JP5030371B2 - Absorbing liquid, apparatus and method for removing CO2 and / or H2S using absorbing liquid - Google Patents
Absorbing liquid, apparatus and method for removing CO2 and / or H2S using absorbing liquid Download PDFInfo
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- JP5030371B2 JP5030371B2 JP2004120787A JP2004120787A JP5030371B2 JP 5030371 B2 JP5030371 B2 JP 5030371B2 JP 2004120787 A JP2004120787 A JP 2004120787A JP 2004120787 A JP2004120787 A JP 2004120787A JP 5030371 B2 JP5030371 B2 JP 5030371B2
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- butylaminoethanol
- ethanediamine
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- 239000007788 liquid Substances 0.000 title claims description 26
- 238000000034 method Methods 0.000 title claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 43
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 claims description 17
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 17
- -1 amine compound Chemical class 0.000 claims description 14
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 14
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical compound CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 claims description 12
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 12
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 12
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 11
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 11
- 229940043276 diisopropanolamine Drugs 0.000 claims description 11
- 229940013085 2-diethylaminoethanol Drugs 0.000 claims description 10
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 claims description 10
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 10
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 10
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 10
- 150000004985 diamines Chemical class 0.000 claims description 9
- VJWZYGQIJWDACM-UHFFFAOYSA-N 2-(2-methylpropylamino)ethanol Chemical compound CC(C)CNCCO VJWZYGQIJWDACM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002250 absorbent Substances 0.000 claims description 7
- 230000002745 absorbent Effects 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 7
- 238000011069 regeneration method Methods 0.000 claims description 7
- BCLSJHWBDUYDTR-UHFFFAOYSA-N 2-(propylamino)ethanol Chemical compound CCCNCCO BCLSJHWBDUYDTR-UHFFFAOYSA-N 0.000 claims description 6
- YTVUVYDVQNALCM-UHFFFAOYSA-N 2-(butan-2-ylamino)ethanol Chemical compound CCC(C)NCCO YTVUVYDVQNALCM-UHFFFAOYSA-N 0.000 claims description 5
- RILLZYSZSDGYGV-UHFFFAOYSA-N 2-(propan-2-ylamino)ethanol Chemical compound CC(C)NCCO RILLZYSZSDGYGV-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- CYXGZZFAAUDHQL-UHFFFAOYSA-N 1-n,1-n'-dimethylpropane-1,1-diamine Chemical compound CCC(NC)NC CYXGZZFAAUDHQL-UHFFFAOYSA-N 0.000 claims description 4
- DTGAZOLNYZSBNH-UHFFFAOYSA-N 1-n,1-n'-di(propan-2-yl)ethane-1,1-diamine Chemical compound CC(C)NC(C)NC(C)C DTGAZOLNYZSBNH-UHFFFAOYSA-N 0.000 claims description 3
- LRCHFVIOCPJXBK-UHFFFAOYSA-N 1-n,1-n'-diethylethane-1,1-diamine Chemical compound CCNC(C)NCC LRCHFVIOCPJXBK-UHFFFAOYSA-N 0.000 claims description 3
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 claims description 3
- COFOBGYBKLTPER-UHFFFAOYSA-N n-methyl-n'-[3-(methylamino)propyl]propane-1,3-diamine Chemical compound CNCCCNCCCNC COFOBGYBKLTPER-UHFFFAOYSA-N 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 description 39
- 239000000243 solution Substances 0.000 description 13
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 9
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000007142 ring opening reaction Methods 0.000 description 6
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 229960002887 deanol Drugs 0.000 description 4
- SALYKAIZVOFAEJ-UHFFFAOYSA-N 2-(pentylamino)ethanol Chemical compound CCCCCNCCO SALYKAIZVOFAEJ-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 2
- YVLHRYOHNHUVOA-UHFFFAOYSA-N 2,2-dimethylpropane-1,1-diamine Chemical compound CC(C)(C)C(N)N YVLHRYOHNHUVOA-UHFFFAOYSA-N 0.000 description 2
- PECYZEOJVXMISF-UHFFFAOYSA-N 3-aminoalanine Chemical compound [NH3+]CC(N)C([O-])=O PECYZEOJVXMISF-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- YJFMFLFJLYHYAQ-UHFFFAOYSA-N 2,2,5,5-tetramethylhexane-3,3-diamine Chemical compound CC(C)(C)CC(N)(N)C(C)(C)C YJFMFLFJLYHYAQ-UHFFFAOYSA-N 0.000 description 1
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-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
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 101100008681 Glycine max DHPS1 gene Proteins 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- QXNDZONIWRINJR-UHFFFAOYSA-N azocane Chemical compound C1CCCNCCC1 QXNDZONIWRINJR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- NWOJEYNEKIVOOF-UHFFFAOYSA-N hexane-2,2-diamine Chemical compound CCCCC(C)(N)N NWOJEYNEKIVOOF-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 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
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- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Description
本発明はガス中に含まれるＣＯ2 （二酸化炭素）又はＨ2Ｓ（硫化水素）又はその双方を除去する吸収液に添加する吸収液、該吸収液を用いたＣＯ2又はＨ2Ｓ又はその双方の除去装置及び方法に関する。 The present invention CO 2 is contained in the gas (carbon dioxide) or H 2 S (hydrogen sulfide) or absorption Osamueki you added to the absorption liquid to remove the both, CO 2 or H 2 S using the absorbing solution Or it is related with the removal apparatus and method of both.
近年、地球の温暖化現象の原因の一つとして、ＣＯ2 による温室効果が指摘され、地球環境を守る上で国際的にもその対策が急務となってきた。ＣＯ2 の発生源としては、化石燃料を燃焼させるあらゆる人間の活動分野に及び、その排出抑制への要求が一層強まる傾向にある。これに伴い大量の化石燃料を使用する火力発電所などの動力発生設備を対象に、ボイラの燃焼排ガスをアルカノールアミン水溶液等と接触させ、ガス中のＣＯ2 を除去し、回収する方法、及び回収されたＣＯ2 を大気へ放出することなく貯蔵する方法が精力的に研究されている。また、ＣＯ2 （二酸化炭素）以外にＨ2Ｓ（硫化水素）等の酸性ガスを除去することが提案されている。 In recent years, the greenhouse effect due to CO 2 has been pointed out as one of the causes of global warming, and countermeasures have become urgent internationally to protect the global environment. The source of CO 2 extends to all human activity fields where fossil fuels are burned, and there is a tendency to further demand for emission control. Along with this, for power generation facilities such as thermal power plants that use a large amount of fossil fuel, the boiler combustion exhaust gas is contacted with an alkanolamine aqueous solution, etc., and CO 2 in the gas is removed and recovered. A method for storing the produced CO 2 without releasing it to the atmosphere has been energetically studied. In addition to CO 2 (carbon dioxide), it has been proposed to remove acidic gases such as H 2 S (hydrogen sulfide).
前記アルカノールアミンとしては、モノエタノールアミン（ＭＥＡ）、トリエタノールアミン、Ｎ−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、ジグリコールアミンなどを挙げることができるが、通常モノエタノールアミン（ＭＥＡ）が好んで用いられる。また、これらのアルカノールアミンに吸収助剤として例えばピペラジン等の環状アミン、エチレンジアミン等の直鎖状アミンを用いることも提案されている（特許文献１、２）。
Examples of the alkanolamine include monoethanolamine (MEA), triethanolamine, N-methyldiethanolamine (MDEA), diisopropanolamine, and diglycolamine, but monoethanolamine (MEA) is usually preferred. Used. It has also been proposed to use a cyclic amine such as piperazine or a linear amine such as ethylenediamine as an absorption aid for these alkanolamines (
しかしながら、下記に示すピペラジン等の環状アミンは、活性が高く、主成分（主剤）或いは、副成分（助剤）として使用されているが長期間の使用において開環すなわち劣化が生じる場合があり、性能低下の要因となる（非特許文献１）。一方、これまでに提唱されている直鎖状のエチレンジアミン（ＮＨ2ＣＨ2ＣＨ2ＮＨ2）は、腐食性が比較的高い１級アミンであるので、高性能で高活性と耐久性および低腐食性を併せ持つ吸収液の出現が切望されている。 However, cyclic amines such as piperazine shown below have high activity and may be used as a main component (main agent) or subcomponent (auxiliary), but ring opening or deterioration may occur in long-term use. It becomes a factor of a performance fall (nonpatent literature 1). On the other hand, the linear ethylenediamine (NH 2 CH 2 CH 2 NH 2 ) proposed so far is a primary amine having a relatively high corrosivity, so it has high performance, high activity, durability and low corrosion. The advent of absorbing liquids that have sex is eagerly desired.
本発明は、前記問題に鑑み、ガス中のＣＯ2又はＨ2Ｓ又はその双方の除去を長時間に亙って安定して除去でき、しかも腐食性が少ない吸収液、 吸収液を用いたＣＯ2又はＨ2Ｓ又はその双方の除去装置及び方法を提供することを課題とする。 In view of the above problems, use over a long period of time CO 2 or H 2 S or removal of both gas can stably removed, moreover corrosive low I吸 Osamueki, the absorbing solution It is an object of the present invention to provide an apparatus and method for removing CO 2 and / or H 2 S.
上述した課題を解決するための本発明の第１の発明は、ガス中のＣＯ2又はＨ2Ｓ又はその双方を吸収する吸収液に含まれるアミン系化合物の主剤が、モノエタノールアミン（ＭＥＡ）、メチルジエタノールアミン（ＭＤＥＡ）、ジエタノールアミン（ＤＥＡ）、トリエタノールアミン（ＴＥＡ）、ジイソプロパノールアミン（ＤＩＰＡ）、３−アミノ−１−プロパノール（ＡＰ）、２−アミノ２−メチルプロパノール（ＡＭＰ）、エチルジエタノールアミン（ＥＤＥＡ）、２−メチルアミノエタノール（ＭＡＥ）、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、２−ｎ−ブチルアミノエタノール（ｎ−ＢＡＥ）、２−ｎ−ペンチルアミノエタノール、２−イソプロピルアミノエタノール、２−ｓｅｃ−ブチルアミノエタノール、２−イソブチルアミノエタノール（ＩＢＡＥ）、２−ジメチルアミノエタノール（ＤＭＡＥ）、又は２−ジエチルアミノエタノール（ＤＥＡＥ）の少なくとも一つであると共に、ジアミン系助剤を含み、且つ前記ジアミン系助剤が、Ｎ，Ｎ’ジメチルエタンジアミン、Ｎ，Ｎ’ジメチルプロパンジアミン、Ｎ，Ｎ’ジエチルエタンジアミン、Ｎ，Ｎ’ジエチループロパンジアミン、Ｎ，Ｎ’ジイソプロピルエタンジアミン、又はＮ，Ｎ’ジターシャルブチルエタンジアミンのいずれかであることを特徴とする吸収液にある。
第２の発明は、ガス中のＣＯ2又はＨ2Ｓ又はその双方を吸収する吸収液に含まれるアミン系化合物の主剤が、モノエタノールアミン（ＭＥＡ）、メチルジエタノールアミン（ＭＤＥＡ）、ジエタノールアミン（ＤＥＡ）、トリエタノールアミン（ＴＥＡ）、ジイソプロパノールアミン（ＤＩＰＡ）、３−アミノ−１−プロパノール（ＡＰ）、２−アミノ２−メチルプロパノール（ＡＭＰ）、エチルジエタノールアミン（ＥＤＥＡ）、２−メチルアミノエタノール（ＭＡＥ）、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、２−ｎ−ブチルアミノエタノール（ｎ−ＢＡＥ）、２−ｎ−ペンチルアミノエタノール、２−イソプロピルアミノエタノール、２−ｓｅｃ−ブチルアミノエタノール、２−イソブチルアミノエタノール（ＩＢＡＥ）、２−ジメチルアミノエタノール（ＤＭＡＥ）、又は２−ジエチルアミノエタノール（ＤＥＡＥ）の少なくとも一つであると共に、トリアミン系助剤を含み、且つ前記トリアミン系助剤が、ビス（２メチルアミノエチル）アミン又はビス（３メチルアミノプロピル）アミンであることを特徴とする吸収液にある。
The first invention of the present invention for solving the above-described problem is that the main component of the amine compound contained in the absorbing solution that absorbs CO 2 or H 2 S or both in the gas is monoethanolamine (MEA). , Methyldiethanolamine (MDEA), diethanolamine (DEA), triethanolamine (TEA), diisopropanolamine (DIPA), 3-amino-1-propanol (AP), 2-amino-2-methylpropanol (AMP), ethyldiethanolamine (EDEA), 2-methylaminoethanol (MAE), 2-ethylaminoethanol (EAE), 2-n-propylaminoethanol, 2-n-butylaminoethanol (n-BAE), 2-n-pentylaminoethanol 2-isopropylaminoethanol, 2-sec-buty It is at least one of aminoethanol, 2-isobutylaminoethanol (IBAE), 2-dimethylaminoethanol (DMAE), or 2-diethylaminoethanol (DEAE) and contains a diamine-based auxiliary, and the diamine-based auxiliary but, N, N 'dimethyl ethanediamine, N, N' dimethyl propanediamine, N, N 'diethyl-ethanediamine, N, N' diethyl-over-propanediamine, N, N 'diisopropyl-ethanediamine, or N, N' Jitasharu The absorbent is characterized by being one of butylethanediamine.
In the second invention, the main component of the amine compound contained in the absorbing liquid that absorbs CO 2 or H 2 S or both in the gas is monoethanolamine (MEA), methyldiethanolamine (MDEA), diethanolamine (DEA). , Triethanolamine (TEA), diisopropanolamine (DIPA), 3-amino-1-propanol (AP), 2-amino-2-methylpropanol (AMP), ethyldiethanolamine (EDEA), 2-methylaminoethanol (MAE) ), 2-ethylaminoethanol (EAE), 2-n-propylaminoethanol, 2-n-butylaminoethanol (n-BAE), 2-n-pentylaminoethanol, 2-isopropylaminoethanol, 2-sec- Butylaminoethanol, 2-isobutyla It is at least one of noethanol (IBAE), 2-dimethylaminoethanol (DMAE), or 2-diethylaminoethanol (DEAE), contains a triamine-based auxiliary, and the triamine-based auxiliary is bis (2 methyl The absorption liquid is characterized by being aminoethyl) amine or bis (3-methylaminopropyl) amine .
第３の発明は、第１又は第２の発明において、前記主剤の濃度が１５〜６５重量％の範囲であると共に、助剤の濃度が１．０〜６５重量％の範囲であることを特徴とする吸収液にある。 A third invention is characterized in that, in the first or second invention, the concentration of the main agent is in the range of 15 to 65% by weight and the concentration of the auxiliary agent is in the range of 1.0 to 65% by weight. It is in the absorption liquid.
第４の発明は、 ＣＯ2又はＨ2Ｓ又はその双方を含有するガスと吸収液とを接触させてＣＯ2又はＨ2Ｓ又はその双方を除去する吸収塔と、ＣＯ2又はＨ2Ｓ又はその双方を吸収した溶液を再生する再生塔と、再生塔でＣＯ2又はＨ2Ｓ又はその双方を除去して再生した溶液を吸収塔で再利用するＣＯ2又はＨ2Ｓ又はその双方の除去装置であって、第１乃至３のいずれか一つの吸収液を用いてなることを特徴とするＣＯ2又はＨ2Ｓ又はその双方の除去装置にある。 According to a fourth aspect of the present invention, there is provided an absorption tower for removing CO 2 or H 2 S or both by bringing a gas containing CO 2 or H 2 S or both into contact with an absorption liquid, CO 2 or H 2 S or a regenerator for reproducing a solution which has absorbed the both regenerator in a CO 2 or H 2 S or CO 2 removal or H 2 S or both reusing solution was regenerated to remove both of the absorption tower An apparatus for removing CO 2 and / or H 2 S, or both, characterized by using any one of the first to third absorbing liquids.
第５の発明は、ＣＯ2又はＨ2Ｓ又はその双方を含有するガスと吸収液とを接触させてＣＯ2又はＨ2Ｓ又はその双方を除去する吸収塔と、ＣＯ2又はＨ2Ｓ又はその双方を吸収した溶液を再生する再生塔と、再生塔でＣＯ2又はＨ2Ｓ又はその双方を除去して再生した溶液を吸収塔で再利用するＣＯ2又はＨ2Ｓ又はその双方の除去方法であって、第１乃至３のいずれか一つの吸収液を用いてＣＯ2又はＨ2Ｓ又はその双方を除去することを特徴とするＣＯ2又はＨ2Ｓ又はその双方の除去方法にある。 According to a fifth aspect of the present invention, there is provided an absorption tower for removing CO 2 or H 2 S or both by bringing a gas containing CO 2 or H 2 S or both into contact with an absorbing solution, and CO 2 or H 2 S or a regenerator for reproducing a solution which has absorbed the both regenerator in a CO 2 or H 2 S or CO 2 removal or H 2 S or both reusing solution was regenerated to remove both of the absorption tower A method for removing CO 2 and / or H 2 S or both, wherein CO 2 and / or H 2 S or both are removed using any one of the first to third absorbing liquids. .
本発明によれば、開環による劣化がない鎖状のジアミン系助剤とトリアミン系助剤とを含む吸収液とするので、ガス中のＣＯ2 又はＨ2Ｓ又はその双方を長期間に亙って、良好な吸収を行うことができる。
また、Ｎ基が一つの環状アミンとするので、開環がしにくくなり、ガス中のＣＯ2 又はＨ2Ｓ又はその双方を長期間に亙って、良好な吸収を行うことができる。
According to the present invention, since the absorbent includes the chain-like diamine-based auxiliary and the triamine-based auxiliary that are not deteriorated by ring-opening, CO 2 or H 2 S in the gas or both can be reduced over a long period of time. Thus, good absorption can be performed.
Further, since the N group is a single cyclic amine, ring opening is difficult, and good absorption can be achieved over a long period of time in CO 2 and / or H 2 S in the gas.
以下、この発明につき図面を参照しつつ詳細に説明する。なお、この実施形態、実施例によりこの発明が限定されるものではない。また、下記実施形態、実施例における構成要素には、当業者が容易に想定できるもの、あるいは実質的に同一のものが含まれる。 Hereinafter, the present invention will be described in detail with reference to the drawings. In addition, this invention is not limited by this embodiment and an Example. In addition, constituent elements in the following embodiments and examples include those that can be easily assumed by those skilled in the art or those that are substantially the same.
［発明の実施形態］
本発明の第１の実施形態にかかる吸収液は、下記特定の主剤（Ｉ）〜（III）に対し、該主剤に添加して下記特定の吸収助剤（１）〜（２）を選定することで、ガス中のＣＯ2やＨ2Ｓ等の酸性ガスを除去するようにしたものである。
[Embodiment of the Invention]
The absorbent according to the first embodiment of the present invention selects the following specific absorption aids (1) to (2) by adding to the main agent with respect to the following main agents (I) to (III). Thus, acid gases such as CO 2 and H 2 S in the gas are removed.
ｘ、ｙは、１≦ｘ≦５、２≦ｙ≦１０であり、
Ｒ1、Ｒ2、Ｒ3、Ｒ4は、−ＣiＨjＯkＮl（ここで、ｉ＝０〜１０、ｊ＝１〜２１、ｋ＝０〜５、ｌ＝０〜５である。）である。
x and y are 1 ≦ x ≦ 5, 2 ≦ y ≦ 10,
R 1 , R 2 , R 3 , R 4 are —C i H j O k N l (where i = 0 to 10, j = 1 to 21, k = 0 to 5, l = 0 to 5 Yes.)
Ｒ5、Ｒ6、Ｒ7、Ｒ9、Ｒ10、Ｒ11は、−ＣaＨbＯc（ここで、ａ＝０〜１０、ｂ＝１〜２１、ｃ＝０〜５である。）であり、
Ｒ8、Ｒ12は、−ＣpＨq（ここで、p＝x−１、ｘ、又はｘ＋１、ｑ＝０〜２ｘ＋２である。）である。
R 5 , R 6 , R 7 , R 9 , R 10 and R 11 are —C a H b O c (where a = 0 to 10, b = 1 to 21, and c = 0 to 5). ) And
R 8 and R 12 are —C p H q (where p = x−1, x, or x + 1, q = 0 to 2x + 2).
そして、両化合物を含有した水溶液を吸収液として使用することにより、各化合物の単独の使用では得られない優れたＣＯ2やＨ2Ｓ等の酸性ガスの吸収性能が発揮される。 And by using the aqueous solution containing both compounds as an absorbing solution, excellent absorption performance of acidic gases such as CO 2 and H 2 S, which cannot be obtained by using each compound alone, is exhibited.
すなわち、図２に示す吸収模式図に示すように、例えば主剤を２−エチルアミノエタノール（ＥＡＥ）とし、助剤をＮ，Ｎ’ジメチルプロパンジアミンとした場合、主剤のＯＨ基における電荷はＯδ-Ｈδ+となり、ジアミンのＮ基では、Ｎδ-Ｈδ+となる。その結果、ＯＨδ+・・・Ｎδ-あるいは、ＮＨδ+・・・Ｏδ-という分子間水素結合が生成して強いアンカー効果が生じると共に、ジアミンの他方のＮ基がＥＡＥのＮ基に作用して、相互作用により、ジアミンのＮ基側のＨが切断され、ここにＣＯ2が結合する。一方、主剤は、プロトン化して重炭酸イオンや炭酸イオンの生成に寄与する。これにより、ＣＯ2等の酸性液の吸収を補完・促進することとなる。 That is, as shown in absorption schematic diagram shown in FIG. 2, for example, when the main agent 2-ethylamino ethanol (EAE), was auxiliaries N, and N 'dimethyl propanediamine, charge in the OH groups of the base resin Oderuta - Hδ + , and in the diamine N group, Nδ − Hδ + . As a result, an intermolecular hydrogen bond of OHδ + ... Nδ − or NHδ + ... Oδ − is generated to cause a strong anchor effect, and the other N group of the diamine acts on the N group of EAE. By the interaction, H on the N group side of the diamine is cleaved, and CO 2 is bonded thereto. On the other hand, the main agent is protonated and contributes to the production of bicarbonate ions and carbonate ions. By this, the complement and promote the absorption of acidic liquid such as CO 2.
ここで、本発明で用いられる式（Ｉ）にかかる主剤は、例えばモノエタノールアミン（ＭＥＡ）、メチルジエタノールアミン（ＭＤＥＡ）、ジエタノールアミン（ＤＥＡ）、トリエタノールアミン（ＴＥＡ）、ジイソプロパノールアミン（ＤＩＰＡ）、３−アミノ−１−プロパノール（ＡＰ）、２−アミノ２−メチルプロパノール（ＡＭＰ）、エチルジエタノールアミン（ＥＤＥＡ）、２−メチルアミノエタノール（ＭＡＥ）、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、２−ｎ−ブチルアミノエタノール（ｎ−ＢＡＥ）、２−ｎ−ペンチルアミノエタノール、２−イソプロピルアミノエタノール、２−ｓｅｃ−ブチルアミノエタノール、２−イソブチルアミノエタノール（ＩＢＡＥ）、２−ジメチルアミノエタノール（ＤＭＡＥ）、２−ジエチルアミノエタノール（ＤＥＡＥ）等を例示することができる。 Here, the main agent according to the formula (I) used in the present invention is, for example, monoethanolamine (MEA), methyldiethanolamine (MDEA), diethanolamine (DEA), triethanolamine (TEA), diisopropanolamine (DIPA), 3-amino-1-propanol (AP), 2-amino-2-methylpropanol (AMP), ethyldiethanolamine (EDEA), 2-methylaminoethanol (MAE), 2-ethylaminoethanol (EAE), 2-n- Propylaminoethanol, 2-n-butylaminoethanol (n-BAE), 2-n-pentylaminoethanol, 2-isopropylaminoethanol, 2-sec-butylaminoethanol, 2-isobutylaminoethanol (IBAE), 2- Dimethylamino Ethanol (DMAE), can be exemplified 2-diethylaminoethanol (DEAE) or the like.
特に、式（Ｉ）において、ｘが２、ｙが４であり、Ｒ1、Ｒ2がＨであるモノエタノールアミン（ＭＥＡ）、或いは式（Ｉ）において、ｘが２、ｙが４であり、Ｒ1、がＣＨ3、Ｒ2がＣ2Ｈ4ＯＨであるメチルジエタノールアミン（ＭＤＥＡ）とするのが、好ましい。 In particular, in formula (I), x is 2 and y is 4 and R 1 and R 2 are H, or monoethanolamine (MEA), or in formula (I), x is 2 and y is 4 , R 1 is preferably CH 3 and R 2 is C 2 H 4 OH, preferably methyldiethanolamine (MDEA).
ここで、本発明で用いられる式（II）にかかる主剤は、例えば２，３−ジアミノプロピオン酸（ＤＡＰＡ）、グリシン等を例示することができる。 Here, examples of the main agent according to the formula (II) used in the present invention include 2,3-diaminopropionic acid (DAPA), glycine and the like.
ここで、本発明で用いられる式（III）にかかる主剤は、例えば１，２−エチレンジアミン等を例示することができる。
なお、これらアミン化合物は、２種以上を混合して用いてもよい。
Here, the main agent concerning Formula (III) used by this invention can illustrate a 1, 2- ethylenediamine etc., for example.
In addition, you may use these amine compounds in mixture of 2 or more types.
また、本発明で用いられる式（１）にかかるジアミン系助剤は、Ｎ，Ｎ’ジメチルエタンジアミン、Ｎ，Ｎ’ジメチルプロパンジアミン、Ｎ，Ｎ’ジエチルエタンジアミン、Ｎ，Ｎ’ジエチループロパンジアミン、Ｎ，Ｎ’ジイソプロピルエタンジアミン、Ｎ，Ｎ’ジターシャルブチルエタンジアミンを例示することができる。 Further, diamine-based aid according to formula (1) used in the present invention is, N, N 'dimethyl ethanediamine, N, N' dimethyl propanediamine, N, N 'diethyl-ethanediamine, N, N' diethyl over propane diamine, N, N 'diisopropyl-ethanediamine, N, N' can be exemplified di-tert-butyl-ethanediamine.
また、本発明で用いられる式（２）にかかるトリアミン系助剤は、ビス（２メチルアミノエチル）アミン、ビス（３メチルアミノプロピル）アミンを例示することができる。 Moreover, the triamine type | system | group adjuvant concerning Formula (2) used by this invention can illustrate bis (2 methylamino ethyl) amine and bis (3 methyl amino propyl) amine.
主剤に対して、式（１）、（２）中のＲ8、Ｒ12が、−ＣpＨq（ここで、p＝x−１、ｘ、又はｘ＋１、ｑ＝０〜２ｘ＋２である。）とすることで、立体的に類似し、アンカー効果と、相互作用とが良好に発揮されることとなる。 R 8 and R 12 in the formulas (1) and (2) are —C p H q (where p = x−1, x, or x + 1, q = 0 to 2x + 2 with respect to the main agent). ), It is three-dimensionally similar, and the anchor effect and the interaction are satisfactorily exhibited.
また、鎖状のアミンであるので、ピペラジンのような開環することで、性能の低下が発生することがなく、長期間に亙って安定して酸性ガスの除去を行うことができる。 Further, since it is a chain amine, ring opening like piperazine does not cause performance degradation, and acid gas can be removed stably over a long period of time.
また、本発明の第２の実施形態にかかる吸収液は、前述した特定の主剤に対し、該主剤に添加して反応を促進する下記特定のＮ基が１つの環状アミンの吸収助剤を選定することで、ガス中のＣＯ2やＨ2Ｓ等の酸性ガスを除去するようにしたものである。 In addition, the absorption liquid according to the second embodiment of the present invention selects an absorption aid for a cyclic amine having one specific N group, which is added to the main agent and promotes the reaction, with respect to the specific main agent described above. By doing so, acidic gases such as CO 2 and H 2 S in the gas are removed.
Ｎ基が１つの環状アミンは、下記に示すような例えばピロリジン、ピペリジン、アゼピン、オクタヒドロアゾシン等を例示することができる。
このように、助剤をＮ基が一つの環状アミンとするので、開環がしにくくなり、ガス中のＣＯ2 又はＨ2Ｓ又はその双方を長期間に亙って、良好な吸収を行うことができる。 In this way, since the auxiliary agent is a cyclic amine having one N group, ring opening is difficult, and CO 2 and / or H 2 S in the gas or both of them are absorbed over a long period of time. be able to.
また、主剤としては、前述した例示にかかる主剤であれば、特に限定されるものではないが、前述した中でも、２−メチルアミノエタノール（ＭＡＥ）、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、２−ｎ−ブチルアミノエタノール（ｎ−ＢＡＥ）、２−ｎ−ペンチルアミノエタノール、２−イソプロピルアミノエタノール、２−ｓｅｃ−ブチルアミノエタノール、２−イソブチルアミノエタノール（ＩＢＡＥ）、２−ジメチルアミノエタノール（ＤＭＡＥ）、２−ジエチルアミノエタノール（ＤＥＡＥ）とするのが好ましい。 In addition, the main agent is not particularly limited as long as it is the main agent according to the above-described examples, but among the above-described examples, 2-methylaminoethanol (MAE), 2-ethylaminoethanol (EAE), 2-n -Propylaminoethanol, 2-n-butylaminoethanol (n-BAE), 2-n-pentylaminoethanol, 2-isopropylaminoethanol, 2-sec-butylaminoethanol, 2-isobutylaminoethanol (IBAE), 2 -Dimethylaminoethanol (DMAE) and 2-diethylaminoethanol (DEAE) are preferable.
ここで、本発明のガスとの接触に用いる吸収液中の前記主剤の濃度は１５〜６５重量％の範囲、より好ましくは３０〜５０重量％の範囲とするのが好ましい。 Here, the concentration of the main agent in the absorbent used for contact with the gas of the present invention is preferably in the range of 15 to 65% by weight, more preferably in the range of 30 to 50% by weight.
一方、助剤の濃度としては、通常１．０〜６５重量％の範囲、より好ましくは１．５〜１５重量％の範囲とするのが好ましい。なお、主剤と助剤との両者の合計濃度が高くなると粘度が上昇するなどの制限から、両者の合計濃度が７０重量％以下で使用することが好ましい。 On the other hand, the concentration of the auxiliary is usually in the range of 1.0 to 65% by weight, more preferably in the range of 1.5 to 15% by weight. It should be noted that the total concentration of both the main agent and the auxiliary agent is preferably 70% by weight or less because of the limitation that the viscosity increases when the total concentration of the main agent and the auxiliary agent increases.
本発明において、ガスとの接触時の吸収液の温度は、通常３０〜７０℃の範囲である。また本発明で用いる吸収液には、必要に応じて腐食防止剤、劣化防止剤などが加えられる。 In the present invention, the temperature of the absorbent at the time of contact with the gas is usually in the range of 30 to 70 ° C. Moreover, a corrosion inhibitor, a deterioration inhibitor, etc. are added to the absorption liquid used by this invention as needed.
さらに、本発明における大気圧下とは、燃焼排ガスを供給するためブロワなどを作用させる程度の大気圧近傍の圧力範囲は含まれるものである。 Furthermore, under atmospheric pressure in the present invention includes a pressure range in the vicinity of atmospheric pressure to the extent that a blower or the like acts to supply combustion exhaust gas.
本発明により処理されるガスとしては、例えば石炭ガス化ガス、合成ガス、コークス炉ガス、石油ガス、天然ガス等を挙げることができるが、これらの限定されるものではなく、ＣＯ2やＨ2Ｓ等の酸性ガスを含むガスであれば、いずれのガスでもよい。 Examples of the gas to be treated according to the present invention include coal gasification gas, synthesis gas, coke oven gas, petroleum gas, natural gas and the like, but are not limited thereto, and CO 2 and H 2 are not limited thereto. Any gas may be used as long as it contains an acid gas such as S.
本発明のガス中のＣＯ2又はＨ2Ｓ又はその双方を除去する方法で採用できるプロセスは、特に限定されないが、ＣＯ2を除去する除去装置の一例について図１を参照しつつ説明する。 The process that can be employed in the method for removing CO 2 and / or H 2 S in the gas of the present invention is not particularly limited, but an example of a removal apparatus for removing CO 2 will be described with reference to FIG.
図１はＣＯ2除去装置の概略図である。図１に示すように、ガスは、ＣＯ2含有ガス供給口４を通って、吸収塔１へ導かれる。吸収塔１に押し込められた該ガスは、ノズル７から供給される一定濃度の主剤と助剤とを含有するＣＯ2吸収液と充填部２で向流接触させられ、ガス中のＣＯ2は、吸収液により吸収除去され、ガスは、脱ＣＯ2ガス排出口５から排出される。吸収塔１に供給される吸収液は、ＣＯ2を吸収し、熱交換器１４、加熱器８に送られ、加熱されて再生塔１５に送られる。該再生塔１５では、吸収液は、ノズル１６より充填部１７を経て、下部に流れる。この間にＣＯ2が脱離して吸収液が再生する。再生した吸収液は、ポンプ９によって熱交換器１４、吸収液冷却器２６を経て、吸収液供給口６から吸収塔１に戻される。一方、再生塔１５の上部において、吸収液から分離されたＣＯ2は、ノズル１８から供給される還流水と接触し、再生塔還流冷却器２３により冷却され、還流ドラム２１にてＣＯ2に同伴した水蒸気が凝縮した還流水と分離し、回収ＣＯ2ライン２２よりＣＯ2回収工程に導かれる。還流水は、還流水ポンプ２０で再生塔１５に送られる。なお、この実施の形態では、あくまでその概要を説明するものであり、付属する機器を一部省略して説明している。
FIG. 1 is a schematic view of a CO 2 removal apparatus. As shown in FIG. 1, the gas is guided to the
以下、実施例に基づき、本発明についてさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail based on examples.
図示しない吸収装置を用いて、ＣＯ2の吸収を行った。本実施例の吸収液組成は、主剤５．６ｍｏｌ／ｋｇ（５０重量％）に対し、助剤を０．３５ｍｏｌ／ｋｇ添加した。
また、温度は４０℃とし、吸収液１５０ｇに対し、ＣＯ2含有ガスを２．０ ＮＬ（ｄｒｙ）／ｍｉｎで流した。なお、ガス組成はＣＯ2:９．９％で、残りをＮ2とした。
CO 2 was absorbed using an absorption device (not shown). In the absorption liquid composition of this example, 0.35 mol / kg of an auxiliary agent was added to 5.6 mol / kg (50% by weight) of the main agent.
The temperature was 40 ° C., and a CO 2 -containing gas was allowed to flow at 2.0 NL (dry) / min with respect to 150 g of the absorbing solution. The gas composition was CO 2 : 9.9%, and the remainder was N 2 .
本実施例において、主剤としては、２−エチルアミノエタノール（ＥＡＥ）を用い、助剤としては、Ｎ，Ｎ’ジメチルプロパンジアミン（実施例１）、ピロリジン（実施例２）、ピペリジン（実施例３）、アゼピン（実施例４）を用いた。なお、比較例の助剤として、メチルピペラジンを用いた。 In this embodiment, as the base resin, using 2-ethylamino ethanol (EAE), as auxiliaries, N, N 'dimethyl-propanediamine (Example 1), pyrrolidine (Example 2), piperidine (Example 3 ), Azepine (Example 4) was used. In addition, methyl piperazine was used as an auxiliary agent in the comparative example.
前記実施例及び比較例にかかるＣＯ2吸収速度の結果を、表１に示す。
ここで、ＣＯ2吸収速度（ｍｏｌ−ＣＯ2／ｈ）とは、１時間当たりで吸収できるＣＯ2吸モル数をいう。本実施例では、ＣＯ2吸収量０．４ｍｏｌ−ＣＯ2／ｍｏｌ−アミン条件において測定した。
Table 1 shows the results of CO 2 absorption rates according to the examples and comparative examples.
Here, the CO 2 absorption rate (mol-CO 2 / h) refers to the number of moles of CO 2 that can be absorbed per hour. In this example, the CO 2 absorption was measured under the condition of 0.4 mol-CO 2 / mol-amine.
表１に示すように、助剤として用いたＮ，Ｎ’ジメチルプロパンジアミン（実施例１）、ピロリジン（実施例２）、ピペリジン（実施例３）、アゼピン（実施例４）は、比較例１のメチルピペラジンに較べてＣＯ2吸収速度が良好であった。 As shown in Table 1, N was used as auxiliaries, N 'dimethyl-propanediamine (Example 1), pyrrolidine (Example 2), piperidine (Example 3), azepine (Example 4), Comparative Example 1 CO 2 absorption rate was better than that of methyl piperazine.
以上のように、本発明にかかる吸収液によれば、開環による劣化を回避し長期間に亙って安定して用いることができ、腐食を押さえ、しかも吸収能力は従来と同等以上であるので、各種ボイラ等のプラント設備の排ガス処理に用いて適している。 As described above, the absorbent according to the present invention can be used stably over a long period of time by avoiding deterioration due to ring opening, suppresses corrosion, and has an absorption capacity equal to or higher than that of the conventional one. Therefore, it is suitable for use in exhaust gas treatment of plant equipment such as various boilers.
１ 吸収塔
１５ 再生塔
1
Claims (5)
モノエタノールアミン（ＭＥＡ）、メチルジエタノールアミン（ＭＤＥＡ）、ジエタノールアミン（ＤＥＡ）、トリエタノールアミン（ＴＥＡ）、ジイソプロパノールアミン（ＤＩＰＡ）、３−アミノ−１−プロパノール（ＡＰ）、２−アミノ２−メチルプロパノール（ＡＭＰ）、エチルジエタノールアミン（ＥＤＥＡ）、２−メチルアミノエタノール（ＭＡＥ）、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、２−ｎ−ブチルアミノエタノール（ｎ−ＢＡＥ）、２−ｎ−ペンチルアミノエタノール、２−イソプロピルアミノエタノール、２−ｓｅｃ−ブチルアミノエタノール、２−イソブチルアミノエタノール（ＩＢＡＥ）、２−ジメチルアミノエタノール（ＤＭＡＥ）、又は２−ジエチルアミノエタノール（ＤＥＡＥ）の少なくとも一つであると共に、ジアミン系助剤を含み、且つ
前記ジアミン系助剤が、Ｎ，Ｎ’ジメチルエタンジアミン、Ｎ，Ｎ’ジメチルプロパンジアミン、Ｎ，Ｎ’ジエチルエタンジアミン、Ｎ，Ｎ’ジエチループロパンジアミン、Ｎ，Ｎ’ジイソプロピルエタンジアミン、又はＮ，Ｎ’ジターシャルブチルエタンジアミンのいずれかであることを特徴とする吸収液。 The main component of the amine compound contained in the absorption liquid that absorbs CO 2 or H 2 S or both in the gas,
Monoethanolamine (MEA), methyldiethanolamine (MDEA), diethanolamine (DEA), triethanolamine (TEA), diisopropanolamine (DIPA), 3-amino-1-propanol (AP), 2-amino-2-methylpropanol (AMP), ethyldiethanolamine (EDEA), 2-methylaminoethanol (MAE), 2-ethylaminoethanol (EAE), 2-n-propylaminoethanol, 2-n-butylaminoethanol (n-BAE), 2 -N-pentylaminoethanol, 2-isopropylaminoethanol, 2-sec-butylaminoethanol, 2-isobutylaminoethanol (IBAE), 2-dimethylaminoethanol (DMAE), or 2-diethylaminoethanol With at least one of (DEAE), it comprises a diamine-based aids, and the diamine-based aid, N, N 'dimethyl ethanediamine, N, N' dimethyl propanediamine, N, N 'diethyl-ethanediamine, N, N 'diethyl-over-propanediamine, N, N' diisopropyl-ethanediamine, or N, the absorption liquid which is characterized in that either N 'di-tert-butyl-ethanediamine.
モノエタノールアミン（ＭＥＡ）、メチルジエタノールアミン（ＭＤＥＡ）、ジエタノールアミン（ＤＥＡ）、トリエタノールアミン（ＴＥＡ）、ジイソプロパノールアミン（ＤＩＰＡ）、３−アミノ−１−プロパノール（ＡＰ）、２−アミノ２−メチルプロパノール（ＡＭＰ）、エチルジエタノールアミン（ＥＤＥＡ）、２−メチルアミノエタノール（ＭＡＥ）、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、２−ｎ−ブチルアミノエタノール（ｎ−ＢＡＥ）、２−ｎ−ペンチルアミノエタノール、２−イソプロピルアミノエタノール、２−ｓｅｃ−ブチルアミノエタノール、２−イソブチルアミノエタノール（ＩＢＡＥ）、２−ジメチルアミノエタノール（ＤＭＡＥ）、又は２−ジエチルアミノエタノール（ＤＥＡＥ）の少なくとも一つであると共に、トリアミン系助剤を含み、且つ
前記トリアミン系助剤が、ビス（２メチルアミノエチル）アミン又はビス（３メチルアミノプロピル）アミンであることを特徴とする吸収液。 The main component of the amine compound contained in the absorption liquid that absorbs CO 2 or H 2 S or both in the gas,
Monoethanolamine (MEA), methyldiethanolamine (MDEA), diethanolamine (DEA), triethanolamine (TEA), diisopropanolamine (DIPA), 3-amino-1-propanol (AP), 2-amino-2-methylpropanol (AMP), ethyldiethanolamine (EDEA), 2-methylaminoethanol (MAE), 2-ethylaminoethanol (EAE), 2-n-propylaminoethanol, 2-n-butylaminoethanol (n-BAE), 2 -N-pentylaminoethanol, 2-isopropylaminoethanol, 2-sec-butylaminoethanol, 2-isobutylaminoethanol (IBAE), 2-dimethylaminoethanol (DMAE), or 2-diethylaminoethanol With at least one of (DEAE), it comprises a triamine based aids, and the triamine-based aid, characterized in that it is a bis (2-methylaminoethyl) amine or bis (3-methyl-aminopropyl) amine Absorbing liquid.
前記主剤の濃度が１５〜６５重量％の範囲であると共に、
助剤の濃度が１．０〜６５重量％の範囲であることを特徴とする吸収液。 In claim 1 or 2,
The concentration of the main agent is in the range of 15 to 65% by weight,
An absorbent, wherein the concentration of the auxiliary agent is in the range of 1.0 to 65% by weight.
請求項１乃至３のいずれか一つの吸収液を用いてなることを特徴とするＣＯ2又はＨ2Ｓ又はその双方の除去装置。 An absorption tower for removing CO 2 or H 2 S or both by bringing a gas containing CO 2 or H 2 S or both into contact with an absorbing solution, and a solution that has absorbed CO 2 or H 2 S or both A regenerator for regenerating CO 2 and / or H 2 S or both in the regenerator, and a CO 2 or H 2 S or both removing apparatus for reusing the solution regenerated in the absorption tower,
An apparatus for removing CO 2 and / or H 2 S or both, wherein the absorbing liquid according to any one of claims 1 to 3 is used.
請求項１乃至３のいずれか一つの吸収液を用いてＣＯ2又はＨ2Ｓ又はその双方を除去することを特徴とするＣＯ2又はＨ2Ｓ又はその双方の除去方法。 An absorption tower for removing CO 2 or H 2 S or both by bringing a gas containing CO 2 or H 2 S or both into contact with an absorbing solution, and a solution that has absorbed CO 2 or H 2 S or both and a regeneration tower for reproducing, a regenerator in a CO 2 or H 2 S or CO 2 or H 2 S or the method of removing its both reusing solution was regenerated to remove both of the absorption tower,
A method for removing CO 2 and / or H 2 S or both, wherein CO 2 and / or H 2 S or both are removed using the absorbing liquid according to any one of claims 1 to 3.
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| KR101142951B1 (en) * | 2008-04-10 | 2012-05-08 | 한국에너지기술연구원 | Composition comprising cyclic ring and terminal amin groups, and use thereof as absorbent for removing flue gas |
| PL2300128T3 (en) * | 2008-06-23 | 2014-01-31 | Basf Se | Absorption medium and method for removing sour gases from fluid streams, in particular from flue gases |
| FR2934172B1 (en) * | 2008-07-28 | 2011-10-28 | Inst Francais Du Petrole | ABSORBENT SOLUTION BASED ON N, N, N'N'-TETRAMETHYLHEXANE -1,6-DIAMINE AND PROCESS FOR REMOVING ACIDIC COMPOUNDS FROM A GASEOUS EFFLUENT |
| US8435325B2 (en) | 2008-10-23 | 2013-05-07 | Hitachi, Ltd. | Method and device for removing CO2 and H2S |
| AU2010283753B2 (en) * | 2009-08-11 | 2013-12-05 | Shell Internationale Research Maatschappij B.V. | Absorbent composition and process for removing CO2 and/or H2S from a gas comprising CO2 and /or H2S |
| JP5506486B2 (en) * | 2010-03-24 | 2014-05-28 | 公益財団法人地球環境産業技術研究機構 | Aqueous solution that effectively absorbs and recovers carbon dioxide contained in gas |
| JP5174216B2 (en) * | 2011-06-08 | 2013-04-03 | 三菱重工業株式会社 | Absorbing liquid, CO2 or H2S removing apparatus and method using absorbing liquid |
| DE102012222157A1 (en) | 2012-12-04 | 2014-06-05 | Evonik Industries Ag | Method for absorbing CO2 from a gas mixture |
| US20160001220A1 (en) * | 2013-02-25 | 2016-01-07 | Research Institute Of Innovative Technology For The Earth | Liquid for absorbing and collecting carbon dioxide in gas, and method for collecting carbon dioxide with use of same |
| CN105561734A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Thermosensitive amine group carbon dioxide absorbent |
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