JP2001120940A - Method and apparatus for carbon dioxide separation / removal using liquid membrane - Google Patents
Method and apparatus for carbon dioxide separation / removal using liquid membraneInfo
- Publication number
- JP2001120940A JP2001120940A JP30542499A JP30542499A JP2001120940A JP 2001120940 A JP2001120940 A JP 2001120940A JP 30542499 A JP30542499 A JP 30542499A JP 30542499 A JP30542499 A JP 30542499A JP 2001120940 A JP2001120940 A JP 2001120940A
- Authority
- JP
- Japan
- Prior art keywords
- carbon dioxide
- dioxide gas
- porous membrane
- carrier liquid
- removal
- 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.)
- Granted
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
- 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
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
(57)【要約】
【目的】 ポリオール類とアミン類とを組み合わせた炭
酸ガスキャリヤー液を圧力勾配下に安定に保持でき、且
つ炭酸ガス・水蒸気を効率よく分離・除去できるよう
に、前記炭酸ガスキャリヤー液体を保持する膜を使用し
た、連続的な炭酸ガス分離・除去方法および該方法のた
めの装置の提供
【構成】 ポリオール類とアミン類とを組み合わせた炭
酸ガスキャリヤー液（Ｃ）を含浸・保持した非膨張、非
ゲル化多孔質膜（Ａ）とこれに隣接して配置された前記
炭酸ガスキャリヤー液に対して撥液性の疎水性多孔質膜
（Ｂ）よりなる積層構造の炭酸ガス分離・除去膜の、前
記炭酸ガスキャリヤー液体を保持した前記非膨張、非ゲ
ル化多孔質膜側を炭酸ガスと水蒸気を含む供給気体に接
触させ、前記疎水性多孔膜側を水蒸気圧以下の減圧部に
接触させて、少なくとも前記炭酸ガスを前記積層構造の
炭酸ガス分離・除去膜により滅圧部に優先的に透過させ
供給気体中から選択的に除去することを特徴とする炭酸
ガス分離・除去方法。
(57) [Abstract] The above-mentioned carbon dioxide gas is used to stably maintain a carbon dioxide gas carrier liquid comprising a combination of a polyol and an amine under a pressure gradient, and to efficiently separate and remove carbon dioxide gas and water vapor. Provided is a method for continuously separating and removing carbon dioxide using a membrane holding a carrier liquid, and an apparatus for the method. [Constitution] A carbon dioxide carrier liquid (C) comprising a combination of a polyol and an amine is impregnated. A carbon dioxide gas having a laminated structure comprising a retained non-expanded, non-gelled porous membrane (A) and a hydrophobic porous membrane (B) that is lyophobic to the carbon dioxide carrier liquid disposed adjacent thereto. The non-expanded, non-gelled porous membrane side of the separation / removal membrane holding the carbon dioxide carrier liquid is brought into contact with a supply gas containing carbon dioxide gas and water vapor, and the hydrophobic porous membrane side is depressurized to a water vapor pressure or less. Wherein the carbon dioxide gas is passed through the decompression section preferentially by the carbon dioxide gas separation / removal film of the laminated structure to selectively remove the carbon dioxide gas from the supply gas. Method.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリオール類とア
ミン類とを組み合わせた炭酸ガスキャリヤー液を圧力勾
配下に安定に保持でき、且つ炭酸ガス・水蒸気を効率よ
く分離・除去できるように、前記炭酸ガスキャリヤー液
体を保持した積層構造の炭酸ガス分離・除去膜を使用し
た、連続的な炭酸ガス分離・除去方法および該方法のた
めの装置に関する。BACKGROUND OF THE INVENTION The present invention relates to a carbon dioxide carrier liquid comprising a combination of a polyol and an amine, which can be stably maintained under a pressure gradient, and which can efficiently separate and remove carbon dioxide gas and water vapor. The present invention relates to a continuous carbon dioxide gas separation / removal method using a carbon dioxide gas separation / removal film having a laminated structure holding a carbon dioxide gas carrier liquid, and an apparatus for the method.
【０００２】[0002]
【従来技術】炭酸ガスを含む混合気体から、炭酸ガスを
分離・除去する技術としては、多くのもが知られてい
る。 １、代表的プロセスとして吸収法がある。これには、ト
リエチレングリコール、炭酸プロピレンなどの物理吸収
液を用いたものと、アミン水溶液、炭酸カリ水溶液など
の化学吸収液を用いる炭酸ガスを選択的に吸収する方法
があり、これらは工業的に用いられている。しかし、こ
の吸収法は吸収液を再利用するためには、炭酸ガスを分
離する再生操作が必要である点で簡便なプロセスとは言
い難い。 ２、また、吸着剤として固体のゼオライトなどを用いた
吸着プロセスもあるが、この場合も前記１、と同様に再
生操作が必要であり、前記と同様の問題がある。2. Description of the Related Art There are many known techniques for separating and removing carbon dioxide from a mixed gas containing carbon dioxide. 1. There is an absorption method as a typical process. This includes a method using a physical absorption liquid such as triethylene glycol and propylene carbonate, and a method of selectively absorbing carbon dioxide using a chemical absorption liquid such as an amine aqueous solution and a potassium carbonate aqueous solution. It is used for However, this absorption method cannot be said to be a simple process in that a regeneration operation for separating carbon dioxide is required in order to reuse the absorbing solution. 2. There is also an adsorption process using solid zeolite or the like as an adsorbent, but also in this case, a regeneration operation is required as in the case of the above 1, and there is the same problem as described above.
【０００３】これに対して、前記再生操作の不都合を改
良し、かつ連続操作が可能な炭酸ガスの選択的除去方法
および装置も知られている。そののようなものとして、 ３、炭酸ガス選択透過性のポリイミドなど高分子膜を用
いる、炭酸ガス選択膜による分離法が提案されている
（特開平６−７１１４８、特開平５−３２９３４３、特
開平８−３１８１４０）。しかし、この方法は、固体高
分子膜を通してガスを透過させるものであるため、透過
量が小さいこと、また、膜が高価である等の問題があっ
た。そこで最近は、前記吸収操作と膜分離操作の中間的
なものともいえる炭酸ガスなどの分離法も提案されてい
る。例えば、 ４．膜吸収と呼ばれる、多孔質膜を介して吸収液に炭酸
ガスを吸収させるプロセスが提案されている（特開平１
０−９９６６５）。該方法は多孔質膜を単位体積あたり
気液接触面積を大きくするために使用しているのであ
り、膜にガスの分離を機能を持たせたものとは言えな
い。また、吸収液の再生が必要なのは前記吸収法と同じ
である。[0003] On the other hand, there is also known a method and an apparatus for selectively removing carbon dioxide gas capable of improving the inconvenience of the regenerating operation and performing continuous operation. As such a method, there has been proposed a separation method using a carbon dioxide gas selective membrane using a polymer membrane such as polyimide having carbon dioxide selective permeability (JP-A-6-71148, JP-A-5-329343, JP-A-5-329343). 8-318140). However, this method involves passing a gas through a solid polymer membrane, and thus has problems such as a small amount of permeation and an expensive membrane. Therefore, recently, a method of separating carbon dioxide or the like, which can be said to be intermediate between the absorption operation and the membrane separation operation, has been proposed. For example: A process called membrane absorption, in which carbon dioxide gas is absorbed by an absorbing solution through a porous membrane, has been proposed (Japanese Patent Laid-Open No. Hei 1 (1998)).
0-99665). In this method, the porous membrane is used to increase the gas-liquid contact area per unit volume, and it cannot be said that the membrane has a function of separating gas. The regeneration of the absorbing solution is the same as in the above-mentioned absorption method.
【０００４】５．これに対して、炭酸ガスの分離機能
を、水ないし炭酸ガス吸収液に持たせた、該液体を含ん
だゲル膜（特開平６−９９０４５）や多孔質膜内に炭酸
ガス吸収性液を表面張力で保持したものを使用して、連
続操作により炭酸ガスなどの分離・除去（濃縮）する方
法が提案されている。米国特許第５２８１２５４号明細
書及び米国特許第４８３４３７７９号明細書にもこれら
の技術が提案されている。これらの方法においては、前
記液体は、ガスキャリヤー液と呼ばれ、該液体のガス成
分の選択的吸着（優先吸着）特性、促進輸送特性（優先
的な透過特性）などを利用している。しかし、前記提案
の炭酸ガスなどの分離・除去の方法では、前記ゲル膜
（膨張膜）、促進輸送膜は膜は、膜の透過側を真空に
し、圧力勾配を前記膜にかけるような操作では、液の漏
れ出しやゲル膜の乾燥がおこるため、実質的に両側をほ
ぼ等圧にして行わなければならないために、高い炭酸ガ
ス選択透過性を示すが効率が良くないという問題があ
る。また、米国特許第５０８２４７２号明細書にも、膨
潤させたポリテトラフルオロエチレン多孔質膜を支持体
機能の膜と積層した炭酸ガス分離膜が記載されている
が、炭酸ガス選択透過膜の、操作時の安定性などの点で
依然として不都合があった。[0004] 5. On the other hand, water or a carbon dioxide gas absorbing liquid is provided with the function of separating carbon dioxide gas, and the carbon dioxide gas absorbing liquid is coated on the surface of a gel film (JP-A-6-99045) or a porous film containing the liquid. There has been proposed a method of separating and removing (concentrating) carbon dioxide and the like by continuous operation using a material held under tension. These techniques are also proposed in US Pat. No. 5,281,254 and US Pat. No. 4,834,779. In these methods, the liquid is called a gas carrier liquid, and utilizes the selective adsorption (priority adsorption) characteristic, the facilitated transport characteristic (priority permeation characteristic), and the like of the gas component of the liquid. However, in the method of separation / removal of carbon dioxide or the like proposed above, the gel membrane (expanded membrane) and the facilitated transport membrane are formed by vacuuming the permeation side of the membrane and applying a pressure gradient to the membrane. In addition, since the liquid leaks out and the gel film is dried, it is necessary to perform the process at substantially the same pressure on both sides. Therefore, it has a problem that it shows high carbon dioxide gas selective permeability but is not efficient. Also, US Pat. No. 5,082,472 describes a carbon dioxide gas separation membrane in which a swollen polytetrafluoroethylene porous membrane is laminated with a membrane having a support function. There were still disadvantages in terms of stability at the time.
【０００５】[0005]
【発明が解決しようとする課題】本発明の課題は、前記
炭酸ガスキャリヤー液体の漏れ出し、ガスの分離・除去
機能を持つ膜がゲル膜であることによる乾燥の問題など
を改善した、圧力勾配下における炭酸ガスの分離・除去
の操作において安定に前記キャリヤー液を保持でき、前
記キャリヤー液を、膜への配合、膜の膨潤、またはゲル
化により保持させる必要がないように、前記キャリヤー
液を保持する膜の材質および構造を改善すると共に、炭
酸ガスキャリヤー液体の組成を工夫して、炭酸ガスキャ
リヤー液体の保持特性を改善した炭酸ガス分離・除去方
法および該方法を実施するための装置を提供することで
ある。前記課題を解決すべく鋭意検討する中で、炭酸ガ
スキャリヤー液体として、グリコール類とアミン類、特
にヒドロキシル基を持ったアミン類、との組み合わせを
用いることと、前記炭酸ガスキャリヤー液体を保持する
膜を、親水性処理をしたポリテトラフルオロエチレン等
からなる親水性の多孔質膜とこれに隣接して配置された
前記炭酸ガスキャリヤー液に対して撥液性の疎水性多孔
質膜よりなる積層構造の膜とすることとの相互作用によ
り、前記親水性の多孔質膜に前記炭酸ガスキャリヤー液
を吸収させるだけで、圧力勾配下における炭酸ガスの分
離・除去の操作において、炭酸ガスキャリヤー液を、安
定な液体膜として保持でき、かつ炭酸ガス分離性が大き
いことを見いだした。ちなみに、前記検討の中で、グリ
コール類単独では、安定な液体膜となるが炭酸ガス分離
性が小さく、また、アミン類単独では、安定な液体膜に
ならないことが分かった。SUMMARY OF THE INVENTION It is an object of the present invention to provide a pressure gradient which has improved the problem of leakage of the carbon dioxide carrier liquid and drying due to the fact that the membrane having the gas separation / removal function is a gel membrane. The carrier liquid can be stably retained in the operation of separating / removing carbon dioxide below, so that the carrier liquid does not need to be retained by blending into a membrane, swelling of the membrane, or gelling. Provided is a carbon dioxide gas separation / removal method in which the material and structure of a film to be retained are improved, and the composition of the carbon dioxide gas carrier liquid is devised to improve the retention characteristics of the carbon dioxide gas carrier liquid, and an apparatus for performing the method. It is to be. In earnest study to solve the above-mentioned problem, using a combination of glycols and amines, particularly amines having a hydroxyl group, as a carbon dioxide gas carrier liquid, and a membrane holding the carbon dioxide gas carrier liquid A laminated structure comprising a hydrophilic porous film made of hydrophilically treated polytetrafluoroethylene or the like, and a hydrophobic porous film lyophobic to the carbon dioxide carrier liquid disposed adjacent thereto. By interacting with the formation of a membrane, only by absorbing the carbon dioxide carrier liquid into the hydrophilic porous membrane, in the operation of separating and removing the carbon dioxide gas under a pressure gradient, the carbon dioxide gas carrier liquid, It has been found that it can be maintained as a stable liquid membrane and has high carbon dioxide gas separation properties. Incidentally, it was found in the above study that a glycol alone could form a stable liquid membrane, but the carbon dioxide gas separation property was low, and that an amine alone did not form a stable liquid membrane.
【０００６】[0006]
【課題を解決するための手段】本発明の第１は、ポリオ
ール類とアミン類とを組み合わせた炭酸ガスキャリヤー
液（Ｃ）を含浸・保持した非膨張、非ゲル化多孔質膜
（Ａ）とこれに隣接して配置された前記炭酸ガスキャリ
ヤー液に対して撥液性の疎水性多孔質膜（Ｂ）よりなる
積層構造の炭酸ガス分離・除去膜の、前記炭酸ガスキャ
リヤー液体を含浸・保持した前記非膨張、非ゲル化多孔
質膜側を炭酸ガスと水蒸気を含む供給気体に接触させ、
前記疎水性多孔膜側を水蒸気圧以下の減圧部に接触させ
て、少なくとも前記炭酸ガスを前記積層構造の炭酸ガス
分離・除去膜により滅圧部に優先的に透過させ前記供給
気体中から選択的に除去することを特徴とする炭酸ガス
分離・除去方法である。好ましくは、ポリオール類がポ
リエチレングリコール、トリエチレングリコール、テト
ラエチレングリコールからなる群から選択される少なく
とも１種であり、またアミン類がジエタノールアミン、
モノエタノールアミン、トリエタノールアミン、ジグリ
コールアミン、ジイソプロパノールアミン、メチルジエ
タノールアミン、2−アミノー2−メチルートプロパノー
ルからなるヒドロキシル基を持つ群から選択される少な
くとも１種であである炭酸ガスキャリヤー液を用いるこ
とを特徴とする前記炭酸ガス分離・除去方法であり、ま
た、好ましくは、炭酸ガスキャリヤー液（Ｃ）を含浸・
保持する非膨張、非ゲル化多孔質膜が親水性ポリテトラ
フルオロエチレン多孔質膜であり、前記炭酸ガスキャリ
ヤー液に対して撥液性の疎水性多孔質膜が、０．００１
から１０ミクロンの平均孔径を有し、空隙率は３０〜８
５％の範囲であり、水の侵入圧力４００ｋＰａ以上およ
びトリエチレングリコールの侵入圧力２００ｋＰａ以上
の特性を有するフッ素含有モノマーの重合により多孔質
膜の内部表面を含む多孔質膜の表面全体を疎水性に改良
したものである積層構造の炭酸ガス分離・除去膜を用い
ることを特徴とする前記炭酸ガス分離・除去方法であ
り、更に好ましくは、前記フッ素含有モノマーの重合に
より多孔質膜の内部表面を含む多孔質膜の表面全体を疎
水性に改良する多孔膜がポリプロピレンまたはフッ化ポ
リビニリデンからなるものであることを特徴とする前記
炭酸ガス分離・除去方法である。である。A first aspect of the present invention is to provide a non-expandable, non-gelling porous membrane (A) impregnated with and holding a carbon dioxide carrier liquid (C) comprising a combination of a polyol and an amine. The carbon dioxide gas carrier liquid is impregnated and retained in a carbon dioxide gas separation / removal film having a laminated structure composed of a hydrophobic porous film (B) that is liquid-repellent to the carbon dioxide gas carrier liquid disposed adjacent thereto. The non-expanded, non-gelled porous membrane side is contacted with a supply gas containing carbon dioxide gas and water vapor,
The hydrophobic porous membrane side is brought into contact with a depressurizing section below the water vapor pressure, and at least the carbon dioxide gas is preferentially transmitted to the decompression section by the carbon dioxide gas separation / removal film of the laminated structure, and selectively from the supply gas. This is a method for separating and removing carbon dioxide gas. Preferably, the polyol is at least one selected from the group consisting of polyethylene glycol, triethylene glycol and tetraethylene glycol, and the amine is diethanolamine.
Monoethanolamine, triethanolamine, diglycolamine, diisopropanolamine, methyldiethanolamine, carbon dioxide gas carrier liquid which is at least one selected from the group having a hydroxyl group consisting of 2-amino-2-methyltopropanol. The method for separating and removing carbon dioxide gas according to the above aspect, wherein the method is preferably such that carbon dioxide carrier liquid (C) is impregnated.
The non-swelling, non-gelling porous membrane to be retained is a hydrophilic polytetrafluoroethylene porous membrane, and the hydrophobic porous membrane that is lyophobic to the carbon dioxide carrier liquid is 0.001.
Has an average pore size of from 10 to 10 microns and a porosity of 30 to 8
The entire surface of the porous membrane including the inner surface of the porous membrane is made hydrophobic by polymerization of a fluorine-containing monomer having a characteristic of a water penetration pressure of 400 kPa or more and a triethylene glycol penetration pressure of 200 kPa or more. The carbon dioxide gas separation / removal method characterized by using a carbon dioxide gas separation / removal film having a laminated structure which is an improved one, more preferably including the inner surface of a porous film by polymerization of the fluorine-containing monomer. The above carbon dioxide gas separation / removal method, wherein the porous membrane for improving the entire surface of the porous membrane to be hydrophobic is made of polypropylene or polyvinylidene fluoride. It is.
【０００７】本発明の第２は、ポリオール類とアミン類
とを組み合わせた炭酸ガスキャリヤー液（Ｃ）を含浸・
保持した非膨張、非ゲル化多孔質膜（Ａ）とこれに隣接
して配置された、０．００１から１０ミクロンの平均孔
径を有し、空隙率が３０〜８５％の範囲であり、水の侵
入圧力が４００ｋＰａ以上およびトリエチレングリコー
ルの侵入圧力が２００ｋＰａ以上の特性を有するフッ素
含有モノマーの重合により多孔質膜の内部表面を含む多
孔質膜の表面全体を疎水性に改良した前記炭酸ガスキャ
リヤー液に対して撥液性の疎水性多孔質膜（Ｂ）よりな
る積層構造の炭酸ガス分離・除去膜、前記積層構造の炭
酸ガス分離・除去膜の前記ポリオール類とアミン類とを
組み合わせた炭酸ガスキャリヤー液（Ｃ）を含浸・保持
した多孔質膜（Ａ）側を炭酸ガスおよび水蒸気を含む供
給気体と接触させて通過させる室と炭酸ガスキャリヤー
液に対して撥液性の疎水性多孔質膜（Ｂ）側を減圧にす
る装置に接続され、前記積層構造の炭酸ガス分離・除去
膜の炭酸ガスの優先透過により減圧部に透過された炭酸
ガスを除去する室とを前記積層構造の炭酸ガス分離・除
去膜を介して設けたことを特徴とする前記炭酸ガス分離
・除去装置である。好ましくは、フッ素含有モノマーの
重合により多孔質膜の内部表面を含む多孔質膜の表面全
体を疎水性に改良する多孔膜がポリプロピレンまたはフ
ッ化ポリビニリデンからなるものであることを特徴とす
る前記炭酸ガス分離・除去装置である。また、必要によ
り、前記積層構造の炭酸ガス分離・除去膜の膜形状を保
持する支持する部材、例えば金属、セラミック焼結板か
らなる部材を設けることができる。本発明者は、炭酸ガ
スキャリヤー液を保持する膜の材質および構造を改善す
ると共に、炭酸ガスキャリヤー液体の組成を工夫して、
炭酸ガスキャリヤー液体の保持特性を改善することによ
って、前記課題を解決したものである。A second aspect of the present invention is to impregnate a carbon dioxide carrier liquid (C) comprising a combination of a polyol and an amine.
A retained non-swelling, non-gelling porous membrane (A), disposed adjacent thereto, having an average pore size of 0.001 to 10 microns, a porosity in the range of 30 to 85%, and water The carbon dioxide carrier in which the entire surface of the porous membrane including the inner surface of the porous membrane is made hydrophobic by polymerization of a fluorine-containing monomer having a penetration pressure of 400 kPa or more and a triethylene glycol penetration pressure of 200 kPa or more. A carbon dioxide gas separation / removal film having a laminated structure composed of a hydrophobic porous membrane (B) that is lyophobic to a liquid, and a carbonic acid obtained by combining the polyols and amines in the carbon dioxide gas separation / removal film having the laminated structure. A chamber through which the porous membrane (A) impregnated and held with the gas carrier liquid (C) is brought into contact with and supplied with a supply gas containing carbon dioxide and water vapor, and is lyophobic to the carbon dioxide carrier liquid. A chamber connected to a device for reducing the pressure on the hydrophobic porous membrane (B) side, wherein the chamber for removing carbon dioxide permeated to the decompression section by preferential permeation of carbon dioxide in the carbon dioxide separation / removal membrane having the laminated structure is provided. The carbon dioxide gas separation / removal device is provided via a carbon dioxide gas separation / removal film having a laminated structure. Preferably, the porous membrane for improving the entire surface of the porous membrane including the inner surface of the porous membrane to be hydrophobic by polymerization of a fluorine-containing monomer is made of polypropylene or polyvinylidene fluoride. It is a gas separation and removal device. If necessary, a supporting member for maintaining the film shape of the carbon dioxide gas separation / removal film having the laminated structure, for example, a member made of a metal or ceramic sintered plate can be provided. The present inventor has improved the material and structure of the film holding the carbon dioxide gas carrier liquid, and devised the composition of the carbon dioxide gas carrier liquid,
The object has been achieved by improving the retention characteristics of the carbon dioxide carrier liquid.
【０００８】[0008]
【本発明の実施の態様】本発明を、図面を参照にしなが
ら詳細に説明する。 １．ポリオール類とアミン類とを組み合わせた炭酸ガス
キャリヤー液（Ｃ）につき説明する。ポリオールとして
は、ポリエチレングリコール（分子量が１０００以
下）、トリエチレングリコール、テトラエチレングリコ
ールのグリコール類を好ましい材料として挙げることが
できる。これらの混合物であっても良い。アミン類とし
ては、ジエタノールアミン、モノエタノールアミン、ト
リエタノールアミン、ジグリコールアミン、ジイソプロ
パノールアミン、メチルジエタノールアミン、エチレン
ジアミン、ポリエチレンイミン、2−アミノー２−メチ
ル−１−プロパノール等を挙げることができ、ヒドロキ
シル基を有するアミン類が特に好ましい材料として挙げ
ることができる。これらの混合物であっても良い。炭酸
ガスキャリヤー液（Ｃ）としては、少なくとも５％のア
ミン類を含有する、特に好ましくは少なくとも１０％の
アミン類を含有することが、炭酸ガス分離・除去特性の
点から好ましい。アミン類の含有量の上限は、炭酸ガス
キャリヤー液に対して撥液性の疎水性多孔質膜（Ｂ）材
質との関連で、差圧３００ｋＰａ程度まで前記膜（Ｂ）
に浸透しないように決定される。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail with reference to the drawings. 1. The carbon dioxide carrier liquid (C) in which a polyol and an amine are combined will be described. As the polyol, preferred are glycols such as polyethylene glycol (having a molecular weight of 1,000 or less), triethylene glycol and tetraethylene glycol. These mixtures may be used. Examples of the amines include diethanolamine, monoethanolamine, triethanolamine, diglycolamine, diisopropanolamine, methyldiethanolamine, ethylenediamine, polyethyleneimine, 2-amino-2-methyl-1-propanol, and the like. The amines having the following are particularly preferred materials. These mixtures may be used. The carbon dioxide carrier liquid (C) preferably contains at least 5% of amines, particularly preferably at least 10% of amines, from the viewpoint of carbon dioxide gas separation / removal characteristics. The upper limit of the content of the amines is related to the material of the hydrophobic porous membrane (B) which is lyophobic to the carbon dioxide carrier liquid, and the differential pressure of the membrane (B) is up to about 300 kPa.
Is determined not to penetrate.
【０００９】２．前記炭酸ガスキャリヤー液（Ｃ）を含
浸・保持する非膨張、非ゲル化多孔質膜（Ａ）につい
て。 多孔質膜としては膜を貫通する細孔を有する構造で多孔
度（空隙率）が１０〜８５％のものであれば特に制限は
なく、市販のナイロン製多孔質膜、親水性処理を施した
ポリテトラフルオロエチレン製多孔質膜、ポリオレフイ
ン製多孔質膜などが使用できる。膜素材が疎水性で前記
炭酸ガスキャリヤー液（Ｃ）が直接膜内に浸透しない場
合には、あらかじめメタノール等に膜を浸漬した後その
膜を液体（Ｃ）に浸漬して、膜内の液を置き換えればよ
い。含浸した液体膜の厚みは通常は前記多孔質膜（Ａ）
の厚み程度となるが、さらに液体厚みを薄くしたい場合
には、液体を水で希釈してから含浸し、その後水を蒸発
させることで、薄くすることができる。 ３．炭酸ガスキャリヤー液に対して撥液性の疎水性多孔
質膜（Ｂ）について。 この膜を設けたことが本発明の特徴であり、その機能は
その表面の撥水（撥液）特性によって、膜の片側が真空
の状態、例えば、飽和水蒸気分圧が室温で２ｋＰａ以下
の低真空でも炭酸ガスキャリヤー液（Ｃ）が漏れ出さな
いたものものである。[0009] 2. About the non-expandable, non-gelled porous membrane (A) impregnated with and holding the carbon dioxide carrier liquid (C). The porous membrane is not particularly limited as long as it has a structure having pores penetrating the membrane and has a porosity (porosity) of 10 to 85%, and a commercially available nylon porous membrane and a hydrophilic treatment are applied. A porous film made of polytetrafluoroethylene, a porous film made of polyolefin, or the like can be used. If the membrane material is hydrophobic and the carbon dioxide carrier liquid (C) does not directly penetrate into the membrane, the membrane is immersed in methanol or the like in advance, and the membrane is immersed in the liquid (C). Should be replaced. The thickness of the impregnated liquid membrane is usually the same as that of the porous membrane (A).
If it is desired to further reduce the thickness of the liquid, the liquid can be diluted by diluting the liquid with water, impregnating the liquid, and then evaporating the water. 3. About the hydrophobic porous membrane (B) which is liquid-repellent to the carbon dioxide carrier liquid. The provision of this film is a feature of the present invention, and its function is that the surface of the film is in a vacuum state, for example, the saturated water vapor partial pressure is as low as 2 kPa or less at room temperature due to the water-repellent (liquid-repellent) characteristics of the surface. The carbon dioxide carrier liquid (C) does not leak even under vacuum.
【００１０】疎水性の多孔質膜を形成するのに適したポ
リマーの代表的なものには、ポリエチレン、ポリプロピ
レン、ポリメチルペンテン等のポリオレフィン；ポリア
ミド；ポリスチレン若しくは置換されたポリスチレン；
ポリ（テトラフルオロエチレン）、フッ化ポリビニリデ
ン（ＰＶＤＦ）等を含むフッ素化ポリマー；ポリサルフ
ォン、ポリエーテルサルフォン等のポリサルフォン；ポ
リエチレンテレフタレート、ポリブチレンテレフタレー
ト等を含むポリエステル；ポリアクリレート及びポリ炭
酸エステル；セルロース系ポリマー；並びにポリ塩化ビ
ニル及びポリアクリロニトリル等のビニルポリマー、が
挙げられる。ブタジエン及びスチレンのコポリマー、フ
ッ素化エチレン−プロピレンコポリマー、エチレン−ク
ロロトリフルオロエチレンコポリマー等のコポリマーも
また用いることができる。前記撥液性の疎水性多孔質膜
（Ｂ）を設けることにより、液体中に吸収された炭酸ガ
スが選択的に真空側へ透過する。これに使用する疎水性
多孔質膜としては、０．００１から１０ミクロンの平均
孔径を有し、空隙率（多孔度）は３０〜８５％の範囲で
あり、水の侵入圧力４００ｋＰａ以上およびトリエチレ
ングリコールの侵入圧力２００ｋＰａ以上の特性を有す
るフッ素含有モノマーの重合により多孔質膜の内部表面
を含む多孔質膜の表面全体を疎水性に改良したものを好
ましい材料として挙げることができ、フツ素モノマーで
表面処理をした、ポリプロピレン多孔質膜およびフツ化
ポリビニリデン（ＰＶＤＦ＝ポリビニリデンジフルオラ
イド）多孔質膜を特に好ましい材料として挙げることが
できる。このような材料は、例えば、ミリポア社から商
品ＵＰＥ、Durapel膜（特開平６−９８１０号公報等参
照）等として市販のものである。この膜の特性は、多孔
度７０％、孔径０．２μm、膜厚み１２０μmであり、水
進入圧は公称４２７ｋＰａである。本発明において使用
される炭酸ガスキャリヤー液体も差圧３００ｋＰａ程度
まで、疎水性多孔質膜中に進入しない。[0010] Representative polymers suitable for forming the hydrophobic porous membrane include polyolefins such as polyethylene, polypropylene, polymethylpentene; polyamides; polystyrene or substituted polystyrene;
Fluorinated polymers including poly (tetrafluoroethylene) and polyvinylidene fluoride (PVDF); polysulfones such as polysulfone and polyethersulfone; polyesters including polyethylene terephthalate, polybutylene terephthalate; polyacrylates and polycarbonates; And vinyl polymers such as polyvinyl chloride and polyacrylonitrile. Copolymers such as butadiene and styrene copolymers, fluorinated ethylene-propylene copolymers, ethylene-chlorotrifluoroethylene copolymers and the like can also be used. By providing the hydrophobic porous film (B) having liquid repellency, the carbon dioxide gas absorbed in the liquid is selectively transmitted to the vacuum side. The hydrophobic porous membrane used for this has an average pore size of 0.001 to 10 microns, a porosity (porosity) in the range of 30 to 85%, a water intrusion pressure of 400 kPa or more, and triethylene. As a preferable material, a material obtained by improving the entire surface of the porous film including the inner surface of the porous film to be hydrophobic by polymerization of a fluorine-containing monomer having a characteristic of a penetration pressure of glycol of 200 kPa or more can be mentioned as a preferable material. Surface-treated porous polypropylene membranes and polyvinylidene fluoride (PVDF = polyvinylidene difluoride) porous membranes can be mentioned as particularly preferred materials. Such materials are commercially available, for example, from Millipore as UPE, Durapel film (see JP-A-6-9810, etc.). The characteristics of this membrane are porosity 70%, pore diameter 0.2 μm, membrane thickness 120 μm, and the water entry pressure is nominally 427 kPa. The carbon dioxide carrier liquid used in the present invention also does not enter the hydrophobic porous membrane up to a differential pressure of about 300 kPa.
【００１１】４．炭酸ガス分離・除去方法および装置に
ついて。 図１（ｂ）が本発明の、図１の（ａ）に示す、炭酸ガス
キャリヤー液（Ｃ）を含浸・保持する非膨張、非ゲル化
多孔質膜（Ａ）と炭酸ガスキャリヤー液に対して撥液性
の疎水性多孔質膜（Ｂ）とが積層された炭酸ガス分離・
除去膜を用いた炭酸ガス分離・除去方法および炭酸ガス
分離・除去装置の一態様である。前記積層構造の膜がス
テンレス製焼結板（Ｓ．Ｐ：積層膜保持部材）上に設置
され、Ｏリング（Ｏ．Ｒ）ではさんで固定される。供給
ガス入り口（Ｇ．Ｉ）から、例えば炭酸ガスと水蒸気を
含むガスを供給し、前記積層膜の透過側（Ｐ．Ｓ）を真
空ポンプ（Ｖ．Ｐ）で水蒸気圧以下の真空に保つことに
より、透過側に濃縮された炭酸ガス（透過ガス）を得
る。供給ガス中の他の成分は空気、メタンなど任意のガ
スであってよい。なお、前記積層構造の膜は、膜を製造
する工程で積層構造にすることができ、また、積層中空
膜構造とすることもできる。4. About carbon dioxide separation / removal method and device. FIG. 1 (b) shows the non-expanded, non-gelled porous membrane (A) impregnated with and holding the carbon dioxide gas carrier liquid (C) and the carbon dioxide gas carrier liquid shown in FIG. 1 (a). Gas separation and lamination with a liquid-repellent hydrophobic porous membrane (B)
It is an aspect of a carbon dioxide separation / removal method and a carbon dioxide separation / removal device using a removal film. The film having the laminated structure is placed on a stainless steel sintered plate (SP: laminated film holding member), and is fixed by an O-ring (OR). A gas containing, for example, carbon dioxide gas and water vapor is supplied from a supply gas inlet (GI), and the permeation side (PS) of the laminated film is maintained at a vacuum lower than the water vapor pressure by a vacuum pump (VP). As a result, concentrated carbon dioxide gas (permeated gas) is obtained on the permeation side. Other components in the feed gas can be any gas, such as air, methane. The film having the laminated structure can be formed into a laminated structure in a process of producing the film, or can be formed into a laminated hollow film structure.
【００１２】[0012]
【実施例】実施例１ 平膜セル（膜面積２２．９ｃｍ2）のステンレス焼結板
上に、炭酸ガスキャリヤー液に対して撥液性の疎水性多
孔膜（Ｂ）（前記ミリポア社製のDurapeI膜）を置き、
その上トリエチレングリコール９０％、ジエタノールア
ミン１０％の混合液（Ｃ）を含浸させた膜厚み３５μ
m、多孔度７９％の親水性ポリテトラフルオロエチレン
多孔質膜（Ａ）（ミリポア社製の市販のもの）を設置す
る。供給ガスとして炭酸ガスとメタンの混合ガスに水蒸
気を混和させたものを１００cm３／minの流量で供給す
る。供給側圧力を１．８Ｋｇ／ｃｍ2（絶対圧）、透過
側を３mmHgに保つ。操作湿度は室温（２８℃）である。
この操作で透過側に０．４ｃｍ3／min程度の透過ガスが
得られ、供給側炭酸ガス濃度１３ｖｏｌ％に対して、透
過ガス中の炭酸ガス濃度は８７ｖｏｌ％に濃縮された。
この実験データより透過係数を推算すると、炭酸ガスに
対して２．７１×１０-8、メタンに対して５．７８×１
０-1ｃｍ3（ＳＴＰ）・cm／(s・ｃｍ2・ｃｍＨｇ）、両
者の理想分離係数は４７が得られた。その他の実験結果
も図２に示す。またこの図中には液体膜をトリエチレン
グリコール１００％とした場合の実験結果を比較例とし
て記載した（▲記号参照）。この比較例から、炭酸ガス
分離性は、本発明の炭酸ガス分離・除去方法の方が高い
炭酸ガス分離性が得られることが理解され、これは、ポ
リオール類とアミン類とを組み合わせた炭酸ガスキャリ
ヤー液を使用することによることがわかる。EXAMPLE 1 A hydrophobic porous membrane (B) (available from Millipore Co.) was repellent to a carbon dioxide carrier liquid on a stainless sintered plate of a flat membrane cell (membrane area: 22.9 cm 2 ). Durape I membrane)
Furthermore, a film thickness of 35 μm impregnated with a mixed solution (C) of 90% triethylene glycol and 10% diethanolamine.
m, a hydrophilic polytetrafluoroethylene porous membrane (A) having a porosity of 79% (commercially available from Millipore) is installed. As a supply gas, a mixture of carbon dioxide and methane mixed with water vapor is supplied at a flow rate of 100 cm3 / min. The supply pressure is maintained at 1.8 kg / cm 2 (absolute pressure) and the permeate side at 3 mmHg. The operating humidity is room temperature (28 ° C.).
By this operation, a permeate gas of about 0.4 cm 3 / min was obtained on the permeate side, and the carbon dioxide gas concentration in the permeate gas was increased to 87 vol% with respect to the supply side carbon dioxide gas concentration of 13 vol%.
From the experimental data, the permeability coefficient was estimated to be 2.71 × 10 −8 for carbon dioxide and 5.78 × 1 for methane.
0 −1 cm 3 (STP) · cm / (s · cm 2 · cmHg), and an ideal separation coefficient of 47 was obtained. Other experimental results are also shown in FIG. In this figure, the experimental results when the liquid film was made of triethylene glycol 100% are described as comparative examples (see the symbol ▲). From this comparative example, it is understood that the carbon dioxide gas separation performance of the method for separating and removing carbon dioxide gas of the present invention is higher than that of the carbon dioxide gas separation and removal method of the present invention. It can be seen that the use of the carrier liquid is used.
【００１３】[0013]
【発明の効果】以上述べたように、本発明は炭酸ガスの
分離法において連続操作が可能な新規な膜分離法を提供
するものであり、本発明は分離係数・透過速度ともに大
きく、かつ装置を構成する各材料が安価であるので小
型、安価な炭酸ガス分離装置を構成できる。膜面積を大
きくすることにより、排気ガス、天然ガスなど各種の炭
酸ガス分離が必要なプロセスに適用できるという優れた
効果がもたらされる。As described above, the present invention provides a novel membrane separation method capable of continuous operation in the method for separating carbon dioxide gas. Since each of the constituent materials is inexpensive, a compact and inexpensive carbon dioxide separation device can be constructed. By increasing the membrane area, an excellent effect of being applicable to processes requiring various types of carbon dioxide separation such as exhaust gas and natural gas is provided.
【図１】 本発明の炭酸ガス吸収性液体を保持する積層
構造の膜（ａ）と炭酸ガス分離装置（ｂ）であるFIG. 1 shows a membrane (a) having a laminated structure for retaining a carbon dioxide-absorbing liquid of the present invention and a carbon dioxide separator (b).
【図２】 本発明の積層膜を用いた炭酸ガスの分離性能FIG. 2 shows the separation performance of carbon dioxide gas using the laminated membrane of the present invention.
（Ａ） 親水性の非膨張、非ゲル化多孔質膜 （Ｂ） 炭酸ガスキャリヤー液に対して撥液性の疎水性
多孔質膜 （Ｃ） 炭酸ガスキャリヤー液 Ｓ．Ｐ 積層膜保持部
材 Ｏ．Ｒ Ｏリング Ｇ．Ｉ 供給ガス入り口 Ｐ．Ｓ
透過側 Ｖ．Ｐ 真空ポンプ(A) hydrophilic non-expandable, non-gelling porous membrane (B) hydrophobic porous membrane lyophobic to carbon dioxide gas carrier liquid (C) carbon dioxide gas carrier liquid P laminated film holding member RO ring G. I Supply gas inlet S
Transmission side P vacuum pump
Claims (6)
た炭酸ガスキャリヤー液（Ｃ）を含浸・保持した非膨
張、非ゲル化多孔質膜（Ａ）とこれに隣接して配置され
た前記炭酸ガスキャリヤー液に対して撥液性の疎水性多
孔質膜（Ｂ）よりなる積層構造の炭酸ガス分離・除去膜
の、前記炭酸ガスキャリヤー液体を含浸・保持した前記
非膨張、非ゲル化多孔質膜側を炭酸ガスと水蒸気を含む
供給気体に接触させ、前記疎水性多孔膜側を水蒸気圧以
下の減圧部に接触させて、少なくとも前記炭酸ガスを前
記積層構造の炭酸ガス分離・除去膜により滅圧部に優先
的に透過させ前記供給気体中から選択的に除去すること
を特徴とする炭酸ガス分離・除去方法。1. A non-expandable, non-gelling porous membrane (A) impregnated with and holding a carbon dioxide carrier liquid (C) comprising a combination of a polyol and an amine, and said carbon dioxide gas disposed adjacent thereto. A non-expanded, non-gelled porous membrane impregnated with and holding the carbon dioxide carrier liquid of a carbon dioxide separation / removal membrane having a laminated structure composed of a hydrophobic porous membrane (B) that is lyophobic to the carrier liquid. Side is contacted with a supply gas containing carbon dioxide gas and water vapor, and the hydrophobic porous membrane side is brought into contact with a depressurizing section below the water vapor pressure, and at least the carbon dioxide gas is decompressed by the carbon dioxide gas separation / removal film of the laminated structure. A carbon dioxide gas separation / removal method, wherein the carbon dioxide gas is preferentially permeated through a section and selectively removed from the supply gas.
ル、トリエチレングリコール、テトラエチレングリコー
ルからなる群から選択される少なくとも１種であり、ま
たアミン類がジエタノールアミン、モノエタノールアミ
ン、トリエタノールアミン、ジグリコールアミン、ジイ
ソプロパノールアミン、メチルジエタノールアミン、2
−アミノー2−メチルートプロパノールからなるヒドロ
キシル基を持つ群から選択される少なくとも１種であで
ある炭酸ガスキャリヤー液を用いることを特徴とする請
求項１に記載の炭酸ガス分離・除去方法。2. The polyols are at least one selected from the group consisting of polyethylene glycol, triethylene glycol and tetraethylene glycol, and the amines are diethanolamine, monoethanolamine, triethanolamine, diglycolamine, diglycolamine and diethanolamine. Isopropanolamine, methyldiethanolamine, 2
2. The method for separating and removing carbon dioxide according to claim 1, wherein a carbon dioxide carrier liquid which is at least one selected from the group having a hydroxyl group consisting of -amino-2-methyltopropanol is used.
持する非膨張、非ゲル化多孔質膜が親水性ポリテトラフ
ルオロエチレン多孔質膜であり、前記炭酸ガスキャリヤ
ー液に対して撥液性の疎水性多孔質膜が、０．００１か
ら１０ミクロンの平均孔径を有し、空隙率は３０〜８５
％の範囲であり、水の侵入圧力４００ｋＰａ以上および
トリエチレングリコールの侵入圧力２００ｋＰａ以上の
特性を有するフッ素含有モノマーの重合により多孔質膜
の内部表面を含む多孔質膜の表面全体を疎水性に改良し
たものである積層構造の炭酸ガス分離・除去膜を用いる
ことを特徴とする請求項１または２に記載の炭酸ガス分
離・除去方法。3. The non-expandable, non-gelling porous membrane impregnated with and holding the carbon dioxide gas carrier liquid (C) is a hydrophilic polytetrafluoroethylene porous film, and has liquid repellency to the carbon dioxide gas carrier liquid. Has an average pore size of 0.001 to 10 microns and a porosity of 30 to 85
%, And the entire surface of the porous film including the inner surface of the porous film is improved to be hydrophobic by polymerization of a fluorine-containing monomer having a characteristic of water penetration pressure of 400 kPa or more and triethylene glycol penetration pressure of 200 kPa or more. The carbon dioxide gas separation / removal method according to claim 1 or 2, wherein a carbon dioxide gas separation / removal film having a laminated structure is used.
膜の内部表面を含む多孔質膜の表面全体を疎水性に改良
する多孔質膜が、ポリプロピレンまたはフッ化ポリビニ
リデンからなるものであることを特徴とする請求項３に
記載の炭酸ガス分離・除去方法。4. A porous membrane for improving hydrophobicity of the entire surface of a porous membrane including an inner surface of the porous membrane by polymerization of a fluorine-containing monomer is made of polypropylene or polyvinylidene fluoride. The method for separating and removing carbon dioxide gas according to claim 3.
た炭酸ガスキャリヤー液（Ｃ）を含浸・保持した非膨
張、非ゲル化多孔質膜（Ａ）とこれに隣接して配置され
た、０．００１から１０ミクロンの平均孔径を有し、空
隙率が３０〜８５％の範囲であり、水の侵入圧力が４０
０ｋＰａ以上およびトリエチレングリコールの侵入圧力
が２００ｋＰａ以上の特性を有するフッ素含有モノマー
の重合により多孔質膜の内部表面を含む多孔質膜の表面
全体を疎水性に改良した前記炭酸ガスキャリヤー液に対
して撥液性の疎水性多孔質膜（Ｂ）よりなる積層構造の
炭酸ガス分離・除去膜、前記積層構造の炭酸ガス分離・
除去膜の前記ポリオール類とアミン類とを組み合わせた
炭酸ガスキャリヤー液（Ｃ）を含浸・保持した多孔質膜
（Ａ）側を炭酸ガスおよび水蒸気を含む供給気体と接触
させて通過させる室と炭酸ガスキャリヤー液に対して撥
液性の疎水性多孔質膜（Ｂ）側を減圧にする装置に接続
され、前記積層構造の炭酸ガス分離・除去膜の炭酸ガス
の優先透過により減圧部に透過された炭酸ガスを除去す
る室とを前記積層構造の炭酸ガス分離・除去膜を介して
設けたことを特徴とする炭酸ガス分離・除去装置。5. A non-expandable, non-gelling porous membrane (A) impregnated with and holding a carbon dioxide gas carrier liquid (C) comprising a combination of a polyol and an amine, and a non-swelling, non-gelling porous membrane (A) disposed adjacent thereto. It has an average pore size of 001 to 10 microns, a porosity in the range of 30-85%, and a water entry pressure of 40
0 kPa or more and the penetration pressure of triethylene glycol is 200 kPa or more. The carbon dioxide carrier liquid in which the entire surface of the porous film including the inner surface of the porous film is improved to be hydrophobic by polymerization of a fluorine-containing monomer having characteristics of 200 kPa or more. A carbon dioxide gas separation / removal film having a laminated structure composed of a liquid-repellent hydrophobic porous film (B), and a carbon dioxide gas separation / removal film having the laminated structure.
A chamber through which the porous membrane (A) impregnated with and holding the carbon dioxide carrier liquid (C) comprising the combination of the polyols and amines of the removal membrane is brought into contact with and passed through a supply gas containing carbon dioxide and water vapor. The device is connected to a device for reducing the pressure of the hydrophobic porous membrane (B), which is liquid-repellent to the gas carrier liquid, and is transmitted to the pressure reducing section by preferential transmission of carbon dioxide in the carbon dioxide gas separation / removal film having the laminated structure. A chamber for removing carbon dioxide gas provided through the carbon dioxide gas separation / removal film having the laminated structure.
膜の内部表面を含む多孔質膜の表面全体を疎水性に改良
する多孔膜がポリプロピレンまたはフッ化ポリビニリデ
ンからなるものであることを特徴とする請求項５に記載
の炭酸ガス分離・除去装置。6. The porous membrane which improves the entire surface of the porous membrane including the inner surface of the porous membrane to be hydrophobic by polymerization of a fluorine-containing monomer is made of polypropylene or polyvinylidene fluoride. The carbon dioxide separation / removal device according to claim 5.
Priority Applications (1)
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|---|---|---|---|
| JP30542499A JP3999423B2 (en) | 1999-10-27 | 1999-10-27 | Carbon dioxide separation and dehumidification method and apparatus using liquid membrane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30542499A JP3999423B2 (en) | 1999-10-27 | 1999-10-27 | Carbon dioxide separation and dehumidification method and apparatus using liquid membrane |
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| Publication Number | Publication Date |
|---|---|
| JP2001120940A true JP2001120940A (en) | 2001-05-08 |
| JP3999423B2 JP3999423B2 (en) | 2007-10-31 |
Family
ID=17944977
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30542499A Expired - Fee Related JP3999423B2 (en) | 1999-10-27 | 1999-10-27 | Carbon dioxide separation and dehumidification method and apparatus using liquid membrane |
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| Country | Link |
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