ES2299373B1 ES 2299373 B1 ES2299373 B1 ES 2299373B1 ES 200602545 A ES200602545 A ES 200602545A ES 200602545 A ES200602545 A ES 200602545A ES 2299373 B1 ES2299373 B1 ES 2299373B1
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- ES
- Spain
- Prior art keywords
- acid
- amino acids
- cycloalkyl amino
- general formula
- combinations
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 150000001413 amino acids Chemical class 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 238000003379 elimination reaction Methods 0.000 title claims abstract description 12
- 230000008030 elimination Effects 0.000 title claims abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title abstract description 74
- 229910002092 carbon dioxide Inorganic materials 0.000 title abstract description 37
- 239000001569 carbon dioxide Substances 0.000 title abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000002250 absorbent Substances 0.000 claims abstract description 32
- 230000002745 absorbent Effects 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 125000006310 cycloalkyl amino group Chemical group 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 28
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 24
- 238000010521 absorption reaction Methods 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 19
- -1 1-piperazinyl Chemical group 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 230000008878 coupling Effects 0.000 claims description 8
- 238000010168 coupling process Methods 0.000 claims description 8
- 238000005859 coupling reaction Methods 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 7
- 238000011069 regeneration method Methods 0.000 claims description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- KDPAWGWELVVRCH-UHFFFAOYSA-N bromoacetic acid Chemical compound OC(=O)CBr KDPAWGWELVVRCH-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 claims description 3
- CHJBSLXUNSLXIN-UHFFFAOYSA-N 2-(pyrimidin-2-ylamino)acetic acid Chemical compound OC(=O)CNC1=NC=CC=N1 CHJBSLXUNSLXIN-UHFFFAOYSA-N 0.000 claims description 3
- DROUDOFWBZQMKW-UHFFFAOYSA-N 2-amino-2-piperazin-1-ylacetic acid Chemical compound NC(N1CCNCC1)C(O)=O DROUDOFWBZQMKW-UHFFFAOYSA-N 0.000 claims description 3
- UNCQVRBWJWWJBF-UHFFFAOYSA-N 2-chloropyrimidine Chemical compound ClC1=NC=CC=N1 UNCQVRBWJWWJBF-UHFFFAOYSA-N 0.000 claims description 3
- KBRJFTVJHKGOAX-UHFFFAOYSA-N N1(CCNCC1)CCNCC(=O)O Chemical compound N1(CCNCC1)CCNCC(=O)O KBRJFTVJHKGOAX-UHFFFAOYSA-N 0.000 claims description 3
- 150000001447 alkali salts Chemical class 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- JSSXHAMIXJGYCS-UHFFFAOYSA-N piperazin-4-ium-2-carboxylate Chemical compound OC(=O)C1CNCCN1 JSSXHAMIXJGYCS-UHFFFAOYSA-N 0.000 claims description 3
- NIPZZXUFJPQHNH-UHFFFAOYSA-N pyrazine-2-carboxylic acid Chemical compound OC(=O)C1=CN=CC=N1 NIPZZXUFJPQHNH-UHFFFAOYSA-N 0.000 claims description 3
- ZXARXWQGLLRGOJ-UHFFFAOYSA-N 2-(pyrimidin-2-ylamino)butanoic acid Chemical compound CCC(C(O)=O)NC1=NC=CC=N1 ZXARXWQGLLRGOJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- MONMFXREYOKQTI-UHFFFAOYSA-N 2-bromopropanoic acid Chemical compound CC(Br)C(O)=O MONMFXREYOKQTI-UHFFFAOYSA-N 0.000 claims 1
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical class NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims 1
- 229910000000 metal hydroxide Inorganic materials 0.000 claims 1
- 150000004692 metal hydroxides Chemical class 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 32
- 239000007864 aqueous solution Substances 0.000 abstract description 15
- 238000000926 separation method Methods 0.000 abstract description 12
- 159000000011 group IA salts Chemical class 0.000 abstract description 9
- 125000000753 cycloalkyl group Chemical group 0.000 abstract 1
- 229940024606 amino acid Drugs 0.000 description 29
- 235000001014 amino acid Nutrition 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 230000008569 process Effects 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 16
- 150000001412 amines Chemical class 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012190 activator Substances 0.000 description 6
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 229920000768 polyamine Polymers 0.000 description 5
- FUOOLUPWFVMBKG-UHFFFAOYSA-N 2-Aminoisobutyric acid Chemical compound CC(C)(N)C(O)=O FUOOLUPWFVMBKG-UHFFFAOYSA-N 0.000 description 4
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 4
- 239000004471 Glycine Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 4
- 239000008246 gaseous mixture Substances 0.000 description 4
- 229960002449 glycine Drugs 0.000 description 4
- ITZPOSYADVYECJ-UHFFFAOYSA-N n'-cyclohexylpropane-1,3-diamine Chemical compound NCCCNC1CCCCC1 ITZPOSYADVYECJ-UHFFFAOYSA-N 0.000 description 4
- 150000004885 piperazines Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- FFDGPVCHZBVARC-UHFFFAOYSA-N N,N-dimethylglycine Chemical compound CN(C)CC(O)=O FFDGPVCHZBVARC-UHFFFAOYSA-N 0.000 description 3
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229940066771 systemic antihistamines piperazine derivative Drugs 0.000 description 3
- 229960003080 taurine Drugs 0.000 description 3
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 2
- BAWRRKZCBDUZKE-UHFFFAOYSA-N 2-(pyrimidin-2-ylamino)propanoic acid Chemical compound OC(=O)C(C)NC1=NC=CC=N1 BAWRRKZCBDUZKE-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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 235000008206 alpha-amino acids Nutrition 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 108700003601 dimethylglycine Proteins 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- HXEACLLIILLPRG-RXMQYKEDSA-N l-pipecolic acid Natural products OC(=O)[C@H]1CCCCN1 HXEACLLIILLPRG-RXMQYKEDSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- HXEACLLIILLPRG-UHFFFAOYSA-N pipecolic acid Chemical compound OC(=O)C1CCCCN1 HXEACLLIILLPRG-UHFFFAOYSA-N 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NILQLFBWTXNUOE-UHFFFAOYSA-N 1-aminocyclopentanecarboxylic acid Chemical compound OC(=O)C1(N)CCCC1 NILQLFBWTXNUOE-UHFFFAOYSA-N 0.000 description 1
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 1
- RRWZZMHRVSMLCT-UHFFFAOYSA-N 2-(butylazaniumyl)acetate Chemical compound CCCCNCC(O)=O RRWZZMHRVSMLCT-UHFFFAOYSA-N 0.000 description 1
- OQMYZVWIXPPDDE-UHFFFAOYSA-N 2-(cyclohexylazaniumyl)acetate Chemical compound OC(=O)CNC1CCCCC1 OQMYZVWIXPPDDE-UHFFFAOYSA-N 0.000 description 1
- XHJGXOOOMKCJPP-UHFFFAOYSA-N 2-[tert-butyl(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(C(C)(C)C)CCO XHJGXOOOMKCJPP-UHFFFAOYSA-N 0.000 description 1
- IOAOAKDONABGPZ-UHFFFAOYSA-N 2-amino-2-ethylpropane-1,3-diol Chemical compound CCC(N)(CO)CO IOAOAKDONABGPZ-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- KEEVZNPZYFDJEK-UHFFFAOYSA-N 2-imidazolidin-2-ylimidazolidine Chemical compound N1CCNC1C1NCCN1 KEEVZNPZYFDJEK-UHFFFAOYSA-N 0.000 description 1
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 1
- AGUZDVQPUZKYPV-UHFFFAOYSA-N 2-piperazin-2-ylpiperazine Chemical compound C1NCCNC1C1NCCNC1 AGUZDVQPUZKYPV-UHFFFAOYSA-N 0.000 description 1
- BCOYLHZEWLUHFE-UHFFFAOYSA-N 2-piperidin-3-ylpiperazine Chemical compound C1CCNCC1C1NCCNC1 BCOYLHZEWLUHFE-UHFFFAOYSA-N 0.000 description 1
- NQHVTVSAFRAXPA-UHFFFAOYSA-N 2-pyrrolidin-2-ylpyrrolidine Chemical compound C1CCNC1C1NCCC1 NQHVTVSAFRAXPA-UHFFFAOYSA-N 0.000 description 1
- JKONEIZKPVUGSO-UHFFFAOYSA-N 3-(2,5-dimethylpiperazin-1-yl)propan-1-amine Chemical compound CC1CN(CCCN)C(C)CN1 JKONEIZKPVUGSO-UHFFFAOYSA-N 0.000 description 1
- IKNFMHZKPYNCLN-UHFFFAOYSA-N 3-piperidin-3-ylpiperidine Chemical compound C1CCNCC1C1CNCCC1 IKNFMHZKPYNCLN-UHFFFAOYSA-N 0.000 description 1
- JJVADOPYVXLUAB-UHFFFAOYSA-N 3-pyrrolidin-3-ylpiperidine Chemical compound C1NCCC1C1CNCCC1 JJVADOPYVXLUAB-UHFFFAOYSA-N 0.000 description 1
- 229910018507 Al—Ni Inorganic materials 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- AMRCOCKNEWRLBQ-UHFFFAOYSA-N CC1N(CC(NC1)C)CC(C(=O)O)N Chemical compound CC1N(CC(NC1)C)CC(C(=O)O)N AMRCOCKNEWRLBQ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 1
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 description 1
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001370 alpha-amino acid derivatives Chemical class 0.000 description 1
- 150000001371 alpha-amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000009582 asparagine Nutrition 0.000 description 1
- 229960001230 asparagine Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001576 beta-amino acids Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 229940078490 n,n-dimethylglycine Drugs 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 101150009274 nhr-1 gene Proteins 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- IMYBWPUHVYRSJG-UHFFFAOYSA-M potassium;2-aminoethanesulfonate Chemical compound [K+].NCCS([O-])(=O)=O IMYBWPUHVYRSJG-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- USPWKWBDZOARPV-UHFFFAOYSA-N pyrazolidine Chemical compound C1CNNC1 USPWKWBDZOARPV-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Gas Separation By Absorption (AREA)
Abstract
Cicloalquil aminoácidos para la eliminación de dióxido de carbono de mezclas de gases.Cycloalkyl amino acids for the elimination of carbon dioxide from gas mixtures.
Cicloalquil aminoácidos para la eliminación de dióxido de carbono, método de preparación de los cicloalquil aminoácidos de fórmula general I y su utilización en disolución acuosa como líquidos para la separación de dióxido de carbono (CO_{2}) de mezclas de gases. Se trata de disoluciones acuosas de sales alcalinas de los aminoácidos seleccionados entre aquellos de fórmula general I. Estos líquidos absorbentes y su utilización adecuada ofrecen un método eficaz para la separación de CO_{2} de mezclas gaseosas.Cycloalkyl amino acids for the elimination of carbon dioxide, cycloalkyl preparation method amino acids of general formula I and their use in solution aqueous as liquids for the separation of carbon dioxide (CO 2) of gas mixtures. It is aqueous solutions of alkaline salts of the amino acids selected from those of general formula I. These absorbent liquids and their use suitable offer an effective method for the separation of CO2 from gas mixtures.
Description
Cicloalquil aminoácidos para la eliminación de dióxido de carbono de mezclas de gases.Cycloalkyl amino acids for the elimination of carbon dioxide from gas mixtures.
Dentro del sector químico y medioambiental, la invención se refiere a líquidos absorbentes que contienen cicloalquil aminoácidos que pueden actuar como precursores de sales de metales alcalinos, así como la aplicación de los líquidos absorbentes para el tratamiento de mezclas gaseosas que contienen CO_{2}.Within the chemical and environmental sector, the invention refers to absorbent liquids containing cycloalkyl amino acids that can act as salt precursors of alkali metals, as well as the application of liquids absorbents for the treatment of gas mixtures containing CO 2.
La captura de CO_{2} mediante diversos métodos viene siendo un tema de investigación importante en los últimos años, y hay una serie de procesos industriales que precisan de la captura de CO_{2}, como son la fabricación de amoniaco, el tratamiento de gas natural y la producción de hidrógeno. Es más, la separación de CO_{2} de los gases de combustión ha alcanzado especial relevancia, debido a la amenaza de calentamiento global causado por una elevada concentración de este gas, responsable del efecto invernadero. Los procesos más importantes de separación de CO_{2} son en la actualidad: absorción, adsorción, métodos criogénicos y separación con membranas. Los primeros tres métodos son los tradicionales, y presentan como principal limitación, el alto consumo energético, y consecuentemente su coste relativamente alto. Los absorbentes de CO_{2} utilizados más comúnmente en los procesos industriales de separación de CO_{2} de mezclas gaseosas son disoluciones acuosas de alcanol aminas, como monoetanol amina (MEA) y dietanol amina (DEA). En estos procedimientos, la mezcla de gases de la alimentación se burbujea a través de la disolución de amina, que retiene preferentemente el CO_{2}, y a continuación se calienta con el fin de que el CO_{2} casi puro se separe del absorbente. Sin embargo, el uso de estas aminas tiene algunas desventajas; por ejemplo, MEA y DEA presentan velocidades de absorción y capacidades de absorción relativamente bajas, y además no son muy estables. Además, durante su manejo y durante el proceso de absorción, las diaminas pueden escapar en parte a la atmósfera y contaminarla. Por ultimo, algunas de estas aminas pueden descomponerse en las condiciones del proceso de absorción, lo que resulta en un aumento de la viscosidad y formación de espumas. Una mejora reciente en la composición de estos líquidos absorbentes ha sido el uso de disoluciones acuosas de aminoácidos, y en esta línea el proceso descrito aquí se basa en alquil y cicloalquil aminoácidos, impedidos y no impedidos estéricamente. Una ventaja del proceso objeto de esta invención, que se ilustrará con los ejemplos específicos que se darán más abajo, es que el líquido separador se puede regenerar, y además, esta recuperación del absorbente se hace sin la necesidad de aditivos.The capture of CO2 by various methods has been an important research topic in recent years, and there are a number of industrial processes that require the capture of CO2, such as the manufacture of ammonia, the treatment of Natural gas and hydrogen production. Moreover, the separation of CO2 from the flue gases has reached special relevance, due to the threat of global warming caused by a high concentration of this gas, responsible for the greenhouse effect. The most important processes of CO2 separation are currently: absorption, adsorption, cryogenic methods and membrane separation. The first three methods are the traditional ones, and have as their main limitation, high energy consumption, and consequently their relatively high cost. The most commonly used CO2 absorbers in the industrial processes of CO2 separation from gaseous mixtures are aqueous solutions of alkanol amines, such as monoethanol amine (MEA) and dietanol amine (DEA). In these processes, the gas mixture of the feed is bubbled through the amine solution, which preferably retains the CO2, and is then heated so that the almost pure CO2 is separated from the absorbent . However, the use of these amines has some disadvantages; for example, MEA and DEA have relatively low absorption rates and absorption capacities, and are also not very stable. In addition, during handling and during the absorption process, diamines can partly escape into the atmosphere and contaminate it. Finally, some of these amines can decompose under the conditions of the absorption process, resulting in an increase in viscosity and foaming. A recent improvement in the composition of these absorbent liquids has been the use of aqueous solutions of amino acids, and in this line the process described here is based on alkyl and cycloalkyl amino acids, sterically hindered and not hindered. An advantage of the process object of this invention, which will be illustrated with the specific examples given below, is that the separating liquid can be regenerated, and in addition, this recovery of the absorbent is done without the need for additives .
La separación de CO_{2} de mezclas de gases mediante la utilización de disoluciones de aminas y aminoácidos ha dado lugar a varios procedimientos ya descritos anteriormente:The separation of CO2 from gas mixtures by using solutions of amines and amino acids has resulted in several procedures already described above:
- La patente Británica Pat. 960648 representa un proceso para la separación de CO_{2} de mezclas de gases mediante el lavado con una disolución acuosa de una sal alcalina y un aminoácido neutro o un ácido aminosulfónico, como por ejemplo glicocola, N,N-dimetilglicocola, N-metiltaurina y N-metil-\alpha-alanina.- British patent Pat. 960648 represents a process for the separation of CO2 from gas mixtures by washing with an aqueous solution of an alkaline salt and a neutral amino acid or aminosulfonic acid, such as glycine, N, N-dimethylglycine, N-methyltaurine and N-methyl-? -Alanine.
- En la patente alemana Pat. Apll. 2211640 se describe que en la utilización de una disolución absorbente conteniendo una o varias sales alcalinas de aminoácidos, que pueden estar substituidos en el grupo amino, es necesario añadir a la disolución ciertos compuestos conteniendo grupos amino, como hidracina o fenilhidracina, con el fin de minimizar la pérdida de capacidad de absorción después de varios ciclos de regeneración y alargar el tiempo de vida útil del sistema absorbente.- In the German patent Pat. App 2211640 se describes that in the use of an absorbent solution containing one or more alkaline salts of amino acids, which may to be substituted in the amino group, it is necessary to add to the dissolution certain compounds containing amino groups, such as hydrazine or phenylhydrazine, in order to minimize the loss of absorption capacity after several regeneration cycles and lengthen the lifetime of the absorbent system.
- La patente Británica Pat. 1543748 describe un procedimiento para la eliminación de CO_{2} y/o H_{2}S de purgas de gases de craqueo mediante tratamiento con una disolución acuosa de sales alcalinas de ácidos N,N-dialquil-\alpha-aminomonocarboxílicos, siendo los grupos alquilo: metil, etil, n-propil, pentil, hexil, y ciclohexil.- British patent Pat. 1543748 describes a procedure for the removal of CO2 and / or H2S from purges of cracking gases by treatment with an aqueous solution of alkaline acid salts N, N-dialkyl-α-aminomonocarboxylic acids, the alkyl groups being: methyl, ethyl, n-propyl, pentyl, hexyl, and cyclohexyl.
- La patente americana Pat. 4405577 se refiere a formulaciones alcalinas que consisten en mezclas definidas de aminoácidos impedidos y no impedidos estéricamente y a su utilización en procesos de separación de gases. El sistema preferido es una mezcla de (i) dietanolamina ó 1,6-hexanodiamina y (ii) N-butilglicocola o ácido pipecolínico. En este proceso se utiliza una cantidad relativamente pequeña de una diamina, para que actúe como activador de los absorbentes de la disolución separadora.- The American patent Pat. 4405577 refers to alkaline formulations consisting of defined mixtures of sterically hindered and non-hindered amino acids and their use in gas separation processes. The system Preferred is a mixture of (i) diethanolamine or 1,6-hexanediamine and (ii) N-butylglycine or pipecolinic acid. In this process a relatively small amount of a diamine, to act as activator of the absorbents of the separating solution.
- En la patente americana Pat. 4919904 se describe la utilización de aminoácidos impedidos estéricamente como intermedios para la formación de sus sales alcalinas y su uso como separadores de gases ácidos. El aminoácido se elige de entre 1-aminociclopentanoico y los de fórmula general NH_{2}-CR_{1}R_{2}-(C)_{n}R_{3}R_{4}-CO_{2}H, donde R_{1} y R_{2} pueden ser CH_{3}, C_{2}H_{5} o C_{3}H_{7}; R_{3} y R_{4} pueden ser H o CH_{3}; y n es 0, 2, o 3. La formulación de la disolución absorbente contiene de 15 a 30% en peso de carbonato potásico, entre 2 y 15% en peso del aminoácido impedido, y una cantidad suficiente de un compuesto de vanadio para que actúe como protector de corrosión.- In the American patent Pat. 4919904 se describes the use of sterically hindered amino acids as intermediates for the formation of its alkaline salts and its use as acid gas separators. The amino acid is chosen from 1-aminocyclopentanoic acid and those of general formula NH 2 -CR 1 R 2 - (C) n R 3 R 4 -CO 2 H, where R 1 and R 2 can be CH 3, C 2 H 5 or C 3 H 7; R 3 and R 4 can be H or CH 3; and n is 0, 2, or 3. The formulation of the absorbent solution contains from 15 to 30% by weight of potassium carbonate, between 2 and 15% by weight of hindered amino acid, and a sufficient amount of a compound of vanadium to act as a corrosion protector.
- La patente americana Pat. 5611843 describe una composición útil para la separación de CO_{2} de corrientes gaseosas que contienen CO_{2}, H_{2}, y CO. La formulación comprende un polímero hidrófilo y al menos una sal de aminoácido en proporción de 10-80% referido al peso total de la mezcla. El polímero hidrofílico puede ser alcohol polivinílico, acetato de polivinilo, polióxido de etileno, polivinil pirrolidona, poliacrilamida, o mezclas de ellos, mientras que las sales de aminoácido se seleccionan entre los siguientes aminoácidos: glicocola, ácido pipecolínico, o ácido aminoisobutírico, y donde el catión metálico tiene valencia de 1 a 3 y se selecciona entre los elementos de los grupos Ia, IIa y IIIa de la Tabla Periódica de los Elementos. Se incluye igualmente un catión amínico de fórmula general NHR_{1}R_{2}-(CH_{2})_{n}-R_{3}, dónde R_{1} y R_{2} son hidrógeno o un grupo alquilo, R_{2} es H, un resto alquílico o una alquilamina con átomos de carbono y átomos de nitrógeno.- The American patent Pat. 5611843 describes a composition useful for the separation of CO2 from streams soda containing CO 2, H 2, and CO. Formulation comprises a hydrophilic polymer and at least one amino acid salt in proportion of 10-80% referred to the total weight of the mixture. The hydrophilic polymer can be polyvinyl alcohol, polyvinyl acetate, ethylene polyoxide, polyvinyl pyrrolidone, polyacrylamide, or mixtures thereof, while salts of Amino acid are selected from the following amino acids: glycine, pipecolinic acid, or aminoisobutyric acid, and where the metallic cation has a valence of 1 to 3 and is selected among the elements of groups Ia, IIa and IIIa of the Periodic Table of the Elements. An amine cation of the formula is also included general NHR 1 R 2 - (CH 2) n -R 3, where R1 and R2 are hydrogen or an alkyl group, R2 is H, an alkyl moiety or an alkylamine with carbon atoms and nitrogen atoms
- La patente americana Pat. 5602279 describe el uso de una disolución acuosa para separar gases por el denominado método "hot-pot". La disolución consiste en hidróxido potásico y el aminoácido 2-aminoisobutírico (AIBA) como reactivo separador. La patente también incluye el procedimiento para la preparación de la disolución, a partir de 2-amino-2-metil-1-propanol (AMP) y un oxidante en presencia de CdO como catalizador. Se menciona también la utilización de una cantidad efectiva de un inhibidor de vanadio, que actúa como inhibidor de corrosión del equipo donde se realiza el proceso.- The American patent Pat. 5602279 describes the use of an aqueous solution to separate gases by the so-called "hot-pot" method. The solution consists of potassium hydroxide and the amino acid 2-aminoisobutyric acid (AIBA) as a separating reagent. The patent also includes the procedure for the preparation of the dissolution, from 2-amino-2-methyl-1-propanol (AMP) and an oxidant in the presence of CdO as catalyst. Be also mentions the use of an effective amount of a vanadium inhibitor, which acts as a corrosion inhibitor of equipment where the process is carried out.
- La patente americana Pat. 6500397 describe un método para la eliminación de CO_{2} en corrientes de gases de combustión, que incluye una etapa de conducción de los gases a una disolución acuosa de una amina impedida, seleccionada del grupo siguiente: 2-amino-2-metil-1-propanol, 2-metilaminoetanol, 2-etilamino-etanol y 2-piperidinetanol; o bien a una disolución acuosa de 100 partes en peso de una amina (X) seleccionada de entre 2-amino-2-metil-1,3-propanodiol, 2-amino-2-metil-1-propanol, 2-amino-2-etil-1,3-propanodiol, t-butildietanolamina y 2-amino-2-hidroximetil-1,3-propanodiol; y 1-25 partes en peso de una amina (Y) seleccionada del grupo: piperazina, piperidina, morfolina, glicocola, 2-metilamino-etanol, 2-piperidinetanol y 2-etilaminoetanol.- The American patent Pat. 6500397 describes a method for the removal of CO2 in gas streams of combustion, which includes a stage of conduction of gases to a aqueous solution of an hindered amine, selected from the group next: 2-amino-2-methyl-1-propanol, 2-methylaminoethanol, 2-ethylamino-ethanol and 2-piperidinetanol; or to an aqueous solution 100 parts by weight of an amine (X) selected from 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1,3-propanediol, t-butyldiethanolamine and 2-amino-2-hydroxymethyl-1,3-propanediol; and 1-25 parts by weight of an amine (Y) selected from the group: piperazine, piperidine, morpholine, glycine, 2-methylamino-ethanol, 2-piperidinetanol and 2-ethylaminoethanol.
- En la patente WO 03/095071 A1 se reclama la invención de un método para la absorción de gases ácidos, tales como CO_{2} y H_{2}S, de mezclas de gases mediante contacto de la mezcla gaseosa con una disolución acuosa de una aminoácido o una sal de aminoácido que forma un precipitado. Los aminoácidos preferidos para la eliminación exclusiva de CO_{2} son los que presentan impedimento estérico, tales como taurina, metiltaurina, metil-\alpha-aminopropionico, N-(\beta-etoxi)taurina y N-(\beta-aminoetil)taurina, así como otros aminoácidos que se describen en la solicitud US-A-3042483. Si la mezcla de gases que hay que tratar contiene a la vez H_{2}S y CO_{2}, la utilización de aminas y aminoácidos impedidos es ventajosa. Algunos ejemplos son anilina y glicocola y derivados de ellos, tales como N-metilanilina y dimetilglicocola. También se pueden utilizar aminoácidos con más de un grupo amino por molécula, como asparragina, glutamina, lisina o histidina. En esta invención se presentan como preferidas las disoluciones de sales potásicas, porque son más solubles a concentraciones altas que las correspondientes al aminoácido sólo, y preferentemente usando una disolución de taurato potásico en concentraciones de sal mayores de 0.2 mol/l.- In WO 03/095071 A1 the invention of a method for the absorption of acid gases, such as CO2 and H2S, of gas mixtures by contacting the gas mixture with an aqueous solution is claimed. of an amino acid or an amino acid salt that forms a precipitate. Preferred amino acids for the exclusive removal of CO2 are those with steric hindrance, such as taurine, methyltaurine, methyl-? -Aminopropionic, N- (? -Ethoxy) taurine and N- (? -Aminoethyl) taurine, as well as other amino acids described in US-A-3042483. If the mixture of gases to be treated contains both H 2 S and CO 2, the use of hindered amines and amino acids is advantageous. Some examples are aniline and glycine and derivatives thereof, such as N-methylaniline and dimethylglycine. You can also use amino acids with more than one amino group per molecule, such as asparagine, glutamine, lysine or histidine. In this invention the solutions of potassium salts are presented as preferred, because they are more soluble at high concentrations than those corresponding to the amino acid only, and preferably using a solution of potassium taurate in salt concentrations greater than 0.2 mol / l .
- En la patente americana Pat. 27183454 se describe la utilización de potasa y otras sales alcalinas en combinación con aminas como monoetanolamina, dietanolamina y trietanolamina, en procesos de eliminación de gases con cierto carácter ácido a partir de mezclas gaseosas. La combinación de metal alcalino y amina supone un incremento en la capacidad de absorción de gases ácidos respecto a aquellos sistemas que utilizan únicamente la amina.- In the American patent Pat. 27183454 se describes the use of potash and other alkaline salts in combination with amines such as monoethanolamine, diethanolamine and triethanolamine, in processes of elimination of gases with certain Acidic character from gaseous mixtures. Metal combination alkaline and amine represents an increase in absorption capacity of acid gases compared to those systems that use only The amine
- La patente americana Pat. 4581209 se refiere al uso de triaminas impedidas estéricamente (N-aminoalquilpiperazinas) y en concreto 1-(3-aminopropil)-2,5-dimetilpiperazina (APDP) como activantes de sales alcalinas en un proceso de captura de gas denominado "hot-pot". Estos compuestos amínicos no solo presentan una alta capacidad y velocidad de absorción de CO_{2} sino que no sufren degradación y la consiguiente formación de compuestos insolubles como ocurre en el caso de N-ciclohexil-1,3-propanodiamina, beta y gamma aminoácidos o el alfa aminoácido, N-ciclohexil glicocola. Además, estos compuestos presentan una menor volatilidad que la N-ciclohexil-1,3-propanodiamina y que las piperazinas incluidas en las patentes americanas Pat. 4094957 y 4112050 por lo que incrementa el ahorro de estos absorbentes.- The American patent Pat. 4581209 refers to the use of sterically hindered triamines (N-aminoalkylpiperazines) and specifically 1- (3-aminopropyl) -2,5-dimethylpiperazine (APDP) as alkaline salt activators in a capture process of gas called "hot-pot". These compounds Amines not only have a high capacity and speed of CO2 absorption but do not suffer degradation and consequent formation of insoluble compounds as occurs in the case of N-cyclohexyl-1,3-propanediamine, beta and gamma amino acids or the alpha amino acid, N-cyclohexyl glycine. In addition, these compounds they show less volatility than N-cyclohexyl-1,3-propanediamine and that the piperazines included in US Pat. 4094957 and 4112050 so it increases the savings of these absorbents
- La patente americana Pat. 5209914 describe la invención de líquidos absorbentes con una mejor capacidad de absorción, los cuales contienen alcanolaminas terciarias así como un activador de la capacidad. Este activador consiste en al menos un compuesto amínico, seleccionado entre polialquilpoliaminas, alquildiaminas, cicloalquildiaminas y alquilaminas derivadas de heterociclos como piperazina, piperidina, furano, tiofeno, tetrahidrofurano y tetrahidrotiofeno.- The American patent Pat. 5209914 describes the invention of absorbent liquids with a better ability to absorption, which contain tertiary alkanolamines as well as a capacity activator. This activator consists of at least one amino compound, selected from polyalkyl polyamines, alkyldiamines, cycloalkyldiamines and alkylamines derived from heterocycles such as piperazine, piperidine, furan, thiophene, tetrahydrofuran and tetrahydrothiophene.
- La patente americana Pat. 5749941 describe el método empleado para la absorción de uno o más gases a través de una membrana, en el que la fase gaseosa conteniendo los componentes a ser absorbidos, se pone en contacto con una fase líquida, y donde ambas fases están únicamente separadas por una membrana de carácter hidrofóbico. La fase líquida consiste en una disolución acuosa de un aminoácido soluble en agua ó de su correspondiente sal.- The American patent Pat. 5749941 describes the method used for the absorption of one or more gases through a membrane, in which the gas phase containing the components to be absorbed, it comes into contact with a liquid phase, and where both phases are only separated by a membrane of character hydrophobic. The liquid phase consists of an aqueous solution of a water soluble amino acid or its corresponding salt.
- En la patente registrada recientemente WO 2004/089512 A1 se reclama el uso de nuevas disoluciones para la captura de CO_{2}, basadas en mezclas de poliamina/sal alcalina. La composición de la disolución incluye una sal alcalina como carbonato potásico y una poliamina como piperazina (PZ), con una relación poliamina/sal alcalina de 0,5 a 2 y preferiblemente de 1 a 2, estando la concentración total de la disolución limitada por la solubilidad del sólido, que es de al menos 3 eq. de H_{2}O por Kg de PZ.- In the recently registered patent WO 2004/089512 A1 claims the use of new solutions for the CO2 capture, based on polyamine / alkali salt mixtures. The composition of the solution includes an alkaline salt as potassium carbonate and a polyamine such as piperazine (PZ), with a polyamine / alkaline salt ratio of 0.5 to 2 and preferably 1 to 2, the total concentration of the solution being limited by the Solubility of the solid, which is at least 3 eq. of H2O per Kg of PZ.
Una variedad de poliaminas, cíclicas, lineales, primarias ó secundarias, pueden ser usadas como componentes de la disolución de dicha invención, incluyendo derivados de piperazina (e.g. aminoetilpiperazina, hidroxietilpiperazina, 2-(2-piperazinil)piperazina), pirazolidina, imidazolidina, 2-(2-pirrolidinil)pirrolidina, 2-(2-imidazolidil)imidazolidina, 3-(3-pirrolidinil)piperidina, 3-(3-piperidinil)piperidina y 3-(2-piperazinil)piperidina.A variety of polyamines, cyclic, linear, primary or secondary, can be used as components of the solution of said invention, including piperazine derivatives (e.g. aminoethylpiperazine, hydroxyethylpiperazine, 2- (2-piperazinyl) piperazine), pyrazolidine, imidazolidine, 2- (2-pyrrolidinyl) pyrrolidine, 2- (2-imidazolidyl) imidazolidine, 3- (3-pyrrolidinyl) piperidine, 3- (3-piperidinyl) piperidine and 3- (2-piperazinyl) piperidine.
Una ventaja de la invención a la que se hace referencia es la elevada velocidad de reacción del CO_{2} con dicha disolución. An advantage of the invention referred to is the high reaction rate of CO2 with said solution .
- En una muy reciente patente americana Pat. 6852144 B1 se demanda el uso de derivados de piperazina como activadores (e.g. piperazina, morfolina y metilpiperidina) en combinación con una alcanolamina alifática (e.g. trietanolamina (TEA) y metildietanolamina (MDEA)) como parte del líquido absorbente para la separación de COS en el tratamiento de mezclas gaseosas de CO_{2} y COS.- In a very recent American patent Pat. 6852144 B1 demands the use of piperazine derivatives as activators (e.g. piperazine, morpholine and methylpiperidine) in combination with an aliphatic alkanolamine (e.g. triethanolamine (TEA) and methyldiethanolamine (MDEA)) as part of the absorbent liquid for the separation of COS in the treatment of gaseous mixtures of CO 2 and COS.
A pesar de que estos absorbentes han sido ensayados con relativo éxito, sin embargo todos ellos presentan una serie de limitaciones. Así, DEA presenta como ya se ha dicho anteriormente una velocidad de absorción y capacidad de absorción relativa bajas y cierta inestabilidad; N-ciclohexil-1,3-propano-diamina (CHPD) necesita un codisolvente y es susceptible de sufrir degradación. Además, algunos de los derivados de piperazina descritos en estas patentes presentan como punto débil su inestabilidad y la volatilidad intrínseca de las aminas. Este problema de la volatilidad sólo se ve parcialmente reducido por el uso de la combinación K^{+}/PZ.Although these absorbents have been rehearsed with relative success, however all of them present a series of limitations. Thus, DEA presents as already stated formerly an absorption rate and absorption capacity relative casualties and some instability; N-cyclohexyl-1,3-propane-diamine (CHPD) needs a co-solvent and is susceptible to suffering degradation. In addition, some of the piperazine derivatives described in these patents have as a weak point their instability and intrinsic volatility of amines. This volatility problem is only partially reduced by the use of the K + / PZ combination.
En la presente invención se reivindican los cicloalquil aminoácidos de fórmula general I, y el método de preparación de los mismos.In the present invention the cycloalkyl amino acids of general formula I, and the method of Preparation of them.
Esta invención se refiere también a su utilización en disolución acuosa como líquidos para la separación de dióxido de carbono (CO_{2}) de mezclas de gases. Se trata de disoluciones acuosas de sales alcalinas de los aminoácidos seleccionados entre aquellos pertenecientes al grupo de fórmula general I. Para la formación de las sales se combinan una base alcalina y un aminoácido en relación comprendida entre 0,5:1 y 2,5:1 y preferiblemente entre 1:1 y 2:1. Estos líquidos absorbentes y su utilización adecuada ofrecen un método eficaz para la separación de CO_{2} de mezclas gaseosas.This invention also relates to its use in aqueous solution as liquids for the separation of carbon dioxide (CO2) from gas mixtures. Is about aqueous solutions of alkaline salts of amino acids selected from those belonging to the formula group general I. For the formation of salts a base is combined alkaline and an amino acid in a ratio between 0.5: 1 and 2.5: 1 and preferably between 1: 1 and 2: 1. These absorbent liquids and their Proper use offer an effective method for separating CO2 of gaseous mixtures.
También se refiere a un proceso de eliminación de CO_{2} presente en una corriente gaseosa, consistente en poner en contacto dicha corriente de gas (1), en una primera operación de absorción, con una disolución acuosa compuesta por (a) una base de metal alcalino seleccionado de entre bicarbonatos, carbonatos e hidróxidos, y (b) un sistema activador o promotor para dicha base alcalina o dicho hidróxido de metal alcalino conteniendo cierta cantidad efectiva de cicloalquil aminoácido, y (2) una operación de regeneración dónde al menos una parte del CO_{2} absorbido es desorbido desde el líquido.It also refers to a process of elimination of CO2 present in a gas stream, consisting of putting in contact said gas stream (1), in a first operation of absorption, with an aqueous solution composed of (a) a base of alkali metal selected from bicarbonates, carbonates and hydroxides, and (b) an activator or promoter system for said base alkaline or said alkali metal hydroxide containing certain effective amount of cycloalkyl amino acid, and (2) an operation of regeneration where at least a part of the absorbed CO2 is desorbed from the liquid.
La presente invención se enfrenta con el problema de proporcionar nuevos procesos de eliminación eficaces de CO_{2} de una mezcla de gases.The present invention faces the problem of providing effective new elimination processes of CO2 of a gas mixture.
Una ventaja del proceso objeto de esta invención, que se ilustrará con los ejemplos específicos que se darán más abajo, es que el líquido separador se puede regenerar, y además, esta recuperación del absorbente se hace sin la necesidad de aditivos (Ejemplo 7), ya que no son susceptibles de sufrir degradación bajo las condiciones del proceso. Este absorbente permite un menor consumo de energía en el proceso de eliminación del CO_{2} absorbido y consiguiente regeneración del absorbente líquido que los métodos descritos anteriormente.An advantage of the process object of this invention, which will be illustrated with the specific examples to be they will give below, is that the separating liquid can be regenerated, and In addition, this recovery of the absorbent is done without the need of additives (Example 7), since they are not susceptible to suffering degradation under process conditions. This absorbent allows a lower energy consumption in the process of elimination of CO2 absorbed and consequent regeneration of the absorbent liquid than the methods described above.
En esta invención se presentan como preferidas las disoluciones de sales potásicas del aminoácido, porque son más solubles a concentraciones altas que disoluciones del aminoácido sólo, y preferentemente usando una disolución de hidróxido potásico en concentraciones de sal mayores de 0.2 mol/l.In this invention they are presented as preferred the solutions of potassium salts of the amino acid, because they are more soluble at high concentrations than amino acid solutions only, and preferably using a solution of potassium hydroxide in salt concentrations greater than 0.2 mol / l.
Así, un objeto de la presente invención se refiere a cicloalquil aminoácidos de fórmula general I:Thus, an object of the present invention is refers to cycloalkyl amino acids of general formula I:
donde:where:
X representa NH o CHX represents NH or CH
Y representa nitrógeno o CH_{2}Y represents nitrogen or CH2
Z representa nitrógenoZ represents nitrogen
R_{1} representa hidrógeno, metilo, CO_{2}H, NHCH_{2}CO_{2}H, NHCH_{2}CH_{2}CO_{2}H, NHCH_{2}CH_{2}CH_{2}CO_{2}HR1 represents hydrogen, methyl, CO2H, NHCH 2 CO 2 H, NHCH 2 CH 2 CO 2 H, NHCH 2 CH 2 CH 2 CO 2 H
R_{2} representa hidrógeno o metiloR2 represents hydrogen or methyl
R_{3}, si el anillo es alifático, puede ser hidrógeno, CH_{2}CO_{2}H, CH(CH_{3})CO_{2}H, CH_{2}CH_{2}NHCH_{2}CO_{2}H, CH_{2}CH_{2}CO_{2}H yR_ {3}, if the ring is aliphatic, it can be hydrogen, CH 2 CO 2 H, CH (CH 3) CO 2 H, CH 2 CH 2 NHCH 2 CO 2 H, CH 2 CH 2 CO 2 H and
el anillo puede ser aromático o alifático.The ring can be aromatic or aliphatic.
De los compuestos de fórmula general I, aquellos donde X representa NH, Y representa CH_{2}, Z representa nitrógeno, R_{1} representa hidrógeno o metilo, R_{2} representa hidrógeno o metilo, R_{3} representa CH_{2}CH_{2}NHCH_{2}CO_{2}H o CH_{2}CH_{2}CO_{2}H y el anillo es alifático, son los particularmente preferidos.Of the compounds of general formula I, those where X represents NH, Y represents CH2, Z represents nitrogen, R 1 represents hydrogen or methyl, R 2 represents hydrogen or methyl, R 3 represents CH 2 CH 2 NHCH 2 CO 2 H or CH 2 CH 2 CO 2 H and the ring is aliphatic, they are particularly preferred.
Otro objeto de la presente invención lo constituye también el proceso de preparación, de los compuestos de fórmula general I-A, I-B, I-C, I-D, I-E, I-F, I-G y I-H.Another object of the present invention is it also constitutes the preparation process of the compounds of general formula I-A, I-B, I-C, I-D, I-E, I-F, I-G and I-H.
Así, los cicloalquil aminoácidos de fórmula general I, pueden ser preparados por acoplamiento directo de los ácidos \alpha-aminoacético, \beta-aminopropionico y \gamma-aminobutirico con 2-cloropirimidina, por reducción directa del ácido pirazina-2-carboxílico, por acoplamiento directo de piperazina con el ácido 2-bromoacético y con el ácido 2-bromopropiónico, por acoplamiento de 1-(2-aminoetilpiperazina) con ácido 2-bromoacético y acoplamiento de 2,5-dimetilpiperazina con acrilato de metilo.Thus, the cycloalkyl amino acids of formula general I, can be prepared by direct coupling of α-aminoacetic acids, β-aminopropionic and γ-aminobutyric with 2-chloropyrimidine, by direct acid reduction pyrazine-2-carboxylic, for direct coupling of piperazine with acid 2-bromoacetic acid and with acid 2-bromopropionic, by coupling 1- (2-aminoethylpiperazine) with acid 2-bromoacetic and coupling 2,5-dimethylpiperazine with methyl acrylate.
Otro objeto de la presente invención lo constituye también el uso de estos compuestos de formula general I como componentes del líquido absorbente en el proceso de eliminación de CO_{2}.Another object of the present invention is it also constitutes the use of these compounds of general formula I as components of the absorbent liquid in the elimination process of CO2.
Otro objeto de la presente invención lo constituye el proceso de preparación de los líquidos absorbentes para eliminación de CO_{2}, basados en compuestos seleccionados de entre el grupo de fórmula general I y bases alcalinas.Another object of the present invention is It is the process of preparing absorbent liquids for CO2 removal, based on selected compounds from among the group of general formula I and alkaline bases.
La composición del líquido absorbente incluye una sal básica o hidróxido de metal alcalino que se selecciona del grupo consistente en: carbonato potásico, hidróxido potásico, hidróxido sódico o hidróxido de litio, y un compuesto de formula general I. Para la formación de las sales se combinan una base alcalina y un aminoácido en relación comprendida entre 0,5:1 y 2,5:1 y preferiblemente entre 1:1 y 2:1.The composition of the absorbent liquid includes a basic salt or alkali metal hydroxide that is selected from the group consisting of: potassium carbonate, potassium hydroxide, sodium hydroxide or lithium hydroxide, and a compound of formula general I. For the formation of salts a base is combined alkaline and an amino acid in a ratio between 0.5: 1 and 2.5: 1 and preferably between 1: 1 and 2: 1.
Una amplia variedad de aminoácidos cíclicos o lineales, \alpha-aminoácidos o \beta-aminoácidos y ácidos piperazinilcarboxílicos, pueden ser utilizados como componentes principales del líquido objeto de la presente invención.A wide variety of cyclic amino acids or linear, α-amino acids or β-amino acids and acids piperazinylcarboxylic, can be used as components main of the liquid object of the present invention.
A continuación se muestran varios ejemplos que ilustran la presente invención.Below are several examples that They illustrate the present invention.
Figura 1 muestra la síntesis de I-A, I-B y I-C descrita en el Ejemplo 1;Figure 1 shows the synthesis of I-A, I-B and I-C described in Example 1;
Figura 2 muestra la síntesis de I-D descrita en el Ejemplo 2;Figure 2 shows the synthesis of I-D described in Example 2;
Figura 3 muestra la síntesis de I-E descrita en el Ejemplo 3;Figure 3 shows the synthesis of I-E described in Example 3;
Figura 4 muestra la síntesis de I-F descrita en el Ejemplo 4;Figure 4 shows the synthesis of I-F described in Example 4;
Figura 5 muestra la síntesis de I-G descrita en el Ejemplo 5;Figure 5 shows the synthesis of I-G described in Example 5;
Figura 6 muestra la síntesis de I-H descrita en el Ejemplo 6.Figure 6 shows the synthesis of I-H described in Example 6.
La preparación de estos compuestos se representa en la Fig. 1.The preparation of these compounds is represented in Fig. 1.
A una disolución 0.1 M del correspondiente \alpha, \beta ó \gamma-aminoácido (1 eq) en EtOH, se añaden 2-cloropirimidina (1.5 eq) y K_{2}CO_{3} (1 eq) y se mantiene agitando a temperatura ambiente durante 24 horas. La disolución se deja reposar y aparece un sólido que se filtra y se lava varias veces con acetona. El filtrado se concentra a vacío dando un sólido naranja. Este sólido se lava varias veces con AcOEt, se filtra y tras secarlo da lugar al producto deseado. Rto: 67-98%.At a 0.1 M solution of the corresponding α, β or γ-amino acid (1 eq) in EtOH, 2-chloropyrimidine (1.5 eq) and K 2 CO 3 (1 eq) and kept stirring at room temperature for 24 hours The solution is allowed to stand and a solid appears which is filtered and washed several times with acetone. The filtrate is concentrate in vacuo giving an orange solid. This solid is washed several times with AcOEt, it is filtered and after drying it results in desired product Rto: 67-98%.
Ácido N-(2-pirimidinil)aminoacético (I-A) N- (2-pyrimidinyl) aminoacetic acid (IA)
^{1}H-RMN (D_{2}O, 300 MHz, ppm): 8.05 (d, 2H, J 4.9, 2H-6); 6.50 (t, 1H, J 4.9, H-7); 3.66 (s, 2H, 2H-2).1 H-NMR (D 2 O, 300 MHz, ppm): 8.05 (d, 2H, J 4.9, 2H-6); 6.50 (t, 1H, J 4.9, H-7); 3.66 (s, 2H, 2H-2).
^{13}C-RMN (D_{2}O, 75 MHz, ppm): 178.4 (C-1); 161.3 (C-4), 158.5 (C-7), 111.0 (C-6), 45.0 (C-2).13 C-NMR (D 2 O, 75 MHz, ppm): 178.4 (C-1); 161.3 (C-4), 158.5 (C-7), 111.0 (C-6), 45.0 (C-2).
MS (ES): 154.1 (MH^{+}, 100).MS (ES): 154.1 (MH +, 100).
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Ácido N-(2-pirimidinil)aminopropionico (I-B) N- (2-pyrimidinyl) aminopropionic acid (IB)
^{1}H-RMN (D_{2}O, 300 MHz, ppm): 8.18 (d, 2H, J 5.0, 2H-7); 6.62 (t, 1H, J 5.0, H-8); 3.44 (t, 2H, J 6.9, 2H-3), 2.43 (t, 2H, J 6.9, 2H-2).1 H-NMR (D 2 O, 300 MHz, ppm): 8.18 (d, 2H, J 5.0, 2H-7); 6.62 (t, 1H, J 5.0, H-8); 3.44 (t, 2H, J 6.9, 2H-3), 2.43 (t, 2H, J 6.9, 2H-2).
^{13}C-RMN (D_{2}O, 75 MHz, ppm): 181.2 (C-1); 161.2 (C-5), 158.6 (C-7), 110.9 (C-6), 38.5 (C-2), 37.1 (C-3).13 C-NMR (D 2 O, 75 MHz, ppm): 181.2 (C-1); 161.2 (C-5), 158.6 (C-7), 110.9 (C-6), 38.5 (C-2), 37.1 (C-3).
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Ácido N-(2-pirimidinil)aminobutanoico (I-C). N- (2-pyrimidinyl) aminobutanoic acid (IC).
^{1}H-RMN (D_{2}O, 300 MHz, ppm): 8.22 (d, 2H, J 5.0, 2H-8); 6.64 (t, 1H, J 5.0, H-9); 3.26 (t, 2H, J 7.0, 2H-4); 2.21 (t, 2H, J 7.6, 2H-2); 1.80 (m, 2H, 2H-3).1 H-NMR (D 2 O, 300 MHz, ppm): 8.22 (d, 2H, J 5.0, 2H-8); 6.64 (t, 1H, J 5.0, H-9); 3.26 (t, 2H, J 7.0, 2H-4); 2.21 (t, 2H, J 7.6, 2H-2); 1.80 (m, 2H, 2H-3).
^{13}C-RMN (D_{2}O, 75 MHz, ppm): 183.3 (C-1); 161.5 (C-6), 158.7 (C-8), 110.7 (C-9), 41.1 (C-4), 35.2 (C-2), 25.7 (C-3).13 C-NMR (D 2 O, 75 MHz, ppm): 183.3 (C-1); 161.5 (C-6), 158.7 (C-8), 110.7 (C-9), 41.1 (C-4), 35.2 (C-2), 25.7 (C-3).
MS (ES): 182.1 (MH^{+}, 100).MS (ES): 182.1 (MH +, 100).
MS (ES): 202.1 (MH^{+}, 100).MS (ES): 202.1 (MH +, 100).
La preparación de este compuesto se representa en la Fig. 2.The preparation of this compound is represented in Fig. 2.
Se prepara una disolución del ácido pirazina-2-carboxílico (20 g, 0.16 mol) en H_{2}O (250 ml) y se añade una disolución 1M de KOH (250 ml). La mezcla se calienta hasta alcanzar la temperatura de 90ºC y se añade, en pequeñas porciones y con precaución, una amalgama de Al-Ni (77.2 g). Pasadas 24 h a dicha temperatura, la mezcla de reacción se lleva a temperatura ambiente y se filtra a través de Celite®. El filtrado obtenido se concentra a vacío para dar un sólido de color marrón que es triturado y lavado varias veces con metanol hasta obtener un sólido ligeramente coloreado (7.13 g, 0.05 mol, 34%).An acid solution is prepared pyrazine-2-carboxylic (20 g, 0.16 mol) in H2O (250 ml) and a 1M solution of KOH (250 is added ml) The mixture is heated to a temperature of 90 ° C and an amalgam of Al-Ni (77.2 g). After 24 hours at that temperature, the reaction mixture is brought to room temperature and filtered to through Celite®. The filtrate obtained is concentrated in vacuo to give a brown solid that is crushed and washed several times with methanol until a slightly colored solid is obtained (7.13 g, 0.05 mol, 34%).
^{1}H-RMN (D_{2}O, 300 MHz, ppm): 3.84 (dd, 1H, J 3.8 y 11.1, 1H-2); 3.70 (dd, 1H, J 3.8 y 13.8, 1H-3), 3.57-3.43 (m, 2H), 3.31-3.13 (m, 3H).1 H-NMR (D 2 O, 300 MHz, ppm): 3.84 (dd, 1H, J 3.8 and 11.1, 1H-2); 3.70 (dd, 1H, J 3.8 and 13.8, 1H-3), 3.57-3.43 (m, 2H), 3.31-3.13 (m, 3H).
^{13}C-RMN (D_{2}O, 75 MHz, ppm): 171.0 (C-1); 55.7 (C-2), 43.9, 40.9 y 40.8 (C-3, C-5 y C-6).13 C-NMR (D 2 O, 75 MHz, ppm): 171.0 (C-1); 55.7 (C-2), 43.9, 40.9 and 40.8 (C-3, C-5 and C-6).
La preparación de este compuesto se representa en la Fig. 3.The preparation of this compound is represented in Fig. 3.
Se prepara una disolución del ácido 2-bromoacético (10 g, 72.5 mmol, 1 eq) y piperazina (12.5 g, 145 mmol, 2 eq) en H_{2}O (50 ml). La disolución se mantiene agitando a temperatura ambiente durante 24 horas y después se elimina el disolvente a vacío dando un sólido ligeramente amarillo, que tras recristalizar en metanol dio el producto deseado como un sólido blanco. Rto: 87%.An acid solution is prepared 2-Bromoacetic acid (10 g, 72.5 mmol, 1 eq) and piperazine (12.5 g, 145 mmol, 2 eq) in H2O (50 ml). The solution is keep stirring at room temperature for 24 hours and then the solvent is removed in vacuo giving a solid slightly yellow, which after recrystallization from methanol gave the desired product Like a white solid Rto: 87%.
^{1}H-RMN (D_{2}O, 300 MHz, ppm): 2.96 (s, 2H, 2H-2); 2.77 (t, 4H, J 5.1, 4H-4); 2.47 (m, 4H, 4H-5).1 H-NMR (D 2 O, 300 MHz, ppm): 2.96 (s, 2H, 2H-2); 2.77 (t, 4H, J 5.1, 4H-4); 2.47 (m, 4H, 4H-5).
^{13}C-RMN (D_{2}O, 75 MHz, ppm): 177.8 (C-1); 62.1 (C-2), 52.8 (C-4), 44.1 (C-5).13 C-NMR (D 2 O, 75 MHz, ppm): 177.8 (C-1); 62.1 (C-2), 52.8 (C-4), 44.1 (C-5).
MS (ES): 145.0 (MH^{+}, 100).MS (ES): 145.0 (MH +, 100).
MS (CI): 157.1 (32), 144.1 (M^{+}, 6), 99.1 (45), 56.1 (100).MS (CI): 157.1 (32), 144.1 (M +, 6), 99.1 (45), 56.1 (100).
La preparación de este compuesto se representa en el esquema de la Fig. 4.The preparation of this compound is represented in the scheme of Fig. 4.
A una disolución del ácido 2-bromopropionico (35.2 g, 0.232 mol, 1 eq) en propanol (200 ml) se añade una disolución 1 M de piperazina (20 g, 0.232 mol, 1 eq) en propanol bajo agitación vigorosa. El precipitado formado se filtra, se lava sucesivamente con propanol y el filtrado obtenido se concentra a vacío dando el producto deseado como un sólido blanco. Rto: 87%.To a solution of the acid 2-bromopropionic (35.2 g, 0.232 mol, 1 eq) in Propanol (200 ml) is added a 1 M solution of piperazine (20 g, 0.232 mol, 1 eq) in propanol under vigorous stirring. The precipitate formed is filtered, washed successively with propanol and the filtrate obtained is concentrated in vacuo giving the desired product as a white solid Rto: 87%.
^{1}H-RMN (DMSO, 300 MHz, ppm): 7.50 (brs, 1H, CO_{2}H); 3.29 (q, 1H, J 7.1, 1H-2); 3.05 (m, 2H, 2H-5), 2.79 (m, 2H, 2H-4), 1.17 (d, 3H, J 7.1, CH_{3}).1 H-NMR (DMSO, 300 MHz, ppm): 7.50 (brs, 1H, CO2H); 3.29 (q, 1H, J 7.1, 1H-2); 3.05 (m, 2H, 2H-5), 2.79 (m, 2H, 2H-4), 1.17 (d, 3H, J 7.1, CH 3).
^{13}C-RMN (DMSO, 75 MHz, ppm): 173.3 (C-1); 61.2 (C-2), 45.3, 43.2 and 42.3 (C-4 y C-5), 14.1 (CH_{3}).13 C-NMR (DMSO, 75 MHz, ppm): 173.3 (C-1); 61.2 (C-2), 45.3, 43.2 and 42.3 (C-4 and C-5), 14.1 (CH 3).
MS (ES): 231.1 (25), 159.1 (MH^{+}, 100).MS (ES): 231.1 (25), 159.1 (MH +, 100).
MS (CI): 185.1 (36), 158.1 (M^{+}, 6), 113.1 (100), 56.1 (48).MS (CI): 185.1 (36), 158.1 (M +, 6), 113.1 (100), 56.1 (48).
La preparación de este compuesto se representa en la Fig.5.The preparation of this compound is represented in Fig. 5.
Se prepara una disolución en MeOH (150 ml) del ácido 2-bromoacético (10 g, 0.071 mol, 1 eq) y 1-(2-aminoetilpiperazina) (14 ml, 0.107 mol, 1.5 eq) en presencia de Na_{2}CO_{3} (15.8 g, 0.149 mol, 2.1 eq). La disolución se mantiene a reflujo durante 24 horas y posteriormente el precipitado formado se filtra lavando con MeOH. La eliminación del disolvente a vacío y posterior cristalización en CHCl_{3}, dio un sólido ligeramente amarillo. Rto: 55%.A solution in MeOH (150 ml) of the 2-Bromoacetic acid (10 g, 0.071 mol, 1 eq) and 1- (2-aminoethylpiperazine) (14 ml, 0.107 mol, 1.5 eq) in the presence of Na2CO3 (15.8 g, 0.149 mol, 2.1 eq). The solution is refluxed for 24 hours and subsequently The precipitate formed is filtered by washing with MeOH. The elimination of the solvent in vacuo and subsequent crystallization in CHCl3, gave a slightly yellow solid. Rto: 55%.
^{1}H-RMN (D_{2}O, 300 MHz, ppm): 2.99 (t, 1H, J 6.9); 2.84 (s, 2H, 2H-2); 2.72 (t, 1H, J 7.2); 2.39-2.30 (m, 10H).1 H-NMR (D 2 O, 300 MHz, ppm): 2.99 (t, 1H, J 6.9); 2.84 (s, 2H, 2H-2); 2.72 (t, 1H, J 7.2); 2.39-2.30 (m, 10H).
^{13}C-RMN (D_{2}O, 75 MHz, ppm): 177.5 (C-1), 61.6 (C-2), 57.4 (C-11), 51.9 (C-5), 38.0 (C-3), 36.7 (C-2).13 C-NMR (D 2 O, 75 MHz, ppm): 177.5 (C-1), 61.6 (C-2), 57.4 (C-11), 51.9 (C-5), 38.0 (C-3), 36.7 (C-2).
MS (ES): 188.1 (MH^{+}, 100).MS (ES): 188.1 (MH +, 100).
La preparación de este compuesto se representa en la Fig. 6.The preparation of this compound is represented in Fig. 6.
En un matraz bajo atmósfera de nitrógeno se
ponen acrilato de metilo (10 g, 0.12 mol, 10.5 ml, 1 eq),
LiClO_{4} (12.8 g, 0.12 mol, 1 eq) y
2,5-dimetilpiperazina (20.5 g, 0.18 mol, 1.5 eq) la
mezcla se mantiene agitando a temperatura ambiente durante 2 h.
Pasado ese tiempo se añade CH_{2}Cl_{2}, se filtra el
LiClO_{4}, y una vez evaporado el disolvente se purifica mediante
columna cromatográfica (Acetona:MeOH 50%) dando el producto deseado
como un aceite. Rto: 77%. Este producto intermedio se usó como tal
en el siguiente paso. Para ello, se disuelve en MeOH (180 ml), y se
calienta a reflujo durante 3 h en una disolución 1 N de NaOH (230
ml, 0.23 mol, 2.5 eq). La cristalización en acetona lleva
a
la obtención del ácido
3-(2,5-dimetil-1-piperazinil)aminopropiónico
como un sólido ligeramente amarillo. Rto: 98%.In a flask under nitrogen atmosphere, methyl acrylate (10 g, 0.12 mol, 10.5 ml, 1 eq), LiClO 4 (12.8 g, 0.12 mol, 1 eq) and 2,5-dimethylpiperazine (20.5 g, 0.18 mol, 1.5 eq) the mixture is kept stirring at room temperature for 2 h. After that time, CH 2 Cl 2 is added, the LiClO 4 is filtered, and once the solvent has evaporated, it is purified by chromatographic column (Acetone: 50% MeOH) to give the desired product as an oil. Rto: 77%. This intermediate product was used as such in the next step. For this, it is dissolved in MeOH (180 ml), and heated at reflux for 3 h in a 1 N solution of NaOH (230 ml, 0.23 mol, 2.5 eq). Crystallization in acetone leads
to obtain 3- (2,5-dimethyl-1-piperazinyl) aminopropionic acid as a slightly yellow solid. Rto: 98%.
^{1}H-RMN (D_{2}O, 300 MHz, ppm): 3.84-346 (m, 5H, 1H-8, 1H-6n, 1H-9 y 2H-3); 3.26 (dd, 1H, J 6.6 y 20, 1H-5); 3.24 (dd, 1H, J 12.9 y 20, 1H-5); 3.07 (dt, 1H, J 12.9 y 1.7); 1.36 (d, 3H, J 6.3, 3H-10 ó 3H-11); 1.26 (d, 3H, J 6.3, 3H-10 ó 3H-11).1 H-NMR (D 2 O, 300 MHz, ppm): 3.84-346 (m, 5H, 1H-8, 1H-6n, 1H-9 and 2H-3); 3.26 (dd, 1H, J 6.6 and 20, 1H-5); 3.24 (dd, 1H, J 12.9 and 20, 1H-5); 3.07 (dt, 1H, J 12.9 and 1.7); 1.36 (d, 3H, J 6.3, 3H-10 or 3H-11); 1.26 (d, 3H, J 6.3, 3H-10 or 3H-11).
^{13}C-RMN (D_{2}O, 75 MHz, ppm): 173.9 (C-1), 56.7 (C-5), 53.3 (C-9), 48.9 (C-6), 48.7 (C-8), 45.6 (C-3), 28.9 (C-2), 15.1 (C-10 ó C-11), 13.7 (C-10 ó C-11).13 C-NMR (D 2 O, 75 MHz, ppm): 173.9 (C-1), 56.7 (C-5), 53.3 (C-9), 48.9 (C-6), 48.7 (C-8), 45.6 (C-3), 28.9 (C-2), 15.1 (C-10 or C-11), 13.7 (C-10 or C-11).
MS (ES): 259.1 (100), 188.1 (MH^{+}, 82).MS (ES): 259.1 (100), 188.1 (MH +, 82).
La capacidad de absorción de los compuestos de fórmula general I contenidos en la presente invención, se investigó mediante el uso del método descrito ampliamente por Derks et al. en su trabajo "Solubility of Carbon Dioxide in Aqueous Piperazine Solutions", AIChE Journal, Vol. 51, Nº 8.The absorption capacity of the compounds of general formula I contained in the present invention was investigated by using the method described extensively by Derks et al . in his work "Solubility of Carbon Dioxide in Aqueous Piperazine Solutions", AIChE Journal, Vol. 51, No. 8.
El líquido absorbente consiste en una disolución 1 M de un único compuesto seleccionado del grupo con fórmula general I, disuelto en agua desionizada y tratado con una cantidad equimolecular de KOH.The absorbent liquid consists of a solution 1 M of a single compound selected from the group with formula general I, dissolved in deionized water and treated with an amount equimolecular of KOH.
Las disoluciones acuosas de MEA aquí incluidas para establecer una comparación, fueron preparadas disolviendo la amina en agua desionizada. Todas las medidas de absorción fueron realizadas a 20ºC. El proceso de regeneración fue realizado calentando la disolución a 85ºC y pasando una corriente de nitrógeno durante 1 hora. Las disoluciones fueron enfriadas a 20ºC antes de llevar a cabo una nueva medida de absorción.The aqueous solutions of MEA included here to establish a comparison, they were prepared by dissolving the Amine in deionized water. All absorption measures were made at 20 ° C. The regeneration process was performed by heating the solution at 85 ° C and passing a stream of nitrogen for 1 hour. The solutions were cooled to 20 ° C before carry out a new absorption measure.
En la Tabla 1 se muestran los valores de la capacidad de absorción de CO_{2} obtenidos después de la primera regeneración.Table 1 shows the values of the CO2 absorption capacity obtained after the first regeneration.
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De los datos recogidos en la Tabla 1 se puede observar que aquellos absorbentes líquidos compuestos por una disolución acuosa de los compuestos I-D, I-E, I-G y I-H presentan mayor capacidad de absorción de CO_{2} por mol que cuando el absorbente es MEA.From the data collected in Table 1 you can observe that those liquid absorbents composed of a aqueous solution of the compounds I-D, I-E, I-G and I-H have a greater capacity of CO2 absorption per mole than when the absorbent is MEA.
Claims (10)
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BRECKENRIDGE, R. y col. Inhibition of [3H] GABA binding to postsynaptic receptors in human cerebellar synaptic membranes by carboxyl and amino derivatives of GABA. Journal of Neurochemistry. 1981, Vol. 37, Nº 4, páginas 837-844, ISSN: 0022-3042. Base de datos HCAPLUS. Recuperado de: STN International, Columbus, Ohio (EE.UU.) Nº de acceso 95:197890. Resumen. Compuesto con RN 79858-46-1. * |
BROWN, H.W.y col. Efficacy of piperazine compounds against Syphacia obvelata, a pinworm of mice. American Journal of Tropical Medicine and Hygiene. 1954, Vol. 3, páginas 504-510, ISSN 0002-9637. Base de datos HCAPLUS. Recuperado de: STN International, Columbus, Ohio (EE.UU.) Nº de acceso 1954:50320. Resumen. Compuesto con RN 825594-88-5. * |
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LARSEN, SCOTT D. y col. Synthesis and biological activity of the antidiabetic/antiobesity agent 3-guanidinopropionic acid: discovery of a novel aminoguanidinoacetic acid antidiabetic agent. Journal of Medicinal Chemistry. 2001, Vol. 44, Nº 8, páginas 1217-1230, ISSN 0022-2623. Base de datos HCAPLUS. Recuperado de: STN International, Columbus, Ohio (EE.UU.) Nº de acceso 2001:353113. Resumen. Compuesto con RN 339195-50-5. * |
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