JP2009106909A - Adsorbent for selectively separating-refining carbon dioxide - Google Patents
Adsorbent for selectively separating-refining carbon dioxide Download PDFInfo
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Abstract
Description
本発明は、工場、自動車等から排出されるガス、又は空気等のガス中に含まれる二酸化炭素、及びＳＯｘ、ＮＯｘ等の酸性ガスを選択的に分離・精製するための新規な吸着剤、及びそれらを用いた二酸化炭素の新規分離・精製方法である。本発明は、アニオンとカチオンから構成される室温で液体であるイオン溶液、又はイオン液体を含む高分子材料等からなる二酸化炭素吸着剤、及び二酸化炭素、酸性ガス等の分離・精製方法を提供するものである。 The present invention provides a novel adsorbent for selectively separating and purifying carbon dioxide contained in a gas discharged from a factory, an automobile or the like, or a gas such as air, and an acidic gas such as SOx and NOx, and It is a new method for separation and purification of carbon dioxide using them. The present invention provides a carbon dioxide adsorbent comprising an ionic solution composed of an anion and a cation, which is a liquid at room temperature, or a polymer material containing the ionic liquid, and a method for separating and purifying carbon dioxide, acid gas, etc. Is.
近年の二酸化炭素量増大に伴う地球温暖化問題に貢献するために、工場排ガス、自動車排ガス、火力発電所等から発せられる二酸化炭素を選択的分離・精製し、貯蔵、分解、化学反応等により、大気中に二酸化炭素を放出させない手法を開発することが必要である。多くの排ガスには、二酸化炭素の他に、酸素、窒素、水素、窒素酸化物、硫黄酸化物、炭化水素等の様々なガスを含む。 In order to contribute to the global warming problem accompanying the recent increase in carbon dioxide amount, carbon dioxide emitted from factory exhaust gas, automobile exhaust gas, thermal power plant, etc. is selectively separated and purified, and storage, decomposition, chemical reaction, etc. It is necessary to develop a method that does not release carbon dioxide into the atmosphere. Many exhaust gases contain various gases such as oxygen, nitrogen, hydrogen, nitrogen oxides, sulfur oxides and hydrocarbons in addition to carbon dioxide.
これらのガスは、人体に有害なガス及び物質は限りなく除かれた状態で大気中に放出されるため、喘息などの公害を発生することは少なくなった。しかし、一方では、地球環境の視点から考慮した場合、大気に比べ、より高濃度の二酸化炭素を含むガスが排気されており、そのことが、二酸化炭素増大の要因のひとつとなっている。 Since these gases are released into the atmosphere with the gas and substances harmful to the human body being removed as much as possible, they are less likely to cause pollution such as asthma. However, on the other hand, when considering from the viewpoint of the global environment, a gas containing a higher concentration of carbon dioxide is exhausted than in the atmosphere, which is one of the causes of an increase in carbon dioxide.
この地球上における二酸化炭素の増大を抑制すべく、様々な技術・手法が開発されている。例えば、最も効果的と考えられている手法に、森林により二酸化炭素を吸収する方法がある。本方法は、効果的である一方、吸収速度が遅い、広大な面積の森林を必要とする、老木では大きな効果が期待できない等の欠点も要する。 Various techniques and methods have been developed to suppress the increase of carbon dioxide on the earth. For example, one of the most effective methods is to absorb carbon dioxide through forests. While this method is effective, it also has drawbacks such as a slow absorption rate, a large forest area, and a large effect that cannot be expected with old trees.
また、化学反応による二酸化炭素利用に関しては、先行技術文献では、二酸化炭素を、化学反応を用いたカーボネート製造法によって二酸化炭素を貯蔵する手法が有るが、製造過程における加熱、物質運搬、反応制御等で必要なエネルギー量を石油換算で見た場合、二酸化炭素量の排出抑制にはなるが、削減までは至らない。 Regarding the use of carbon dioxide by chemical reaction, in the prior art literature, there is a method of storing carbon dioxide by carbonic acid production method using chemical reaction, but heating, substance transportation, reaction control, etc. in the production process If you look at the amount of energy required in terms of oil, the amount of carbon dioxide emissions will be suppressed, but it will not be reduced.
また、ガス中の二酸化炭素の除去あるいは分離・精製方法として、アミン化合物を用いた手法が報告されているが（特許文献４〜１１）、アミンと二酸化炭素は化学反応によりカルバメート化合物になり、分離・精製が可能である。しかし、逆に、アミンの再生、二酸化炭素の分離に多大なるエネルギーを要し、二酸化炭素排出削減に寄与することは難しい。 In addition, as a method for removing or separating / purifying carbon dioxide in a gas, a method using an amine compound has been reported (Patent Documents 4 to 11).・ Purification is possible. However, on the contrary, much energy is required for amine regeneration and carbon dioxide separation, and it is difficult to contribute to carbon dioxide emission reduction.
また、排ガスを固定、吸収又は捕捉させる固定化剤等が提案されているが（特許文献１２〜１４）、イオン液体を吸収剤とするものではない。また、貯蔵媒体に、イオン液体を用いる場合があるが、これは、二酸化炭素ではなく、容器に対する腐食性が激しいガス、爆発性ガス等が対象であり、化学反応によるイオン液体中での貯蔵になり、先の事例と同様に、ガスの再生等には大きなエネルギーを有し、しかも、貯蔵が目的であり、分離・精製には不適当である。 Moreover, although the fixing agent etc. which fix, absorb or capture exhaust gas are proposed (patent documents 12-14), an ionic liquid is not used as an absorber. In some cases, an ionic liquid is used as a storage medium, but this is not carbon dioxide, but a highly corrosive gas, explosive gas, etc. for containers, and is used for storage in an ionic liquid by a chemical reaction. Thus, as in the previous case, it has a large energy for gas regeneration, etc., and is intended for storage, and is unsuitable for separation and purification.
このような状況の中で、本発明者らは、上記従来技術に鑑みて、二酸化炭素及びＳＯｘ、ＮＯｘなど酸性ガスの貯蔵・分離・精製のために有用な材料として、化学反応によらない、物理吸着による手法をそれらガスの分離・精製に用いること着目し、化学反応による手法に比べ、より省エネルギーで行うことを可能とする新しい手法を鋭意検討した結果、アニオンとカチオンから構成される室温で液体であるイオン液体、又はイオン液体を含む高分子材料、無機材料、有機材料を用いることで、より少ないエネルギーで二酸化炭素等の分離・精製を行うことが可能となることを見出し、本発明を完成するに至った。 Under such circumstances, the present inventors, in view of the above prior art, do not rely on chemical reaction as a material useful for storage / separation / purification of acidic gases such as carbon dioxide and SOx, NOx, Focusing on the use of the physical adsorption method for the separation and purification of these gases, we have intensively studied a new method that can save energy compared to the chemical reaction method. It has been found that by using a liquid ionic liquid, or a polymer material, inorganic material, or organic material containing an ionic liquid, it becomes possible to separate and purify carbon dioxide etc. with less energy, and the present invention It came to be completed.
本発明は、イオン間相互作用、水素結合、双極子相互作用、ファンデルワールス力による二酸化炭素及びＳＯｘ、ＮＯｘ等の酸性ガスと本発明に関わる材料との物理的相互作用により、他のガスと比較して、二酸化炭素及びＳＯｘ、ＮＯｘ等の酸性ガスと材料とのより強い相互作用を利用することによる、それらガスの貯蔵・分離・精製に関する技術を提供することを目的とするものである。 The present invention is based on the physical interaction of carbon dioxide, SOx, NOx and other acidic gases with the materials related to the present invention by inter-ionic interactions, hydrogen bonds, dipole interactions, van der Waals forces, and other gases. In comparison, the object is to provide a technique relating to storage, separation, and purification of carbon dioxide, acidic gas such as SOx, NOx, and the like by utilizing stronger interaction between the materials.
また、アミンを用いる二酸化炭素分離・精製法の場合、二酸化炭素を化学的に吸収するため、吸収液の再生行程に、反応熱＋液昇温熱＋蒸気損失熱等のエネルギーが必要であり、３．０ＭＪ／Ｋｇ（吸収液）のエネルギーが必要である。本発明は、イオン液体を用いるため、液分離移動などの行程のみですみ、必要とされるエネルギーが０．３ＭＪ／Ｋｇ（イオン液体）以下という少ないエネルギーで二酸化炭素等を分離・精製することが可能な新しい技術を提供することを目的とするものである。 In the case of the carbon dioxide separation / purification method using an amine, carbon dioxide is chemically absorbed, so that energy such as reaction heat + liquid heating temperature + vapor loss heat is required in the regeneration process of the absorption liquid. An energy of 0.0 MJ / Kg (absorbing liquid) is required. Since the present invention uses an ionic liquid, only a process such as liquid separation and transfer is required, and carbon dioxide and the like can be separated and purified with a small energy of 0.3 MJ / Kg (ionic liquid) or less. It aims to provide possible new technologies.
上記課題を解決するための本発明は、以下の技術的手段から構成される。
（１）二酸化炭素、又はＳＯｘ、ＮＯｘの酸性ガスの貯蔵・分離・精製に用いるイオン液体からなる吸着剤であって、イオン液体として、次の一般式（化１）
The present invention for solving the above-described problems comprises the following technical means.
(1) An adsorbent comprising an ionic liquid used for storage, separation, and purification of carbon dioxide, or SOx, NOx acid gas, and the ionic liquid is represented by the following general formula (Formula 1)
（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４はいずれも水素であるか、又はそれらの少なくとも一部が置換又は非置換の炭化水素基であるか、あるいはＲ１、Ｒ２、Ｒ３、Ｒ４は相互に結合して環又は縮合環系を形成しても良い。）で表される少なくとも１種類以上のカチオンを含むイオン液体を用いたことを特徴とする二酸化炭素又は酸性ガス吸着剤。
（２）イオン液体が、上記イオン液体を含む高分子材料、無機材料、又は有機材料のイオン液体である、前記（１）に記載の吸着剤。
（３）アニオンとして、Ｃｌ−、Ｂｒ−、Ｉ−、ＰＦ６ −、ＢＦ４ −、ｐ−ＣＨ３−Ｃ６Ｈ４ＳＯ３ −、ＣＦ３ＳＯ３ −、（ＣＦ３ＳＯ２）２Ｎ−、（Ｃ２Ｆ５ＳＯ２）２Ｎ−、（ＮＣ）２Ｎ−、（ＣＦ３ＳＯ２）３Ｃ−、ＣＨ３ＣＯＯ−及びＣＦ３ＣＯＯ−から選択される少なくとも１種類以上を含んだイオン液体である、前記（１）に記載の吸着剤。
（４）Ｒ１、Ｒ２がメチル基、エチル基、又はブチル基、Ｒ３が水素又はメチル基である一般式で表されるカチオンと、アニオンが（ＣＦ３ＳＯ２）２Ｎ−であるイオン液体からなる、前記（１）又は（２）に記載の吸着剤。
（５）イオン液体として、Ｃｌ−、Ｂｒ−、Ｉ−、ＰＦ６ −、ＢＦ４ −、ｐ−ＣＨ３−Ｃ６Ｈ４ＳＯ３ −、ＣＦ３ＳＯ３ −、（ＣＦ３ＳＯ２）２Ｎ−、（Ｃ２Ｆ５ＳＯ２）２Ｎ−、（ＮＣ）２Ｎ−、（ＣＦ３ＳＯ２）３Ｃ−、ＣＨ３ＣＯＯ−及びＣＦ３ＣＯＯ−から選択されるアニオンと、テトラアルキルホスホニウム、テトラアルキルアンモニウム、Ｎ−アルキルピリジニウム、及び１、３−ジアルキルイミダゾリウム，１，２，３，トリアルキルイミダゾリウムから選択されるカチオンを含むイオン液体を用いた、前記（１）又は（２）に記載の吸着剤。
（６）イオン液体のカチオンが、１−ブチル−３−メチルイミダゾリウム、１−エチル−３−メチルイミダゾリウム、１−ヘキシル−３−メチルイミダゾリウム、１−ブチル−２，３−ジメチルイミダゾリウム、Ｎ−ヘキシルピリジニウム、１−ブチル−１−メチルピロリジニウム、トリヘキシル（テトラデシル）ホスホニウム、メチル（トリオクチル）アンモニウム、１−アルキル−３−（３−シアノプロピル）イミダゾリウム、１−メトキシエチル−３−メチルイミダゾリウム、及び（Ｓ）−４−イソプロピル−２−エチル−３−メチル−４，５−ジヒドロオキサゾール−３−イウムから選択される１種以上を含む、１）から（５）のいずれかに記載の吸着剤。
（７）前記（１）から（６）のいずれかに記載の吸着剤を用いて、二酸化炭素又は酸性ガスの貯蔵・分離・精製を行う方法であって、二酸化炭素、又はＳＯｘ、ＮＯｘの酸性ガス、あるいは、それらを含有したガス、ないしはそれらを含む超臨界流体を、アニオン及びカチオンからなるイオン液体、ないしは該イオン液体を含む高分子材料、無機材料、有機材料から少なくとも１種類以上選択される材料と接触させることにより、物理的に吸収させることを特徴とする二酸化炭素又は酸性ガスの貯蔵・分離・精製方法。
（８）二酸化炭素、二酸化炭素含有ガスないしはこれらを含む超臨界流体を、少なくとも常圧以上での加圧条件下で接触させる、前記（７）に記載の方法。
（９）二酸化炭素、二酸化炭素含有ガスないしはこれらを含む超臨界流体を、少なくとも０℃以上１００℃以下の温度条件下で接触させる、前記（７）に記載の方法。
(Wherein R 1 , R 2 , R 3 and R 4 are all hydrogen, or at least a part of them is a substituted or unsubstituted hydrocarbon group, or R 1 , R 2 , R 3 and R 4 may be bonded to each other to form a ring or a condensed ring system.) Carbon dioxide or acidic gas, characterized by using an ionic liquid containing at least one kind of cation represented by Adsorbent.
(2) The adsorbent according to (1), wherein the ionic liquid is an ionic liquid of a polymer material, an inorganic material, or an organic material containing the ionic liquid.
(3) As anions, Cl − , Br − , I − , PF 6 − , BF 4 − , p—CH 3 —C 6 H 4 SO 3 − , CF 3 SO 3 − , (CF 3 SO 2 ) 2 N -, (C 2 F 5 SO 2) 2 N -, (NC) 2 N -, (CF 3 SO 2) 3 C -, CH 3 COO - and CF 3 COO - comprise at least one or more selected from The adsorbent according to (1), which is an ionic liquid.
(4) A cation represented by the general formula in which R 1 and R 2 are a methyl group, an ethyl group, or a butyl group, and R 3 is hydrogen or a methyl group, and an anion is (CF 3 SO 2 ) 2 N — . The adsorbent according to (1) or (2), comprising an ionic liquid.
(5) As an ionic liquid, Cl − , Br − , I − , PF 6 − , BF 4 − , p—CH 3 —C 6 H 4 SO 3 − , CF 3 SO 3 − , (CF 3 SO 2 ) 2 N -, (C 2 F 5 SO 2) 2 N -, (NC) 2 N -, (CF 3 SO 2) 3 C -, CH 3 COO - and CF 3 COO - and anion selected from tetraalkyl (1) or (2) using an ionic liquid containing a cation selected from phosphonium, tetraalkylammonium, N-alkylpyridinium, and 1,3-dialkylimidazolium, 1,2,3, trialkylimidazolium ).
(6) The cation of the ionic liquid is 1-butyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-butyl-2,3-dimethylimidazolium. N-hexylpyridinium, 1-butyl-1-methylpyrrolidinium, trihexyl (tetradecyl) phosphonium, methyl (trioctyl) ammonium, 1-alkyl-3- (3-cyanopropyl) imidazolium, 1-methoxyethyl-3 Any one of 1) to (5), including one or more selected from -methylimidazolium and (S) -4-isopropyl-2-ethyl-3-methyl-4,5-dihydrooxazole-3-ium The adsorbent according to crab.
(7) A method for storing, separating, and purifying carbon dioxide or acid gas using the adsorbent according to any one of (1) to (6), wherein the carbon dioxide, or the acidity of SOx or NOx The gas or the gas containing them or the supercritical fluid containing them is selected from at least one kind selected from an ionic liquid composed of anions and cations, a polymer material containing the ionic liquid, an inorganic material, and an organic material. A method for storing, separating, and purifying carbon dioxide or acid gas, wherein the carbon dioxide or acid gas is physically absorbed by contacting with a material.
(8) The method according to (7), wherein carbon dioxide, a carbon dioxide-containing gas, or a supercritical fluid containing these is contacted under a pressurized condition at least at normal pressure.
(9) The method according to (7), wherein carbon dioxide, a carbon dioxide-containing gas, or a supercritical fluid containing these is contacted under a temperature condition of at least 0 ° C to 100 ° C.
次に、本発明について更に詳細に説明する。
本発明は、二酸化炭素、又はＳＯｘ、ＮＯｘの酸性ガスの貯蔵・分離・精製に用いるイオン液体からなる吸着剤であって、イオン液体として、前記一般式で表される少なくとも１種類以上のカチオンを含むイオン液体を用いたことを特徴とするものである。
Next, the present invention will be described in more detail.
The present invention is an adsorbent comprising an ionic liquid used for storage / separation / purification of carbon dioxide or SOx / NOx acid gas, and the ionic liquid contains at least one cation represented by the above general formula. The ionic liquid containing is used.
また、本発明は、上記の吸着剤であって、イオン液体が、上記イオン液体を含む高分子材料、無機材料、又は有機材料のイオン液体であることを特徴とするものである。 Further, the present invention is the above adsorbent, characterized in that the ionic liquid is a polymer material, inorganic material, or organic material ionic liquid containing the ionic liquid.
本発明は、近年の二酸化炭素量増大に伴う地球温暖化問題に貢献すべく、工場排ガス、自動車排ガス、火力発電所等から発せられるガス、又は空気等のガス中に含まれる二酸化炭素を選択的に分離・貯蔵・精製するための新規な吸着材料、それらを用いた二酸化炭素の新規分離・貯蔵・精製方法を提供するものである。すなわち、ガス中に含まれる二酸化炭素を選択的に分離・貯蔵・精製し、大気中に放出する二酸化炭素を抑制させる手法である。 In order to contribute to the global warming problem accompanying the increase in the amount of carbon dioxide in recent years, the present invention selectively selects carbon dioxide contained in gas such as factory exhaust gas, automobile exhaust gas, thermal power plant and the like, or air. The present invention provides a novel adsorbent material for separation, storage and purification, and a novel method for separation, storage and purification of carbon dioxide using them. That is, it is a technique for selectively separating, storing and refining carbon dioxide contained in a gas and suppressing carbon dioxide released into the atmosphere.
本発明で、二酸化炭素の分離・貯蔵・精製に用いる材料は、アニオン及びカチオンからなるイオン液体、ないしはイオン液体を含む高分子材料、無機材料、有機材料の少なくとも１種類以上から選択される材料である。イオン液体を含む高分子材料、無機材料、有機材料の少なくとも１種類以上から選択される材料は、液体であっても固体であっても良い。 In the present invention, the material used for separation / storage / purification of carbon dioxide is a material selected from at least one of an ionic liquid composed of anions and cations, or a polymer material containing the ionic liquid, an inorganic material, and an organic material. is there. The material selected from at least one of a polymer material containing an ionic liquid, an inorganic material, and an organic material may be a liquid or a solid.
イオン液体を含む高分子材料としては、ポリエチレン、ポリスチレン、ナイロン、ポリウレタン、ポリ塩化ビニル等の高分子のうちの何れか１種類以上の高分子から選択されるもので、例えば、塊状、粒状、粉末状、粒子状、ナノ粒子、シート状、網状、糸状等のものが例示されるが、それらの形態は問わない。 The polymer material containing the ionic liquid is selected from one or more kinds of polymers such as polyethylene, polystyrene, nylon, polyurethane, polyvinyl chloride and the like. Examples thereof include, but are not limited to, shapes, particles, nanoparticles, sheets, nets, and threads.
イオン液体を含む無機材料としては、メソポーラスシリカ、ゼオライト、無機層状化合物、粘土等の無機材料の何れか１種類以上から選択されるもので、例えば、塊状、粒状、粉末状、粒子状、ナノ粒子、シート状、網状、糸状等のものが例示されるが、それらの形態は問わない。 The inorganic material containing the ionic liquid is selected from one or more of inorganic materials such as mesoporous silica, zeolite, inorganic layered compound, clay, etc., for example, lump, granule, powder, particle, nanoparticle Examples thereof include sheet, net, and thread, but the form is not limited.
イオン液体を含む有機材料としては、界面活性剤、フタロシアニン等の有機材料のいずれか１種類以上から選択されるもので、例えば、塊状、粒状、粉末状、粒子状、ナノ粒子、シート状、網状、糸状等のものが例示されるが、それらの形態は問わない。 The organic material containing the ionic liquid is selected from one or more of organic materials such as surfactants and phthalocyanines. For example, the lumps, granules, powders, particles, nanoparticles, sheets, and nets Examples of the thread shape and the like are exemplified, but their form is not limited.
用いるイオン液体は、アニオンとカチオンからなる液体の塩で、−３０℃以上１００℃以下で液体の塩、好ましくは、０℃以上１００℃以下で液体である塩、最も好ましくは室温（２５℃）以上１００℃以下で液体である塩であれば良い。具体的には、例えば、アニオンは、Ｃｌ−、Ｂｒ−、Ｉ−、ＰＦ６ −、ＢＦ４ −、ｐ−ＣＨ３−Ｃ６Ｈ４ＳＯ３ −、ＣＦ３ＳＯ３ −、（ＣＦ３ＳＯ２）２Ｎ−、（ＮＣ）２Ｎ−、（ＣＦ３ＳＯ２）３Ｃ−、ＣＨ３ＣＯＯ−及びＣＦ３ＣＯＯ−から少なくとも１種類以上が選択される。また、カチオンは、次の一般式（化２） The ionic liquid to be used is a liquid salt composed of an anion and a cation and is a liquid salt at -30 ° C. or higher and 100 ° C. or lower, preferably a salt which is liquid at 0 ° C. or higher and 100 ° C. or lower, most preferably room temperature (25 ° C.). A salt that is liquid at 100 ° C. or lower may be used. Specifically, for example, the anions include Cl − , Br − , I − , PF 6 − , BF 4 − , p-CH 3 —C 6 H 4 SO 3 − , CF 3 SO 3 − , (CF 3 SO 2) 2 N -, (NC ) 2 N -, (CF 3 SO 2) 3 C -, CH 3 COO - and CF 3 COO - at least one kind from is selected. The cation has the following general formula (Formula 2)
（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４はいずれも水素であるか、又はそれらの少なくとも一部が置換又は非置換の１〜２４個の炭素原子からなる炭化水素基であるか、あるいはＲ１、Ｒ２、Ｒ３、Ｒ４は１〜２４個の炭素原子からなる炭化水素基で、相互に結合して環又は縮合環系を形成しても良い。）で表される少なくとも１種類以上から選択されるカチオンであれば良い。 (Wherein, R 1 , R 2 , R 3 , R 4 are all hydrogen, or at least a part of them is a substituted or unsubstituted hydrocarbon group of 1 to 24 carbon atoms? Or R 1 , R 2 , R 3 and R 4 are hydrocarbon groups of 1 to 24 carbon atoms, which may be bonded to each other to form a ring or a condensed ring system. Any cation selected from at least one kind may be used.
具体的には、例えば、Ｒ１、Ｒ２がメチル基、エチル基、又はブチル基、Ｒ３が水素又はメチル基である、上記一般式で表されるカチオンと、アニオンが（ＣＦ３ＳＯ２）２Ｎ−であるイオン液体を用いることができる。 Specifically, for example, R 1 and R 2 are a methyl group, an ethyl group, or a butyl group, R 3 is hydrogen or a methyl group, and a cation represented by the above general formula and an anion (CF 3 SO 2 ) 2 N - can be used in which ionic liquids.
更に、イオン液体のアニオンとして、Ｃｌ−、Ｂｒ−、Ｉ−、ＰＦ６ −、ＢＦ４ −、ｐ−ＣＨ３−Ｃ６Ｈ４ＳＯ３ −、ＣＦ３ＳＯ３ −、（ＣＦ３ＳＯ２）２Ｎ−、（ＮＣ）２Ｎ−、（ＣＦ３ＳＯ２）３Ｃ−、ＣＨ３ＣＯＯ−及びＣＦ３ＣＯＯ−から選択されるアニオンが用いられる。また、テトラアルキルホスホニウム、テトラアルキルアンモニウム、Ｎ−アルキルピリジニウム、カルボカチオン及び１、３−ジアルキルイミダゾリウム，１，２，３，トリアルキルイミダゾリウムの少なくとも１種類以上から選択されるカチオンからなるイオン液体も用いることができる。 Further, as anions of the ionic liquid, Cl − , Br − , I − , PF 6 − , BF 4 − , p—CH 3 —C 6 H 4 SO 3 − , CF 3 SO 3 − , (CF 3 SO 2 ) Anions selected from 2 N − , (NC) 2 N − , (CF 3 SO 2 ) 3 C − , CH 3 COO − and CF 3 COO − are used. Further, an ionic liquid comprising a cation selected from at least one of tetraalkylphosphonium, tetraalkylammonium, N-alkylpyridinium, carbocation and 1,3-dialkylimidazolium, 1,2,3, trialkylimidazolium. Can also be used.
具体的には、イオン液体のカチオンが、１−ブチル−３−メチルイミダゾリウム、１−エチル−３−メチルイミダゾリウム、１−ヘキシル−３−メチルイミダゾリウム、１−ブチル−２，３−ジメチルイミダゾリウム、Ｎ−ヘキシルピリジニウム、１−ブチル−１−メチルピロリジニウム、トリヘキシル（テトラデシル）ホスホニウム、メチル（トリオクチル）アンモニウム、１−アルキル−３−（３−シアノプロピル）イミダゾリウム、１−メトキシエチル−３−メチルイミダゾリウム、及び（Ｓ）−４−イソプロピル−２−エチル−３−メチル−４，５−ジヒドロオキサゾール−３−イウムから選択される１種以上を含むイオン液体を用いることができる。 Specifically, the cation of the ionic liquid is 1-butyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-butyl-2,3-dimethyl. Imidazolium, N-hexylpyridinium, 1-butyl-1-methylpyrrolidinium, trihexyl (tetradecyl) phosphonium, methyl (trioctyl) ammonium, 1-alkyl-3- (3-cyanopropyl) imidazolium, 1-methoxyethyl An ionic liquid containing at least one selected from -3-methylimidazolium and (S) -4-isopropyl-2-ethyl-3-methyl-4,5-dihydrooxazole-3-ium can be used. .
二酸化炭素の分離方法として、イオン液体ないしはイオン液体を含む材料と二酸化炭素ないしは二酸化炭素を含むガスを０ＭＰａ＜で５０ＭＰａ以下の加圧条件下、好ましくは常圧以上３０ＭＰａ以下、最も好ましくは常圧以上１５ＭＰａ以下で接触させることで、二酸化炭素を選択的にイオン液体ないしはイオン液体を含む材料に物理的に吸収させ、イオン液体ないしはイオン液体を含む材料中に吸収されたガスの二酸化炭素含有量を増大、ないしは残ったガス中の二酸化炭素含有量を減少させることができる。 As a method for separating carbon dioxide, an ionic liquid or a material containing an ionic liquid and carbon dioxide or a gas containing carbon dioxide are used under pressure conditions of 0 MPa <and 50 MPa or less, preferably normal pressure or higher and 30 MPa or lower, most preferably normal pressure or higher. By contacting at 15 MPa or less, carbon dioxide is selectively physically absorbed by the ionic liquid or the material containing the ionic liquid, and the carbon dioxide content of the gas absorbed in the ionic liquid or the material containing the ionic liquid is increased. In addition, the carbon dioxide content in the remaining gas can be reduced.
ただし、純粋な二酸化炭素を用いた場合は、その含有量は変わらない。また、物理的に吸収するには、イオン間相互作用、水素結合、双極子相互作用、ファンデルワールス力から選択される少なくとも１種類以上の相互作用を用いることで、二酸化炭素の貯蔵・分離・精製を行うことが可能である。 However, when pure carbon dioxide is used, its content does not change. In addition, for physical absorption, at least one kind of interaction selected from ion-ion interaction, hydrogen bond, dipole interaction, and van der Waals force is used to store / separate carbon dioxide. Purification can be performed.
本発明では、二酸化炭素の分離方法として、イオン液体ないしはイオン液体を含む材料と、二酸化炭素ないしは二酸化炭素を含むガスを、−７３℃以上３００℃以下、好ましくは０℃以上２００℃以下、最も好ましくは０℃以上１００℃以下の温度条件下で接触させる。それにより、二酸化炭素を選択的にイオン液体ないしはイオン液体を含む材料に物理的に吸収させ、イオン液体ないしはイオン液体を含む材料中に吸収されたガスの二酸化炭素含有量を増大ないしは残ったガス中の二酸化炭素含有量を減少させることができる。 In the present invention, as a method for separating carbon dioxide, an ionic liquid or a material containing an ionic liquid and carbon dioxide or a gas containing carbon dioxide are −73 ° C. or higher and 300 ° C. or lower, preferably 0 ° C. or higher and 200 ° C. or lower, most preferably. Is contacted under temperature conditions of 0 ° C. or higher and 100 ° C. or lower. As a result, carbon dioxide is selectively absorbed physically in the ionic liquid or the material containing the ionic liquid, and the carbon dioxide content of the gas absorbed in the ionic liquid or the material containing the ionic liquid is increased or in the remaining gas. The carbon dioxide content of can be reduced.
また、イオン液体ないしはイオン液体に含まれたガスを分離する場合、接触させた場合の圧力以下の条件下ないしは接触させた場合の温度以上の条件下で分離することができる。分離・精製の際に必要な温度は、接触時の温度に対して、０℃〜１００℃の差、好ましくは５℃〜５０℃の差、最も好ましくは１０℃〜３０℃の時に必要とするエネルギーを少なくすることができる。圧力は、接触時の圧力に対して、０ＭＰａ＜で５０ＭＰａ以下の差、好ましくは５ＭＰａ〜３０ＭＰａ、最も好ましくは、１０ＭＰａ〜２０ＭＰａの時に分離・精製に必要とするエネルギーを少なくすることが好適に実現できる。 Further, when the ionic liquid or the gas contained in the ionic liquid is separated, the separation can be performed under the condition below the pressure when contacted or the condition above the temperature when contacted. The temperature required for separation / purification is required when the temperature is 0 to 100 ° C., preferably 5 to 50 ° C., most preferably 10 to 30 ° C. Energy can be reduced. The pressure is suitably realized to reduce the energy required for separation / purification when the pressure is 0 MPa <and 50 MPa or less, preferably 5 MPa to 30 MPa, and most preferably 10 MPa to 20 MPa. it can.
本発明により、次のような効果が奏される。
（１）二酸化炭素、ＳＯｘ、ＮＯｘ等の酸性ガスを選択的に、分離・精製するためのイオン性液体からなる新規二酸化炭素等の吸着剤を提供することができる。
（２）アニオンとカチオンから構成される室温で液体であるイオン液体、該イオン液体を含む高分子材料、無機材料、有機材料を用いた二酸化炭素吸着剤を提供することができる。
（３）上記吸着剤を用いた、二酸化炭素等の新規分離・精製方法を提供することができる。
The present invention has the following effects.
(1) It is possible to provide an adsorbent such as new carbon dioxide made of an ionic liquid for selectively separating and purifying acidic gases such as carbon dioxide, SOx, and NOx.
(2) An ionic liquid composed of an anion and a cation, which is a liquid at room temperature, a polymer material containing the ionic liquid, an inorganic material, and a carbon dioxide adsorbent using an organic material can be provided.
(3) A novel separation / purification method for carbon dioxide and the like using the adsorbent can be provided.
次に、本発明を実施例に基づいて具体的に説明するが、本発明は、これらの実施例によって何ら限定されるものではない。 EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by these Examples.
前記一般式に記載のアミド型カチオンを含んだイオン液体を合成するために、所定量のアミドに、等量のアニオンを氷浴上で滴下して、酸−塩基型のイオン液体を得た。その後、試料は、エバポレータ及び真空ポンプで十分に乾燥し、揮発性の原料や水分の除去を行なった。一方、（ＣＦ３ＳＯ２）２Ｎ−などの酸は非常に強酸であるため、まず最初に所定量のアミドに等量の硝酸を氷浴上で滴下して硝酸塩とした後、同じく等量のＬｉ塩（Ｌｉ（ＣＦ３ＳＯ２）２Ｎ）水溶液を加えることでイオン液体を合成した。 In order to synthesize an ionic liquid containing the amide type cation described in the above general formula, an equal amount of anion was dropped into a predetermined amount of amide on an ice bath to obtain an acid-base type ionic liquid. Thereafter, the sample was sufficiently dried with an evaporator and a vacuum pump to remove volatile raw materials and moisture. On the other hand, (CF 3 SO 2) 2 N - for acid such as are very strong after the nitrate initially dropwise on an ice bath an equivalent amount of nitric acid in a predetermined amount of the amide First, also an equal amount An ionic liquid was synthesized by adding an aqueous solution of Li salt (Li (CF 3 SO 2 ) 2 N).
（ＣＦ３ＳＯ２）２Ｎ−等を含む疎水性のイオン液体の場合は、水相とイオン液体相とに分離したため、イオン液体相のみを分取した。その後、イオン液体相に残存したＬｉ＋を取り除くため、希硝酸水溶液で数回洗浄を行なった。更に、エバポレータ及び真空ポンプで試料を十分に乾燥して、揮発性の残存物並びに水の除去を行なった。合成した試料は、水分量が〜１００ｐｐｍ以下であることを、カールフィッシャー法で滴定し、Ｌｉ＋の残存も〜２０ｐｐｍ以下であることを、原子吸光分析法より確認した。 (CF 3 SO 2) 2 N - If such a hydrophobic ionic liquid comprising, for separated into an aqueous phase and an ionic liquid phase was purified by preparative only ionic liquid phase. Thereafter, in order to remove Li + remaining in the ionic liquid phase, washing was performed several times with a dilute nitric acid aqueous solution. Further, the sample was sufficiently dried with an evaporator and a vacuum pump to remove volatile residues and water. The synthesized sample was titrated by the Karl Fischer method to have a water content of ˜100 ppm, and it was confirmed by atomic absorption spectrometry that the remaining Li + was ˜20 ppm.
上記の操作により、一般式中のＲ１、Ｒ２、Ｒ３がそれぞれ図１の表の置換基をもつアミド型カチオンとアニオンに（ＣＦ３ＳＯ２）２Ｎ−をもつイオン液体を合成し、精製した（図１）。 By the above operation, an ionic liquid in which R 1 , R 2 and R 3 in the general formula each have an amide-type cation having a substituent in the table of FIG. 1 and an anion with (CF 3 SO 2 ) 2 N — is synthesized. And purified (FIG. 1).
イオン液体は、カチオンとアニオンとからなり、それらは電荷キャリアーとなるため、高い電気伝導性をもつことが知られている。既に二酸化炭素の吸収量が分かっているイオン液体では、電気伝導度は二酸化炭素の吸収量に比例して増加することが確認されている。 An ionic liquid consists of a cation and an anion, and since they become charge carriers, they are known to have high electrical conductivity. In ionic liquids whose carbon dioxide absorption is already known, it has been confirmed that the electrical conductivity increases in proportion to the carbon dioxide absorption.
そこで、図２に示した高温・高圧条件下で測定可能な電気伝導度測定セル（特開２００５−６１９７５号公報）を用いて、イオン液体に二酸化炭素を加圧、吸収させた場合の電気伝導度の変化を測定した。図中、ａは電極（ｅｌｅｃｔｒｏｄｅ）、ｂは撹拌器（ｍａｇｎｅｔｉｃ ｓｔｉｒｒｅｒ ｂａｒ）、ｃは溶液Ａ（イオン液体）、ｄは溶液Ｂ（ＣＯ２）、ｅはサファイア窓、ｆはサーミスター、ｇはガス入口、ｈはガス出口、ｉは電気の導入リード、を示す。なお、本電気伝導度測定セルは、セル内を可視化するための窓が設けてあるため、二酸化炭素を吸収したときのイオン液体の相状態や体積変化をあわせて観察することが可能である。 Therefore, using the electric conductivity measurement cell (Japanese Patent Laid-Open No. 2005-61975) that can be measured under high temperature and high pressure conditions shown in FIG. 2, the electric conduction when carbon dioxide is pressurized and absorbed in the ionic liquid. The change in degree was measured. In the figure, a is an electrode, b is a magnetic stirrer bar, c is solution A (ionic liquid), d is solution B (CO 2 ), e is a sapphire window, f is a thermistor, g is A gas inlet, h is a gas outlet, and i is an electricity introduction lead. In addition, since this electric conductivity measuring cell is provided with a window for visualizing the inside of the cell, it is possible to observe the phase state and volume change of the ionic liquid when carbon dioxide is absorbed.
図３に示した通り、イミダゾール系のイオン液体に二酸化炭素を加圧していくと、７〜８ＭＰａまでの領域では、電気伝導度はほぼ直線的に増加することが分かる。これは、二酸化炭素が低圧では圧力増加にともない、ほぼ直線的にイオン液体に吸収されるためである（図４、文献：Ｓ．Ｎ．Ｖ．Ｋ．Ａｋｉ，Ｂ．Ｒ．Ｍｅｌｌｅｉｎ，Ｅ．Ｍ．Ｓａｕｒｅｒ， ａｎｄ Ｊ．Ｆ．Ｂｒｅｎｎｅｃｋｅ，“Ｈｉｇｈ−Ｐｒｅｓｓｕｒｅ Ｐｈａｓｅ Ｂｅｈａｖｉｏｒ ｏｆ Ｃａｒｂｏｎ Ｄｉｏｘｉｄｅ ｗｉｔｈ Ｉｍｉｄａｚｏｌｉｕｍ−Ｂａｓｅｄ Ｉｏｎｉｃ Ｌｉｑｕｉｄｓ，”Ｊ．Ｐｈｙｓ．Ｃｈｅｍ．Ｂ，２００４，１０８，２０３５５）。 As shown in FIG. 3, it can be seen that when carbon dioxide is pressurized to an imidazole-based ionic liquid, the electric conductivity increases almost linearly in the region from 7 to 8 MPa. This is because carbon dioxide is absorbed almost linearly by the ionic liquid as the pressure increases at low pressure (FIG. 4, literature: SNVK Aki, BR Mellein, E., et al. M. Saurer, and J. F. Brennecke, “High-Pressure Phase Behavior of Carbon Dioxide With Imidazolium-Based Ionic Liquids,” J. Phys. 203.
一方、７〜８ＭＰａを超えた領域では、電気伝導度は、ほとんど変化せず、ほぼ一定の値を示す。これは、二酸化炭素のイオン液体への吸収が飽和し、吸収量がほとんど増加しないことを反映したもので、図４の吸収曲線と良い相関を示す。 On the other hand, in the region exceeding 7-8 MPa, the electrical conductivity hardly changes and shows a substantially constant value. This reflects that the absorption of carbon dioxide into the ionic liquid is saturated and the absorption amount hardly increases, and shows a good correlation with the absorption curve of FIG.
以上のように、イオン液体の電気伝導度は、一般的に、二酸化炭素の吸収により顕著に増加し、非常に良い相関を示すため、二酸化炭素の吸収を確認するための良い指標となることが分かる。 As described above, the electrical conductivity of an ionic liquid generally increases significantly due to the absorption of carbon dioxide, and shows a very good correlation. Therefore, it can be a good indicator for confirming the absorption of carbon dioxide. I understand.
なお、上記のイミダゾール系イオン液体の二酸化炭素加圧実験では、二酸化炭素相が溶解性に優れた超臨界状態に達しても、イオン液体の溶出は認められなかった。また、二酸化炭素を大量に吸収しても、イオン液体の体積は２〜３割程度しか体積膨張されないことが観察された。 In the carbon dioxide pressurization experiment of the imidazole ionic liquid, the ionic liquid was not eluted even when the carbon dioxide phase reached a supercritical state with excellent solubility. Further, it was observed that even when a large amount of carbon dioxide was absorbed, the volume of the ionic liquid expanded only about 20 to 30%.
図１に示した種々のアミド型イオン液体に、二酸化炭素を加圧、吸収させたときの電気伝導度の変化を図５に示す。図から分かるとおり、アミド型イオン液体においても、電気伝導度は、イミダゾール系イオン液体と同様の圧力依存性を示し、多量の二酸化炭素を吸収することが明らかとされた。 FIG. 5 shows changes in electrical conductivity when carbon dioxide is pressurized and absorbed in the various amide type ionic liquids shown in FIG. As can be seen from the figure, even in the amide type ionic liquid, the electric conductivity showed the same pressure dependency as that of the imidazole type ionic liquid, and it was revealed that a large amount of carbon dioxide was absorbed.
対比のためにプロットした３−ブチル−１−メチルイミダゾリウム ビス（トリフルオロスルホニル）イミド（［ＢＭＩＭ］［Ｔｆ２Ｎ］）の電気伝導度の変化と比べても、同等、更にはそれ以上の変化を示すものもあり、二酸化炭素吸収能力に優れていることが分かる。 Compared with the change in electrical conductivity of 3-butyl-1-methylimidazolium bis (trifluorosulfonyl) imide ([BMIM] [Tf 2 N]) plotted for comparison, it is equal or even higher. Some of them show a change, and it can be seen that the carbon dioxide absorption capacity is excellent.
窓からセル内部を可視化して観察したところ、二酸化炭素が溶解性に優れた超臨界状態に達しても、イオン液体の溶出は認められなかった。また、イオン液体が二酸化炭素を大量に吸収しても、その体積膨張は２〜３割程度であることが観察により確認された。以上の結果は、アミド型イオン液体が二酸化炭素などの酸性ガス吸収・分離材料として優れた性能をもつことを示すものである。 When the inside of the cell was visualized and observed through the window, elution of the ionic liquid was not observed even when carbon dioxide reached a supercritical state with excellent solubility. Moreover, even if the ionic liquid absorbed a large amount of carbon dioxide, it was confirmed by observation that the volume expansion was about 20 to 30%. The above results indicate that the amide type ionic liquid has excellent performance as an acid gas absorption / separation material such as carbon dioxide.
以上詳述したように、本発明は、二酸化炭素を選択的に分離・精製するための吸着剤に係るものであり、本発明により、二酸化炭素、ＳＯｘ、ＮＯｘ等の酸性ガスを選択的に、分離・精製するためのイオン性液体からなる新規二酸化炭素等の吸着剤を提供することができる。また、本発明は、アニオンとカチオンから構成される室温で液体であるイオン液体、該イオン液体を含む高分子材料、無機材料、有機材料を用いた二酸化炭素吸着剤を提供することができる。また、本発明は、上記吸着剤を用いた、二酸化炭素等の新規分離・精製方法を提供することができる。更に、本発明は、工場、自動車等から排出されるガス、又は空気等のガス中に含まれる二酸化炭素、及びＳＯｘ、ＮＯｘ等の酸性ガスを選択的に分離・精製するための新規な吸着剤、及びそれらを用いた二酸化炭素の新規分離・精製方法である。本発明は、アニオンとカチオンから構成される室温で液体であるイオン溶液、又はイオン液体を含む高分子材料等からなる二酸化炭素吸着剤、及び二酸化炭素、酸性ガス等の分離・精製方法を提供するものとして有用である。 As described in detail above, the present invention relates to an adsorbent for selectively separating and purifying carbon dioxide, and according to the present invention, an acidic gas such as carbon dioxide, SOx, NOx is selectively selected. An adsorbent such as a novel carbon dioxide comprising an ionic liquid for separation and purification can be provided. In addition, the present invention can provide an ionic liquid which is a liquid at room temperature composed of an anion and a cation, a polymer material containing the ionic liquid, an inorganic material, and a carbon dioxide adsorbent using an organic material. The present invention can also provide a novel separation / purification method for carbon dioxide and the like using the adsorbent. Furthermore, the present invention provides a novel adsorbent for selectively separating and purifying carbon dioxide contained in gas discharged from factories, automobiles, etc., or gas such as air, and acidic gases such as SOx and NOx. , And a novel method for separating and purifying carbon dioxide using them. The present invention provides a carbon dioxide adsorbent comprising an ionic solution composed of an anion and a cation, which is a liquid at room temperature, or a polymer material containing the ionic liquid, and a method for separating and purifying carbon dioxide, acid gas, etc. Useful as a thing.
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