JPH037413B2 - - Google Patents
Info
- Publication number
- JPH037413B2 JPH037413B2 JP60069530A JP6953085A JPH037413B2 JP H037413 B2 JPH037413 B2 JP H037413B2 JP 60069530 A JP60069530 A JP 60069530A JP 6953085 A JP6953085 A JP 6953085A JP H037413 B2 JPH037413 B2 JP H037413B2
- Authority
- JP
- Japan
- Prior art keywords
- adsorbent
- carbon dioxide
- regeneration
- mmhg
- present
- 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)
Description
〔産業上の利用分野〕
本発明は、潜水艦や宇宙船などの環境制御装置
における炭酸ガスの除去方法に関するものであ
り、詳しくは多孔質表面を有する固体に炭酸ガス
との親和性の強いポリエチレンイミンを付着させ
たCO2吸着材を用いる時、この薬剤のCO2吸収力
を損うことなく、効率良く再生することのできる
炭酸ガスの除去方法に関するものである。
〔従来の技術〕
従来、アミン系炭酸ガス吸収剤は液状で使用さ
れているが、実験報告書として多孔質材にポリエ
チレンイミンを付着させたものが示されている。
しかしこうした固体吸着材についての実験の装置
の例は見られない。
ポリエチレンイミンは１級あるいは２級のアミ
ノ基を有する側鎖のポリマーであり、300〜
100000の分子量をもつものが一般的である。この
ポリエチレンイミンがCO2と吸着する方式は化学
的な反応よりも物理吸着に近いものであり、次の
ように表現することができる。
Ｒ−NH＋CO2Ｒ−NH・CO2＋ｑ（ｑは吸着時
発熱）
このため脱着は吸着材を90〜100℃に熱するだ
けで簡単に起こるが、この時、加熱によつてポリ
エチレンイミンより揮発性の低分子のアミンに部
分的に分解し、一部飛散する。この低分子アミン
は分解時にアミノ基を持ち去るため再生の回数が
増す毎に、CO2と親和性のあるアミノ基が減少し
徐々にCO2吸収力を減ずることとなる。このこと
は再生式の炭酸ガス除去装置ではあつても、長時
間の使用には、新しい吸着材の補充が必要となる
ことを意味する。
〔発明が解決しようとする問題点〕
外部環境とほぼ隔絶した密閉空間内に生存する
人間等の生物が、その生態を維持していく上で、
ある量の酸素の供給とともに、排出されるCO2の
除去が不可欠である。しかもこゝで、炭酸ガス吸
着材を再生するに際して、上記のように揮発性の
低分子のアミンが発生して、環境空間内に排出さ
れることは好ましくなく、またこうしたアミンが
発生することは吸着材の劣化を意味するので、再
生時に低分子のアミンを発生させない事が必要で
ある。
〔問題点を解決するための手段および作用〕
本発明は上記の問題点を解決しようとするもの
である。すなわち、本発明は吸着材の劣化を招く
ことなく、かつ環境空間内に有害成分である低分
子の揮発性アミンを排出することのないように再
生温度を低くするところにねらいがある。このた
めに、再生時の酸素分圧を低くし（４mmHg以
下）、これとともに再生温度を低くして、低分子
の揮発性アミンの発生を抑制するようにした。
本発明は、再生時の再生条件に着目し、ポリエ
チレンイミンが低分子アミンに分解することな
く、したがつてCO2の吸収力をサイクル時間に比
例して低下する現象を抑制し、よつて高性能の再
生式炭酸ガス除去装置を提供することを目的とす
るものである。すなわち本発明は、外部環境とほ
とんど隔絶した密閉空間内において、人間等の排
出するCO2ガスを乾式で吸着除去するための吸着
材に、表面にポリエチレンイミンを付着させた固
体の多孔質材を用いる炭酸ガス吸収方法におい
て、その再生条件として吸着材の加熱温度を90℃
以下、再生時の酸素分圧を４mmHg以下において
吸着材を再生する炭酸ガス吸収方法を特徴とする
ものである。
本発明者は、前記目的のために、種々検討を行
つた結果、最適温度、最適酸素分圧で再生するこ
とによつて、吸着材のCO2吸着力をほとんど減ず
ることなく、CO2の吸収と再生を半永久的に継続
できることを見い出し、本発明を完成するに至つ
た。また本発明は、再生時に装置のダクト中に残
存するエア中の酸素の損失をも極力抑えることが
でき、これによつて酸素消費量も抑制することが
できる。
以下、図面をもつて本発明をさらに詳しく説明
する。図面は固体吸着材を用いたCO2除去装置の
基本フローを示したものである。そのシステム
は、まず密閉空間内の呼吸ガスをフアン１等によ
つて固体吸着材を充てんした充てん層２に吸引し
内部の固体吸着材３によつて充てん層を吸着せし
め、切換弁４を介して、望ましくはフイルター６
を介して再び密閉空間へ処理済エアとしてもどす
ものである。ここで、もう１つの充てん層７は、
充てん層２と同じ構造からなり、内部に固体吸着
材を充てんしたものである。ここでは既にCO2を
吸着し終つた吸着材を加熱、あるいは減圧吸引に
よつてCO2を分離脱着し、空間内エア循環流路と
は異なる流路８を通して、空間の外部へ排出ある
いは蓄積する構成となつている。この操作によつ
て充てん層７は再びCO2吸着力を回復し充てん層
２がCO2吸着力を失なつた時点で弁４を切り換え
ることで、CO2の吸着を開始する。この複数個の
キヤニスター（充てん層）を有する図面のCO2除
去装置は、空間内エアの浄化とCO2の除去を同時
に連続的に行うことができる。なお５，１３はラ
イン、１０はコンプレツサー、１１はCO2タン
ク、１２は加熱・冷却ライン、１４，１５は切換
弁である。
本発明の炭酸ガスの吸収方法における再生方法
は、再生充てん層７のガス流入側の弁４を閉じ、
８のラインを開いて真空ポンプ等で充てん容器７
の内部を100〜200mmHg以下まで減圧する（予備
減圧）。このとき、真空ポンプ排出側は、空間内
に接続しており（５のライン）、充てん容器中の
エアと吸着材表面に物理吸着した酸素は損失する
ことなく空間内にもどされる。充てん容器内の圧
力が100〜200mmHgに達すると、吸着材の表面付
着酸素はほぼ脱着されるため、次にライン５を閉
じ、ライン１３を開くと同時に充てん容器を90℃
以下、望ましくは80〜90℃に加熱し、かつ酸素分
圧を４mmHg以下にするために、たとえば容器内
圧力を20mmHg以下に減圧して吸着CO2を脱着さ
せる。この時、周辺にO2はほとんど存在しない
ため、ポリエチレンイミンの分解飛散は、きわめ
て少なくなる。なお上記の真空排気に代えて、酸
素を含まないか、あるいは酸素分圧が４mmHg以
下になるような気体を充てん層７に通気すること
も同様の効果がある。しかし現在のところ、真空
排気が最も簡便な方法として用いられる。ここ
で、予備排気をするのは、吸着材表面の酸素を脱
着させて酸素を除去して、再生時の吸着材の劣化
を防止するとともに、環境空間内に酸素を戻すた
めである。
〔実施例〕
以下に実施例を上げて、本発明をさらに具体的
に説明するが、本発明はこれらの実施例によつて
限定されるものではなく、種々応用実施できる。
実施例
第１表は、図面のようなCO2吸収装置を用いて
酸素分圧を下げる手段として真空排気して、1Hr
吸収、1Hr再生を100回繰返した後のCO2吸収力
を明示した実験結果である。
[Industrial Application Field] The present invention relates to a method for removing carbon dioxide from environmental control devices such as submarines and spacecraft. The present invention relates to a method for removing carbon dioxide gas that can be efficiently regenerated without impairing the CO 2 absorption ability of the agent when using a CO 2 adsorbent to which CO 2 adsorbent is attached. [Prior Art] Conventionally, amine-based carbon dioxide absorbents have been used in liquid form, but experimental reports have shown that polyethyleneimine is attached to a porous material.
However, there are no examples of experimental equipment for such solid adsorbents. Polyethyleneimine is a side chain polymer with primary or secondary amino groups, and
Those with a molecular weight of 100,000 are common. This method of adsorption of CO 2 by polyethyleneimine is closer to physical adsorption than a chemical reaction, and can be expressed as follows. R-NH+CO 2 R-NH・CO 2 +q (q is heat generated during adsorption) Therefore, desorption can easily occur by simply heating the adsorbent to 90 to 100°C, but at this time, heating causes it to volatilize from polyethyleneimine. It partially decomposes into low-molecular-weight amines and some of them are scattered. This low-molecular-weight amine removes amino groups when it is decomposed, so as the number of regeneration increases, the number of amino groups that have an affinity for CO 2 decreases, gradually reducing the CO 2 absorption capacity. This means that even if the device is a regenerative type carbon dioxide removal device, it will be necessary to replenish the adsorbent with new adsorbent if used for a long time. [Problems to be solved by the invention] In order to maintain the ecology of living organisms such as humans, which live in a closed space that is almost isolated from the external environment,
Along with the supply of a certain amount of oxygen, the removal of the emitted CO 2 is essential. Moreover, when regenerating the carbon dioxide adsorbent, it is undesirable that volatile low-molecular amines are generated and discharged into the environment as described above, and it is also important to avoid the generation of such amines. Since this means deterioration of the adsorbent, it is necessary not to generate low-molecular amines during regeneration. [Means and effects for solving the problems] The present invention aims to solve the above problems. That is, the present invention aims to lower the regeneration temperature without causing deterioration of the adsorbent and without emitting low-molecular volatile amines, which are harmful components, into the environment. To this end, the oxygen partial pressure during regeneration was lowered (4 mmHg or less) and the regeneration temperature was also lowered to suppress the generation of low molecular weight volatile amines. The present invention focuses on the regeneration conditions during regeneration, and prevents polyethyleneimine from decomposing into low-molecular-weight amines, thereby suppressing the phenomenon in which the CO 2 absorption capacity decreases in proportion to the cycle time, and thus achieving high The purpose of the present invention is to provide a regenerative carbon dioxide removal device with high performance. That is, the present invention uses a solid porous material with polyethyleneimine attached to its surface as an adsorbent for dry adsorption and removal of CO 2 gas emitted by humans etc. in a closed space that is almost isolated from the external environment. In the carbon dioxide absorption method used, the heating temperature of the adsorbent is set to 90℃ as a regeneration condition.
The following features a carbon dioxide absorption method in which an adsorbent is regenerated at an oxygen partial pressure of 4 mmHg or less during regeneration. As a result of various studies for the above purpose, the inventors of the present invention have found that by regenerating at the optimum temperature and optimum oxygen partial pressure, CO 2 absorption can be achieved without substantially reducing the CO 2 adsorption power of the adsorbent. They discovered that the regeneration could be continued semi-permanently and completed the present invention. Furthermore, the present invention can also suppress the loss of oxygen in the air remaining in the duct of the apparatus during regeneration to the utmost, and thereby the amount of oxygen consumed can also be suppressed. Hereinafter, the present invention will be explained in more detail with reference to the drawings. The drawing shows the basic flow of a CO 2 removal device using solid adsorbents. In this system, breathing gas in a closed space is first sucked into a packed layer 2 filled with a solid adsorbent using a fan 1, etc., the filled layer is adsorbed by the solid adsorbent 3 inside, and the gas is sucked through a switching valve 4. and preferably filter 6
The treated air is returned to the closed space via the Here, the other filling layer 7 is
It has the same structure as the packed layer 2, and is filled with a solid adsorbent inside. Here, CO 2 is separated and desorbed by heating the adsorbent that has already adsorbed CO 2 or by vacuum suction, and then discharged or accumulated to the outside of the space through a channel 8 different from the air circulation channel in the space. It is structured as follows. Through this operation, the filled layer 7 regains its CO 2 adsorption ability, and when the filled layer 2 loses its CO 2 adsorption ability, the valve 4 is switched to start CO 2 adsorption. The CO 2 removal device shown in the drawing, which has a plurality of canisters (filled layers), can simultaneously and continuously purify the air in the space and remove CO 2 . Note that 5 and 13 are lines, 10 is a compressor, 11 is a CO 2 tank, 12 is a heating/cooling line, and 14 and 15 are switching valves. The regeneration method in the carbon dioxide absorption method of the present invention includes closing the valve 4 on the gas inflow side of the regeneration packed layer 7;
Open line 8 and fill container 7 with a vacuum pump, etc.
Reduce the internal pressure to 100 to 200 mmHg or less (preliminary pressure reduction). At this time, the vacuum pump discharge side is connected to the space (line 5), and the air in the filling container and the oxygen physically adsorbed on the surface of the adsorbent are returned to the space without loss. When the pressure inside the filling container reaches 100 to 200 mmHg, most of the oxygen adhering to the surface of the adsorbent is desorbed, so next, close line 5 and open line 13, at the same time heating the filling container to 90°C.
Thereafter, the adsorbed CO 2 is desirably heated to 80 to 90° C., and the internal pressure of the container is reduced to, for example, 20 mmHg or less in order to reduce the oxygen partial pressure to 4 mmHg or less, thereby desorbing the adsorbed CO 2 . At this time, since there is almost no O 2 in the surrounding area, the decomposition and scattering of polyethyleneimine is extremely small. Note that instead of the above-mentioned evacuation, the same effect can be obtained by venting a gas that does not contain oxygen or has an oxygen partial pressure of 4 mmHg or less into the filled layer 7. However, at present, vacuum evacuation is the simplest method used. The purpose of pre-evacuation is to desorb and remove oxygen on the surface of the adsorbent to prevent deterioration of the adsorbent during regeneration and to return oxygen to the environmental space. [Examples] The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples and can be applied and implemented in various ways. Example Table 1 shows how the CO 2 absorber shown in the drawing was used to reduce the oxygen partial pressure by evacuation for 1 hour.
These are experimental results showing the CO 2 absorption capacity after repeating absorption and regeneration for 1 hour 100 times.
【表】
第１表に示すごとく予備減圧は100〜200mmHg
とし、再生条件をmmHg（すなわち酸素分圧４mm
Hg）、90℃以下にすることによつて、初期のCO2
吸収力をほぼ維持できる。
第２表は、吸着材表面に付着する酸素の吸着性
を示したものである。室温で酸素は100mmHgで多
量に脱着していることが明らかであり、この実施
例から予備減圧を100〜200mmHgとするのが最適
であることがわかる。[Table] As shown in Table 1, the preliminary decompression is 100 to 200 mmHg.
and the regeneration condition is mmHg (i.e. oxygen partial pressure 4 mm
Hg), by lowering the temperature to below 90°C, the initial CO 2
Absorption capacity can be almost maintained. Table 2 shows the adsorption properties of oxygen adhering to the surface of the adsorbent. It is clear that a large amount of oxygen is desorbed at 100 mmHg at room temperature, and this example shows that it is optimal to set the preliminary vacuum to 100 to 200 mmHg.
以上の如く、本発明は固体多孔質材にポリエチ
レン系イミンを付着させた固体吸着材を用いる炭
酸ガス吸収方法において、その吸着材の劣化を招
かないすぐれた再生を可能とし、潜水艦、宇宙船
等の環境制御用の炭酸ガス吸収装置を、環境内の
空気を汚染することなく、安定して長時間稼動さ
せることを可能にするものである。
As described above, the present invention enables excellent regeneration without causing deterioration of the adsorbent in a carbon dioxide absorption method using a solid adsorbent in which polyethylene-based imine is attached to a solid porous material, and is used in submarines, spacecraft, etc. This enables a carbon dioxide absorption device for environmental control to operate stably for a long time without contaminating the air in the environment.
図面は本発明の方法を実施する装置の一例を示
すフローシートである。
１……フアン、２，７……充てん層、３……吸
着材、４……切換弁、５……ライン、６……フイ
ルター、８……流路、１０……コンプレツサー、
１１……CO2タンク、１２……加熱・冷却ライ
ン、１３……ライン、１４，１５……切換弁。
The drawing is a flow sheet showing an example of an apparatus for carrying out the method of the present invention. 1...Fan, 2,7...Filled layer, 3...Adsorbent, 4...Switching valve, 5...Line, 6...Filter, 8...Flow path, 10...Compressor,
11... CO2 tank, 12...Heating/cooling line, 13...Line, 14, 15...Switching valve.
Claims (1)
おいて、人間等の排出するCO2ガスを乾式で吸着
除去するに際して、その吸着材に固体の多孔質材
の表面にポリエチレンイミンを付着させた固体状
アミン吸着材を用いる炭酸ガス吸収方法におい
て、その再生条件として吸着材の加熱温度を90℃
以下とし、吸着材を充てんした容器内部の酸素分
圧を４mmHg以下とすることを特徴とする炭酸ガ
スの除去方法。1. A solid amine with polyethyleneimine attached to the surface of a solid porous material is used as an adsorbent when CO 2 gas emitted by humans etc. is removed by dry adsorption in a closed space that is almost isolated from the external environment. In the carbon dioxide absorption method using an adsorbent, the heating temperature of the adsorbent is set to 90℃ as a regeneration condition.
A method for removing carbon dioxide gas, characterized in that the oxygen partial pressure inside a container filled with an adsorbent is set to 4 mmHg or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60069530A JPS61227821A (en) | 1985-04-01 | 1985-04-01 | Removing method for carbonic acid gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60069530A JPS61227821A (en) | 1985-04-01 | 1985-04-01 | Removing method for carbonic acid gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61227821A JPS61227821A (en) | 1986-10-09 |
| JPH037413B2 true JPH037413B2 (en) | 1991-02-01 |
Family
ID=13405366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60069530A Granted JPS61227821A (en) | 1985-04-01 | 1985-04-01 | Removing method for carbonic acid gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61227821A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9073004B2 (en) | 2011-12-09 | 2015-07-07 | Kawasaki Jukogyo Kabushiki Kaisha | Carbon dioxide separation apparatus |
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|---|---|---|---|---|
| US7491359B2 (en) * | 2003-10-16 | 2009-02-17 | Graham Packaging Pet Technologies Inc. | Delamination-resistant multilayer container, preform, article and method of manufacture |
| US8075966B2 (en) | 2004-07-22 | 2011-12-13 | Graham Packaging Company, Ltd. | Delamination-resistant multilayer container, preform, article and method with oxygen barrier formulations |
| US7795175B2 (en) * | 2006-08-10 | 2010-09-14 | University Of Southern California | Nano-structure supported solid regenerative polyamine and polyamine polyol absorbents for the separation of carbon dioxide from gas mixtures including the air |
| JP4922326B2 (en) * | 2009-02-20 | 2012-04-25 | 株式会社東芝 | Carbon dioxide absorbent and carbon dioxide recovery method |
| EP3653584B1 (en) | 2010-02-10 | 2025-08-06 | Queen's University At Kingston | Draw solution with switchable salt additive and method for desalinating an aqueous solution with this draw solution |
| JP5646892B2 (en) * | 2010-07-01 | 2014-12-24 | 旭化成株式会社 | Carbon dioxide absorbent and method for separating carbon dioxide using the same |
| US8709367B2 (en) * | 2010-07-30 | 2014-04-29 | General Electric Company | Carbon dioxide capture system and methods of capturing carbon dioxide |
| US20120027664A1 (en) * | 2010-07-30 | 2012-02-02 | General Electric Company | Carbon dioxide capture system and methods of capturing carbon dioxide |
| CN103459439B (en) | 2010-12-15 | 2017-09-12 | 金斯顿女王大学 | Use the system and method for the water with convertible ionic strength |
| JP5785443B2 (en) * | 2011-06-06 | 2015-09-30 | 川崎重工業株式会社 | Carbon dioxide separation and recovery equipment |
| JP6330204B2 (en) * | 2014-09-04 | 2018-05-30 | 本田技研工業株式会社 | Carbon dioxide recovery device |
| JP7716255B2 (en) * | 2021-07-16 | 2025-07-31 | 株式会社豊田中央研究所 | Carbon dioxide separation and capture material, and carbon dioxide separation or capture method using the same |
| WO2023181676A1 (en) * | 2022-03-25 | 2023-09-28 | 公益財団法人地球環境産業技術研究機構 | Carbon dioxide separator, and method for separating or recovering carbon dioxide |
| WO2024034511A1 (en) * | 2022-08-09 | 2024-02-15 | 株式会社大真空 | Carbon dioxide capture module |
-
1985
- 1985-04-01 JP JP60069530A patent/JPS61227821A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9073004B2 (en) | 2011-12-09 | 2015-07-07 | Kawasaki Jukogyo Kabushiki Kaisha | Carbon dioxide separation apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61227821A (en) | 1986-10-09 |
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