JP4652359B2 - Decomposition treatment method of ionic liquid - Google Patents
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- JP4652359B2 JP4652359B2 JP2007060371A JP2007060371A JP4652359B2 JP 4652359 B2 JP4652359 B2 JP 4652359B2 JP 2007060371 A JP2007060371 A JP 2007060371A JP 2007060371 A JP2007060371 A JP 2007060371A JP 4652359 B2 JP4652359 B2 JP 4652359B2
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- 239000002608 ionic liquid Substances 0.000 title claims description 91
- 238000000354 decomposition reaction Methods 0.000 title claims description 54
- 238000000034 method Methods 0.000 title claims description 35
- 238000010335 hydrothermal treatment Methods 0.000 claims description 47
- 239000011941 photocatalyst Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 28
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims description 3
- 229910016467 AlCl 4 Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 description 37
- -1 1,3-dimethylimidazolium ion Chemical class 0.000 description 23
- 238000004458 analytical method Methods 0.000 description 17
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- 150000001768 cations Chemical group 0.000 description 9
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- NNIBKGZUMJNHID-UHFFFAOYSA-N 1,2-dimethyl-3-propan-2-ylimidazol-1-ium Chemical compound CC(C)[N+]=1C=CN(C)C=1C NNIBKGZUMJNHID-UHFFFAOYSA-N 0.000 description 1
- XUAXVBUVQVRIIQ-UHFFFAOYSA-N 1-butyl-2,3-dimethylimidazol-3-ium Chemical compound CCCCN1C=C[N+](C)=C1C XUAXVBUVQVRIIQ-UHFFFAOYSA-N 0.000 description 1
- IRGDPGYNHSIIJJ-UHFFFAOYSA-N 1-ethyl-2,3-dimethylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1C IRGDPGYNHSIIJJ-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、イオン液体を含む混合液、例えば、イオン液体含有の廃液等の廃液処理に関すものであって、水熱処理を施すことによりイオン液体を分解して廃棄を可能にするイオン液体の分解処理方法に関するものである。 The present invention relates to a waste liquid treatment of a mixed liquid containing an ionic liquid, for example, a waste liquid containing an ionic liquid, and the decomposition of the ionic liquid that enables the disposal by decomposing the ionic liquid by hydrothermal treatment It relates to a processing method.
近年、有機溶媒や水に代わる新しい溶媒として、イオン液体が注目されている。上記イオン液体は、不揮発性，難燃性，耐熱性，低粘性，高導電性等の特徴を有していることから、環境調和型反応溶媒として、あるいはリチウム電池等二次電池や燃料電池，太陽電池等の電気化学分野、潤滑油等幅広い用途への応用が期待され、開発が進められている。 In recent years, ionic liquids have attracted attention as new solvents that replace organic solvents and water. Since the ionic liquid has characteristics such as non-volatility, flame retardancy, heat resistance, low viscosity, and high conductivity, it is used as an environmentally conscious reaction solvent, or as a secondary battery such as a lithium battery, a fuel cell, It is expected to be applied to a wide range of uses such as electrolysis fields such as solar cells and lubricants, and development is underway.
このような現状において、イオン液体の応用に関しては様々な研究が進められているが、イオン液体を使用した後の、イオン液体を含有する混合液である廃液による汚染が懸念されている。すなわち、イオン液体は、難分解性物質であり、生分解性を有するものでもなく、自然界や人体に対する影響は不明な部分が多く、将来的にその使用量の増加に伴い廃棄物として問題となることが予想され、その処理方法の開発が望まれている。 Under such circumstances, various studies have been conducted on the application of ionic liquids, but there is a concern about contamination with waste liquids that are mixed liquids containing ionic liquids after using ionic liquids. In other words, ionic liquids are hardly degradable substances, are not biodegradable, have many unclear effects on the natural world and the human body, and will become a problem as waste as their usage increases in the future. Therefore, development of the processing method is desired.
このような状況の中、例えば、界面活性剤や表面処理剤等として使用されている難分解性のフッ素系有機化合物を、金属粉の存在する密閉容器中で熱水処理して分解させる方法が提案されている（特許文献１参照）。
しかしながら、上記特許文献１の熱水分解法における分解処理対象となるフッ素系有機化合物は、前述のように、従来から界面活性剤や表面処理剤等に用いられる、炭素原子に結合するフッ素原子を少なくとも一つ有する化合物であり、いわゆるイオン液体を対象とするものではない。このように、イオン液体の分解処理に関しては未だ有効な方法が開発されていないのが実情である。 However, as described above, the fluorine-based organic compound to be subjected to the decomposition treatment in the hydrothermal decomposition method of Patent Document 1 described above is a fluorine atom bonded to a carbon atom, which has been conventionally used for a surfactant or a surface treatment agent. It is a compound having at least one, and is not intended for a so-called ionic liquid. Thus, the fact is that an effective method has not yet been developed for the ionic liquid decomposition treatment.
本発明は、このような事情に鑑みなされたもので、未だ有効な処理方法が開発されていないイオン液体を分解し、無害化して安全に廃棄可能とするイオン液体の分解処理方法の提供をその目的とする。 The present invention has been made in view of such circumstances, and provides an ionic liquid decomposition treatment method that decomposes an ionic liquid for which an effective treatment method has not yet been developed, renders it harmless, and can be safely discarded. Objective.
上記の目的を達成するため、本発明は、イミダゾリウムカチオンを有するイオン液体を含有する水性混合液を、水熱処理の温度１００〜４００℃で、かつ水熱処理の圧力１５０〜５０，０００ｋＰａにて、鉱化剤の存在下で水熱処理することにより、イオン液体を分解するイオン液体の分解処理方法をその要旨とする。 In order to achieve the above object, the present invention provides an aqueous mixed solution containing an ionic liquid having an imidazolium cation at a hydrothermal treatment temperature of 100 to 400 ° C. and a hydrothermal treatment pressure of 150 to 50,000 kPa. The gist of the decomposition treatment method of an ionic liquid is to decompose the ionic liquid by hydrothermal treatment in the presence of a mineralizer .
すなわち、本発明者らは、上記事情に鑑み、イオン液体の分解を目的として種々検討を重ねた結果、イオン液体を含有する水性混合液を水熱処理すると、イオン液体が分解され、結果、安全に廃棄することができるようになることを見出し本発明に到達した。 That is, in view of the above circumstances, the present inventors have made various studies for the purpose of decomposing ionic liquid, and as a result, when an aqueous mixed solution containing the ionic liquid is hydrothermally treated, the ionic liquid is decomposed, and as a result, safely The present invention has been found out that it can be discarded.
本発明は、イオン液体を含有する水性混合液を水熱処理することにより、イオン液体を分解するイオン液体の分解処理方法である。このように、液中に含有されているイオン液体が分解されることから、安全に処理することが可能となる。したがって、例えば、イオン液体が含有された廃液に対して、安全かつ効果的に処理することが可能となり産業上有用な技術となりうる。 The present invention is an ionic liquid decomposition treatment method for decomposing an ionic liquid by hydrothermally treating an aqueous liquid mixture containing the ionic liquid. As described above, since the ionic liquid contained in the liquid is decomposed, it is possible to safely process the liquid. Therefore, for example, a waste liquid containing an ionic liquid can be treated safely and effectively, which can be an industrially useful technique.
そして、上記イオン液体を含有する水性混合液の水熱処理を、鉱化剤の存在下で行なうと、水熱処理により分解されたイオン液体のアニオン部の分解物をトラップして不溶性の塩を形成し、固液分離が容易となりイオン液体を含有する水性混合液の廃棄等の処理の向上が図られる。 Then, when hydrothermal treatment of the aqueous mixture containing the ionic liquid is carried out in the presence of a mineralizer, the decomposition product of the anion portion of the ionic liquid decomposed by the hydrothermal treatment is trapped to form an insoluble salt. As a result, solid-liquid separation is facilitated, and processing such as disposal of an aqueous mixed solution containing an ionic liquid is improved.
さらに、上記水熱処理の前段工程または後段工程おいて、光触媒の存在下、水性混合液に光照射を行なうと、イオン液体の分解処理がより一層促進され好ましいものである。 Furthermore, when the aqueous mixed solution is irradiated with light in the presence of a photocatalyst in the preceding or subsequent step of the hydrothermal treatment, the decomposition treatment of the ionic liquid is further promoted, which is preferable.
つぎに、本発明の実施の形態について詳しく説明する。
本発明におけるイオン液体とは、融点が１５０℃以下でカチオン部とアニオン部からなるイオン性物質のことを表す。なお、本発明においては、融点が上記範囲外であっても本発明の分解処理方法を用いて処理可能な比較的低融点のイオン性物質もイオン液体に含むものである。
Next, embodiments of the present invention will be described in detail.
The ionic liquid in the present invention represents an ionic substance having a melting point of 150 ° C. or lower and consisting of a cation part and an anion part. In the present invention, the ionic liquid also includes an ionic substance having a relatively low melting point that can be treated using the decomposition treatment method of the present invention even if the melting point is outside the above range.
本発明のイオン液体の分解処理方法において、分解処理対象となるイオン液体は、そのアニオン部は、特に限定されるものではなく、さらに、分解処理されるイオン液体としては、１種類に限定されるものではなく、２種以上のイオン液体が混合したものであってもよい。 In the decomposition treatment process of the ionic liquid of the present invention, ionic liquid as a decomposition treatment subject A anion portion of its is not limited in particular, further, as the ionic liquid to be decomposed, limited to one Instead, it may be a mixture of two or more ionic liquids.
そして、上記分解処理対象となるイオン液体のカチオン部は、イミダゾリウムカチオンである。 The cation portion of the ionic liquid including the above-described decomposition process target is Ru Lee Mi Dazo cation der.
上記イミダゾリウムカチオンとしては、例えば、１，３−ジメチルイミダゾリウムイオン、１−エチル−３−メチルイミダゾリウムイオン、１−メチル−３−プロピルイミダゾリウムイオン、１−ブチル−３−メチルイミダゾリウムイオン、１−メチル−３−ペンチルイミダゾリウムイオン、１−ヘキシル−３−メチルイミダゾリウムイオン、１−ヘプチル−３−メチルイミダゾリウムイオン、１−メチル−３−オクチルイミダゾリウムイオン、１−デシル−３−メチルイミダゾリウムイオン、１−ドデシル−３−メチルイミダゾリウムイオン、１−エチル−３−プロピルイミダゾリウムイオン、１−ブチル−３−エチルイミダゾリウムイオン等のジアルキルイミダゾリウムイオン；３−エチル−１，２−ジメチル−イミダゾリウムイオン、１，２−ジメチル−３−プロピルイミダゾリウムイオン、１−ブチル−２，３−ジメチルイミダゾリウムイオン、１，２−ジメチル−３−ヘキシルイミダゾリウムイオン、１，２−ジメチル−３−オクチルイミダゾリウムイオン、１−エチル−３，４−ジメチルイミダゾリウムイオン、１−イソプロピル−２，３−ジメチルイミダゾリウムイオン等のトリアルキルイミダゾリウムイオン等をあげることができる。 Examples of the imidazolium cation include 1,3-dimethylimidazolium ion, 1-ethyl-3-methylimidazolium ion, 1-methyl-3-propylimidazolium ion, and 1-butyl-3-methylimidazolium ion. 1-methyl-3-pentylimidazolium ion, 1-hexyl-3-methylimidazolium ion, 1-heptyl-3-methylimidazolium ion, 1-methyl-3-octylimidazolium ion, 1-decyl-3 -Dialkylimidazolium ions such as methylimidazolium ion, 1-dodecyl-3-methylimidazolium ion, 1-ethyl-3-propylimidazolium ion, 1-butyl-3-ethylimidazolium ion; 3-ethyl-1 , 2-dimethyl-imidazolium ion, , 2-dimethyl-3-propylimidazolium ion, 1-butyl-2,3-dimethylimidazolium ion, 1,2-dimethyl-3-hexylimidazolium ion, 1,2-dimethyl-3-octylimidazolium ion And trialkylimidazolium ions such as 1-ethyl-3,4-dimethylimidazolium ion and 1-isopropyl-2,3-dimethylimidazolium ion.
一方、上記分解処理対象となるイオン液体のアニオン部としては、通常、Ｃｌ- 、Ｂｒ- 、Ｉ- 、ＢＦ4 - 、ＢＦ3 Ｃ2 Ｆ5 - 、ＰＦ6 - 、ＮＯ3 - 、ＣＦ3 ＣＯ2 - 、ＣＦ3 ＳＯ3 - 、（ＣＦ3 ＳＯ2 ）2 Ｎ- 、（ＦＳＯ2 ）2 Ｎ- 、（ＣＦ3 ＳＯ2 ）3 Ｃ- 、（Ｃ2 Ｆ5 ＳＯ2 ）2 Ｎ- 、ＡｌＣｌ4 - 、Ａｌ2 Ｃｌ7 - 等があげられる。 On the other hand, the anion portion of the ionic liquid to be decomposed is usually Cl − , Br − , I − , BF 4 − , BF 3 C 2 F 5 − , PF 6 − , NO 3 − , CF 3 CO. 2 − , CF 3 SO 3 − , (CF 3 SO 2 ) 2 N − , (FSO 2 ) 2 N − , (CF 3 SO 2 ) 3 C − , (C 2 F 5 SO 2 ) 2 N − , AlCl 4 -, Al 2 Cl 7 -, and the like.
本発明のイオン液体の分解処理方法は、上記イオン液体を含有する水性混合液に対して水熱処理を行なうことによりイオン液体を分解処理する方法である。なお、本発明において、上記水熱処理とは、水存在下で、処理対象となるイオン液体を積極的に加熱処理することをいう。 The method for decomposing ionic liquid of the present invention is a method for decomposing ionic liquid by subjecting the aqueous mixture containing the ionic liquid to hydrothermal treatment. In the present invention, the hydrothermal treatment means that the ionic liquid to be treated is actively heat-treated in the presence of water.
また、本発明において、水性混合液とは、水とイオン液体を含有するものであって、水熱処理による分解処理を阻害しない範囲であれば、上記水、イオン液体以外に他の各種溶媒、例えば、低級アルコール、低級アルカン、アセトン、アセトニトリル、アセトアルデヒド、ベンゼン等が混合されていてもよい。 Further, in the present invention, the aqueous mixed liquid contains water and an ionic liquid, and is in a range that does not inhibit the decomposition treatment by hydrothermal treatment, in addition to the above water and ionic liquid, various other solvents, for example, , Lower alcohol, lower alkane, acetone, acetonitrile, acetaldehyde, benzene and the like may be mixed.
本発明における水熱処理は、鉱化剤の存在下に行なわれる。上記鉱化剤は、分解されたイオン液体のアニオン部の分解物、例えば、フッ素イオンやリンイオンと結合して不溶性の塩を形成するという作用を奏し、結果、分解処理された溶液の固液分離を容易にする効果が得られる。なお、上記鉱化剤は、水熱処理前に水性混合液に含有されていてもよいし、水熱処理後に添加してもよく、好ましくは水熱処理前に水性混合液に含有させ、水熱処理を鉱化剤の存在下で行なうことである。 Hydrothermal treatment of the present invention, the row of dividing in the presence of a mineralizer. The mineralizer has an effect of forming an insoluble salt by combining with a decomposition product of anion part of the decomposed ionic liquid, for example, fluorine ion or phosphorus ion, and as a result, solid-liquid separation of the decomposed solution The effect of facilitating is obtained. The mineralizer may be contained in the aqueous mixed solution before hydrothermal treatment, or may be added after hydrothermal treatment, and is preferably contained in the aqueous mixed solution before hydrothermal treatment. In the presence of an agent.
上記鉱化剤としては、温度を上昇させると溶解度が下がる特性を有する化合物であれば特に限定するものではなく、例えば、このような特性を有する無機化合物、好ましくは無機の塩基性化合物、より具体的には、アルカリ土類金属の水酸化物があげられる。なかでも、コスト、不溶性塩の形成容易性等の観点から、水酸化カルシウムあるいは塩化カルシウム等のカルシウム化合物が好適に用いられ、特には水酸化カルシウムが好適に用いられる。そして、上記鉱化剤は、単独でもしくは２種以上併せて用いることができる。 The mineralizer is not particularly limited as long as it is a compound having a property of decreasing the solubility when the temperature is raised. For example, an inorganic compound having such a property, preferably an inorganic basic compound, more specifically. Specifically, alkaline earth metal hydroxides can be mentioned. Of these, calcium compounds such as calcium hydroxide or calcium chloride are preferably used from the viewpoints of cost, ease of formation of insoluble salts, and calcium hydroxide is particularly preferably used. And the said mineralizer can be used individually or in combination of 2 or more types.
また、上記鉱化剤として、上記アルカリ土類金属の水酸化物以外に、遷移金属（Ｐｂ，Ｃｒ等）の水酸化物を用いることもできる。 In addition to the alkaline earth metal hydroxide, transition metal (Pb, Cr, etc.) hydroxide can also be used as the mineralizer.
上記鉱化剤の含有量は、特に限定するものではなく、分解処理対象であるイオン液体の種類，含有量，さらには処理条件等により適宜に設定される。例えば、バッチ式の場合、鉱化剤の含有量は、イオン液体１モルに対して５０モル以下であることが好ましく、その下限値としては、好適には０．７モルである。かかる含有量が多すぎると、未反応の鉱化剤が大量に発生することになり不経済である。 The content of the mineralizer is not particularly limited, and is appropriately set depending on the type and content of the ionic liquid to be decomposed and the processing conditions. For example, in the case of a batch type, the content of the mineralizer is preferably 50 mol or less with respect to 1 mol of the ionic liquid, and its lower limit is preferably 0.7 mol. If the content is too large, a large amount of unreacted mineralizer is generated, which is uneconomical.
さらに、上記イオン液体を含有する水性混合液には、上記鉱化剤以外の、他の添加物を適宜配合することができる。 Furthermore, other additives other than the mineralizer can be appropriately blended in the aqueous mixed solution containing the ionic liquid.
上記他の添加剤としては、アニオン部のさらなる分解を促進する等の目的から、鉄粉等の金属粉を用いることができる。 As said other additive, metal powders, such as iron powder, can be used for the objective of accelerating | stimulating the further decomposition | disassembly of an anion part.
また、イオン液体を含有する水性混合液のｐＨをアルカリ性領域に調整する目的から、ｐＨ調整剤が用いられる。なお、上記ｐＨ調整剤の配合によるｐＨの調整以外に、前述の鉱化剤を配合することにより所望のｐＨに調整してもよい。したがって、上記ｐＨ調整剤の配合量は、特に限定するものではなく所望のｐＨに調整可能な量であればよい。
このように、本発明では、イオン液体を含有する水性混合液のｐＨは、アルカリ性領域であることが好ましく、特に好ましくはｐＨ＝７〜１４の範囲、更に好ましくはｐＨ＝８〜１２である。
Moreover, a pH adjuster is used for the purpose of adjusting the pH of the aqueous mixture containing the ionic liquid to an alkaline region. In addition to adjusting the pH by adding the pH adjusting agent, it may be adjusted to a desired pH by adding the mineralizer described above. Therefore, the blending amount of the pH adjusting agent is not particularly limited as long as it can be adjusted to a desired pH.
Thus, in this invention, it is preferable that the pH of the aqueous liquid mixture containing an ionic liquid is an alkaline area | region, Especially preferably, it is the range of pH = 7-14, More preferably, it is pH = 8-12.
さらには、アルカリ性領域のｐＨを変化させない酸化剤を配合することも好ましく、特には過酸化水素（Ｈ2 Ｏ2 ）を配合することが好ましい。 Furthermore, it is also preferable to mix an oxidizing agent that does not change the pH of the alkaline region, and it is particularly preferable to mix hydrogen peroxide (H 2 O 2 ).
つぎに、本発明のイオン液体の分解処理方法は、例えば、オートクレーブ内にて分解反応が行われるものであり、上記分解反応に際しての処理条件について詳しく述べる。 Next, in the method for decomposing ionic liquid of the present invention, for example, the decomposition reaction is performed in an autoclave, and the processing conditions for the decomposition reaction will be described in detail.
イオン液体を含有する水性混合液を水熱処理する際の水熱処理の温度は、分解処理対象であるイオン液体の種類，含有量，さらには処理時の圧力や時間等により適宜選択される。かかる水熱処理の温度は、１００〜４００℃であり、より好ましくは１２０〜３００℃であり、特に好ましくは１５０〜２５０℃である。すなわち、水熱処理温度が低すぎると、イオン液体が充分に分解処理され難い傾向があり、高すぎると、分解処理の向上が望めることもなく、コスト的に不利となる傾向がみられるからである。 The temperature of the hydrothermal treatment at the time of hydrothermal treatment of the aqueous mixture containing the ionic liquid is appropriately selected depending on the type and content of the ionic liquid to be decomposed, the pressure and time during the treatment, and the like. Temperature of such hydrothermal treatment, 1 from 00 to 400 ° C. der is, more preferably from 120 to 300 ° C., particularly preferably from 150 to 250 ° C.. That is, if the hydrothermal treatment temperature is too low, the ionic liquid tends not to be sufficiently decomposed, and if it is too high, an improvement in the decomposition treatment cannot be expected, and the cost tends to be disadvantageous. .
水熱処理における反応時間は、イオン液体の種類、その含有量、さらには水熱処理時の処理温度、圧力等により適宜に設定される。かかる反応時間は、例えば、水熱処理をバッチ式で行なう場合、１〜５０時間であることが好ましく、より好ましくは３〜３０時間、特に好ましくは１０〜２５時間である。 The reaction time in the hydrothermal treatment is appropriately set depending on the type of ionic liquid, its content, and the treatment temperature, pressure, etc. during the hydrothermal treatment. The reaction time is preferably 1 to 50 hours, more preferably 3 to 30 hours, and particularly preferably 10 to 25 hours, for example, when hydrothermal treatment is performed in a batch system.
水熱処理における圧力条件としては、液相保持可能な圧力であればよく、具体的には、１５０〜５０，０００ｋＰａであり、更には１５０〜１０，０００ＫＰａであることが好ましい。かかる圧力が低すぎると、イオン液体の分解が進行し難くなる傾向があり、高すぎると処理装置の耐圧性能の点からコスト的に不利となる傾向がある。 The pressure condition in the hydrothermal treatment may be a pressure capable of maintaining a liquid phase, specifically 150 to 50,000 kPa, more preferably 150 to 10,000 KPa. If the pressure is too low, the decomposition of the ionic liquid tends to be difficult to proceed, and if it is too high, the cost tends to be disadvantageous in terms of pressure resistance performance of the processing apparatus.
つぎに、イオン液体を含有する水性混合液におけるイオン液体の濃度は、例えば、水性混合液中の水に対して０．０１〜３０重量％であることが好ましく、特に好ましくは０．１〜２０重量％である。かかる含有量が多すぎると、一度の処理では分解しにくい傾向があり、また鉱化剤を使用する場合においてはその使用量が増加し、経済的でない傾向がある。 Next, the concentration of the ionic liquid in the aqueous liquid mixture containing the ionic liquid is preferably 0.01 to 30% by weight, particularly preferably 0.1 to 20%, based on the water in the aqueous liquid mixture. % By weight. If the content is too large, decomposition tends to be difficult with a single treatment, and when a mineralizer is used, the amount used tends to increase, which tends to be uneconomical.
本発明のイオン液体の分解処理方法では、先に述べたように、オートクレーブにて行われるがこれに限定するものではなく、バッチ式であっても連続式であっても差し支えない。さらには、水熱処理工程中、イオン液体を含有する水性混合液を静置しても、あるいは攪拌してもよい。 In the method for decomposing ionic liquid according to the present invention, as described above, it is carried out by an autoclave, but the method is not limited to this, and it may be a batch type or a continuous type. Furthermore, during the hydrothermal treatment step, the aqueous mixed solution containing the ionic liquid may be left still or stirred.
つぎに、本発明のイオン液体の分解処理方法では、上記水熱処理にて分解処理した後の後処理工程として、例えば、降圧し冷却することにより、沈殿物である固形分（鉱化剤とアニオン部の分解物との塩）を各種フィルター等を用いて吸引濾過等により分離する工程を経由することが好ましい。すなわち、鉱化剤を用いた場合、この鉱化剤とアニオン部の分解物との塩が形成されるが、この塩が溶解しないよう素早く冷却し、固形分を分離可能となる状態にすることが好ましい。 Next, in the ionic liquid decomposition treatment method of the present invention, as a post-treatment step after the decomposition treatment by the hydrothermal treatment, for example, by reducing the pressure and cooling, solid content (mineralizer and anion) It is preferable to pass through a step of separating the salt with the decomposed product of the portion by suction filtration using various filters or the like. That is, when a mineralizer is used, a salt is formed between the mineralizer and the decomposition product of the anion portion, but the salt is cooled quickly so that the salt does not dissolve, so that the solid content can be separated. Is preferred.
本発明のイオン液体の分解処理方法では、上記水熱処理によるイオン液体の分解処理工程に加えて、光触媒の存在下、光照射を行なう光分解処理を行なってもよい。上記水熱処理に加えて光分解処理を行なうことにより、イオン液体の分解処理が一層促進されることになり好ましい。なお、上記光分解処理は、水熱処理の前段工程で行なってもよいし、後段工程で行なってもよく、その順序は限定するものではないが、好適には、分解処理の促進効率等を考慮した場合、水熱処理を施した後、続いて光分解処理を行なう工程の順序が好ましい。 In the ionic liquid decomposition treatment method of the present invention, in addition to the ionic liquid decomposition treatment step by hydrothermal treatment, a photodecomposition treatment in which light irradiation is performed in the presence of a photocatalyst may be performed. It is preferable to perform the photolysis treatment in addition to the hydrothermal treatment because the decomposition treatment of the ionic liquid is further accelerated. The photodecomposition treatment may be performed in the preceding step of the hydrothermal treatment, or may be performed in the subsequent step, and the order thereof is not limited, but preferably the decomposition treatment promotion efficiency is considered. In this case, the order of the steps of performing the photolysis after the hydrothermal treatment is preferable.
上記光分解処理は、イオン液体を含有する水性混合液に、光触媒の存在下で光照射を行なうものである。 In the photolysis treatment, an aqueous mixture containing an ionic liquid is irradiated with light in the presence of a photocatalyst.
上記光触媒としては、特に限定するものではなく従来公知の各種光触媒が用いられ、例えば、遷移金属の酸化物，硫化物，窒化物等があげられる。これらの中でも、遷移金属の酸化物が好ましく、特にはコスト等の観点から、酸化チタン（ＴｉＯ2 ）が好適に用いられる。また、上記光触媒は、単独で用いてもよいし２種以上を併用してもよい。 The photocatalyst is not particularly limited, and various conventionally known photocatalysts are used, and examples thereof include transition metal oxides, sulfides, and nitrides. Among these, transition metal oxides are preferable, and titanium oxide (TiO 2 ) is preferably used from the viewpoint of cost and the like. Moreover, the said photocatalyst may be used independently and may use 2 or more types together.
上記酸化チタンに関して、より詳しく述べると、一般的には、アナターゼ型の結晶構造を有するものが好適に用いられる。また、上記酸化チタンとしては、その表面積が数ｍ2 ／ｇ〜数百ｍ2 ／ｇであればよく、具体的には１〜４００ｍ2 ／ｇが好ましい。さらに、その粒径に関しては、粉末状として用いる場合、平均粒子径１ｎｍ〜１ｍｍの範囲内のものが好適に用いられる。 The titanium oxide will be described in more detail. Generally, those having an anatase type crystal structure are preferably used. Further, as the titanium oxide may be a surface area of several m 2 / g to several hundred m 2 / g, specifically 1~400m 2 / g are preferred. Furthermore, regarding the particle diameter, when used as a powder, those having an average particle diameter in the range of 1 nm to 1 mm are preferably used.
上記光触媒の含有量としては、イオン液体の濃度、光照射等の処理条件により適宜に設定されるが、水性混合液が過度に濁ることがなく、照射された光が水性混合液内部にまで到達可能な状態となる透明性が保持可能な量であればよい。例えば、バッチ式で行なう場合、水性混合液基準として、０．０１〜１０００ｇ／ｌ、特には０．１〜１０ｇ／ｌであることが好ましい。かかる含有量が少なすぎると、分解処理に長時間を要する傾向がみられ、逆に多すぎても添加効果の向上はみられず不経済である。 The content of the photocatalyst is appropriately set according to the processing conditions such as the concentration of the ionic liquid and light irradiation, but the aqueous mixture does not become excessively turbid, and the irradiated light reaches the inside of the aqueous mixture. What is necessary is just the quantity which can maintain the transparency which will be in a possible state. For example, when carried out in a batch system, it is preferably 0.01 to 1000 g / l, particularly 0.1 to 10 g / l, based on the aqueous mixture. If the content is too small, the decomposition treatment tends to take a long time. On the other hand, if the content is too large, the addition effect is not improved, which is uneconomical.
そして、光照射によるイオン液体の分解処理の一層の促進向上を目的に、上記光触媒とともに触媒助剤を併せて配合することができる。上記触媒助剤としては、例えば、白金（Ｐｔ）、パラジウム（Ｐｄ）、ルテニウム（Ｒｕ）、金（Ａｕ）、銀（Ａｇ）、銅（Ｃｕ）、マンガン（Ｍｎ）、鉄（Ｆｅ）等があげられる。上記触媒助剤は、単独で用いてもよいし２種以上を併用してもよい。 Then, for the purpose of further promoting and improving the decomposition treatment of the ionic liquid by light irradiation, a catalyst aid can be blended together with the photocatalyst. Examples of the catalyst auxiliary include platinum (Pt), palladium (Pd), ruthenium (Ru), gold (Au), silver (Ag), copper (Cu), manganese (Mn), iron (Fe), and the like. can give. The catalyst assistants may be used alone or in combination of two or more.
上記触媒助剤の含有量は、特に限定するものではなく、例えば、光触媒に対して、０．００１〜１０重量％であることが好ましく、特には０．０１〜１重量％であることが好ましい。かかる含有量が少なすぎると、添加効果が得られにくい傾向があり、逆に多すぎても添加効果の向上がみられ難く、経済的ではない傾向がみられる。そして、上記触媒助剤は水性混合液中に直接添加してもよいが、例えば、光触媒に予め物理的に混合して焼成する方法、触媒助剤を含む化合物の溶液を光触媒に含浸させ乾燥，焼成する方法、触媒助剤を含む化合物の溶液中で光触媒による光還元により光触媒表面に触媒助剤である金属を析出させる方法等も好ましく用いられる。 The content of the catalyst auxiliary is not particularly limited, and is preferably 0.001 to 10% by weight, particularly preferably 0.01 to 1% by weight with respect to the photocatalyst. . If the content is too small, the effect of addition tends to be difficult to obtain. Conversely, if the content is too large, improvement of the effect of addition is difficult to be seen, and there is a tendency that is not economical. The catalyst auxiliary may be added directly to the aqueous mixture. For example, a method in which the photocatalyst is physically mixed beforehand and calcined, a photocatalyst impregnated with a solution of a compound containing the catalyst auxiliary, and dried. A method of firing, a method of depositing a metal as a catalyst auxiliary on the surface of the photocatalyst by photoreduction with a photocatalyst in a solution of a compound containing the catalyst auxiliary, and the like are also preferably used.
なお、上記光触媒、さらにこの光触媒とともに触媒助剤を併用する態様に関しては、特に限定されるものではなく、例えば水性混合液中に直接懸濁する方法、処理後の分離を容易にするためにフィルター状の支持体に光触媒（あるいは光触媒と触媒助剤）をコーティングして利用する方法、ガラスビーズやセラミックス粒子等の支持体に光触媒や触媒助剤を含む光触媒を担持する方法を用いることができる。 Note that the above-mentioned photocatalyst and the mode in which a catalyst auxiliary is used in combination with the photocatalyst are not particularly limited, and for example, a method of directly suspending in an aqueous mixture, a filter for facilitating separation after treatment A method in which a photocatalyst (or a photocatalyst and a catalyst auxiliary) is coated on a substrate-like support, or a method in which a photocatalyst containing a photocatalyst or a catalyst auxiliary is supported on a support such as glass beads or ceramic particles can be used.
また、水性混合液を投入する容器の内周表面に、光触媒（あるいは光触媒と触媒助剤）を用いてコーティング等により膜状に形成しても上記光触媒によるイオン液体の光分解効果が得られる。 Further, the photodecomposition effect of the ionic liquid by the photocatalyst can be obtained even if the photocatalyst (or photocatalyst and catalyst auxiliary) is used to form a film by coating or the like on the inner peripheral surface of the container into which the aqueous mixed solution is charged.
さらに、本発明のイオン液体の分解処理方法には、上記光触媒および触媒助剤以外に、イオン液体の分解処理の促進等を目的として、必要に応じて他の添加物を適宜配合することができる。上記他の添加剤としては、例えば、鉄イオンなどの遷移金属イオン、過酸化水素などの酸化剤等があげられる。 Furthermore, in addition to the photocatalyst and the catalyst auxiliary, other additives can be appropriately blended in the ionic liquid decomposition method of the present invention as necessary for the purpose of promoting the decomposition treatment of the ionic liquid. . Examples of the other additives include transition metal ions such as iron ions and oxidizing agents such as hydrogen peroxide.
つぎに、光照射による処理条件について詳しく述べる。 Next, processing conditions by light irradiation will be described in detail.
本発明の、イオン液体と光触媒と水性媒体を含有する水性混合液に照射される光線としては、使用する光触媒を励起できる波長の光を含んでいれば特に限定するものではない。例えば、光触媒として酸化チタンを用いる場合には、紫外線光（ＵＶ光：波長２００〜４００ｎｍ）を含む光であれば特に限定するものではない。また、光源となる光照射装置も特に限定されるものではなく、例えば、キセノンランプ、水銀ランプ、ブラックライト、発光ダイオード（ＬＥＤ）等があげられる。 The light beam applied to the aqueous mixed solution containing the ionic liquid, the photocatalyst and the aqueous medium of the present invention is not particularly limited as long as it contains light having a wavelength capable of exciting the photocatalyst to be used. For example, when titanium oxide is used as a photocatalyst, there is no particular limitation as long as it includes ultraviolet light (UV light: wavelength 200 to 400 nm). Moreover, the light irradiation apparatus used as a light source is not specifically limited, For example, a xenon lamp, a mercury lamp, a black light, a light emitting diode (LED) etc. are mentioned.
上記光照射の照射強度は、その照射機器等に依存するものであり特に限定するものではないが、例えば、０．１〜１００００ｍＷ／ｃｍ2 であればよい。 The irradiation intensity of the light irradiation depends on the irradiation device and the like and is not particularly limited, but may be, for example, 0.1 to 10000 mW / cm 2 .
上記光照射の際には、水性混合液中に溶存酸素が含有されていればよく、大気開放下で光照射による分解反応を行ってもよいし、また水性混合液中に酸素を積極的に導入してもよい。好ましくは水性混合液中に積極的に酸素を導入することである。 At the time of the light irradiation, it is sufficient that dissolved oxygen is contained in the aqueous mixture, and the decomposition reaction by light irradiation may be performed in the open atmosphere, and oxygen is actively added to the aqueous mixture. It may be introduced. Preferably, oxygen is positively introduced into the aqueous mixture.
また、上記光照射における温度条件としては、水性混合液が凍結等せず液状態が保持可能であれば特に限定するものではなく、０〜１００℃であればよい。通常、かかる光照射は、室温（２５±１０℃）程度で行われる。 In addition, the temperature condition in the light irradiation is not particularly limited as long as the aqueous mixed solution is not frozen and the liquid state can be maintained, and may be 0 to 100 ° C. Usually, such light irradiation is performed at room temperature (25 ± 10 ° C.).
上記光照射による反応時間としては、分解処理の各種条件等のレベルに応じて適宜に選択されるが、通常、５分〜２４時間程度で行なわれる。 The reaction time by the light irradiation is appropriately selected according to the level of various conditions of the decomposition treatment, etc., but is usually about 5 minutes to 24 hours.
上記イオン液体を含有する水性混合液における光照射の圧力雰囲気の条件として、常圧下であっても加圧下であってもよく、特に限定するものではない。 The conditions of the pressure atmosphere of the light irradiation in the aqueous mixture containing the ionic liquid may be normal pressure or pressure, and are not particularly limited.
本発明において光分解処理は、バッチ式、連続式のいずれの方法で行なわれてもよく、反応容器（装置）等も水性混合液に有効波長を含む照射光が充分にとどくものであれば、特に限定されるものではない。 In the present invention, the photodecomposition treatment may be carried out by either a batch type or a continuous type, and the reaction vessel (apparatus) and the like, as long as the irradiation light containing an effective wavelength in the aqueous mixed solution sufficiently reaches, It is not particularly limited.
そして、上記光照射にて分解処理した後の後処理工程としては、光照射を止め、光触媒と水性混合液を分離除去する工程を経由することが好ましい。分離の方法としては例えば、沈殿物である固形分（光触媒等）を各種フィルター等を用いて吸引濾過等により分離してもよいし、フィルター等の支持体に光触媒等が支持されている場合には単にその支持体を分離すればよい。 And as a post-processing process after decomposing | disassembling by the said light irradiation, it is preferable to pass through the process of stopping light irradiation and separating and removing a photocatalyst and an aqueous liquid mixture. As a separation method, for example, a solid content (such as a photocatalyst) that is a precipitate may be separated by suction filtration using various filters or the like, or when a photocatalyst or the like is supported on a support such as a filter. Simply separate the support.
本発明のイオン液体の分解処理方法により分解処理されてなる水性混合液の分析方法としては、分解処理する前後のイオン液体を含有する水性混合液を、イオンクロマトグラフにより分析測定し、分解処理（水熱処理）前の分析結果に対する分解処理（水熱処理）後の分析結果の比較（比率）から、水性混合液中のイオン液体の分解率を算出する方法が挙げられる。 As an analysis method of the aqueous mixed solution obtained by the decomposition treatment by the ionic liquid decomposition treatment method of the present invention, the aqueous mixture containing the ionic liquid before and after the decomposition treatment is analyzed and measured by ion chromatography, and the decomposition treatment ( A method of calculating the decomposition rate of the ionic liquid in the aqueous mixture from the comparison (ratio) of the analysis results after the decomposition treatment (hydrothermal treatment) with respect to the analysis results before the hydrothermal treatment).
また、前記固液分離により分離された沈殿物である固形分（鉱化剤とアニオン部の分解物との塩）については、粉末Ｘ線回折を用いて定性的に分析することができる。 Further, the solid content (salt of the mineralizer and the decomposition product of the anion portion) that is a precipitate separated by the solid-liquid separation can be qualitatively analyzed using powder X-ray diffraction.
以下、実施例および比較例を示して本発明をより具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
本発明で用いた各種分析方法の測定方法、測定条件は以下のとおりである。
＜イオン液体の分解率の測定＞
水熱処理前の０．２重量％のイオン液体を含有する試料（水性混合液）についてイオンクロマトグラフを用いて、カチオン部及びアニオン部のピークエリアをそれぞれ測定した。ついで、水熱処理後試料（水性混合液）の液層について、同様にイオンクロマトグラフにて分析を行ない、カチオン部及びアニオン部について、水熱処理前の試料（水性混合液）のピークエリアに対する、水熱処理後の液層のピークエリアの比から、分解率を算出した。なお、イオンクロマトグラフの分析条件は下記のとおりである。
The measurement methods and measurement conditions of the various analysis methods used in the present invention are as follows.
<Measurement of decomposition rate of ionic liquid>
The peak area of the cation portion and the anion portion was measured for each sample (aqueous mixed solution) containing 0.2 wt% ionic liquid before hydrothermal treatment using an ion chromatograph. Subsequently, the liquid layer of the sample after hydrothermal treatment (aqueous mixture) is similarly analyzed by ion chromatography, and the cation part and the anion part are subjected to water with respect to the peak area of the sample (aqueous mixture) before hydrothermal treatment. The decomposition rate was calculated from the ratio of the peak areas of the liquid layer after the heat treatment. The analysis conditions of the ion chromatograph are as follows.
［カチオン部の測定条件］
使用機器：Dionex4040i イオンクロマトグラフ装置
使用カラム：Dionex IonPac CS12A+CG12A
使用溶離液：３０ｍＭ Methanesulfonic acid／１５（Ｖ／Ｖ）％Acetonitrile aq.
移動相流量：１．２ｍｌ／ｍｉｎ
カラム温度：室温
検出：電気伝導度検出器
Suppressor：CSRS ULTRAII 4-mm AutoSuppression External Water Mode
[Measurement conditions for the cation moiety]
Equipment used: Dionex4040i ion chromatograph equipment Column used: Dionex IonPac CS12A + CG12A
Eluent used: 30 mM Methanesulfonic acid / 15 (V / V)% Acetonitrile aq.
Mobile phase flow rate: 1.2 ml / min
Column temperature: Room temperature Detection: Electrical conductivity detector
Suppressor: C SRS ULTRAII 4-mm AutoSuppression External Water Mode
［アニオン部の測定条件］
使用機器：Dionex DX-500 イオンクロマトグラフ装置
使用カラム：Dionex IonPac AS12A+AG12A
使用溶離液：２．７ｍＭ Na2CO3／０．３ｍＭ NaHCO3／３５（Ｖ／Ｖ）％Acetonitrile aq. 移動相流量：１．５ｍｌ／ｍｉｎ
カラム温度：室温
検出：電気伝導度検出器
Suppressor:ASRS ULTRAII 4-mm AutoSuppression External Water Mode
[Measurement conditions for anion moiety]
Equipment used: Dionex DX-500 ion chromatograph equipment Column used: Dionex IonPac AS12A + AG12A
Eluent:. 2.7mM Na 2 CO 3 /0.3mM NaHCO 3/35 (V / V)% Acetonitrile aq mobile phase flow rate: 1.5 ml / min
Column temperature: Room temperature Detection: Electrical conductivity detector
Suppressor: ASRS ULTRAII 4-mm AutoSuppression External Water Mode
＜固体生成物（沈殿）の分析方法＞
得られた沈澱生成物を、粉末Ｘ線回折装置を用いて試料中に含まれる無機化合物の分析を行ない、得られた回折パターンから生成化合物を同定した。なお、分析条件は以下の通りである。
［粉末Ｘ線回折の測定条件］
使用機器：RIGAKU RINT2500TTR、試料水平型、加熱ステージ
Ｘ線：ＣｕＫα
<Method for analyzing solid product (precipitation)>
The resulting precipitated product was analyzed for inorganic compounds contained in the sample using a powder X-ray diffractometer, and the resulting compound was identified from the obtained diffraction pattern. The analysis conditions are as follows.
[Measurement conditions for powder X-ray diffraction]
Equipment used: RIGAKU RINT2500TTR, horizontal sample type, heating stage X-ray: CuKα
〔実施例１〕
（１）試料（水性混合液）の調製
イオン液体〔カチオン部：１−エチル−３−メチルイミダゾリウムイオン（ＥＭＩ+ ）、アニオン部：ＰＦ6 - 〕２ｇを電子天秤によって精秤し、これにイオン交換水を添加して全量を１Ｌとすることにより、０．２重量％のイオン液体を含有する試料（水性混合液）を作製した。
[Example 1]
(1) Preparation of sample (aqueous mixture) 2 g of ionic liquid [cation part: 1-ethyl-3-methylimidazolium ion (EMI + ), anion part: PF 6 − ] was precisely weighed with an electronic balance. A sample (aqueous mixed solution) containing 0.2% by weight of ionic liquid was prepared by adding ion-exchanged water to make the total amount 1 L.
（２）水熱処理
上記試料３０ｍｌをＣａ（ＯＨ）2 ０．３ｇ（キシダ化学社製、試薬特級）とともに、テフロン（Ｒ）内張り耐圧容器に封入した後、２００℃に設定したヒーター中に導入することにより水熱処理を施した。上記耐圧容器内の圧力は、水熱処理温度における飽和水蒸気圧によって規定されるものであり、２００℃において１．６ＭＰａであった。また、水熱処理時間は、ヒーターに導入した時点からの時間であり、２４時間とした。
(2) Hydrothermal treatment 30 ml of the sample together with 0.3 g of Ca (OH) 2 (manufactured by Kishida Chemical Co., Ltd., reagent special grade) is sealed in a Teflon (R) lined pressure vessel and then introduced into a heater set at 200 ° C. Hydrothermal treatment was performed. The pressure in the pressure vessel was defined by the saturated water vapor pressure at the hydrothermal treatment temperature, and was 1.6 MPa at 200 ° C. Moreover, the hydrothermal treatment time is the time from the time of introduction to the heater, and is 24 hours.
（３）固液分離工程
上記テフロン（Ｒ）内張り耐圧容器をヒーターから取り出した後、室温（２５℃）にて扇風機を用い１時間の放冷を行ない、容器中の温度、圧力を常温常圧（２５℃×１０１ｋＰａ）とした。その後、０．２μｍの孔径を持つポリテトラフルオロエチレン（ＰＴＦＥ）メンブレンフィルターを用いて吸引濾過を行ない、固液分離した。
(3) Solid-liquid separation step After taking out the above-mentioned Teflon (R) lined pressure resistant container from the heater, it is allowed to cool for 1 hour using a fan at room temperature (25 ° C), and the temperature and pressure in the container are set to normal temperature and normal pressure. (25 ° C. × 101 kPa). Thereafter, suction filtration was performed using a polytetrafluoroethylene (PTFE) membrane filter having a pore diameter of 0.2 μm, and solid-liquid separation was performed.
（４）分析
上記固液分離により得られた固体生成物を５０℃に設定した乾燥機中にて２４時間放置して乾燥させ、前述の粉末Ｘ線回折装置を用いて分析を行なった。一方、分離した液層（水性液）については、前述のイオンクロマトグラフ分析を行なった。
(4) Analysis The solid product obtained by the above solid-liquid separation was left to dry in a dryer set at 50 ° C. for 24 hours, and analyzed using the above-mentioned powder X-ray diffractometer. On the other hand, the separated liquid layer (aqueous liquid) was subjected to the ion chromatographic analysis described above.
〔固体生成物（沈殿）の分析〕
分析の結果、固体生成物は、Ｃａ5 （ＰＯ4 ）3 （ＯＨ）、ＣａＦ2 であった。
[Analysis of solid product (precipitation)]
As a result of analysis, the solid products were Ca 5 (PO 4 ) 3 (OH) and CaF 2 .
〔液層の分析〕
イオンクロマトグラフを用いた測定の結果、１−エチル−３−メチルイミダゾリウムイオン（ＥＭＩ+ ）の分解率は３６．１％、ＰＦ6 - の分解率は９９．８％であった。
(Liquid layer analysis)
As a result of measurement using an ion chromatograph, the decomposition rate of 1-ethyl-3-methylimidazolium ion (EMI + ) was 36.1%, and the decomposition rate of PF 6 − was 99.8%.
〔実施例２〕
イオン液体として、〔カチオン部：１−ブチル−３−メチルイミダゾリウムイオン（ＢＭＩ+ ）、アニオン部：ＢＦ4 - 〕を用いた。それ以外は実施例１と同様にして水熱処理を行なった。そして、実施例１と同様にして固液分離を行ない、得られた固体生成物について実施例１と同様に分析を行なった。また、分離した液層について実施例１と同様に分析を行なった。
[Example 2]
[Cation part: 1-butyl-3-methylimidazolium ion (BMI + ), anion part: BF 4 − ] was used as the ionic liquid. Otherwise, hydrothermal treatment was performed in the same manner as in Example 1. Then, solid-liquid separation was performed in the same manner as in Example 1, and the obtained solid product was analyzed in the same manner as in Example 1. The separated liquid layer was analyzed in the same manner as in Example 1.
〔固体生成物（沈殿）の分析〕
粉末Ｘ線回折の結果、固体生成物は、ＣａＦ2 、Ｃａ2 Ｂ2 Ｏ5 ・Ｈ2 Ｏであった。
〔液層の分析〕
イオンクロマトグラフを用いた測定の結果、１−ブチル−３−メチルイミダゾリウムイオン（ＢＭＩ+ ）の分解率は３６．３％、ＢＦ4 - の分解率は９９．９％であった。
[Analysis of solid product (precipitation)]
As a result of powder X-ray diffraction, the solid product was CaF 2 and Ca 2 B 2 O 5 .H 2 O.
(Liquid layer analysis)
As a result of measurement using an ion chromatograph, the decomposition rate of 1-butyl-3-methylimidazolium ion (BMI + ) was 36.3%, and the decomposition rate of BF 4 − was 99.9%.
〔実施例３〕
実施例１の工程（１）〜（３）の後、得られた液層に対して、さらに下記に示す光分解処理を行なった。
（４）光分解処理
実施例１と同様にして水熱処理を施した後、固液分離することで得られた溶液を１０倍に希釈後、光触媒（０．２重量％のＰｔを添加してなる酸化チタン）０．１ｇとともに、石英製反応セルに導入した。ついで、セル内を通過させるよう、反応セルの上方から通して排出されるよう酸素ガスを流通させながら、常温・常圧下（２５℃、１０１ｋＰａ）、反応セル内でのマグネチックスターラーを用いた攪拌子による攪拌を続けた。そして、３００Ｗのキセノンランプを光源として用い、直接光照射するのではなく反応セルの下方に設置した鏡の反射を利用して反応セルの下方から光を間接的に照射した。なお、上記キセノンランプの照射光の強度分布は、１９ｍＷ／ｃｍ2 （波長２２０〜３００ｎｍ）、７１ｍＷ／ｃｍ2 （３１０〜４００ｎｍ）、１７５ｍＷ／ｃｍ2 （３６０〜４７０ｎｍ）であった。また、反応時間は光を照射した時間とし、２４時間とした。
Example 3
After the steps (1) to (3) of Example 1, the obtained liquid layer was further subjected to the following photolysis treatment.
(4) Photolysis treatment After hydrothermal treatment in the same manner as in Example 1, the solution obtained by solid-liquid separation was diluted 10 times, and then a photocatalyst (0.2% by weight of Pt was added thereto). Together with 0.1 g of titanium oxide), it was introduced into a quartz reaction cell. Next, stirring is performed using a magnetic stirrer in the reaction cell at room temperature and normal pressure (25 ° C., 101 kPa) while circulating oxygen gas so that the gas passes through the cell and is discharged from above. Stirring by the child was continued. Then, a 300 W xenon lamp was used as a light source, and light was indirectly irradiated from below the reaction cell using reflection of a mirror installed below the reaction cell instead of direct light irradiation. The intensity distribution of the irradiation light of the xenon lamp was 19 mW / cm 2 (wavelength 220 to 300 nm), 71 mW / cm 2 (310 to 400 nm), and 175 mW / cm 2 (360 to 470 nm). The reaction time was set to 24 hours with light irradiation.
（５）固液分離工程
キセノンランプを用いた光の照射を止めた後、１０分間程度放冷し、その後、０．２μｍの孔径を持つＰＴＦＥメンブレンフィルターを用いて吸引濾過を行ない、固液分離した。
(5) Solid-liquid separation process After light irradiation using a xenon lamp is stopped, the mixture is allowed to cool for about 10 minutes, and then subjected to suction filtration using a PTFE membrane filter having a pore size of 0.2 μm to separate the solid and liquid. did.
（６）分析
工程（３）で得られた固体生成物、および工程（５）で得られた液層（水性液）について下記に示す分析を行なった。
(6) Analysis The following analysis was performed on the solid product obtained in the step (3) and the liquid layer (aqueous liquid) obtained in the step (5).
〔固体生成物（沈殿）の分析〕
粉末Ｘ線回折の結果、光触媒（０．０２重量％のＰｔを添加してなる酸化チタン）を除く固体物は、Ｃａ5 （ＰＯ4 ）3 （ＯＨ）、ＣａＦ2 であった。
〔液層の分析〕
イオンクロマトグラフを用いた測定の結果、１−エチル−３−メチルイミダゾリウムイオン（ＥＭＩ+ ）の分解率は９９．９％、ＰＦ6 - の分解率は９９．９％であった。
[Analysis of solid product (precipitation)]
As a result of powder X-ray diffraction, the solid substance excluding the photocatalyst (titanium oxide formed by adding 0.02% by weight of Pt) was Ca 5 (PO 4 ) 3 (OH) and CaF 2 .
(Liquid layer analysis)
As a result of measurement using an ion chromatograph, the decomposition rate of 1-ethyl-3-methylimidazolium ion (EMI + ) was 99.9%, and the decomposition rate of PF 6 − was 99.9%.
〔比較例〕
試料を封入した耐圧容器をヒーター中に導入せず、すなわち、水熱処理を行なわず、常温常圧（２５℃、１０１ｋＰａ）状態のまま２４時間保持した。これ以外は実施例１と同様にして処理を行なおうとしたが、試料は固液分離も生じず何ら変化は確認されなかった。また、この２４時間保持後の試料について、実施例１と同様に分析を行なったが、イオン液体はほとんど分解されていなかった。
[Comparative example]
The pressure vessel enclosing the sample was not introduced into the heater, that is, hydrothermal treatment was not performed, and the sample was kept for 24 hours in a normal temperature and normal pressure (25 ° C., 101 kPa) state. Other than this, an attempt was made in the same manner as in Example 1, but no solid-liquid separation occurred in the sample, and no change was confirmed. Further, the sample after being held for 24 hours was analyzed in the same manner as in Example 1. However, the ionic liquid was hardly decomposed.
上記イオンクロマトグラフを用いた分析の結果から、水熱処理により特にイオン液体のアニオン部が高い分解率で分解されることが明らかとなった。さらに、粉末Ｘ線回折の結果、水熱処理で得られた固体生成物（沈殿）は、鉱化剤であるＣａ（ＯＨ）2 のカルシウムイオンがイオン液体から分離したアニオン部（ＰＦ6 - ，ＢＦ4 - ）に含まれるＰ，Ｆ，Ｂをトラップして形成された塩であることが明らかとなった。
また、実施例３の結果から、水熱処理に引き続き光分解処理を施すことによりイオン液体のカチオン部も高い分解率にて分解されることがわかった。
上記結果からも明らかなように、本発明の分解処理方法を用いるとイオン液体を無害化して処理することが可能となる。
From the results of the analysis using the ion chromatograph, it has been clarified that the anion portion of the ionic liquid is decomposed at a high decomposition rate by hydrothermal treatment. Furthermore, as a result of powder X-ray diffraction, the solid product (precipitation) obtained by hydrothermal treatment is an anion portion (PF 6 − , BF) in which calcium ions of Ca (OH) 2 as a mineralizer are separated from the ionic liquid. 4 - P contained in), it was found to be a F, trapped formed salt of B.
Further, from the results of Example 3, it was found that the cation portion of the ionic liquid is also decomposed at a high decomposition rate by performing the photolysis treatment following the hydrothermal treatment.
As is apparent from the above results, the ionic liquid can be rendered harmless and treated when the decomposition treatment method of the present invention is used.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5268065A (en) * | 1975-11-29 | 1977-06-06 | Bayer Ag | Method of treating effluents by pressure hydrolysis |
| JP2003507185A (en) * | 1999-08-19 | 2003-02-25 | ブリテイツシユ・ニユークリア・ヒユーエルズ・ピー・エル・シー | How to recycle ionic liquids |
| JP2005538039A (en) * | 2002-03-01 | 2005-12-15 | ソルベント イノベーション ゲーエムベーハー | Halogen-free ionic liquid |
| JP2006517546A (en) * | 2003-02-14 | 2006-07-27 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Salt with cyanoborate anion |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5268065A (en) * | 1975-11-29 | 1977-06-06 | Bayer Ag | Method of treating effluents by pressure hydrolysis |
| JP2003507185A (en) * | 1999-08-19 | 2003-02-25 | ブリテイツシユ・ニユークリア・ヒユーエルズ・ピー・エル・シー | How to recycle ionic liquids |
| JP2005538039A (en) * | 2002-03-01 | 2005-12-15 | ソルベント イノベーション ゲーエムベーハー | Halogen-free ionic liquid |
| JP2006517546A (en) * | 2003-02-14 | 2006-07-27 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Salt with cyanoborate anion |
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