JP2011194388A - Aqueous solution which effectively absorbs and recovers carbon dioxide contained in gas - Google Patents
Aqueous solution which effectively absorbs and recovers carbon dioxide contained in gas Download PDFInfo
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- JP2011194388A JP2011194388A JP2010067480A JP2010067480A JP2011194388A JP 2011194388 A JP2011194388 A JP 2011194388A JP 2010067480 A JP2010067480 A JP 2010067480A JP 2010067480 A JP2010067480 A JP 2010067480A JP 2011194388 A JP2011194388 A JP 2011194388A
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- Prior art keywords
- carbon dioxide
- aqueous solution
- absorption
- reaction
- propanol
- Prior art date
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 282
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 141
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 141
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 82
- 238000010521 absorption reaction Methods 0.000 claims abstract description 75
- -1 amine compound Chemical class 0.000 claims abstract description 38
- 238000011084 recovery Methods 0.000 claims abstract description 27
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 30
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 24
- FBXBSCUQZWUZDD-UHFFFAOYSA-N 3-(ethylamino)propan-1-ol Chemical compound CCNCCCO FBXBSCUQZWUZDD-UHFFFAOYSA-N 0.000 claims description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N 1-propanol Substances CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 9
- RILLZYSZSDGYGV-UHFFFAOYSA-N 2-(propan-2-ylamino)ethanol Chemical compound CC(C)NCCO RILLZYSZSDGYGV-UHFFFAOYSA-N 0.000 claims description 9
- PVNNOLUAMRODAC-UHFFFAOYSA-N 4-(ethylamino)butan-1-ol Chemical compound CCNCCCCO PVNNOLUAMRODAC-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- KZTWONRVIPPDKH-UHFFFAOYSA-N 2-(piperidin-1-yl)ethanol Chemical compound OCCN1CCCCC1 KZTWONRVIPPDKH-UHFFFAOYSA-N 0.000 claims description 6
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 claims description 5
- KRGXWTOLFOPIKV-UHFFFAOYSA-N 3-(methylamino)propan-1-ol Chemical compound CNCCCO KRGXWTOLFOPIKV-UHFFFAOYSA-N 0.000 claims description 4
- MGRXNAJUQKEJJB-UHFFFAOYSA-N 4-(propylamino)butan-1-ol Chemical compound CCCNCCCCO MGRXNAJUQKEJJB-UHFFFAOYSA-N 0.000 claims description 4
- VBDTYFWEVNRBAZ-UHFFFAOYSA-N 1-(butylamino)propan-1-ol Chemical compound CCCCNC(O)CC VBDTYFWEVNRBAZ-UHFFFAOYSA-N 0.000 claims description 3
- IFNWESYYDINUHV-UHFFFAOYSA-N 2,6-dimethylpiperazine Chemical compound CC1CNCC(C)N1 IFNWESYYDINUHV-UHFFFAOYSA-N 0.000 claims description 3
- BCLSJHWBDUYDTR-UHFFFAOYSA-N 2-(propylamino)ethanol Chemical compound CCCNCCO BCLSJHWBDUYDTR-UHFFFAOYSA-N 0.000 claims description 3
- VKBVRNHODPFVHK-UHFFFAOYSA-N 2-[2-(diethylamino)ethoxy]ethanol Chemical compound CCN(CC)CCOCCO VKBVRNHODPFVHK-UHFFFAOYSA-N 0.000 claims description 3
- YSAANLSYLSUVHB-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]ethanol Chemical compound CN(C)CCOCCO YSAANLSYLSUVHB-UHFFFAOYSA-N 0.000 claims description 3
- VVBMMWYCAMYUSW-UHFFFAOYSA-N 3-(propylamino)propan-1-ol Chemical compound CCCNCCCO VVBMMWYCAMYUSW-UHFFFAOYSA-N 0.000 claims description 3
- OPUJAKVDYGQVHP-UHFFFAOYSA-N 4-(butylamino)butan-1-ol Chemical compound CCCCNCCCCO OPUJAKVDYGQVHP-UHFFFAOYSA-N 0.000 claims description 3
- QCTOLMMTYSGTDA-UHFFFAOYSA-N 4-(dimethylamino)butan-1-ol Chemical compound CN(C)CCCCO QCTOLMMTYSGTDA-UHFFFAOYSA-N 0.000 claims description 3
- DBKSSENEKWOVKL-UHFFFAOYSA-N 4-(methylamino)butan-1-ol Chemical compound CNCCCCO DBKSSENEKWOVKL-UHFFFAOYSA-N 0.000 claims description 3
- UEXRIBOEINFZJS-UHFFFAOYSA-N 5-(propan-2-ylamino)pentan-1-ol Chemical compound CC(C)NCCCCCO UEXRIBOEINFZJS-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 66
- 239000000243 solution Substances 0.000 abstract description 9
- 229960004424 carbon dioxide Drugs 0.000 description 128
- 239000007789 gas Substances 0.000 description 31
- 150000001412 amines Chemical class 0.000 description 29
- 238000003795 desorption Methods 0.000 description 21
- 125000003158 alcohol group Chemical group 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 230000007704 transition Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 150000003335 secondary amines Chemical class 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 6
- 239000002250 absorbent Substances 0.000 description 6
- 230000002745 absorbent Effects 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 150000003512 tertiary amines Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 5
- 150000003141 primary amines Chemical group 0.000 description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229940044613 1-propanol Drugs 0.000 description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 229940043276 diisopropanolamine Drugs 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229960005335 propanol Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- VKKTUDKKYOOLGG-UHFFFAOYSA-N 1-(diethylamino)propan-1-ol Chemical compound CCC(O)N(CC)CC VKKTUDKKYOOLGG-UHFFFAOYSA-N 0.000 description 1
- VSYGKZKULIGNSA-UHFFFAOYSA-N 1-(propan-2-ylamino)butan-2-ol Chemical group CCC(O)CNC(C)C VSYGKZKULIGNSA-UHFFFAOYSA-N 0.000 description 1
- NFQKYETWLZATMO-UHFFFAOYSA-N 1-aminoheptan-1-ol Chemical compound CCCCCCC(N)O NFQKYETWLZATMO-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- MXZROAOUCUVNHX-UHFFFAOYSA-N 2-Aminopropanol Chemical compound CCC(N)O MXZROAOUCUVNHX-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 1
- PQSKSJLILUQYQM-UHFFFAOYSA-N 3-(butylamino)propan-1-ol Chemical compound CCCCNCCCO PQSKSJLILUQYQM-UHFFFAOYSA-N 0.000 description 1
- WKCYFSZDBICRKL-UHFFFAOYSA-N 3-(diethylamino)propan-1-ol Chemical compound CCN(CC)CCCO WKCYFSZDBICRKL-UHFFFAOYSA-N 0.000 description 1
- PYSGFFTXMUWEOT-UHFFFAOYSA-N 3-(dimethylamino)propan-1-ol Chemical compound CN(C)CCCO PYSGFFTXMUWEOT-UHFFFAOYSA-N 0.000 description 1
- GZCPWFOPXIDRDP-UHFFFAOYSA-N 3-(propan-2-ylamino)propan-1-ol Chemical compound CC(C)NCCCO GZCPWFOPXIDRDP-UHFFFAOYSA-N 0.000 description 1
- KHYKXDSWXWVQTA-UHFFFAOYSA-N 4-(diethylamino)butan-1-ol Chemical compound CCN(CC)CCCCO KHYKXDSWXWVQTA-UHFFFAOYSA-N 0.000 description 1
- IPLWOCGPIGUXOR-UHFFFAOYSA-N 4-(propan-2-ylamino)butan-1-ol Chemical compound CC(C)NCCCCO IPLWOCGPIGUXOR-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
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- 239000004202 carbamide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
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Classifications
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- 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
Abstract
Description
本発明は、ガス中に含まれる二酸化炭素（CO2）を吸収及び回収するための水溶液に関するものである。更に、当該水溶液を使用した二酸化炭素の吸収及び回収方法に関する。 The present invention relates to an aqueous solution for absorbing and recovering carbon dioxide (CO 2 ) contained in a gas. Furthermore, the present invention relates to a method for absorbing and recovering carbon dioxide using the aqueous solution.
近年、地球温暖化に起因すると考えられる気象変動や災害の頻発が、農業生産、住環境、エネルギー消費等に多大の影響を及ぼしている。この地球温暖化は、人間の活動が活発になることに付随して増大する二酸化炭素、メタン、亜酸化窒素、フロン等の温室効果ガスが大気中に増大するためであると考えられている。その温室効果ガスの中で最も主要なものとして、大気中の二酸化炭素があげられており、二酸化炭素放出量の削減に向けての対策が緊急に必要となっている。 In recent years, meteorological fluctuations and frequent disasters that are thought to be caused by global warming have greatly affected agricultural production, living environment, energy consumption, and the like. This global warming is considered to be due to an increase in the atmosphere of greenhouse gases such as carbon dioxide, methane, nitrous oxide, and chlorofluorocarbon, which increase with the increase of human activities. The most important greenhouse gas is carbon dioxide in the atmosphere, and there is an urgent need for measures to reduce carbon dioxide emissions.
二酸化炭素の発生源としては石炭、重油、天然ガス等を燃料とする火力発電所、製造所のボイラーあるいはセメント工場のキルン、コークスで酸化鉄を還元する製鐵所の高炉、そしてガソリン、重油、軽油等を燃料とする自動車、船舶、航空機等の輸送機器などがある。これらのうち輸送機器を除くものについては固定的な設備であり、二酸化炭素の放出を削減する対策を施しやすい設備として期待されている。近年、大規模な二酸化炭素の発生源からの二酸化炭素の削減方法としてCCS技術(Carbondioxide Capture & Storage)の開発が進められているが、この場合の発生コストの60%多くが二酸化炭素の回収工程より発生しており、CCS技術の実現の為にも低コストでの二酸化炭素の回収技術の開発が望まれている。 Sources of carbon dioxide include coal, heavy oil, natural gas and other thermal power plants, factory boilers or kilns in cement plants, blast furnace blast furnaces that reduce iron oxide with coke, gasoline, heavy oil, There are transportation equipment such as automobiles, ships, and aircraft that use light oil as fuel. Of these, those other than transportation equipment are fixed facilities, and are expected to be easy to implement measures to reduce carbon dioxide emissions. In recent years, CCS technology (Carbondioxide Capture & Storage) has been developed as a method for reducing carbon dioxide from large-scale carbon dioxide sources. Development of carbon dioxide recovery technology at low cost is also desired in order to realize CCS technology.
ガス中の二酸化炭素を回収する方法としてはこれまでもいくつかの方法が知られている。そしてまた現在も広く種々の方法が研究されている。 Several methods have been known so far for recovering carbon dioxide in gas. And now, various methods are widely studied.
例えば、二酸化炭素を含むガスを吸収塔内でアルカノールアミン水溶液と接触させて二酸化炭素を吸収させた後、その二酸化炭素回収用水溶液を加熱して脱離塔で二酸化炭素を脱離回収させる方法は、1930年代から開発され、尿素合成プラント等で実用化されている。この方法は、経済的でありかつ大型化しやすいものである。 For example, after a gas containing carbon dioxide is brought into contact with an alkanolamine aqueous solution in an absorption tower to absorb carbon dioxide, the carbon dioxide recovery aqueous solution is heated to desorb and recover carbon dioxide in the desorption tower. Developed since the 1930s and put into practical use at urea synthesis plants. This method is economical and easy to enlarge.
ここでアルカノールアミンとしては、モノエタノールアミン（MEA）、ジエタノールアミン（DEA）、トリエタノールアミン（TEA）、メチルジエタノールアミン（MDEA）、ジイソプロパノールアミン（DIPA）、ジグリコールアミン（DGA）等が知られているが、通常MEAが用いられている。 Here, monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), methyldiethanolamine (MDEA), diisopropanolamine (DIPA), diglycolamine (DGA), etc. are known as alkanolamines. Usually, MEA is used.
しかし、これらのアルカノールアミンの水溶液を吸収液として用いた場合、装置材質の腐食性が高いため、装置に高価な耐食鋼を用いる必要があったり、吸収液中のアミン濃度を下げる必要がある。また、吸収した二酸化炭素が脱離しにくいために、１２０℃と高い温度に加熱して脱離、回収する必要があった。また、それとは別に二酸化炭素を吸収液から脱離するのに必要なエネルギーが、80 kJ/molCO2と高いという欠点もある。例えば、この方法を用いて発電所において二酸化炭素を回収するには、発電量の２０％にもあたる余分なエネルギーが必要となってしまう。二酸化炭素の発生の削減、省エネルギー及び省資源が求められる時代においては、この高エネルギー消費は二酸化炭素吸収、回収設備の実用化を阻む大きな要因となっている。 However, when an aqueous solution of these alkanolamines is used as the absorbing solution, the corrosiveness of the device material is high, and therefore it is necessary to use expensive corrosion-resistant steel for the device or to reduce the amine concentration in the absorbing solution. Further, since the absorbed carbon dioxide is difficult to desorb, it is necessary to desorb and recover by heating to a high temperature of 120 ° C. In addition, the energy required for desorbing carbon dioxide from the absorbing solution is also high at 80 kJ / mol CO 2 . For example, in order to collect carbon dioxide at a power plant using this method, extra energy equivalent to 20% of the power generation amount is required. In an era where reduction of carbon dioxide generation, energy saving and resource saving are required, this high energy consumption is a major factor that impedes the practical use of carbon dioxide absorption and recovery equipment.
例えば、特許文献１には、アミノ基周辺にアルキル基等の立体障害があるいわゆるヒンダードアミンの水溶液と大気圧下の燃焼排ガスとを接触させ、当該水溶液に二酸化炭素を吸収させることによる、燃料排ガス中の二酸化炭素の除去方法が記載されている。 For example, in Patent Document 1, a so-called hindered amine aqueous solution having a steric hindrance such as an alkyl group around an amino group is brought into contact with combustion exhaust gas under atmospheric pressure, and carbon dioxide is absorbed in the aqueous solution. A method for removing carbon dioxide is described.
当該特許文献１には、ヒンダードアミンとして２−メチルアミノエタノール（ＭＡＥ）及び２−エチルアミノエタノール（ＥＡＥ）の実施例が記され、ＭＡＥ及びＥＡＥの水溶液が、二酸化炭素の吸収に好ましいと記載されている。 The patent document 1 describes examples of 2-methylaminoethanol (MAE) and 2-ethylaminoethanol (EAE) as hindered amines, and describes that an aqueous solution of MAE and EAE is preferable for absorption of carbon dioxide. Yes.
特許文献２には、アミン水溶液と混合ガスとを接触させて二酸化炭素を吸収する工程及び当該水溶液から二酸化炭素を脱離する工程を含む二酸化炭素の回収方法が記載されており、そこでは、アミン水溶液として、２級もしくは３級炭素と結合した２級アミノ基又は３級炭素と結合した１級アミンを有する化合物、例えば、２−メチルピペラジン（2MPZ）、２−アミノ−２-メチル−１−プロパノール（AMP）等が記載されている。 Patent Document 2 describes a method for recovering carbon dioxide, which includes a step of bringing an aqueous amine solution into contact with a mixed gas to absorb carbon dioxide and a step of desorbing carbon dioxide from the aqueous solution. As an aqueous solution, a compound having a secondary amino group bonded to a secondary or tertiary carbon or a primary amine bonded to a tertiary carbon, such as 2-methylpiperazine (2MPZ), 2-amino-2-methyl-1- Propanol (AMP) and the like are described.
特許文献３には、吸収液の成分として分子内に1級、2級、3級の窒素を2つ以上又はすべてを有するアミン化合物を含む混合物が例示されており、1-(2-アミノエチル)ピペラジン、(1-メチル)(2-アミノ)-(5メチルアミノ)ピロリジン等が例示されている。 Patent Document 3 exemplifies a mixture containing an amine compound having two or more primary, secondary, and tertiary nitrogen atoms in the molecule as a component of the absorbing solution, and 1- (2-aminoethyl Examples include piperazine, (1-methyl) (2-amino)-(5methylamino) pyrrolidine, and the like.
特許文献４には、第3級アルカノールアミンと第2級アルカノールアミンの混合物を使用する、流体から酸性ガスを除去するための吸収剤が記載され、メチルジエタノールアミンとヒドロキシエチルピペラジンを有する組成が例示されている。 Patent Document 4 describes an absorbent for removing acid gas from a fluid using a mixture of a tertiary alkanolamine and a secondary alkanolamine, and illustrates a composition having methyldiethanolamine and hydroxyethylpiperazine. ing.
二酸化炭素の回収方法は、排ガス中からの二酸化炭素の除去、すなわち水溶液への二酸化炭素の吸収工程、及び二酸化炭素を吸収した水溶液からの二酸化炭素の脱離工程が高効率に行われ、その間の二酸化炭素回収に消費される回収エネルギーが低いことが要求されており、これを達成させる吸収液の開発が重要である。 In the method for recovering carbon dioxide, the removal of carbon dioxide from the exhaust gas, that is, the absorption process of carbon dioxide into the aqueous solution and the desorption process of carbon dioxide from the aqueous solution that absorbed carbon dioxide are performed with high efficiency. The recovery energy consumed for carbon dioxide recovery is required to be low, and it is important to develop an absorbent that can achieve this.
これまでの吸収液でのCO2回収エネルギーのレベルは経済性視点からみてまだ不充分であり大きな課題になっていると言わざるを得ない。特に回収エネルギーの大きな部分を占める二酸化炭素とアミン成分との反応に関する反応熱は、低減が難しくその開発には多くの努力がなされてきた。 It must be said that the level of CO 2 recovery energy in the absorbent so far is still insufficient from an economic point of view and is a major issue. In particular, it has been difficult to reduce the heat of reaction related to the reaction between carbon dioxide, which accounts for a large portion of the recovered energy, and the amine component, and many efforts have been made to develop it.
前述の様に各種の二酸化炭素を含むガスから二酸化炭素を効率よく回収する吸収液の開発が望まれており、特に二酸化炭素を吸収及び脱離して回収する際の単位重量当たりに必要な回収エネルギーが低い吸収液の開発が大きな課題である。 As described above, the development of an absorbing solution that efficiently recovers carbon dioxide from various carbon dioxide-containing gases is desired. In particular, the energy required per unit weight when recovering by absorbing and desorbing carbon dioxide. The development of a low absorption liquid is a major issue.
回収エネルギーの低減に必要な吸収液に求められる基本性能には、低反応熱、吸収・脱離工程間での高いローディング差、高い吸収速度等が挙げられるがそれぞれの性能間にはトレードオフの関係があることが知られており単一のアミン化合物ですべてを満たすことは難しく、実用上は特定の性能に優れる化合物を複数種組み合わせて吸収液の総合性能を調整する処方が取られてきている。例えば反応熱と吸収速度では、回収エネルギーの低減に有利な低反応熱アミンは吸収速度が遅く実用上に問題が生じる。その結果、各種の基本性能の優れたアミンを開発し、吸収液全体の性能を設計し、全体としての回収エネルギーを低減することが必要となる。 The basic performance required for the absorption liquid required to reduce the recovery energy includes low reaction heat, high loading difference between absorption and desorption processes, high absorption rate, etc., but there is a trade-off between each performance. It is known that there is a relationship, and it is difficult to satisfy all with a single amine compound, and in practice, a formulation that adjusts the overall performance of the absorbent by combining multiple types of compounds that excel in specific performance has been taken Yes. For example, with regard to the heat of reaction and the absorption rate, a low-reaction heat amine that is advantageous for reducing the recovered energy has a slow absorption rate and causes a practical problem. As a result, it is necessary to develop amines with various basic performances, design the performance of the entire absorbent, and reduce the overall recovery energy.
以上の従来技術の問題点に鑑み、本発明は、ガス中二酸化炭素の吸収及び回収を高効率に行う為、低い回収エネルギーで二酸化炭素を回収できる水溶液を提供することを目的とする。具体的には、二酸化炭素との反応熱が低く、吸収速度の高いアミン化合物を含むことにより、二酸化炭素の吸収及び回収に要する全体の回収エネルギーを低下させ高純度の二酸化炭素を低コストで回収できる水溶液を提供することを目的とするものである。 In view of the above problems of the prior art, an object of the present invention is to provide an aqueous solution capable of recovering carbon dioxide with low recovery energy in order to efficiently absorb and recover carbon dioxide in a gas. Specifically, by containing an amine compound that has a low heat of reaction with carbon dioxide and a high absorption rate, the overall recovery energy required for absorption and recovery of carbon dioxide is reduced, and high-purity carbon dioxide is recovered at low cost. It aims at providing the aqueous solution which can be performed.
本発明者らは、上記課題を解決するために、鋭意研究した結果、一般式〔１〕で表される第2級アミン化合物の二酸化炭素との反応速度が従来の第2級アミンより高いことを見出した。前述のように吸収に用いるアミンの性能を特徴付ける反応熱、反応速度、吸収量、脱離量の各性能はトレードオフの関係があり、一般的には吸収速度が速いアミンは反応熱が増大する欠点を持つが、本発明による第2級アミンは、驚くべきことにこれらの性能低下が小さく従来には無い特性を持つものであり、従来のトレードオフの関係に縛られない優れた性能を持つことがわかった。この二酸化炭素とアミン化合物の反応熱の低下及び吸収速度の向上は、結果として二酸化炭素の脱離時に加える熱エネルギーの低減に繋がり二酸化炭素回収における全体の回収エネルギーの低減を可能とし本発明の課題を解決するものである。 As a result of intensive studies to solve the above problems, the present inventors have found that the reaction rate of the secondary amine compound represented by the general formula [1] with carbon dioxide is higher than that of the conventional secondary amine. I found. As described above, the reaction heat, reaction rate, absorption amount, and desorption amount performance that characterize the performance of the amine used for absorption are in a trade-off relationship. Generally, an amine with a high absorption rate increases the heat of reaction. Despite the disadvantages, the secondary amines according to the present invention have surprisingly small performance degradation and unprecedented characteristics, and have excellent performance that is not bound by conventional trade-off relationships. I understood it. This reduction in the heat of reaction and improvement in the absorption rate of carbon dioxide and an amine compound result in a reduction in the thermal energy applied during the desorption of carbon dioxide, which makes it possible to reduce the overall recovery energy in carbon dioxide recovery. Is a solution.
本発明の化合物〔1〕を主成分とする水溶液、並びに化合物〔1〕を1部として含み且つ他のアルカノールアミン化合物及び／又はピペラジン化合物を含む水溶液は、二酸化炭素を工業的、経済的に回収するために要請される吸収速度を持ちなおかつ全体の回収エネルギーが従来より小さいという優れた性能を持つことを見出した。かかる知見に基づき、更に研究を重ねた結果、本発明を完成するに至った。 An aqueous solution containing the compound [1] of the present invention as a main component, and an aqueous solution containing the compound [1] as one part and containing another alkanolamine compound and / or piperazine compound, recovers carbon dioxide industrially and economically. It has been found that it has an excellent performance that it has the absorption rate required to achieve this, and the total recovered energy is smaller than the conventional one. As a result of further research based on this knowledge, the present invention has been completed.
即ち、本発明は以下の項１から項７の構成をなすものである。 That is, the present invention comprises the following items 1 to 7.
項１．二酸化炭素を含むガスから二酸化炭素を吸収及び回収するための水溶液であって、一般式〔1〕で表される第2級アミン化合物を少なくとも1種含むことを特徴とする水溶液。
一般式〔1〕：
R-NH-(CH2)n-OH
(式中、Rは炭素数1〜4の直鎖状又は分枝鎖状のアルキル基を表し、nは3〜5から選ばれる。)
Item 1. An aqueous solution for absorbing and recovering carbon dioxide from a gas containing carbon dioxide, wherein the aqueous solution contains at least one secondary amine compound represented by the general formula [1].
General formula [1]:
R-NH- (CH 2 ) n -OH
(In the formula, R represents a linear or branched alkyl group having 1 to 4 carbon atoms, and n is selected from 3 to 5.)
項２．前記第2級アミン化合物以外の第2級又は第3級アルカノールアミン化合物をさらに含むことを特徴とする、項１に記載の水溶液。 Item 2. Item 2. The aqueous solution according to Item 1, further comprising a secondary or tertiary alkanolamine compound other than the secondary amine compound.
項３．ピペラジン化合物をさらに含むことを特徴とする、項１又は２に記載の水溶液。 Item 3. Item 3. The aqueous solution according to Item 1 or 2, further comprising a piperazine compound.
項４． 前記一般式〔1〕で表される第2級アミン化合物が、3-メチルアミノ-1-プロパノール、3-エチルアミノ-1-プロパノール、3-n-プロピルアミノ-1-プロパノール、3-イソプロピルアミノ-1-プロパノール、4-n-ブチルアミノ-1-プロパノール、4-メチルアミノ-1-ブタノール、4-エチルアミノ-1-ブタノール、4-n-プロピルアミノ-1-ブタノール、4-イソプロピルアミノ-1-ブタノール、4-n-ブチルアミノ-1-ブタノール、及び5-イソプロピルアミノ-1-ペンタノールからなる群から選択されることを特徴とする、項１〜３のいずれかに記載の水溶液。 Item 4. The secondary amine compound represented by the general formula [1] is 3-methylamino-1-propanol, 3-ethylamino-1-propanol, 3-n-propylamino-1-propanol, 3-isopropylamino. -1-propanol, 4-n-butylamino-1-propanol, 4-methylamino-1-butanol, 4-ethylamino-1-butanol, 4-n-propylamino-1-butanol, 4-isopropylamino- Item 4. The aqueous solution according to any one of Items 1 to 3, which is selected from the group consisting of 1-butanol, 4-n-butylamino-1-butanol, and 5-isopropylamino-1-pentanol.
項５．前記第2級又は第3級アルカノールアミン化合物が、2-(イソプロピルアミノ)エタノール、2-(エチルアミノ)エタノール、2-(n-プロピルアミノ)エタノール、1-(2-ヒドロキシエチル)ピペリジン、3-(ジメチルアミノ)プロパノール、4-(ジメチルアミノ)ブタノール、2-(2-ジエチルアミノエトキシ)エタノール、及び2-(2-ジメチルアミノエトキシ)エタノールからなる群から選択されることを特徴とする、項２〜４のいずれかに記載の水溶液。 Item 5. The secondary or tertiary alkanolamine compound is 2- (isopropylamino) ethanol, 2- (ethylamino) ethanol, 2- (n-propylamino) ethanol, 1- (2-hydroxyethyl) piperidine, 3 A term characterized by being selected from the group consisting of-(dimethylamino) propanol, 4- (dimethylamino) butanol, 2- (2-diethylaminoethoxy) ethanol, and 2- (2-dimethylaminoethoxy) ethanol The aqueous solution in any one of 2-4.
項６．前記ピペラジン化合物が、ピペラジン、2-メチルピペラジン、及び2,6-ジメチルピペラジンからなる群から選択されることを特徴とする、項３〜５のいずれかに記載の水溶液。 Item 6. Item 6. The aqueous solution according to any one of Items 3 to 5, wherein the piperazine compound is selected from the group consisting of piperazine, 2-methylpiperazine, and 2,6-dimethylpiperazine.
項７．（１）項１〜６のいずれかに記載の水溶液を二酸化炭素を含むガスと接触させ、ガスから二酸化炭素を吸収する工程、及び
（２）上記（１）で得られた二酸化炭素が吸収された水溶液を加熱して、二酸化炭素を脱離して回収する工程、
を含む二酸化炭素の吸収及び回収方法。
Item 7. (1) The step of bringing the aqueous solution according to any one of Items 1 to 6 into contact with a gas containing carbon dioxide, and absorbing carbon dioxide from the gas; and (2) the carbon dioxide obtained in (1) above is absorbed. Heating the aqueous solution to desorb and recover carbon dioxide,
Carbon dioxide absorption and recovery method comprising:
本発明の水溶液を用いた二酸化炭素の分離回収方法は、公知の二酸化炭素の吸収用水溶液に比較して、高い吸収速度を持ち、且つ低い反応熱でガス中の二酸化炭素を吸収及び脱離して二酸化炭素を効果的に回収することができる。結果として二酸化炭素単位重量当たりの回収エネルギーの低減が可能となり、現在課題となっている回収コストの削減に繋がるものである。又、吸収速度の向上は、二酸化炭素を回収及び脱離する為の吸収塔、脱離塔及びこれらに付随する装置を小型化が可能となり、建設費を減らし二酸化炭素の回収にかかる全体コスト低減に寄与するものである。 The method for separating and recovering carbon dioxide using the aqueous solution of the present invention has a high absorption rate and absorbs and desorbs carbon dioxide in the gas with a low reaction heat as compared with known carbon dioxide absorbing aqueous solutions. Carbon dioxide can be effectively recovered. As a result, it is possible to reduce the recovered energy per unit weight of carbon dioxide, which leads to reduction of the recovery cost that is currently a problem. In addition, the improvement in the absorption rate enables the absorption tower, the desorption tower, and the equipment associated therewith to recover and desorb carbon dioxide to be reduced in size, reducing the construction cost and reducing the overall cost for collecting carbon dioxide. It contributes to.
以下、本発明を詳述する。 The present invention is described in detail below.
二酸化炭素を吸収及び回収するための水溶液
本発明の二酸化炭素を含むガスから二酸化炭素を吸収及び回収するための水溶液は、一般式〔1〕で表される第2級アミン化合物を少なくとも1種含むことを特徴とする。
一般式〔1〕：
R-NH-(CH2)n-OH
(式中、Rは炭素数1〜4の直鎖状又は分枝鎖状のアルキル基を表し、nは3〜5から選ばれる。)
具体的には、Rとしては、メチル、エチル、n-プロピル、イソプロピル、n-ブチルなどが挙げられ、Rは好ましくはエチル、n-プロピル、及びイソプロピルである。
Aqueous solution for absorbing and recovering carbon dioxide The aqueous solution for absorbing and recovering carbon dioxide from the gas containing carbon dioxide of the present invention contains at least one secondary amine compound represented by the general formula [1]. It is characterized by that.
General formula [1]:
R-NH- (CH 2 ) n -OH
(In the formula, R represents a linear or branched alkyl group having 1 to 4 carbon atoms, and n is selected from 3 to 5.)
Specifically, examples of R include methyl, ethyl, n-propyl, isopropyl, n-butyl, and the like. R is preferably ethyl, n-propyl, and isopropyl.
アルコール部位の構造としては、1-プロパノール、1-ブタノール、及び1-ペンタノールが挙げられ、nは好ましくは3、4である。 Examples of the structure of the alcohol moiety include 1-propanol, 1-butanol, and 1-pentanol, and n is preferably 3 or 4.
一般式〔1〕で表される第2級アミン化合物としては、それらを組み合わせた3-メチルアミノ-1-プロパノール(MAPA)、3-エチルアミノ-1-プロパノール(EAP)、3-n-プロピルアミノ-1-プロパノール(NPAP)、4-エチルアミノ-1-ブタノール(EAB)、3-イソプロピルアミノ-1-プロパノール(IPAP)、4-イソプロピルアミノ-1-ブタノール(IPAB)、3-n-ブチルアミノ-1-プロパノール(NBAP)、4-n-プロピルアミノ-1-ブタノール(NPAB)、4-n-プロピルアミノ-1-ブタノール(NPAB)、5-イソプロピルアミノ-1-ペンタノール(IPAPE)、4-n-ブチルアミノ-1-プロパノール、4-メチルアミノ-1-ブタノール、4-n-ブチルアミノ-1-ブタノール等が挙げられ、好ましくは3-エチルアミノ-1-プロパノール(EAP)、3-n-プロピルアミノ-1-プロパノール(NPAP)、3-n-ブチルアミノ-1-プロパノール(NBAP)、3-イソプロピルアミノ-1-プロパノール(IPAP)、及び4-エチルアミノ-1-ブタノール(EAB)である。 The secondary amine compound represented by the general formula [1] includes 3-methylamino-1-propanol (MAPA), 3-ethylamino-1-propanol (EAP), 3-n-propyl combined with them Amino-1-propanol (NPAP), 4-ethylamino-1-butanol (EAB), 3-isopropylamino-1-propanol (IPAP), 4-isopropylamino-1-butanol (IPAB), 3-n-butyl Amino-1-propanol (NBAP), 4-n-propylamino-1-butanol (NPAB), 4-n-propylamino-1-butanol (NPAB), 5-isopropylamino-1-pentanol (IPAPE), 4-n-butylamino-1-propanol, 4-methylamino-1-butanol, 4-n-butylamino-1-butanol and the like, preferably 3-ethylamino-1-propanol (EAP), 3 -n-propylamino-1-propanol (NPAP), 3-n-butylamino-1-propanol (NBAP), 3-isopropylamino-1-propano (IPAP), and 4-ethylamino-1-butanol (EAB).
本発明の化合物〔1〕が、吸収速度が速く且つ反応熱が低く、結果として吸収及び脱離の 全体の回収エネルギー低減に効果を示す理由は、以下の様に推定している。一般に化学反応の進行は複数の化合物が一番優位な最適な配置である遷移状態を経て最終的にエネルギーが一番小さい安定な化合物になる過程を経て進むとされている。本吸収反応においては、二酸化炭素、アミン化合物、及び水の3種が反応に関与しており以下に示される3種の複合体からなる遷移状態を経て、二酸化炭素とアミンとの反応が進む。 The reason why the compound [1] of the present invention has a high absorption rate and a low reaction heat, and as a result is effective in reducing the total recovery energy of absorption and desorption, is estimated as follows. In general, the progress of a chemical reaction is said to proceed through a process in which a plurality of compounds finally pass through a transition state in which the most advantageous and optimal arrangement is achieved and finally become a stable compound having the lowest energy. In this absorption reaction, carbon dioxide, an amine compound, and water are involved in the reaction, and the reaction between carbon dioxide and the amine proceeds through a transition state composed of the three types of complexes shown below.
これらの遷移状態の構造とその場合の活性化エネルギーは複数の量子化学計算モデルで計算することが可能である。例えばRをイソプロピル基とした場合、アルコール部位の炭素鎖長を変えた場合の計算を密度汎関数法、及びCOSMO-RS溶媒和モデルでn=2〜4のケースで計算すると、上に示す構造に於いてn=3の場合に遷移状態の活性化エネルギーは、2.8 kcal/mol-CO2で一番低くなった。その結果、吸収速度を向上させることに繋がると考えられる。因みにn=2、4での同等の計算では活性化エネルギーは、それぞれ3.8、4.0 kcal/mol-CO2と計算され、遷移状態におけるアルコール部の鎖長の差による影響が計算の結果示された。これは、アルコール鎖長の差が遷移状態での立体配置の双極子モーメント(μ)の違いを生み水溶液中での遷移状態のエネルギー差に繋がったものと推定している。これらのアミンの吸収速度は、n=3の時が5.2 g-CO2/l/minであるのに対して、n=2、4のときはそれぞれ4.8、4.7 g-CO2/l/minであり活性化エネルギーの計算値と同等の傾向を示す。 The structure of these transition states and the activation energy in that case can be calculated by a plurality of quantum chemical calculation models. For example, when R is an isopropyl group, the calculation when the carbon chain length of the alcohol moiety is changed is calculated in the case of n = 2 to 4 in the density functional method and the COSMO-RS solvation model. When n = 3, the activation energy in the transition state was lowest at 2.8 kcal / mol-CO 2 . As a result, it is considered that the absorption rate is improved. By the way, the activation energy was calculated to be 3.8 and 4.0 kcal / mol-CO 2 respectively in the same calculation with n = 2 and 4, and the calculation results showed the influence of the chain length of the alcohol part in the transition state. . This is presumed that the difference in alcohol chain length produced the difference in configuration dipole moment (μ) in the transition state, which led to the energy difference in the transition state in the aqueous solution. The absorption rate of these amines is 5.2 g-CO 2 / l / min when n = 3, while 4.8 and 4.7 g-CO 2 / l / min when n = 2 and 4, respectively. It shows the same tendency as the calculated activation energy.
従来から、二酸化炭素の吸収剤として各種のアルカノールアミンが提案されてきたが、この様に反応時の遷移状態の解析より構造との相関を比較した例はなく、且つ、その構造が性能発現に大きく関与していることを見出したことは驚くべきことで、分子レベルでの反応経路のエネルギー計算からも本発明の化合物の構造と性能相関が見出された意義は大きい。 Conventionally, various alkanolamines have been proposed as carbon dioxide absorbents, but there is no example of comparing the correlation with the structure based on the analysis of the transition state at the time of the reaction as described above, and the structure exhibits the performance. It was surprising to find that it was greatly involved, and it was significant that the structure and performance correlation of the compound of the present invention was found from the energy calculation of the reaction pathway at the molecular level.
又、一般式〔1〕の化合物群が吸収速度が向上したにも拘らず反応熱の増加に繋がらない理由としては以下の推定をしている。 Further, the reason why the compound group of the general formula [1] does not lead to an increase in the heat of reaction although the absorption rate is improved is estimated as follows.
一般的には、アミンと二酸化炭素との反応においては、アミンの価数によってカーバメート結合を形成する場合と、バイカーボネート結合を形成する場合の2つの反応形態があることが知られている。カーバメート結合がアミンと二酸化炭素とが共有結合を形成するのに対してバイカーボネート結合ではプロトン化アミンと重炭酸イオンとがイオン対を形成という差により、反応熱はバイカーボネート形成の方が低くなることが実験的にも知られている。 In general, it is known that there are two reaction modes in the reaction between an amine and carbon dioxide, when a carbamate bond is formed depending on the valence of the amine and when a carbonate bond is formed. Carbamate bonds form covalent bonds between amines and carbon dioxide, whereas bicarbonate bonds reduce the reaction heat of bicarbonate formation due to the difference that protonated amines and bicarbonate ions form ion pairs. It is also known experimentally.
アミンと二酸化炭素の反応形態(Aはアミンを示す)
カーバメート系 CO2 + 2A ⇒ A-COO- + A-H+
バイカーボネート系 CO2 + H2O + A ⇒ HCO3 - + A-H+
アミンの価数で見ると1級アミンはカーバメート反応が主であり高い反応熱を示す、3級アミンはバイカーボネート結合が主であり反応熱は1級アミンより低い値を示す。2級アミンについては、アミノ基の置換アルキル基の種類によってカーバメート結合、及びバイカーボネート結合が混在するとされており反応熱はその反応形態比率により変動する特徴を持つ。因みに、二酸化炭素の吸収によく使用される前述のMEAは代表的な第1級アミンであり主としてカーバメート結合で反応しており、二酸化炭素との反応熱は約80 kJ/モルCO2であるが、第3級アミンの代表例であるMDEAではバイカーボネートが主で反応熱は約60 kJ/モルCO2と大幅に低い数値となる。
Reaction form of amine and carbon dioxide (A indicates amine)
Carbamate CO 2 + 2A ⇒ A-COO - + AH +
Bicarbonate-based CO 2 + H 2 O + A ⇒ HCO 3 - + AH +
In terms of the valence of the amine, the primary amine mainly exhibits a carbamate reaction and exhibits a high heat of reaction, and the tertiary amine mainly exhibits a bicarbonate bond and the heat of reaction is lower than that of the primary amine. Regarding secondary amines, carbamate bonds and bicarbonate bonds are mixed depending on the type of substituted alkyl group of the amino group, and the reaction heat varies depending on the reaction form ratio. Incidentally, the above-mentioned MEA, which is often used for carbon dioxide absorption, is a typical primary amine and mainly reacts with a carbamate bond, and the reaction heat with carbon dioxide is about 80 kJ / mole CO 2. In MDEA, which is a typical example of a tertiary amine, bicarbonate is mainly used, and the heat of reaction is about 60 kJ / mole CO 2, which is a significantly low value.
しかしながら、反応速度の相対比はMEAを1.0とすると、MDEAは、0.2と小さく反応熱の低減が反応速度の低下を招くというトレードオフの関係にあるのは前述の通りである。 However, as described above, when the relative ratio of reaction rates is 1.0 for MEA, MDEA is as small as 0.2, and a reduction in reaction heat leads to a decrease in reaction rate.
本発明の化合物〔1〕は2級アミンであるので二酸化炭素との反応は上記の2つの形態で進むが、この比率は吸収後の液の13CNMRの測定より分別が可能である。 Since the compound [1] of the present invention is a secondary amine, the reaction with carbon dioxide proceeds in the above two forms. This ratio can be fractionated by 13 CNMR measurement of the liquid after absorption.
化合物〔1〕を含む水溶液に二酸化炭素を吸収させた後に13CNMRを測定した。なお、13C-NMRの測定は、日本電子(株)のJNM-ECA400で周波数100MHz、ロック溶媒を重水とした系で逆ゲート付きデカップリング法(待ち時間30秒、積算回数400回で測定)により行った。その結果、R基がエチル基であるEAP、EABの場合をアルコール部位がエチルの2-エチルアミノエタノール(EAE)と比較すると、カーバメート/（カーバメート+バイカーボネート）で表される比率は、EAEが0.33に対してEAP、EABは0.12、0.04と小さい結果となった。又、Rがイソプロピル基の場合、アルコール部位がエチルの2-イソプロピルアミノ-エタノール(IPAE)が0.04であるのに対してIPAP、IPAB、IPAPEの化合物では、カーバメート結合による生成物は検出限界以下でありバイカーボネート形態で優先的に反応が進行していることが分かった。これらの事実は、一般式〔1〕の化合物は低反応熱型のバイカーボネート結合で進む結果、反応熱も低い結果となると考えられる。 After absorbing carbon dioxide in the aqueous solution containing the compound [1], 13 CNMR was measured. The measurement of 13 C-NMR was performed by JEM JEC-ECA400 with a frequency of 100 MHz and a decoupling method with a reverse gate in a system using a lock solvent as heavy water (measured at a waiting time of 30 seconds and an accumulation count of 400 times). It went by. As a result, when EAP and EAB in which the R group is an ethyl group are compared with 2-ethylaminoethanol (EAE) in which the alcohol moiety is ethyl, the ratio expressed by carbamate / (carbamate + bicarbonate) is EAP and EAB were 0.12 and 0.04, which were smaller than 0.33. In addition, when R is isopropyl group, the alcohol moiety is ethyl 2-isopropylamino-ethanol (IPAE) is 0.04, whereas in IPAP, IPAB and IPAPE compounds, the product due to carbamate bond is below the detection limit. It was found that the reaction proceeded preferentially in the form of bicarbonate. From these facts, it is considered that the compound of the general formula [1] proceeds with a low reaction heat type bicarbonate bond, resulting in a low reaction heat.
又、2つの反応形態では上記の反応式より推定される様に、カーバメート結合ではアミン1モルに対する二酸化炭素の反応率(ローディング値で表す)は最大0.5であるのに対して、バイカーバメート形態では最大1.0である。そのため、水溶液中のアミンに対する二酸化炭素の吸収効率の面でも、一般式〔1〕の化合物ではバイカーボネート形態が主であることにより、単位アミン当たりの吸収量も高く吸収液としては理想的な性能を持つ水溶液を提供するものである。 In addition, as estimated from the above reaction formula in the two reaction forms, the reaction rate of carbon dioxide with respect to 1 mol of amine (expressed by loading value) is 0.5 at maximum in the carbamate bond, whereas in the bicarbamate form. The maximum is 1.0. Therefore, in terms of carbon dioxide absorption efficiency with respect to amines in aqueous solution, the compound of general formula [1] is mainly in the form of bicarbonate, so the amount of absorption per unit amine is high and ideal performance as an absorbing solution. An aqueous solution having a water content is provided.
本発明の水溶液は、一般式〔1〕で表される第2級アミン化合物を必須成分とし、必要に応じて他の成分を混合し水溶液全体の性能を調整する。化合物〔1〕の使用により結果として水溶液としての反応熱の低減、反応速度の向上を達成することが可能となり、二酸化炭素の吸収及び回収に伴う全体のエネルギー消費も低減され経済的な効果が発揮されることとなる。ここで、当該反応熱及び反応速度は実施例に記載の方法により測定することができる。 In the aqueous solution of the present invention, the secondary amine compound represented by the general formula [1] is an essential component, and other components are mixed as necessary to adjust the performance of the entire aqueous solution. As a result, the use of compound [1] makes it possible to reduce the heat of reaction as an aqueous solution and increase the reaction rate, and to reduce the overall energy consumption associated with the absorption and recovery of carbon dioxide, thus providing an economic effect. Will be. Here, the heat of reaction and reaction rate can be measured by the methods described in the Examples.
本発明の水溶液としては、基本性能の優れた一般式〔1〕の第2級アミン化合物を単独で使用することも可能であるが、吸収量、放散性能等の他の性能をより向上させる為に水溶液を構成する他のアミン成分として第2級又は第3級アルカノールアミン化合物(一般式〔1〕で表される第2級アミン化合物は除く)及び／又はピペラジン化合物を使用することも可能である。 As the aqueous solution of the present invention, it is possible to use the secondary amine compound of the general formula [1] having excellent basic performance alone, but in order to further improve other performance such as absorption amount and diffusion performance. It is also possible to use secondary or tertiary alkanolamine compounds (excluding secondary amine compounds represented by the general formula [1]) and / or piperazine compounds as other amine components constituting the aqueous solution. is there.
第2級アルカノールアミン化合物としては、好ましくは、2-(イソプロピルアミノ)エタノール(IPAE)、2-(エチルアミノ)エタノール(EAE)、2-(n-プロピルアミノ)エタノール(NPAE)が選ばれる。IPAEは、その立体特性より高い二酸化炭素の脱離性能を持っており、EAEは分子量が小さい為、重量当りの吸収容量が大きく、NPAEは高い吸収速度を持つ特徴があり、これらを併用することで本発明の水溶液はさらに高い性能を得ることが可能となる。 As the secondary alkanolamine compound, 2- (isopropylamino) ethanol (IPAE), 2- (ethylamino) ethanol (EAE), or 2- (n-propylamino) ethanol (NPAE) is preferably selected. IPAE has higher carbon dioxide desorption performance than its steric properties, EAE has a low molecular weight, so it has a large absorption capacity per weight, and NPAE has a high absorption rate. Thus, the aqueous solution of the present invention can obtain higher performance.
第3級アルカノールアミン化合物としては、好ましくは、1-(2-ヒドロキシエチル)ピペリジン(2HE-PP)、3-(ジメチルアミノ)プロパノール(DMAP)、4-(ジメチルアミノ)ブタノール(DMAB)、3-(ジエチルアミノ)プロパノール、4-(ジエチルアミノ)ブタノール、2-(2-ジエチルアミノエトキシ)エタノール、2-(2-ジメチルアミノエトキシ)エタノール等が選ばれる。これらは第3級アミンであることにより、併用することで反応熱低減に寄与する。 The tertiary alkanolamine compound is preferably 1- (2-hydroxyethyl) piperidine (2HE-PP), 3- (dimethylamino) propanol (DMAP), 4- (dimethylamino) butanol (DMAB), 3 -(Diethylamino) propanol, 4- (diethylamino) butanol, 2- (2-diethylaminoethoxy) ethanol, 2- (2-dimethylaminoethoxy) ethanol and the like are selected. These are tertiary amines that contribute to reducing reaction heat when used in combination.
ピペラジン化合物はとしては、好ましくは、ピペラジン(PZ)、2-メチルピペラジン(2MPZ)、2,6-ジメチルピペラジン等が選ばれる。これらは二酸化炭素の吸収時の反応活性剤として機能し吸収速度の促進に寄与することが知られている。 As the piperazine compound, piperazine (PZ), 2-methylpiperazine (2MPZ), 2,6-dimethylpiperazine and the like are preferably selected. These are known to function as a reaction activator at the time of absorption of carbon dioxide and contribute to acceleration of the absorption rate.
上記化合物は、市販品を入手できるか又は公知の方法により製造できる。 The said compound can acquire a commercial item, or can be manufactured by a well-known method.
上記水溶液中の一般式〔1〕で表される第2級アミン化合物を単独で使用する場合の含有量は、通常20〜65重量%、好ましくは30〜60重量%、より好ましくは35〜55重量%であり、第2級又は第3級アルカノールアミン化合物及び／又はピペラジン化合物と併用する場合の含有量は、通常20〜45重量%、好ましくは23〜43重量%、更に好ましくは25〜40重量%である。 When the secondary amine compound represented by the general formula [1] in the aqueous solution is used alone, the content is usually 20 to 65% by weight, preferably 30 to 60% by weight, more preferably 35 to 55%. The content when used in combination with a secondary or tertiary alkanolamine compound and / or piperazine compound is usually 20 to 45% by weight, preferably 23 to 43% by weight, more preferably 25 to 40%. % By weight.
上記水溶液中の一般式〔1〕で表される第2級アミン化合物を第2級又は第3級アルカノールアミン化合物と併用する場合、第2級又は第3級アルカノールアミン化合物の含有量は、通常5〜30重量%、好ましくは10〜25重量%、より好ましくは12〜22重量%である。 When the secondary amine compound represented by the general formula [1] in the aqueous solution is used in combination with a secondary or tertiary alkanolamine compound, the content of the secondary or tertiary alkanolamine compound is usually 5 to 30% by weight, preferably 10 to 25% by weight, more preferably 12 to 22% by weight.
又、一般式〔1〕で表される第2級アミン化合物をピペラジン化合物と併用する場合、水溶液中のピペラジン化合物の含有量は、通常0.5〜10重量%、好ましくは1〜8重量%、より好ましくは1.5〜6重量%である。 When the secondary amine compound represented by the general formula [1] is used in combination with a piperazine compound, the content of the piperazine compound in the aqueous solution is usually 0.5 to 10% by weight, preferably 1 to 8% by weight, Preferably it is 1.5 to 6% by weight.
上記水溶液中の各アミン成分の比率は、各々のアミンの反応熱、吸収量、吸収速度、脱離性能等を考慮して最適な組成が選ばれる。第3級アミンの組成比率を上げることが水溶液全体の反応熱を低下させる効果はあるが、実用的には吸収量、脱離量等も含めた性能設計が必要であり、これらの調整を実施し水溶液組成の比率を設定する。 As the ratio of each amine component in the aqueous solution, an optimum composition is selected in consideration of the heat of reaction of each amine, the amount of absorption, the absorption rate, the desorption performance, and the like. Increasing the composition ratio of tertiary amines has the effect of reducing the reaction heat of the entire aqueous solution, but practically performance design including absorption and desorption is necessary, and these adjustments are made. The ratio of the aqueous solution composition is set.
本発明の水溶液の全アミン化合物の含量は、通常20〜65重量%の範囲が選ばれるが、好ましくは30〜60重量%の範囲が選ばれる。一般的にはアミン成分の濃度が高い方が単位液容量あたりの二酸化炭素の吸収量、脱離量及び脱離速度が大きく、エネルギー消費やプラント設備の大きさや効率からは望ましいが、重量濃度として70％を越える場合、粘度の上昇、二酸化炭素を吸収する際の泡立ちや乳化状態になる等の問題が生じることもある。 The content of all amine compounds in the aqueous solution of the present invention is usually in the range of 20 to 65% by weight, preferably in the range of 30 to 60% by weight. In general, the higher the concentration of the amine component, the greater the amount of carbon dioxide absorbed, the amount of desorption, and the rate of desorption per unit liquid volume, which is desirable in terms of energy consumption and the size and efficiency of plant equipment. If it exceeds 70%, problems such as an increase in viscosity, foaming when absorbing carbon dioxide, and emulsification may occur.
又、本発明の水溶液には、必要に応じて腐食防止剤、酸化安定剤等を加えても良い。 Moreover, you may add a corrosion inhibitor, an oxidation stabilizer, etc. to the aqueous solution of this invention as needed.
二酸化炭素の吸収及び回収方法
本発明の二酸化炭素の吸収及び回収方法は、以下の工程を含むことを特徴とする：
（１）上記水溶液を二酸化炭素を含むガスと接触させ、ガスから二酸化炭素を吸収する工程、及び
（２）上記（１）で得られた二酸化炭素が吸収された水溶液を加熱して、二酸化炭素を脱離して回収する工程。
Carbon dioxide absorption and recovery method The carbon dioxide absorption and recovery method of the present invention comprises the following steps:
(1) contacting the aqueous solution with a gas containing carbon dioxide to absorb carbon dioxide from the gas; and (2) heating the aqueous solution in which carbon dioxide obtained in (1) is absorbed, The process of removing and recovering.
・二酸化炭素吸収工程
本発明の方法は、上記水溶液を二酸化炭素を含むガスと接触させ二酸化炭素を吸収させる工程を含むが、二酸化炭素を含むガスを水溶液に接触させる方法に特に限定はない。例えば該水溶液に二酸化炭素を含むガスをバブリングさせて吸収させる方法や、磁製や金属網製の充填材の入った吸収塔での向流接させる方法でも良い。吸収時の温度は、通常室温から60℃の範囲で行われ、好ましくは50℃以下、より好ましくは20-45℃である。
Carbon dioxide absorption step The method of the present invention includes a step of bringing the aqueous solution into contact with a gas containing carbon dioxide to absorb carbon dioxide, but there is no particular limitation on the method of bringing the gas containing carbon dioxide into contact with the aqueous solution. For example, a method in which a gas containing carbon dioxide is bubbled into the aqueous solution and absorbed, or a countercurrent contact method in an absorption tower containing a magnetic or metal mesh filler may be used. The temperature at the time of absorption is usually in the range of room temperature to 60 ° C., preferably 50 ° C. or less, more preferably 20-45 ° C.
二酸化炭素を含むガスとしては、例えば、重油、天然ガス等を燃料とする火力発電所、製造所のボイラーあるいはセメント工場のキルン、コークスで酸化鉄を還元する製鐵所の高炉、銑鉄中の炭素を燃焼して製鋼する同じく製鉄所の転炉等からの排ガスが挙げられ、該ガス中の二酸化炭素濃度は、通常5〜30体積％程度、特に6〜25体積%程度であればよい。かかる二酸化炭素濃度範囲では、本発明の作用効果が好適に発揮される。なお、二酸化炭素を含むガスには、二酸化炭素以外に水蒸気、CO、H2S、COS、SO2、水素等のガスが含まれていてもよい。 Examples of the gas containing carbon dioxide include a thermal power plant fueled with heavy oil, natural gas, etc., a boiler in a factory or a kiln in a cement factory, a blast furnace in a steelworks that reduces iron oxide with coke, and carbon in pig iron Exhaust gas from a converter of the same steel mill that burns steel to produce steel, and the concentration of carbon dioxide in the gas is usually about 5 to 30% by volume, particularly about 6 to 25% by volume. In such a carbon dioxide concentration range, the effects of the present invention are suitably exhibited. The gas containing carbon dioxide may contain a gas such as water vapor, CO, H 2 S, COS, SO 2 , and hydrogen in addition to carbon dioxide.
・二酸化炭素脱離工程
本発明の方法は、二酸化炭素吸収工程で得られた水溶液を加熱して二酸化炭素を脱離して回収する工程を含む。
Carbon dioxide desorption step The method of the present invention includes a step of heating and recovering the carbon dioxide by heating the aqueous solution obtained in the carbon dioxide absorption step.
吸収後の二酸化炭素の脱離工程はスプレー塔、棚段塔、充填塔等で接触界面を広げて加熱する方法が用いられる。脱離時の温度は通常70℃以上で行われるが、好ましくは80℃以上、より好ましくは90〜130℃の範囲が例示される。もちろん、二酸化炭素脱離時の温度が上昇するに従い、二酸化炭素脱離量もさらに向上する。二酸化炭素を脱離した後の水溶液は、再び二酸化炭素吸収工程に送られ循環再使用される。この間、二酸化炭素脱離工程で加えられた熱は、循環過程において水溶液との熱交換により水溶液の昇温に有効に利用されて回収工程全体のエネルギーの低減が計られる。 In the desorption process of carbon dioxide after absorption, a method of heating by expanding the contact interface with a spray tower, a plate tower, a packed tower or the like is used. The temperature at the time of desorption is usually 70 ° C. or higher, preferably 80 ° C. or higher, more preferably 90 to 130 ° C. Of course, as the temperature during carbon dioxide desorption increases, the amount of carbon dioxide desorption further increases. The aqueous solution from which carbon dioxide has been desorbed is sent again to the carbon dioxide absorption step and recycled. During this time, the heat applied in the carbon dioxide desorption process is effectively used to increase the temperature of the aqueous solution by heat exchange with the aqueous solution in the circulation process, thereby reducing the energy of the entire recovery process.
このようにして回収された二酸化炭素の純度は、通常95〜99.9体積％程度、より適切及び安定に実施した場合には99.0〜99.9体積％程度と極めて純度が高いものである。この純粋な二酸化炭素あるいは高濃度の二酸化炭素は、化学品、高分子物質の合成原料、食品冷凍用の冷剤等として用いられる。その他、回収した二酸化炭素を、現在CCS技術として開発されつつある地下等へ隔離貯蔵することも可能である。 The purity of the carbon dioxide recovered in this manner is usually about 95 to 99.9% by volume, and when it is carried out more appropriately and stably, it is about 99.0 to 99.9% by volume, which is extremely high in purity. This pure carbon dioxide or high-concentration carbon dioxide is used as a chemical, a raw material for synthesizing high-molecular substances, a cooling agent for freezing foods, and the like. In addition, the recovered carbon dioxide can be sequestered and stored in the underground, which is currently being developed as a CCS technology.
次に、本発明について実施例及び比較例を用いて詳細に説明するが、本発明はこの実施例に限定されるものではない。尚、本実施例中において、特に指定しない限り、％とは重量％を示す。 Next, although this invention is demonstrated in detail using an Example and a comparative example, this invention is not limited to this Example. In the examples, unless otherwise specified, “%” means “% by weight”.
実施例１
液の温度が40℃になるように設定した恒温水槽内に、ガラス製のガス吸収ビンを浸し、これにIPAP 30重量％(2.5 M/L)を含む水溶液50 mlを充填した。この液の中に、目の粗さ100μm、直径13 mmのガラスフィルターを通して、大気圧下、0.7 L/分で二酸化炭素20体積％及びN280体積％を含む混合ガスを泡状に分散させて吸収させた。
Example 1
A glass gas absorption bottle was immersed in a constant temperature water bath set to a temperature of 40 ° C., and 50 ml of an aqueous solution containing 30% by weight (2.5 M / L) of IPAP was filled therein. A mixed gas containing 20% by volume of carbon dioxide and 80% by volume of N 2 at a pressure of 0.7 L / min is dispersed in a foam form through this glass filter with a coarseness of 100 μm and a diameter of 13 mm in this liquid. Absorbed.
水溶液入口及び水溶液出口のガス中の二酸化炭素濃度を、赤外線式の二酸化炭素計(HORIBA GAS ANALYZER VA-3000)で連続的に測定して、入口及び出口の二酸化炭素流量の差から二酸化炭素吸収量を測定した。必要により水溶液中の無機炭素量をガスクロマトグラフ式の全有機炭素計(SHIMADZU TOC-VCSH)で測定し赤外線式二酸化炭素計から算出される値と比較した。飽和吸収量は水溶液出口の二酸化炭素濃度が入口の二酸化炭素濃度に一致する時点における量とした。吸収速度は飽和吸収量の1/2を吸収した時点の吸収速度で比較することとし、二酸化炭素吸収速度は、飽和吸収量の1/2の二酸化炭素を吸収した時点において赤外線式二酸化炭素計を用いて測定した。その結果、二酸化炭素飽和吸収量は100.0 g/Lで、飽和量の1/2を吸収した時点での吸収速度は5.31 g/L/minであった。 The carbon dioxide concentration in the gas at the aqueous solution inlet and outlet is continuously measured with an infrared carbon dioxide meter (HORIBA GAS ANALYZER VA-3000). Was measured. If necessary, the amount of inorganic carbon in the aqueous solution was measured with a gas chromatographic total organic carbon meter (SHIMADZU TOC-VCSH) and compared with the value calculated from the infrared carbon dioxide meter. The saturated absorption amount was the amount at the time when the carbon dioxide concentration at the outlet of the aqueous solution coincided with the carbon dioxide concentration at the inlet. The absorption rate is compared with the absorption rate at the time when 1/2 of the saturated absorption amount is absorbed, and the carbon dioxide absorption rate is determined by the infrared carbon dioxide meter at the time when 1/2 of the saturated absorption amount is absorbed. And measured. As a result, the saturated absorption amount of carbon dioxide was 100.0 g / L, and the absorption rate at the time when 1/2 of the saturation amount was absorbed was 5.31 g / L / min.
ついで同じガス気流中で液温を数分にて70℃に上げて、液からの二酸化炭素脱離量を測定した結果、27.0 g/Lであった。又、試験例1に示した方法により測定した吸収時の反応熱は72.4 kJ/モルCO2であった。 Then, the temperature of the liquid was raised to 70 ° C. within a few minutes in the same gas stream, and the amount of carbon dioxide desorbed from the liquid was measured. As a result, it was 27.0 g / L. Further, the heat of reaction at the time of absorption measured by the method shown in Test Example 1 was 72.4 kJ / mol CO 2 .
実施例2〜9
IPAP 30重量%を含む水溶液に代えて、表１に記載のNPAP、EAP、EAB、IPAP、IPAP+IPAE+PZ、IPAP+EAE+PZ、EAP+2HE-PP、IPAP+IPAE+2MPZを表１に記載の濃度で含む水溶液を用いた以外は実施例１と同様にして、二酸化炭素の飽和吸収量、吸収速度、反応熱、及び脱離量の測定を行った。得られた結果を表１に示した。なお、表１において〔1〕は本発明に基づく第2級アミン化合物の組成名、重量%を、〔2〕は第2級又は第3級アルカノールアミン化合物の組成名、重量%を、〔3〕はピペラジン化合物の組成名、重量%を示している。
Examples 2-9
Table 1 shows NPAP, EAP, EAB, IPAP, IPAP + IPAE + PZ, IPAP + EAE + PZ, EAP + 2HE-PP, IPAP + IPAE + 2MPZ listed in Table 1 instead of an aqueous solution containing 30% by weight of IPAP. The saturated absorption amount, absorption rate, heat of reaction, and desorption amount of carbon dioxide were measured in the same manner as in Example 1 except that the aqueous solution containing the concentration described in 1 was used. The obtained results are shown in Table 1. In Table 1, [1] is the composition name and weight% of the secondary amine compound based on the present invention, and [2] is the composition name and weight% of the secondary or tertiary alkanolamine compound. ] Indicates the composition name and weight% of the piperazine compound.
試験例1
恒温槽中に設置された同一形状のガラス製反応槽及びリファレンス槽からなる示差熱型反応熱量計（SETARAM社、DRC）を用いて二酸化炭素吸収の反応熱を測定した。反応槽及びリファレンス槽にそれぞれ150 mLの実施例2の水溶液を充填し、槽のジャケット部分に40℃の恒温水を循環させた。この状態で反応槽の水溶液に100％濃度の二酸化炭素ガスを200 ml/分で吹込み、液の温度上昇を二酸化炭素吸収が終了するまで温度記録計にて連続的に記録し、事前に測定された反応槽とジャケット水間の総括伝熱係数を用いて、反応熱を算出した。その結果、二酸化炭素吸収の反応熱は73.0 kJ/molCO2であった。
Test example 1
The reaction heat of carbon dioxide absorption was measured using a differential thermal reaction calorimeter (SETARAM, DRC) consisting of a glass reaction tank and a reference tank of the same shape installed in a thermostat. Each of the reaction tank and the reference tank was filled with 150 mL of the aqueous solution of Example 2, and 40 ° C. constant temperature water was circulated through the jacket of the tank. In this state, 100% carbon dioxide gas was blown into the reaction vessel aqueous solution at 200 ml / min, and the temperature rise of the liquid was continuously recorded with a temperature recorder until the carbon dioxide absorption was completed, and measured in advance. The reaction heat was calculated using the overall heat transfer coefficient between the reaction tank and the jacket water. As a result, the reaction heat of carbon dioxide absorption was 73.0 kJ / mol CO 2 .
比較例1〜3
IPAP 30重量%を含む水溶液に代えて、表２に記載のIPAE、NPAE、EAE、AMP、DEAPを表２に記載の濃度で含む水溶液を用いた以外は実施例１と同様にして、二酸化炭素の飽和吸収量、吸収速度、反応熱、及び脱離量の測定を行った。得られた結果を表２に示した。
Comparative Examples 1-3
Carbon dioxide was prepared in the same manner as in Example 1 except that an aqueous solution containing IPAE, NPAE, EAE, AMP, and DEAP shown in Table 2 at the concentrations shown in Table 2 was used instead of the aqueous solution containing 30% by weight of IPAP. The saturated absorption amount, absorption rate, reaction heat, and desorption amount of were measured. The obtained results are shown in Table 2.
表１及び２に示されるように、本発明の第2級アミン化合物である実施例1-4は、従来から知られているアルコール部位がエタノール構造の比較例1-3の対応する２級アミンと比較して反応熱、吸収速度及び飽和吸収量に於いて優れており、これらのアミンの特異的な高性能が確認できた。 As shown in Tables 1 and 2, Example 1-4, which is the secondary amine compound of the present invention, has a corresponding secondary amine of Comparative Example 1-3 in which the alcohol site is conventionally known having an ethanol structure. The reaction heat, the absorption rate and the saturated absorption amount were excellent, and the specific high performance of these amines could be confirmed.
又、アルコール部位がプロパノール分枝構造を持つAMP（2-アミノ-2-メチル-1-プロパノール）の性能を比較例4に示すが、本化合物が1級アミン構造を持つことにより反応熱が高い上に、吸収速度は低い性能であり、アルコール部位が直鎖の実施例群の方が反応熱及び吸収速度の面で優位であることが分かる。これは前述の様に直鎖のアルコール系では遷移状態での安定化構造がとれるのに対して、AMPではアミノ基のα位にメチル基が2個置換することにより安定な環状構造が取れないことによると考えられる。 The performance of AMP (2-amino-2-methyl-1-propanol) having a propanol branched structure at the alcohol moiety is shown in Comparative Example 4, but the reaction heat is high due to the primary amine structure of this compound. In addition, it can be seen that the absorption rate is a low performance, and the example group having a linear alcohol moiety is superior in terms of reaction heat and absorption rate. This is because, as described above, a linear alcohol system can have a stable structure in the transition state, whereas AMP cannot form a stable cyclic structure by substituting two methyl groups at the α-position of the amino group. It is thought that.
比較例5には、DEAE(N,N-ジエチルアミノ-1-プロパノール)の測定例を示す。DEAPはアルコール部位が直鎖のプロパノール構造を持つが、アミノ基にエチル基が2個結合した3級アミンである。類似構造を持つ2級アミンである実施例3のEAPとの性能比較より、反応熱が低い優位な性能を持つが、3級アミンである為に吸収速度が遅く実用上は問題が大きい。この性能差は、DEAEではアミノ基がバルキーなアルキル基2個で置換されており、この為、反応途中の遷移状態で安定な環状構造が取れないため速度面での性能差が出ていると推察される。アルコール部位は同じ構造のEAPとDEAPとの性能差は、アミノ基の置換構造との差と考えられる。 Comparative Example 5 shows a measurement example of DEAE (N, N-diethylamino-1-propanol). DEAP is a tertiary amine in which the alcohol moiety has a linear propanol structure, but two ethyl groups are bonded to the amino group. Compared with the performance of EAP of Example 3 which is a secondary amine having a similar structure, it has superior performance with low reaction heat. However, since it is a tertiary amine, the absorption rate is slow and there is a large problem in practical use. This difference in performance is due to the fact that in DEAE, the amino group is substituted with two bulky alkyl groups, and therefore a stable cyclic structure cannot be obtained in the transition state during the reaction, so there is a difference in performance in terms of speed. Inferred. The difference in performance between EAP and DEAP having the same structure at the alcohol site is considered to be a difference from the substitution structure of the amino group.
この様に、2級アミン構造を持ち且つアルコール部位のアルコール鎖長が3〜4の構造を持つアミンは、従来二酸化炭素の吸収及び回収に用いられていたアミンとは異なる性能を持つことが分かる。 Thus, it can be seen that an amine having a secondary amine structure and having an alcohol chain structure with an alcohol chain length of 3 to 4 has different performance from that of an amine conventionally used for absorption and recovery of carbon dioxide. .
又、実施例6〜9に示す様に［1］の化合物と他のアミン類との混合により、［1］単独使用よりは、高い吸収量及び脱離量を持つ水溶液の調製が可能であり、二酸化炭素の回収エネルギーの低減が可能となる。 In addition, as shown in Examples 6 to 9, by mixing the compound of [1] with other amines, it is possible to prepare an aqueous solution having higher absorption and desorption than when using [1] alone. This makes it possible to reduce the carbon dioxide recovery energy.
現在工業的に使用されているMEAは反応熱が80 kJ/mol-CO2と高く回収エネルギーの低減には限界があるが、本発明のアミン化合物よりなる水溶液はこの点での改良がなされており、本分野の課題である二酸化炭素の回収エネルギーの低減に繋がるものである。 MEA currently used industrially has a high heat of reaction of 80 kJ / mol-CO 2 and there is a limit to reducing the recovery energy, but the aqueous solution comprising the amine compound of the present invention has been improved in this respect. This leads to a reduction in carbon dioxide recovery energy, which is a problem in this field.
Claims (7)
一般式〔1〕：
R-NH-(CH2)n-OH
(式中、Rは炭素数1〜4の直鎖状又は分枝鎖状のアルキル基を表し、nは3〜5から選ばれる。) An aqueous solution for absorbing and recovering carbon dioxide from a gas containing carbon dioxide, wherein the aqueous solution contains at least one secondary amine compound represented by the general formula [1].
General formula [1]:
R-NH- (CH 2 ) n -OH
(In the formula, R represents a linear or branched alkyl group having 1 to 4 carbon atoms, and n is selected from 3 to 5.)
（２）上記（１）で得られた二酸化炭素が吸収された水溶液を加熱して、二酸化炭素を脱離して回収する工程、
を含む二酸化炭素の吸収及び回収方法。 (1) A step of bringing the aqueous solution according to any one of claims 1 to 6 into contact with a gas containing carbon dioxide to absorb carbon dioxide from the gas; and (2) carbon dioxide obtained in (1) above is absorbed. Heating the resulting aqueous solution to desorb and recover carbon dioxide,
Carbon dioxide absorption and recovery method comprising:
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