JP3276527B2 - How to remove carbon dioxide in gas - Google Patents
How to remove carbon dioxide in gasInfo
- Publication number
- JP3276527B2 JP3276527B2 JP06403195A JP6403195A JP3276527B2 JP 3276527 B2 JP3276527 B2 JP 3276527B2 JP 06403195 A JP06403195 A JP 06403195A JP 6403195 A JP6403195 A JP 6403195A JP 3276527 B2 JP3276527 B2 JP 3276527B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- absorption
- aqueous solution
- amine compound
- amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Landscapes
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、例えば燃焼排ガスなど
のガス中に含まれるＣＯ2 （二酸化炭素）を除去する方
法に関する。さらに詳しくは、特定のアミン化合物を含
有する水溶液を用いて大気圧下の燃焼排ガスなどのガス
中のＣＯ2 を効率よく除去する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing CO 2 (carbon dioxide) contained in a gas such as a combustion exhaust gas. More specifically, the present invention relates to a method for efficiently removing CO 2 in a gas such as a combustion exhaust gas at atmospheric pressure using an aqueous solution containing a specific amine compound.
【０００２】[0002]
【従来の技術】従来より、天然ガス、合成ガスなどの化
学プラントで製造される各種産業ガス、燃焼排ガスなど
のガス（処理対象ガス）中に含まれる酸性ガス、特にＣ
Ｏ2 を回収・除去する方法が研究され、種々の方法が提
案されてきた。燃焼排ガスを例にとると、燃焼排ガス中
のＣＯ2 をアルカノールアミン水溶液と接触させて除去
して回収する方法、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。
アルカノールアミンとしては、モノエタノールアミン、
ジエタノールアミン、トリエタノールアミン、メチルジ
エタノールアミン、ジイソプロパノールアミン、ジグリ
コールアミンなどをあ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。2. Description of the Related Art Conventionally, acidic gases, particularly C, contained in various industrial gases produced in chemical plants such as natural gas and synthesis gas, and gases such as flue gas (gas to be treated).
Methods for recovering and removing O 2 have been studied, and various methods have been proposed. Taking virtue of flue gas as an example, we are vigorously researching methods of removing and collecting CO 2 in flue gas by contacting it with an alkanolamine aqueous solution and storing CO 2 without releasing it to the atmosphere. Have been.
As alkanolamines, monoethanolamine,
Examples thereof include diethanolamine, triethanolamine, methyldiethanolamine, diisopropanolamine, and diglycolamine, and monoethanolamine (MEA) is usually preferably used.
【０００３】しかし、ＭＥＡに代表される上記のような
アルカノールアミン水溶液をガス中のＣＯ2 を吸収・除
去する吸収剤として用いても、所定濃度のアミン水溶液
の所定量当たりのＣＯ2 の吸収量、所定濃度のアミン水
溶液の単位アミンモル当たりのＣＯ2 吸収量、所定濃度
におけるＣＯ2 の吸収速度、さらには吸収後のアルカノ
ールアミン水溶液の再生に要する熱エネルギなどに照ら
して、必ずしも満足のできるものではない。However, even with an aqueous alkanolamine solution, such as described above typified by MEA as an absorbent for absorbing and removing CO 2 in the gas, the absorption amount of CO 2 per predetermined amount of the aqueous amine solution having a predetermined concentration In view of the amount of CO 2 absorbed per unit amine mole of the aqueous amine solution having a predetermined concentration, the rate of absorption of CO 2 at the predetermined concentration, and the heat energy required for regeneration of the aqueous alkanolamine solution after absorption, it is not always satisfactory. Absent.
【０００４】ところで、各種混合ガスからアミン化合物
を用いて酸性ガスを分離する技術は数多く知られてい
る。特開昭５３−１００１８０号公報には、（１）環の
一部分であって、かつ第二炭素原子もしくは第三炭素原
子のどちらかに結合された少なくとも１個の第二アミノ
基または第三炭素原子に結合された第一アミノ基を含有
する立体障害アミン少なくとも５０モル％と第三アミノ
アルコール少なくとも約１０モル％とよりなるアミン混
合物及び（２）酸性ガスに対する物理的吸収剤である前
記アミン混合物用の溶媒からなるアミン−溶媒液体吸収
剤に通常ガス状の混合物を接触させることからなる酸性
ガスの除去法が記載されている。立体障害アミンとして
は２−ピペリジンエタノール〔２−（２−ヒドロキシエ
チル）−ピペリジン〕及び３−アミノ−３−メチル−１
−ブタノールなどが、また溶媒としては２５重量％まで
の水を含んでもよいスルホキシド化合物などが、さらに
処理ガスの例としては同公報１１頁左上欄に「高濃度の
二酸化炭素及び硫化水素、例えば３５％のＣＯ2及び１
０〜１２％のＨ2 Ｓを有する通常ガス状の混合物」が例
示され、また実施例にはＣＯ2 そのものが使用されてい
る。There are many known techniques for separating an acidic gas from various mixed gases using an amine compound. JP-A-53-100180 discloses (1) at least one secondary amino group or tertiary carbon which is part of a ring and is bonded to either a secondary carbon atom or a tertiary carbon atom. An amine mixture comprising at least 50 mol% of a sterically hindered amine containing a primary amino group bonded to an atom and at least about 10 mol% of a tertiary amino alcohol, and (2) the amine mixture which is a physical absorbent for an acidic gas A method for removing acidic gases comprising contacting a gaseous mixture with an amine-solvent liquid absorbent comprising a solvent for use is described. As sterically hindered amines, 2-piperidineethanol [2- (2-hydroxyethyl) -piperidine] and 3-amino-3-methyl-1
-Butanol, etc., as a solvent, a sulfoxide compound which may contain up to 25% by weight of water, etc., and as an example of a processing gas, a high concentration of carbon dioxide and hydrogen sulfide such as 35 % CO 2 and 1
Normally gaseous mixture with 0 to 12% of the H 2 S "is illustrated, also in the embodiment CO 2 itself is used.
【０００５】特開昭６１−７１８１９号公報には、立体
障害アミン及びスルホランなどの非水溶媒を含む酸性ガ
ススクラッピング用組成物が記載されている。また本公
報にはＣＯ2 の吸収に対し、立体障害アミンの有利性を
反応式を用いて説明している。JP-A-61-71819 describes a composition for scraping an acidic gas containing a non-aqueous solvent such as a sterically hindered amine and sulfolane. In addition, this publication describes the advantage of sterically hindered amines with respect to CO 2 absorption using a reaction formula.
【０００６】ケミカルエンジニアリングサイエンス（ C
hemical Engineering Science ) 、４１巻、４号、９９
７〜１００３頁には、ヒンダードアミンである２−アミ
ノ−２−メチル−１−プロパノール（ＡＭＰ）水溶液の
炭酸ガス吸収挙動が開示されている。吸収させるガスと
しては大気圧のＣＯ2 及びＣＯ2 と窒素の混合物が用い
られている。[0006] Chemical Engineering Science (C
chemical Engineering Science), Vol. 41, No. 4, 99
Pages 7 to 1003 disclose the carbon dioxide absorption behavior of an aqueous solution of hindered amine 2-amino-2-methyl-1-propanol (AMP). As a gas to be absorbed, atmospheric pressure CO 2 and a mixture of CO 2 and nitrogen are used.
【０００７】ケミカルエンジニアリングサイエンス（ C
hemical Engineering Science ) 、４１巻、２号、４０
５〜４０８頁には、常温付近において、ＡＭＰのような
ヒンダードアミンとＭＥＡのような直鎖アミンの各水溶
液のＣＯ2 やＨ2 Ｓに対する吸収速度が報告されてい
る。Chemical Engineering Science (C)
chemical Engineering Science), Vol. 41, No. 2, 40
On pages 5 to 408, the absorption rates of hindered amines such as AMP and linear amines such as MEA for CO 2 and H 2 S are reported at around normal temperature.
【０００８】米国特許３，６２２，２６７号明細書には
メチルジエタノールアミン及びモノエチルモノエタノー
ルアミンを含有する水性混合物を用い、原油などの部分
酸化ガスなどの合成ガスに含まれる高分圧のＣＯ2 、例
えば４０気圧の３０％ＣＯ2含有合成ガスを精製する技
術が開示されている。US Pat. No. 3,622,267 uses an aqueous mixture containing methyldiethanolamine and monoethylmonoethanolamine, and uses a high partial pressure of CO 2 contained in a synthesis gas such as a partially oxidized gas such as crude oil. For example, a technique for purifying a synthesis gas containing 30% CO 2 at 40 atm is disclosed.
【０００９】ドイツ公開特許１，５４２，４１５号公報
にはＣＯ2 、Ｈ2 Ｓ、ＣＯＳの吸収速度の向上のためモ
ノアルキルアルカノールアミンなどを物理または化学吸
収剤に添加する技術が開示されている。同様にドイツ公
開特許１，９０４，４２８号公報には、モノメチルエタ
ノールアミンがメチルジエタノールアミンの吸収速度を
向上させる目的で添加される技術が開示されている。[0009] German Patent Publication No. 1,542,415 discloses a technique of adding a monoalkylalkanolamine or the like to a physical or chemical absorbent in order to improve the absorption rate of CO 2 , H 2 S and COS. . Similarly, German Offenlegungsschrift 1,904,428 discloses a technique in which monomethylethanolamine is added for the purpose of improving the absorption rate of methyldiethanolamine.
【００１０】米国特許４，３３６，２３３号明細書に
は、天然ガス、合成ガス、ガス化石炭ガスの精製にピペ
ラジンの０．８１〜１．３モル／リットル水溶液が洗浄
液として、またピペラジンがメチルジエタノールアミ
ン、トリエタノールアミン、ジエタノールアミン、モノ
メチルエタノールアミンなどの溶媒と共に水溶液で洗浄
液として使用される技術が開示されている。US Pat. No. 4,336,233 discloses that a 0.81-1.3 mol / l aqueous solution of piperazine is used as a washing liquid for purification of natural gas, synthesis gas and gasified coal gas, and that piperazine is methyl. A technique is disclosed which is used as a washing solution in an aqueous solution together with a solvent such as diethanolamine, triethanolamine, diethanolamine, and monomethylethanolamine.
【００１１】同様に特開昭５２−６３１７１号公報に
は、第三級アルカノールアミン、モノアルキルアルカノ
ールアミンなどにピペラジンまたはヒドロキシエチルピ
ペラジンなどのピペラジン誘導体を促進剤として加えた
ＣＯ2 吸収剤が開示されている。Similarly, Japanese Patent Application Laid-Open No. 52-63171 discloses a CO 2 absorbent in which a piperazine derivative such as piperazine or hydroxyethylpiperazine is added as an accelerator to a tertiary alkanolamine, a monoalkylalkanolamine or the like. ing.
【００１２】[0012]
【発明が解決しようとする課題】前述のように各種ガス
からＣＯ2 を効率よく除去する方法が望まれている。特
に、一定濃度のＣＯ2 吸収剤（アミン化合物）を含む水
溶液でガスを処理する場合、吸収剤単位モル当たりのＣ
Ｏ2 吸収量、水溶液の単位体積当たりのＣＯ2 の吸収量
及び吸収速度の大きい吸収剤を選択することが当面の大
きな課題である。さらにはＣＯ2 の吸収後、ＣＯ2 を分
離して吸収液を再生させる際に必要な熱エネルギの少な
い吸収剤が望まれる。一種類のアミン化合物の使用で
は、これらの全ての望ましい要件を満たすことは困難で
あるとしても、幾つかの要件を満足する化合物が見い出
されれば、他のアミン化合物との混合などにより更に好
ましい要件に近づける可能性もあり得る。従って、吸収
剤単位モル当たりのＣＯ2 吸収量が大きければ、吸収速
度は別途改善される可能性も残されている。As described above, there is a need for a method for efficiently removing CO 2 from various gases. In particular, when the gas is treated with an aqueous solution containing a certain concentration of a CO 2 absorbent (amine compound), C
It is a major problem for the time being to select an absorbent having a large O 2 absorption amount, a large CO 2 absorption amount per unit volume of the aqueous solution, and a high absorption rate. Furthermore after absorption of CO 2, heat energy less absorbent necessary for regenerating the absorbing solution by separating the CO 2 it is desired. Although it is difficult to satisfy all of these desirable requirements with the use of one type of amine compound, if a compound that satisfies some requirements is found, more desirable requirements such as mixing with other amine compounds are used. May be approached. Therefore, there is a possibility that the absorption rate may be separately improved if the amount of CO 2 absorbed per unit mole of the absorbent is large.
【００１３】[0013]
【課題を解決するための手段】本発明者らは前記課題に
鑑み、ガス中のＣＯ2 を除去する際に用いられる吸収剤
について鋭意検討した結果、特定のアミン化合物の水溶
液のＣＯ2 吸収量が大きいとの知見を得て、本発明を完
成させるに至った。すなわち本発明によれば、下記一般
式〔１〕で示されるアミン化合物を含有する水溶液とガ
スとを接触させることを特徴とするガス中のＣＯ2 を除
去する方法が提供される。SUMMARY OF THE INVENTION The present inventors have in view of the above problems, a result of intensive studies for absorber used in removing CO 2 in the gas, CO 2 absorption amount of an aqueous solution of a specific amine compound Was obtained, and the present invention was completed. That is, according to the present invention, there is provided a method for removing CO 2 from a gas, which comprises contacting an aqueous solution containing an amine compound represented by the following general formula [1] with a gas.
【化２】 Ｒ1 ＮＨＣ（ＣＨ3 ）2 ＣＨ2 ＯＨ 〔１〕 （式中、Ｒ1 は炭素数１〜４の低級アルキル基であ
る。）Embedded image R 1 NHC (CH 3 ) 2 CH 2 OH [1] (In the formula, R 1 is a lower alkyl group having 1 to 4 carbon atoms.)
【００１４】また本発明によれば、Ｒ1 がイソプロピル
基であるアミン化合物を用いる前記ガス中のＣＯ2 を除
去する方法、濃度が１５〜６５重量％の範囲である一般
式〔１〕で示されるアミン化合物の水溶液を用いる前記
ガス中のＣＯ2 を除去する方法及びガスが大気圧下の燃
焼排ガスである前記ガス中のＣＯ2 を除去する方法が提
供される。Further, according to the present invention, there is provided a method for removing CO 2 from the above-mentioned gas using an amine compound wherein R 1 is an isopropyl group, represented by the general formula [1] having a concentration in the range of 15 to 65% by weight. how and gas to remove CO 2 in the gas using an aqueous solution of amine compound is a method for removing CO 2 in the gas is a combustion exhaust gas under atmospheric pressure is provided.
【００１５】[0015]
【作用】本発明で用いられる一般式〔１〕で示されるア
ミン化合物において、Ｒ1 の炭素数１〜４の低級アルキ
ル基としては、メチル基、エチル基、ｎ−プロピル基、
イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ
−ブチル基、ｔｅｒｔ−ブチル基を例示することがで
き、特に炭素数１〜３のアルキル基であることが化合物
の製造のしやすさ、ＣＯ2 吸収量、水溶性の点から好ま
しい。一般式〔１〕で示されるアミン化合物の具体例と
しては、２−メチルアミノ−２−メチル−１−プロパノ
ール、２−エチルアミノ−２−メチル−１−プロパノー
ル、２−プロピルアミノ−２−メチル−１−プロパノー
ル、２−イソプロピルアミノ−２−メチル−１−プロパ
ノール、２−ｎ−ブチルアミノ−２−メチル−１−プロ
パノール、２−イソブチルアミノ−２−メチル−１−プ
ロパノール、２−ｓｅｃ−ブチルアミノ−２−メチル−
１−プロパノール、２−ｔｅｒｔ−ブチルアミノ−２−
メチル−１−プロパノールをあげることができ、中でも
２−イソプロピルアミノ−２−メチル−１−プロパノー
ルが好ましい。一般式〔１〕で示されるアミン化合物
は、各々単独で用いられるほか、二種以上を混合して用
いることも可能である。In the amine compound represented by the general formula [1] used in the present invention, as the lower alkyl group having 1 to 4 carbon atoms for R 1 , a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, isobutyl group, sec
- it can be exemplified butyl group, tert- butyl group, in particular ease of the preparation of that compound is an alkyl group having 1 to 3 carbon atoms, CO 2 absorption is preferred from the viewpoint of water solubility. Specific examples of the amine compound represented by the general formula [1] include 2-methylamino-2-methyl-1-propanol, 2-ethylamino-2-methyl-1-propanol, and 2-propylamino-2-methyl -1-propanol, 2-isopropylamino-2-methyl-1-propanol, 2-n-butylamino-2-methyl-1-propanol, 2-isobutylamino-2-methyl-1-propanol, 2-sec- Butylamino-2-methyl-
1-propanol, 2-tert-butylamino-2-
Methyl-1-propanol can be mentioned, and among them, 2-isopropylamino-2-methyl-1-propanol is preferable. The amine compounds represented by the general formula [1] can be used alone or in combination of two or more.
【００１６】本発明のガスとの接触に用いる前記アミン
化合物の水溶液（以下、吸収液とも称す）の濃度は通常
１５〜６５重量％、好ましくは３０〜５０重量％であ
る。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。The concentration of the aqueous solution of the amine compound (hereinafter, also referred to as absorption liquid) used for contact with the gas of the present invention is usually 15 to 65% by weight, preferably 30 to 50% by weight. The temperature of the absorbent at the time of contact with gas is usually 30 to 70 ° C.
Range.
【００１７】また本発明で用いる吸収液には、必要に応
じて腐蝕防止剤、劣化防止剤などが加えられる。さらに
吸収液のＣＯ2 吸収量や吸収速度などの吸収能力を増す
ために、一般式〔１〕で示されるアミン化合物に他のア
ミン化合物の１種または２種以上を混合して用いてもよ
い。他のアミン化合物としては、例えば２−メチルアミ
ノエタノール、２−エ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−ｎ−ブチルアミノエタ
ノール、ピペラジン、２−メチルピペラジン、２，５−
ジメチルピペラジン、ピペリジン、２−ピペリジンエタ
ノールなどをあげることができる。これらの他のアミン
化合物を使用するときは、これらが一般式〔１〕のアミ
ン化合物と共に水に可溶である限り、これら他のアミン
化合物の単独の濃度は通常１．５〜５０重量％の範囲、
好ましくは５〜４０重量％の範囲である。Further, a corrosion inhibitor, a deterioration inhibitor and the like are added to the absorbing solution used in the present invention, if necessary. Further, in order to increase the absorption capacity such as the CO 2 absorption amount and the absorption rate of the absorbing solution, one or more other amine compounds may be mixed with the amine compound represented by the general formula [1]. . Other amine compounds include, for example, 2-methylaminoethanol, 2-ethylaminoethanol, 2-isopropylaminoethanol, 2-n-butylaminoethanol, piperazine, 2-methylpiperazine, 2,5-
Dimethylpiperazine, piperidine, 2-piperidineethanol and the like can be mentioned. When these other amine compounds are used, as long as they are soluble in water together with the amine compound of the general formula [1], the concentration of these other amine compounds alone is usually 1.5 to 50% by weight. range,
Preferably it is in the range of 5 to 40% by weight.
【００１８】本発明における処理対象ガスとしては、天
然ガス、合成ガスなどの化学プラントで製造される各種
産業ガス、燃焼排ガスなどがあげられるが、特に大気圧
下のガス、とりわけ大気圧下の燃焼排ガスに適用するこ
とが好ましい。大気圧下とは、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。以下、燃焼排ガスを処理対象ガスとす
る場合を例にとり、本発明を説明する。Examples of the gas to be treated in the present invention include various industrial gases produced by chemical plants such as natural gas and synthesis gas, and combustion exhaust gas. It is preferably applied to exhaust gas. The term "atmospheric pressure" includes a pressure range near the atmospheric pressure at which a blower or the like acts to supply gas. Hereinafter, the present invention will be described with reference to an example in which combustion exhaust gas is used as a gas to be treated.
【００１９】本発明により燃焼排ガス中のＣＯ2 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、
その一例について図１によって説明する。図１では主要
設備のみ示し、付属設備は省略した。図１において、１
は脱ＣＯ2 塔、２は下部充填部、３は上部充填部または
トレイ、４は脱ＣＯ2 塔燃焼排ガス供給口、５は脱ＣＯ
2 燃焼排ガス排出口、６は吸収液供給口、７はノズル、
８は必要に応じて設けられる燃焼排ガス冷却器、９はノ
ズル、１０は充填部、１１は加湿冷却水循環ポンプ、１
２は補給水供給ライン、１３はＣＯ2 を吸収した吸収液
排出ポンプ、１４は熱交換器、１５は吸収液再生（以
下、「再生」とも略称）塔、１６はノズル、１７は下部
充填部、１８は再生加熱器（リボイラ）、１９は上部充
填部、２０は還流水ポンプ、２１はＣＯ2 分離器、２２
は回収ＣＯ2 排出ライン、２３は再生塔還流冷却器、２
４はノズル、２５は再生塔還流水供給ライン、２６は燃
焼排ガス供給ブロワ、２７は必要に応じて設けられる冷
却器である。The process that can be employed in the method for removing CO 2 in flue gas according to the present invention is not particularly limited,
One example will be described with reference to FIG. In FIG. 1, only the main equipment is shown, and the auxiliary equipment is omitted. In FIG. 1, 1
Is a CO 2 removal tower, 2 is a lower filling portion, 3 is an upper filling portion or tray, 4 is a CO 2 removal flue gas supply port, and 5 is a CO 2 removal portion.
2 combustion exhaust gas outlet, 6 is an absorption liquid supply port, 7 is a nozzle,
8 is a flue gas cooler provided as required, 9 is a nozzle, 10 is a filling unit, 11 is a humidification cooling water circulation pump, 1
2 is a makeup water supply line, 13 is an absorption liquid discharge pump absorbing CO 2 , 14 is a heat exchanger, 15 is an absorption liquid regeneration (hereinafter also abbreviated as “regeneration”) tower, 16 is a nozzle, and 17 is a lower filling section , 18 is a regenerative heater (reboiler), 19 is an upper filling section, 20 is a reflux water pump, 21 is a CO 2 separator, 22
Is a recovered CO 2 discharge line, 23 is a regenerator reflux condenser, 2
Reference numeral 4 denotes a nozzle, 25 denotes a regeneration tower reflux water supply line, 26 denotes a combustion exhaust gas supply blower, and 27 denotes a cooler provided as necessary.
【００２０】図１において、燃焼排ガスは燃焼排ガス供
給ブロワ２６により燃焼排ガス冷却器８に押込められ、
ノズル９からの加湿冷却水と充填部１０で接触し、加湿
冷却され、脱ＣＯ2 塔燃焼排ガス供給口４を通って脱Ｃ
Ｏ2 塔１へ導かれる。燃焼排ガスと接触した加湿冷却水
は燃焼排ガス冷却器８の下部に溜り、ポンプ１１により
ノズル９へ循環使用される。加湿冷却水は燃焼排ガスを
加湿冷却することにより徐々に失われるので、補給水供
給ライン１２により補充される。In FIG. 1, the flue gas is pushed into the flue gas cooler 8 by the flue gas supply blower 26,
Contact with humidifying cooling water and the filling section 10 from the nozzle 9, is fogging, de-C through the de-CO 2 tower combustion exhaust gas feed port 4
It is led to the O 2 tower 1. The humidified cooling water in contact with the combustion exhaust gas accumulates in the lower part of the combustion exhaust gas cooler 8 and is circulated to the nozzle 9 by the pump 11. Since the humidified cooling water is gradually lost by humidifying and cooling the combustion exhaust gas, it is replenished through the makeup water supply line 12.
【００２１】脱ＣＯ2 塔１に押し込められた燃焼排ガス
はノズル７から供給される一定濃度の吸収液と下部充填
部２で向流接触させられ、燃焼排ガス中のＣＯ2 は吸収
液により吸収除去され、脱ＣＯ2 燃焼排ガスは上部充填
部３へと向う。脱ＣＯ2 塔１に供給される吸収液はＣＯ
2 を吸収し、その吸収による反応熱のため通常吸収液供
給口６における温度よりも高温となり、ＣＯ2 を吸収し
た吸収液排出ポンプ１３により熱交換器１４に送られ、
加熱されて再生塔５へ導かれる。ＣＯ2 を吸収した吸収
液の温度調節は熱交換器１４により行うことができる。The combustion exhaust gas pushed into the CO 2 removal tower 1 is brought into countercurrent contact with the absorption liquid of a constant concentration supplied from the nozzle 7 in the lower filling section 2, and CO 2 in the combustion exhaust gas is absorbed and removed by the absorption liquid. Then, the CO 2 -free flue gas is directed to the upper filling section 3. The absorbing solution supplied to the CO 2 removal tower 1 is CO
2 is absorbed, the temperature of the reaction is normally higher than the temperature at the absorption liquid supply port 6 due to the heat of reaction caused by the absorption, and is sent to the heat exchanger 14 by the absorption liquid discharge pump 13 that has absorbed CO 2 ,
It is heated and led to the regeneration tower 5. The temperature of the absorbing solution that has absorbed CO 2 can be adjusted by the heat exchanger 14.
【００２２】再生塔１５では、再生加熱器１８による加
熱で吸収液が再生され、熱交換器１４及び必要に応じて
熱交換器１４と吸収液供給口６の間に設けられた冷却器
２７により冷却され脱ＣＯ2 塔１へ戻される。再生塔１
５の上部において、吸収液から分離されたＣＯ2 はノズ
ル２４より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、ＣＯ2 分離器２１にてＣＯ2 に
同伴した水蒸気が凝縮した還流水と分離され、回収ＣＯ
2 排出ライン２２より図示省略のＣＯ2 回収工程へ導か
れる。還流水の一部はノズル２４を介して再生塔１５へ
還流される。In the regeneration tower 15, the absorbent is regenerated by heating by the regeneration heater 18, and the heat is exchanged by the heat exchanger 14 and, if necessary, the cooler 27 provided between the heat exchanger 14 and the absorbent supply port 6. It is cooled and returned to the CO 2 removal tower 1. Regeneration tower 1
In the upper part of 5, the CO 2 separated from the absorbing solution comes into contact with the reflux water supplied from the nozzle 24, is cooled by the regenerator cooling condenser 23, and the steam accompanying the CO 2 in the CO 2 separator 21 Separated from condensed reflux water, recovered CO
It is led from the 2 discharge line 22 to a CO 2 recovery step (not shown). Part of the reflux water is returned to the regeneration tower 15 via the nozzle 24.
【００２３】[0023]
【実施例】以下、本発明で採用する一般式〔１〕で示さ
れるアミン化合物のＣＯ2 吸収能力を小規模吸収試験で
調べた実施例により、本発明を具体的に説明する。The present invention will be specifically described below with reference to examples in which the CO 2 absorption capacity of the amine compound represented by the general formula [1] employed in the present invention was examined by a small-scale absorption test.
【００２４】（実施例１、比較例１〜２）恒温槽内に設
置したガラス製反応容器に一般式〔１〕においてＲ1 が
イソプロピル基である２−イソプロピルアミノ−２−メ
チル−１−プロパノール（ＩＰＡＭＰ）の３０重量％水
溶液５０ｍｌを入れた。温度４０℃で攪拌しながら、Ｃ
Ｏ 2 ガスを大気圧下１リットル／分の流速で、バブルを
発生しやすいようにフィルタを介して１時間吸収液に通
した。１時間後、吸収液に含まれるＣＯ2 をＣＯ2分析
計（全有機炭素計）を用いて測定し、吸収量（モルＣＯ
2 ／モル吸収剤）を求めた。また、比較例１及び２とし
て、ＭＥＡ水溶液及びＡＭＰ水溶液による同様の吸収試
験を行った。その結果を表−１に示した。(Example 1, Comparative Examples 1 and 2)
In the glass reaction vessel placed in the reactor, R in the general formula [1]1But
2-isopropylamino-2-me that is an isopropyl group
30% by weight water of chill-1-propanol (IPAMP)
50 ml of the solution were charged. While stirring at a temperature of 40 ° C., C
O TwoBubble gas at a flow rate of 1 liter / min.
Through the filter for one hour through a filter so that
did. One hour later, CO contained in the absorbing solutionTwoTo COTwoanalysis
Using a total organic carbon meter and the amount of absorption (mol CO
Two/ Mol absorber). Comparative Examples 1 and 2
The same absorption test with MEA aqueous solution and AMP aqueous solution
Test was carried out. The results are shown in Table 1.
【００２５】[0025]
【表１】 [Table 1]
【００２６】表−１の結果から明らかなように、本発明
で使用するアミン化合物の一つである２−イソプロピル
アミノ−２−メチル−１−プロパノール（ＩＰＡＭＰ）
の水溶液をＣＯ2 ガスの吸収液として用いることによ
り、ＭＥＡ水溶液やＡＭＰ水溶液を用いる場合よりもモ
ル当たりのＣＯ2 吸収量に優れていることが分かる。As is clear from the results in Table 1, one of the amine compounds used in the present invention is 2-isopropylamino-2-methyl-1-propanol (IPAMP).
It can be seen that the use of the aqueous solution of CO 2 as the CO 2 gas absorbing solution is superior in the amount of CO 2 absorbed per mole as compared with the case of using the MEA aqueous solution or the AMP aqueous solution.
【００２７】[0027]
【発明の効果】以上詳細に述べたごとく、本発明の方法
により処理対象ガスに一般式〔１〕で示されるアミン化
合物の水溶液を吸収液として接触させることにより、従
来使用されていたＭＥＡ水溶液などを用いる場合より
も、吸収剤化合物単位モル当たりのＣＯ2 吸収量を増す
ことができることとなった。また一般式〔１〕で示され
るアミン化合物は分子構造より判断すると、ＭＥＡやＡ
ＭＰよりもアミノ基のヒンダード性が増しており、ＣＯ
2 吸収後の吸収液の加熱による再生熱エネルギも少なく
て済むことが推測でき、総合的にＣＯ2 の回収エネルギ
の小さいプロセスが期待できる。As described above in detail, the aqueous solution of the amine compound represented by the general formula [1] is brought into contact with the gas to be treated by the method of the present invention as an absorbing solution, whereby a conventionally used MEA aqueous solution or the like is used. Thus, the amount of CO 2 absorbed per unit mole of the absorbent compound can be increased as compared with the case where is used. Further, judging from the molecular structure, the amine compound represented by the general formula [1] has MEA and A
The hindered nature of the amino group is higher than MP
(2) It can be inferred that the regeneration heat energy by heating the absorption liquid after absorption can be reduced, and a process with a small overall CO 2 recovery energy can be expected.
【図１】本発明の適用例として、燃焼排ガス中のＣＯ2
を除去するプロセスの一例の説明図。FIG. 1 shows an example of application of the present invention to CO 2 in combustion exhaust gas.
FIG. 4 is an explanatory diagram of an example of a process for removing a hologram.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 三村 富雄 大阪府大阪市北区中之島３丁目３番22号 関西電力株式会社内 (72)発明者 飯島 正樹 東京都千代田区丸の内二丁目５番１号 三菱重工業株式会社 本社内 (72)発明者 光岡 薫明 広島県広島市西区観音新町四丁目６番22 号 三菱重工業株式会社 広島研究所内 (72)発明者 岩木 貫 広島県広島市西区観音新町四丁目６番22 号 三菱重工業株式会社 広島研究所内 (56)参考文献 特開 平８−89756（ＪＰ，Ａ) 特開 平６−285333（ＪＰ，Ａ) 特開 平５−337334（ＪＰ，Ａ) 特開 平５−301024（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01D 53/34 - 53/85 ＣＡＰＬＵＳ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Tomio Mimura 3-3-22 Nakanoshima, Kita-ku, Osaka-shi, Osaka Inside Kansai Electric Power Company (72) Inventor Masaki Iijima 2-5-1 Marunouchi, Chiyoda-ku, Tokyo Mitsubishi Heavy Industries, Ltd.Headquarters (72) Inventor Kaoru Mitsuoka 4-2-2 Kannon Shinmachi, Nishi-ku, Hiroshima, Hiroshima Prefecture Inside Mitsubishi Heavy Industries, Ltd. No. 6-22 Mitsubishi Heavy Industries, Ltd. Hiroshima Laboratory (56) References JP-A-8-89756 (JP, A) JP-A-6-285333 (JP, A) JP-A-5-337334 (JP, A) Kaihei 5-301024 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B01D 53/34-53/85 CAPLUS (STN)
Claims (4)
物を含有する水溶液とＣＯ2 含有ガスとを接触させるこ
とを特徴とするガス中のＣＯ2 を除去する方法。 【化１】 Ｒ1 ＮＨＣ（ＣＨ3 ）2 ＣＨ2 ＯＨ 〔１〕 （式中、Ｒ1 は炭素数１〜４の低級アルキル基であ
る。）1. A method for removing CO 2 in a gas, comprising bringing an aqueous solution containing an amine compound represented by the following general formula [1] into contact with a CO 2 -containing gas. Embedded image R 1 NHC (CH 3 ) 2 CH 2 OH [1] (In the formula, R 1 is a lower alkyl group having 1 to 4 carbon atoms.)
物を用いる請求項１記載のガス中のＣＯ2 を除去する方
法。2. A method in which R 1 CO 2 removal in the gas according to claim 1, wherein an amine compound is an isopropyl group.
般式〔１〕で示されるアミン化合物の水溶液を用いる請
求項１または２記載のガス中のＣＯ2 を除去する方法。3. The method for removing CO 2 in a gas according to claim 1, wherein an aqueous solution of an amine compound represented by the general formula [1] having a concentration of 15 to 65% by weight is used.
である請求項１〜３のいずれかに記載のガス中のＣＯ2
を除去する方法。4. CO 2 containing gas is in the gas according to claim 1 which is a combustion exhaust gas under atmospheric pressure CO 2
How to remove.
Priority Applications (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06403195A JP3276527B2 (en) | 1995-03-23 | 1995-03-23 | How to remove carbon dioxide in gas |
| US08/511,290 US5618506A (en) | 1994-10-06 | 1995-08-04 | Process for removing carbon dioxide from gases |
| NO19953103A NO313789B1 (en) | 1994-10-06 | 1995-08-08 | Procedure for removing carbon dioxide from gases |
| DE69522837T DE69522837T2 (en) | 1994-10-06 | 1995-08-16 | Process for eliminating carbon dioxide from gases |
| EP98202417A EP0880991B1 (en) | 1994-10-06 | 1995-08-16 | Process for removing carbon dioxide from gases |
| DE69522772T DE69522772T2 (en) | 1994-10-06 | 1995-08-16 | Process for eliminating carbon dioxide from gases |
| DE69526525T DE69526525T2 (en) | 1994-10-06 | 1995-08-16 | Process for eliminating carbon dioxide from gases |
| DE69526874T DE69526874T2 (en) | 1994-10-06 | 1995-08-16 | Process for eliminating carbon dioxide from gases |
| EP95305722A EP0705637B1 (en) | 1994-10-06 | 1995-08-16 | Process for removing carbon dioxide from gases |
| EP98202412A EP0880990B1 (en) | 1994-10-06 | 1995-08-16 | Process for removing carbon dioxide from gases |
| EP98202413A EP0879631B1 (en) | 1994-10-06 | 1995-08-16 | Process for removing carbon dioxide from gases |
| CN95115093A CN1057018C (en) | 1994-10-06 | 1995-08-17 | Method for removing carbon dioxide from gas |
| NO20022033A NO334495B1 (en) | 1994-10-06 | 2002-04-29 | Procedure for removing carbon dioxide from gases |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06403195A JP3276527B2 (en) | 1995-03-23 | 1995-03-23 | How to remove carbon dioxide in gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08257355A JPH08257355A (en) | 1996-10-08 |
| JP3276527B2 true JP3276527B2 (en) | 2002-04-22 |
Family
ID=13246359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06403195A Expired - Lifetime JP3276527B2 (en) | 1994-10-06 | 1995-03-23 | How to remove carbon dioxide in gas |
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| Country | Link |
|---|---|
| JP (1) | JP3276527B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006240966A (en) * | 2005-03-07 | 2006-09-14 | Research Institute Of Innovative Technology For The Earth | Method for recovering carbon dioxide in exhaust gas by absorption and releasing |
| DE102005050385A1 (en) * | 2005-10-20 | 2007-04-26 | Basf Ag | Absorbent and method for removing carbon dioxide from gas streams |
| EP2168658A4 (en) | 2007-06-28 | 2012-06-20 | Res Inst Innovative Tech Earth | Method for efficiently recovering carbon dioxide in gas |
| JP5637809B2 (en) | 2010-10-21 | 2014-12-10 | 株式会社東芝 | Carbon dioxide recovery method and carbon dioxide recovery steam power generation system |
| JP5637808B2 (en) | 2010-10-21 | 2014-12-10 | 株式会社東芝 | Carbon dioxide recovery method and carbon dioxide recovery steam power generation system |
| JP5558310B2 (en) * | 2010-10-22 | 2014-07-23 | 株式会社東芝 | Carbon dioxide recovery method and carbon dioxide recovery steam power generation system |
| JP5659127B2 (en) * | 2010-12-22 | 2015-01-28 | 株式会社東芝 | Acid gas absorbent, acid gas removal method, and acid gas removal apparatus |
| CN112351831A (en) | 2018-06-26 | 2021-02-09 | 碳清洁解决方案有限公司 | Solvent and process for removing carbon dioxide from gas mixtures having a high partial pressure of carbon dioxide |
| GB201813839D0 (en) | 2018-06-26 | 2018-10-10 | Carbon Clean Solutions Ltd | System and process of capturing carbon dioxide from flue gases |
-
1995
- 1995-03-23 JP JP06403195A patent/JP3276527B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH08257355A (en) | 1996-10-08 |
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