JP4777153B2 - Gas separation method and gas collection method - Google Patents
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Description
本発明は、気体吸着する材料を用いた気体分離方法及び気体収集方法に関する。 The present invention relates to a gas separation method and a gas collection method using a gas adsorbing material.
従来、気体すなわちガスの吸着材料には様々な多孔質材料が用いられている。これら多孔質材料は、細孔径が２ｎｍ以下のマイクロポーラス、２〜５０ｎｍのメソポーラス、５０ｎｍ以上のマクロポーラスに分類され、吸着ガス分子の大きさ等によって材料を使い分けている。 Conventionally, various porous materials are used as gas, that is, gas adsorbing materials. These porous materials are classified into microporous with a pore diameter of 2 nm or less, mesoporous with 2 to 50 nm, and macroporous with 50 nm or more, and the materials are properly used depending on the size of adsorbed gas molecules.
一方、ガスの分離及び精製法に関しては一般的に不純物ガスに対する化学反応を用いる方法がある。特許文献１には、酸素を含む混合ガスの中に水素を供給し酸素を水に転化して除去することが提案されている。 On the other hand, as a gas separation and purification method, there is generally a method using a chemical reaction with an impurity gas. Patent Document 1 proposes supplying hydrogen into a mixed gas containing oxygen to convert oxygen into water and removing it.
不純物ガスを選択的に吸着する吸着材を利用して不純物ガスを分離する方法も多く用いられる。これには、圧力によりＡｒの吸着量が異なることを利用するＰＳＡ（Ｐｒｅｓｓｕｒｅ Ｓｗｉｎｇ Ａｄｓｏｒｐｔｉｏｎ）法と、温度による吸着量の差を合わせて利用するＰＴＳＡ（Ｐｒｅｓｓｕｒｅ ａｎｄ Ｔｅｍｐｅｒａｔｕｒｅ Ｓｗｉｎｇ Ａｄｓｏｒｐｔｉｏｎ）法が知られている。 A method of separating the impurity gas using an adsorbent that selectively adsorbs the impurity gas is often used. For this, there are known a PSA (Pressure Swing Adsorption) method that utilizes the difference in the amount of adsorption of Ar depending on pressure, and a PTSA (Pressure and Temperature Swing Adsorption) method that utilizes the difference in the amount of adsorption depending on the temperature. .
特許文献２には、窒素を特異的に吸着するゼオライトを吸着材料として、空気から窒素を分離する方法が提案されている。特許文献３には、吸着量と圧力の関係（脱吸着特性）がヒステリシスを示す吸着材を用いるガス貯蔵方法が開示されている。また、特許文献４には、通常の吸着材を脱吸着特性にヒステリシスを持つ吸着材で被覆した吸着材が提案されている。
従来の吸着材を用いる気体分離方法は、目的の気体のみを選択的に多く吸着し、そのほかの構成成分は吸着しない吸着材料を選ぶ必要がある。目的気体以外の構成成分をも吸着する場合は、分離すべき構成成分気体の吸着圧力が他の構成成分気体の吸着圧力と十分離れていることが必要である。 In the conventional gas separation method using an adsorbent, it is necessary to select an adsorbent material that selectively adsorbs only a target gas and does not adsorb other constituent components. When adsorbing a constituent component other than the target gas, it is necessary that the adsorption pressure of the constituent gas to be separated is sufficiently separated from the adsorption pressure of the other constituent gas.
本発明の目的は、構成成分を選択的に吸着する吸着材を用いない気体分離方法を提供することである。 An object of the present invention is to provide a gas separation method that does not use an adsorbent that selectively adsorbs constituent components.
本発明に従って、吸着材を用いて、混合気体から特定の気体を分離する気体分離方法であって、
（１）気体の圧力を上昇させる過程における第１の気体の吸着量に対して、気体の圧力を減じる過程における第１の気体の吸着量が、吸着した第１の気体の脱離を生じにくいヒステリシスを示す吸着材を備えた気密容器内に、前記第１の気体と、前記圧力上昇過程における前記吸着材への吸着量と前記圧力を減じる過程における前記吸着材への吸着量とが同様に変化する第２の気体と、を含む混合気体を導入し、該混合気体を第１の圧力で前記吸着材に接触させ、第１及び第２の気体を該吸着材に吸着させる工程、と
（２）前記気密容器内の前記混合気体を、第１の圧力より低く、かつ第１の気体について前記ヒステリシスを示す範囲内にある第２の圧力として、第２の気体を前記吸着材より脱離させ、第１の気体と第２の気体とを分離する工程、と
を有することを特徴とする気体分離方法が提供される。
According to the present invention, by using the adsorbent, the gas mixture to a gas separation method for separating a specific gas,
(1) The amount of adsorption of the first gas in the process of reducing the gas pressure is less likely to cause desorption of the adsorbed first gas than the amount of adsorption of the first gas in the process of increasing the gas pressure. In the airtight container provided with the adsorbent exhibiting hysteresis, the first gas, the adsorbed amount on the adsorbent in the pressure increasing process, and the adsorbed amount on the adsorbent in the process of reducing the pressure are the same. introducing a mixed gas containing a second gas changing, and the mixed gas wherein the contacting the adsorbent at a first pressure, the first and second gas adsorbing the adsorbing material, and ( 2) the mixed gas in the hermetic vessel, as a second pressure which is within the range indicating the hysteresis for less than the first pressure, and a first gas, desorption from the adsorbent to the second gas It is, separating the first gas and the second gas Extent, a gas separation method characterized by having a <br/> is provided.
本発明により、従来は限られた吸着材でのみ可能であったアルゴンと窒素の分離など、分子量と分子サイズが近い値の気体を分離することができる。 According to the present invention, it is possible to separate a gas having a molecular weight and a molecular size close to each other, such as separation of argon and nitrogen, which is conventionally possible only with a limited adsorbent.
以下、本発明の実施の形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明の気体分離方法は、有機金属錯体の脱着側吸着量と吸着側吸着量との差を利用して、不純物気体を含んだ混合気体に対して吸着脱着過程を繰り返すことにより、アルゴン等の気体中の不純物気体を分離し精製する。 The gas separation method of the present invention uses the difference between the adsorption side adsorption amount and the adsorption side adsorption amount of the organometallic complex, and repeats the adsorption / desorption process with respect to the mixed gas containing the impurity gas, so The impurity gas in the gas is separated and purified.
本発明で用いられる吸着材は、細孔直径が２ｎｍ以下の細孔を有する有機金属錯体であって、混合気体中の特定の成分気体に対して、分離を行う温度領域で測定した脱吸着等温線が、ヒステリシスを持つ。ヒステリシスは、低圧領域で大きな幅を持つことが好ましく、具体的には、液体窒素温度で測定したヒステリシスが、飽和蒸気圧に対する相対圧力０．０５〜０．１で脱着側吸着量と吸着側吸着量の比が１．２０以上のヒステリシスループ領域が存在することが好ましい。 The adsorbent used in the present invention is an organometallic complex having pores having a pore diameter of 2 nm or less, and is desorbed isothermally measured in a temperature region in which a specific component gas in the mixed gas is separated. The line has hysteresis. The hysteresis preferably has a large width in the low-pressure region. Specifically, the hysteresis measured at the liquid nitrogen temperature is 0.05 to 0.1 relative to the saturated vapor pressure, and the desorption-side adsorption amount and the adsorption-side adsorption. It is preferable that a hysteresis loop region having an amount ratio of 1.20 or more exists.
ヒステリシス幅が狭いと、不純物気体との分離精製に回数がかかり効率が低下する。ヒステリシス幅の上限は特になく、高ければ分離精製が効率的に行える。 If the hysteresis width is narrow, the separation and purification from the impurity gas takes a lot of time and the efficiency is lowered. There is no particular upper limit on the hysteresis width, and separation and purification can be performed efficiently if the hysteresis width is high.
本発明にかかる吸着材に用いられる有機金属錯体は、細孔直径が２ｎｍ以下の細孔を有する。直径が２ｎｍ以下の細孔はマイクロポーラスとよばれ、分子量の小さい気体、例えば、窒素及びアルゴンの吸着に適していており、本発明では気体分離精製法の対象気体としてはアルゴンが好ましい。 The organometallic complex used for the adsorbent according to the present invention has pores having a pore diameter of 2 nm or less. A pore having a diameter of 2 nm or less is called microporous and is suitable for adsorption of a gas having a small molecular weight, for example, nitrogen and argon. In the present invention, argon is preferable as a target gas for the gas separation and purification method.
本発明で用いられる吸着材は、先に本発明者が引用文献５（特開２００４−２３１６３９号公報）で提案した下記の材料が好ましく用いられる。 As the adsorbent used in the present invention, the following materials previously proposed by the present inventor in Reference 5 (Japanese Patent Laid-Open No. 2004-231539) are preferably used.
すなわち、細孔直径が２ｎｍ以下の細孔を有する有機金属錯体であって、下記一般式（１）で示され、より好ましくは下記一般式（２）で示される材料が用いられる。 That is, an organometallic complex having pores having a pore diameter of 2 nm or less, represented by the following general formula (1), more preferably a material represented by the following general formula (2).
Ｍ・Ｌ（Ａ，Ｂ）３ （１）
式中、Ｍは金属原子を示し、ＬはＡ、Ｂによって構成された配位子を示し、Ａ、Ｂはそれぞれ無置換又は置換基を有してもよい環状基を示す。Ａ、Ｂが有する置換基はハロゲン原子、ニトロ基又はトリアルキルシリル基（該アルキル基はそれぞれ独立して炭素原子数１〜８の直鎖状もしくは分岐状のアルキル基）である。
ML (A, B) 3 (1)
In the formula, M represents a metal atom, L represents a ligand composed of A and B, and A and B each represent a cyclic group which may be unsubstituted or have a substituent. The substituents A and B have are a halogen atom, a nitro group, or a trialkylsilyl group (the alkyl groups are each independently a linear or branched alkyl group having 1 to 8 carbon atoms).
式中、Ｍは金属原子を示し、Ａ、Ｂはそれぞれ無置換もしくは置換基を有してもよい環状基、又は炭素原子数１〜２０の直鎖状もしくは分岐状のアルキル基（該アルキル基中の１つもしくは隣接しない２つ以上のメチレン基は−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−で置換されていてもよく、該アルキル基中の水素原子はフッ素原子に置換されてもよい。）を示す。Ａ、Ｂが有する置換基はハロゲン原子、ニトロ基又はトリアルキルシリル基（該アルキル基はそれぞれ独立して炭素原子数１〜８の直鎖状もしくは分岐状のアルキル基）である。 In the formula, M represents a metal atom, and A and B are each an unsubstituted or substituted cyclic group or a linear or branched alkyl group having 1 to 20 carbon atoms (the alkyl group). One or two or more methylene groups in it are —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH—, —C≡C—. It may be substituted, and a hydrogen atom in the alkyl group may be substituted with a fluorine atom). The substituents A and B have are a halogen atom, a nitro group, or a trialkylsilyl group (the alkyl groups are each independently a linear or branched alkyl group having 1 to 8 carbon atoms).
前記一般式（１）及び（２）の金属原子Ｍに結合した環状基Ａ及びＢのうち少なくとも一つは、ピリジン、ピリミジン、ピラゾリン、ピロール、ピラゾール、キノリン、イソキノリン、イミダゾール、キノン、ベンゾアゼビン、カテコール、フェノール、フェニル、ナフチル、チエニル、ベンゾチエニル、キノリル、フェノチアジン、ベンゾチアゾール、ベンゾオキサゾール及びベンゾイミダゾールからなる群から選ばれることが好ましく、より好ましくはフェニル及びイソキノリンである。 At least one of the cyclic groups A and B bonded to the metal atom M in the general formulas (1) and (2) is pyridine, pyrimidine, pyrazoline, pyrrole, pyrazole, quinoline, isoquinoline, imidazole, quinone, benzoazebin, catechol. , Phenol, phenyl, naphthyl, thienyl, benzothienyl, quinolyl, phenothiazine, benzothiazole, benzoxazole and benzimidazole, more preferably phenyl and isoquinoline.
前記一般式（１）及び（２）の金属原子Ｍとしては、コバルト及びイリジウム等が挙げられ、好ましくはイリジウムである。 Examples of the metal atom M in the general formulas (1) and (2) include cobalt and iridium, and preferably iridium.
前記一般式（２）で示される有機金属錯体化合物の合成経路は、Ｋｅｖｉｎ Ｒ．ｅｔ ａｌ．，Ｏｒｇ．Ｌｅｔｔ．，１９９９年，１，５５３−１，５５６頁に開示されている。イリジウム配位化合物を例とした合成経路を以下に示す。 The synthesis route of the organometallic complex compound represented by the general formula (2) is Kevin R. et al. et al. Org. Lett. 1999, pp. 1,553-1,556. A synthetic route using an iridium coordination compound as an example is shown below.
イリジウム配位化合物の合成 Synthesis of iridium coordination compounds
式中、Ｌは配位子を示す。 In the formula, L represents a ligand.
得られた化合物を溶媒に溶かし込みその後、析出させることにより２ｎｍ以下の細孔を有する有機金属錯体を得ることができる。 An organometallic complex having pores of 2 nm or less can be obtained by dissolving the obtained compound in a solvent and then precipitating it.
上記材料を吸着材として用いることにより、気体を貯蔵し、気体を分離精製することができる。 By using the above material as an adsorbent, gas can be stored and gas can be separated and purified.
以下、実施例を挙げて更に詳細に本発明を説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.
（材料の生成方法）
一般式（１）で示される有機金属錯体において、Ｍがイリジウム、Ａがフェニル、Ｂがイソキノリンで表される有機金属錯体を以下の手順で合成した。
(Material generation method)
In the organometallic complex represented by the general formula (1), an organometallic complex in which M is iridium, A is phenyl, and B is isoquinoline was synthesized by the following procedure.
東京化成製イソキノリンＮ−オキシド６９．３ｇ（４４８ｍｍｏｌｅ）、クロロホルム２２５ｍｌを１リットルの３つ口フラスコに入れて溶かし、氷冷攪拌下、内温を１５〜２０℃に保ってオキシ塩化リン２１９．６ｇ（１４３２ｍｍｏｌｅ）をゆっくり滴下した。その後昇温し、３時間還流攪拌を行った。反応物を室温まで放冷し、氷水中に注入した。酢酸エチルで抽出し、有機層を中性になるまで水洗し、溶媒を減圧乾固した。残渣をシリカゲルカラムクロマト（溶離液：クロロホルム／へキサン：５／１）で精製し、１−クロロイソキノリンの白色結晶３５．５ｇ（収率４４．９％）を得た。 69.3 g (448 mmole) of isoquinoline N-oxide manufactured by Tokyo Chemical Industry and 225 ml of chloroform were dissolved in a 1 liter three-necked flask, and the internal temperature was maintained at 15 to 20 ° C. with stirring under ice cooling, and 219.6 g of phosphorus oxychloride. (1432 mmole) was slowly added dropwise. Thereafter, the temperature was raised, and the mixture was stirred for 3 hours under reflux. The reaction was allowed to cool to room temperature and poured into ice water. Extraction was performed with ethyl acetate, the organic layer was washed with water until neutrality, and the solvent was evaporated to dryness. The residue was purified by silica gel column chromatography (eluent: chloroform / hexane: 5/1) to obtain 35.5 g (yield 44.9%) of 1-chloroisoquinoline white crystals.
１００ｍｌの３つ口フラスコにフェニルボロン酸３．０４ｇ（２４．９ｍｍｏｌｅ）、１−クロロイソキノリン４．０９ｇ（２５．０ｍｍｏｌｅ）、トルエン２５ｍｌ、エタノール１２．５ｍｌ及び２Ｍ−炭酸ナトリウム水溶液２５ｍｌを入れ、窒素気流下室温で攪拌しながらテトラキス−（トリフェニルホスフィン）パラジウム（０）０．９８ｇ（０．８５ｍｍｏｌｅ）を加えた。その後、窒素気流下で８時間還流攪拌した。反応終了後、反応物を冷却して冷水及びトルエンを加えて抽出した。有機層を食塩水で洗浄し、硫酸マグネシウムで乾燥して溶媒を減圧乾固した。残渣をシリカゲルカラムクロマト（溶離液：クロロホルム／メタノール：１０／１）で精製し、１−フェニルイソキノリン２．２０ｇ（収率４３．０％）を得た。 A 100 ml three-necked flask was charged with 3.04 g (24.9 mmole) of phenylboronic acid, 4.09 g (25.0 mmole) of 1-chloroisoquinoline, 25 ml of toluene, 12.5 ml of ethanol and 25 ml of 2M aqueous sodium carbonate solution, and nitrogen. While stirring at room temperature under an air stream, 0.98 g (0.85 mmole) of tetrakis- (triphenylphosphine) palladium (0) was added. Thereafter, the mixture was stirred under reflux for 8 hours under a nitrogen stream. After completion of the reaction, the reaction product was cooled and extracted by adding cold water and toluene. The organic layer was washed with brine, dried over magnesium sulfate, and the solvent was evaporated to dryness. The residue was purified by silica gel column chromatography (eluent: chloroform / methanol: 10/1) to obtain 2.20 g of 1-phenylisoquinoline (yield 43.0%).
１００ｍｌの４つ口フラスコにグリセロール５０ｍｌを入れ、窒素バブリングしながら１３０〜１４０℃で２時間加熱攪拌した。グリセロールを１００℃まで放冷し、１−フェニルイソキノリン１．０３ｇ（５．０２ｍｍｏｌｅ）、イリジウム（ＩＩＩ）アセチルアセトネート０．５０ｇ（１．０２ｍｍｏｌｅ）を入れ、窒素気流下２１０℃付近で７時間加熱攪拌した。反応物を室温まで冷却して１Ｎ−塩酸３００ｍｌに注入し、沈殿物を濾取・水洗した。この沈殿物をクロロホルムを溶離液としたシリカゲルカラムクロマトで精製し、イリジウム（ＩＩＩ）トリス（１−フェニルイソキノリン）の赤色粉末０．２２ｇ（収率２６．８％）を得た。図１に単結晶構造解析から導き出されたイリジウム（ＩＩＩ）トリス（１−フェニルイソキノリン）の結晶構造を示す。図１からもわかるようにこの結晶は細孔を有し、その細孔の直径は約０．８ｎｍであった。 50 ml of glycerol was placed in a 100 ml four-necked flask, and heated and stirred at 130 to 140 ° C. for 2 hours while bubbling nitrogen. Glycerol is allowed to cool to 100 ° C., 1.03 g (5.02 mmole) of 1-phenylisoquinoline and 0.50 g (1.02 mmole) of iridium (III) acetylacetonate are added, and heated at 210 ° C. for 7 hours under a nitrogen stream. Stir. The reaction product was cooled to room temperature and poured into 300 ml of 1N hydrochloric acid, and the precipitate was collected by filtration and washed with water. The precipitate was purified by silica gel column chromatography using chloroform as an eluent to obtain 0.22 g (yield 26.8%) of iridium (III) tris (1-phenylisoquinoline) red powder. FIG. 1 shows the crystal structure of iridium (III) tris (1-phenylisoquinoline) derived from the single crystal structure analysis. As can be seen from FIG. 1, this crystal had pores, and the diameter of the pores was about 0.8 nm.
（脱吸着特性の測定）
このようにして得られたイリジウム（ＩＩＩ）トリス（１−フェニルイソキノリン）粉末を１０−３Ｐａ以下、１２０℃で１２時間乾燥させた後に液体窒素温度下で窒素、アルゴンについてガス吸着測定装置を用いて脱吸着等温線の測定を行った。測定結果を表１、曲線を図２及び図３に示す。
(Measurement of desorption characteristics)
The iridium (III) tris (1-phenylisoquinoline) powder thus obtained was dried at 10 −3 Pa or less at 120 ° C. for 12 hours, and then a gas adsorption measuring device was used for nitrogen and argon at a liquid nitrogen temperature. The desorption isotherm was measured. The measurement results are shown in Table 1, and the curves are shown in FIGS.
図２、図３において、横軸のＰはガスの圧力、Ｐ０は飽和蒸気圧であって、窒素では、Ｐ０＝７４７ｍｍＨｇ、アルゴンでは、Ｐ０＝２００ｍｍＨｇである。縦軸は吸着材１グラムあたりの吸着ガス体積を表す。圧力を上げて行く過程での吸着量（吸着側）と、下げていった過程での吸着量（脱着側）を示す。表１の単位はｃｃ／ｇである。 2 and 3, P on the horizontal axis is the gas pressure, P 0 is the saturated vapor pressure, P 0 = 747 mmHg for nitrogen, and P 0 = 200 mmHg for argon. The vertical axis represents the adsorbed gas volume per gram of adsorbent. The adsorption amount (adsorption side) in the process of increasing the pressure and the adsorption amount (desorption side) in the process of decreasing the pressure are shown. The unit of Table 1 is cc / g.
表１と図２、図３に示されるとおり、窒素に関してはヒステリシスの無い脱吸着等温線になっているが、アルゴンでは非常に大きなヒステリシスを持つ。飽和蒸気圧Ｐ０に対する圧力Ｐの比Ｐ／Ｐ０の値で０．０５の脱着側吸着量と吸着側吸着量の比は１．２５であり非常に特徴的なアルゴンガスの脱吸着特性を示す。この材料を使いアルゴンガスに不純物気体を含んだ混合気体や窒素ガスに不純物としてアルゴンガスが含まれた混合気体に対して吸着脱着過程を繰り返すことによって不純物気体との分離及び精製が可能となる。 As shown in Table 1, FIG. 2 and FIG. 3, nitrogen is a desorption isotherm with no hysteresis, but argon has a very large hysteresis. The ratio P / P 0 of the pressure P to the saturated vapor pressure P 0 is 0.05, and the ratio of the desorption side adsorption amount to the adsorption side adsorption amount of 1.25 is 1.25. Show. By using this material, the adsorption and desorption process is repeated for a mixed gas containing an impurity gas in an argon gas or a mixed gas containing an argon gas as an impurity in a nitrogen gas, thereby allowing separation and purification from the impurity gas.
（ガス分離方法）
図４に本発明の気体分離方法の概略図を示す。
(Gas separation method)
FIG. 4 shows a schematic diagram of the gas separation method of the present invention.
本発明の気体分離方法に用いられる装置は、原料の混合気体を供給する原料気体供給設備１、実施例１の吸着材２を装備した密閉容器である吸着槽３、ポンプ４、吸着材２から脱着される気体を収集する収集槽５、吸着材２により吸着されなかった気体を吸着槽から回収する回収槽６からなっている。各槽はパイプで連結され、途中のバルブ（不図示）を開閉して流れをコントロールできるようになっている。 The apparatus used for the gas separation method of the present invention includes a raw material gas supply facility 1 for supplying a mixed gas of raw materials, an adsorbing tank 3, a pump 4, and an adsorbing material 2, which are sealed containers equipped with the adsorbing material 2 of Example 1. It consists of a collection tank 5 for collecting the desorbed gas and a collection tank 6 for collecting the gas not adsorbed by the adsorbent 2 from the adsorption tank. Each tank is connected by a pipe, and a valve (not shown) in the middle can be opened and closed to control the flow.
第１の工程において、不純物として窒素（Ｎ２）が含まれたアルゴン（Ａｒ）原料気体は、ｐ１の圧力で供給設備１から吸着槽３に導入される。また、吸収槽３に導入された後、ｐ１に加圧されてもよい。 In the first step, an argon (Ar) source gas containing nitrogen (N 2 ) as an impurity is introduced from the supply facility 1 into the adsorption tank 3 at a pressure of p1. Further, after being introduced into the absorption tank 3, it may be pressurized to p1.
圧力ｐ１は、アルゴンの飽和蒸気圧又はそれ以上になるように設定される。分圧は窒素とアルゴンのモル比で決まり、窒素のモル含有率をｘとすると、アルゴンのモル含有率は１−ｘなので、窒素の分圧はｘ・ｐ１、アルゴンの分圧は（１−ｘ）ｐ１となる。窒素の含有率が少ないときは、アルゴンの分圧が全圧の大部分である。 The pressure p1 is set to be a saturated vapor pressure of argon or higher. The partial pressure is determined by the molar ratio of nitrogen and argon. When the molar content of nitrogen is x, the molar content of argon is 1-x, so the partial pressure of nitrogen is x · p1, and the partial pressure of argon is (1- x) p1. When the nitrogen content is low, the argon partial pressure is the majority of the total pressure.
吸収槽内では、窒素とアルゴンが共に吸着材２に吸着される。 In the absorption tank, both nitrogen and argon are adsorbed by the adsorbent 2.
図２と図３に示されるとおり、圧力を増加させる過程では、窒素とアルゴンは、飽和蒸気圧に対する相対圧力が同じならほぼ同じ吸着量を示す。つまり、本発明における吸着材は、アルゴン又は窒素の一方のみを選択的に吸着するものではない。 As shown in FIG. 2 and FIG. 3, in the process of increasing the pressure, nitrogen and argon show almost the same amount of adsorption if the relative pressure with respect to the saturated vapor pressure is the same. That is, the adsorbent in the present invention does not selectively adsorb only one of argon and nitrogen.
このように、吸着に関しては窒素とアルゴンは同じ分子のように振舞うので、吸着材の上でも窒素とアルゴンは気体のモル比とほぼ同じ比率で吸着されている。したがって、このままでは、吸着された気体も残りの気体も原料気体と同じ組成になり、分離が行われないことになる。 As described above, since nitrogen and argon behave like the same molecule in terms of adsorption, nitrogen and argon are adsorbed on the adsorbent at the same ratio as the molar ratio of the gas. Therefore, in this state, the adsorbed gas and the remaining gas have the same composition as the raw material gas, and separation is not performed.
しかし、本発明における吸着材は、アルゴンに対しては、減圧過程で脱離が起こりにくく、ヒステリシス特性をもつ。これを利用すれば窒素とアルゴンを分離することができる。以下、それを説明する。 However, the adsorbent in the present invention is less susceptible to desorption in the depressurization process with respect to argon and has hysteresis characteristics. If this is utilized, nitrogen and argon can be separated. This will be described below.
圧力ｐ１で吸着槽内に導入された原料ガスは、十分な時間の後、吸着が平衡に達して、それ以上の吸着が進まない状態に達する。 After a sufficient time, the raw material gas introduced into the adsorption tank at the pressure p1 reaches a state where the adsorption reaches equilibrium and no further adsorption proceeds.
次いで、第２の工程として、真空ポンプ４で平行に達した吸着槽内の気体を減圧して、圧力をｐ１より低いｐ２にする。このとき、一部の窒素分子は吸着材上から脱離し気体に戻るので、図２の特性曲線に沿って吸着量が減少する。一方、アルゴンは、分圧がヒステリシスの範囲内にある限りほとんど脱離せず、元の吸着量を保っている。この結果、吸着材の上では窒素に対するアルゴン比率が増加し、一方、残留ガスのアルゴン比率は減少する。 Next, as a second step, the gas in the adsorption tank that has reached in parallel by the vacuum pump 4 is decompressed, and the pressure is set to p2 lower than p1. At this time, some of the nitrogen molecules desorb from the adsorbent and return to the gas, so that the amount of adsorption decreases along the characteristic curve of FIG. On the other hand, as long as the partial pressure is within the hysteresis range, argon is hardly desorbed and maintains the original adsorption amount. As a result, the argon to nitrogen ratio increases on the adsorbent, while the residual gas argon ratio decreases.
減圧後の圧力ｐ２は、アルゴン分圧がヒステリシス範囲内にあり、吸着量が維持される値で、かつ窒素の脱離が多く進むように、できるだけ低く設定される。窒素含有率が非常に低くて無視できるときは、ｐ１をアルゴンの飽和蒸気圧２００ｍｍＨｇに設定し、ｐ２をヒステリシス範囲の下限圧力近くの１０ｍｍＨｇないし２０ｍｍＨｇに設定することが好ましい。 The pressure p2 after depressurization is set as low as possible so that the argon partial pressure is within the hysteresis range, the adsorption amount is maintained, and a large amount of nitrogen desorption proceeds. When the nitrogen content is very low and can be ignored, it is preferable to set p1 to a saturated vapor pressure of argon of 200 mmHg and p2 to 10 mmHg to 20 mmHg near the lower limit pressure of the hysteresis range.
ｐ１からｐ２への減圧によって吸着槽３から排出される混合気体は回収槽６に導かれる。回収槽６に導かれた混合気体は、上で述べたとおり、原料気体に対してアルゴン比率が減少し窒素含有率が増えた混合気体になっている。これを再び吸着槽３に導き、上の過程を繰り返すことにより更に窒素含有率を高めることもできる。回収する必要がないときは、回収槽６を設けず、そのまま排気してもよい。 The mixed gas discharged from the adsorption tank 3 by the pressure reduction from p1 to p2 is guided to the recovery tank 6. As described above, the mixed gas introduced into the recovery tank 6 is a mixed gas in which the argon ratio is reduced and the nitrogen content is increased with respect to the raw material gas. By introducing this again into the adsorption tank 3 and repeating the above process, the nitrogen content can be further increased. When there is no need to recover, the recovery tank 6 may not be provided and the exhaust may be performed as it is.
第３の工程で、吸着槽３の吸着材２から吸着物を脱離させ、出てくる気体を収集槽５に収集する。この工程は、真空ポンプ４で吸着槽内を更に減圧し、ヒステリシス範囲内のｐ２より低くかつヒステリシスの範囲外にある圧力ｐ３にする又は吸着材を加熱して温度を上げることにより脱離させることことによって行う。脱離が終了し再生した吸着材２は、吸着槽３内で次の吸着に用いられる。 In the third step, the adsorbate is desorbed from the adsorbent 2 in the adsorption tank 3, and the gas that comes out is collected in the collection tank 5. In this step, the inside of the adsorption tank is further depressurized by the vacuum pump 4 so that the pressure is lower than p2 within the hysteresis range and outside the hysteresis range, or desorbed by heating the adsorbent and raising the temperature. By doing. The adsorbent 2 that has been desorbed and regenerated is used for the next adsorption in the adsorption tank 3.
収集槽５に収集された気体は、アルゴン含有率が原料気体よりも高く、原料気体が精製されたものとなっている。これを再び吸着槽３内に導き、先の工程を繰り返すことにより、精製を更に進めることもできる。アルゴンを収集する必要がないときは収集槽５を設けず、そのまま排気してもよい。 The gas collected in the collection tank 5 has a higher argon content than the raw material gas, and the raw material gas is purified. By reintroducing this into the adsorption tank 3 and repeating the previous steps, purification can be further advanced. When it is not necessary to collect argon, the collection tank 5 may not be provided and the air may be exhausted as it is.
以上説明したように、本実施例に用いる吸着材は、特定の気体を選択的に吸着するものではなく、その代わりに、特定の気体に対して脱吸着特性がヒステリシスを示す材料である。このヒステリシスを利用して気体の分離を行うことができる。気体の分離精製だけでなく、本発明における吸着材はまた特定気体の貯蔵材として用いることもできる。 As described above, the adsorbent used in the present embodiment is not a material that selectively adsorbs a specific gas, but instead is a material whose desorption characteristic exhibits hysteresis with respect to a specific gas. Gas separation can be performed using this hysteresis. In addition to separation and purification of gases, the adsorbent in the present invention can also be used as a storage material for specific gases.
１ 原料気体供給設備
２ 吸着材
３ 吸着槽
４ ポンプ
５ 収集槽
６ 回収槽
DESCRIPTION OF SYMBOLS 1 Raw material gas supply equipment 2 Adsorbent 3 Adsorption tank 4 Pump 5 Collection tank 6 Collection tank
Claims (9)
（１）気体の圧力を上昇させる過程における第１の気体の吸着量に対して、気体の圧力を減じる過程における第１の気体の吸着量が、吸着した第１の気体の脱離を生じにくいヒステリシスを示す吸着材を備えた気密容器内に、前記第１の気体と、前記圧力上昇過程における前記吸着材への吸着量と前記圧力を減じる過程における前記吸着材への吸着量とが同様に変化する第２の気体と、を含む混合気体を導入し、該混合気体を第１の圧力で前記吸着材に接触させ、第１及び第２の気体を該吸着材に吸着させる工程、と
（２）前記気密容器内の前記混合気体を、第１の圧力より低く、かつ第１の気体について前記ヒステリシスを示す範囲内にある第２の圧力として、第２の気体を前記吸着材より脱離させ、第１の気体と第２の気体とを分離する工程、と
を有することを特徴とする気体分離方法。 Using an adsorbent, the gas mixture to a gas separation method for separating a specific gas,
(1) The amount of adsorption of the first gas in the process of reducing the gas pressure is less likely to cause desorption of the adsorbed first gas than the amount of adsorption of the first gas in the process of increasing the gas pressure. In the airtight container provided with the adsorbent exhibiting hysteresis, the first gas, the adsorbed amount on the adsorbent in the pressure increasing process, and the adsorbed amount on the adsorbent in the process of reducing the pressure are the same. introducing a mixed gas containing a second gas changing, and the mixed gas wherein the contacting the adsorbent at a first pressure, the first and second gas adsorbing the adsorbing material, and ( 2) the mixed gas in the hermetic vessel, as a second pressure which is within the range indicating the hysteresis for less than the first pressure, and a first gas, desorption from the adsorbent to the second gas It is, separating the first gas and the second gas Extent, a gas separation method characterized by having a <br/>.
Ｍ・Ｌ（Ａ，Ｂ）３ （１）
｛式中、Ｍは金属原子を示し、ＬはＡ、Ｂによって構成された配位子を示し、Ａ、Ｂはそれぞれ無置換又は置換基を有してもよい環状基を示す。Ａ、Ｂが有する置換基はハロゲン原子、ニトロ基又はトリアルキルシリル基（該アルキル基はそれぞれ独立して炭素原子数１〜８の直鎖状もしくは分岐状のアルキル基）である。｝。 The gas separation method according to claim 1, wherein the adsorbent is an organometallic complex represented by the following general formula (1);
ML (A, B) 3 (1)
{In the formula, M represents a metal atom, L represents a ligand composed of A and B, and A and B each represent a cyclic group which may be unsubstituted or have a substituent. The substituents A and B have are a halogen atom, a nitro group, or a trialkylsilyl group (the alkyl groups are each independently a linear or branched alkyl group having 1 to 8 carbon atoms). }.
｛式中、Ｍは金属原子を示し、Ａ、Ｂはそれぞれ無置換もしくは置換基を有してもよい環状基、又は炭素原子数１〜２０の直鎖状もしくは分岐状のアルキル基（該アルキル基中の１つもしくは隣接しない２つ以上のメチレン基は−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−で置換されていてもよく、該アルキル基中の水素原子はフッ素原子に置換されてもよい。）を示す。Ａ、Ｂが有する置換基はハロゲン原子、ニトロ基又はトリアルキルシリル基（該アルキル基はそれぞれ独立して炭素原子数１〜８の直鎖状もしくは分岐状のアルキル基）である。｝ The gas separation method according to claim 5 , wherein the general formula (1) is represented by the following general formula (2).
{In the formula, M represents a metal atom, A and B are each an unsubstituted or substituted cyclic group, or a linear or branched alkyl group having 1 to 20 carbon atoms (the alkyl One or two or more non-adjacent methylene groups in the group are —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH—, —C≡C—. And a hydrogen atom in the alkyl group may be substituted with a fluorine atom). The substituents A and B have are a halogen atom, a nitro group, or a trialkylsilyl group (the alkyl groups are each independently a linear or branched alkyl group having 1 to 8 carbon atoms). }
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