JP2018104578A - Method for decomposing fluorine atom-containing polymer and apparatus for decomposing fluorine atom-containing polymer - Google Patents
Method for decomposing fluorine atom-containing polymer and apparatus for decomposing fluorine atom-containing polymer Download PDFInfo
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Abstract
【課題】焼却でも埋め立てでもなく、比較的穏和な条件で実現可能なフッ素原子含有ポリマーの分解方法、及びそのような分解方法に適用可能な分解装置を提供すること。【解決手段】過マンガン酸塩の存在下、分解対象であるフッ素原子含有ポリマーを２００℃以上の亜臨界水に接触させる工程を備えることを特徴とするフッ素原子含有ポリマーの分解方法を用いればよい。なお、亜臨界水の温度は、３００℃以上であることがより好ましい。【選択図】なしDisclosed is a method for decomposing a fluorine atom-containing polymer that can be realized under relatively mild conditions, not incineration or landfill, and a decomposing apparatus applicable to such a decomposing method. A method for decomposing a fluorine atom-containing polymer, comprising a step of bringing a fluorine atom-containing polymer to be decomposed into contact with subcritical water at 200 ° C. or higher in the presence of permanganate may be used. . The temperature of subcritical water is more preferably 300 ° C. or higher. [Selection figure] None
Description
本発明は、フッ素原子含有ポリマーの分解方法、及びフッ素原子含有ポリマーの分解装置に関するものである。 The present invention relates to a method for decomposing a fluorine atom-containing polymer and an apparatus for decomposing a fluorine atom-containing polymer.
フッ素原子を含んだポリマーは、その化学的安定性や熱に対する耐久性の高さなどの特性が評価され、理化学医療機器を初めとして諸々の生活用品に至るまで様々な分野に応用されている。その反面、これらのポリマーは、こうした化学的安定性や熱に対する耐久性の高さなどの裏返しとして、廃棄物処理の問題を抱えがちである。すなわち、これらのポリマーを焼却しようとすれば、共有結合の中で最強である炭素・フッ素結合の存在によりその分解には高温での処理が必要になるばかりでなく、焼却により発生するフッ化水素ガスによる焼却炉材の劣化を招くことになる。このため、これらのポリマーを廃棄処分しようとすれば埋め立て処理が必要となるが、廃棄物の最終処分場が逼迫している現状ではそれも問題である。したがって、フッ素原子含有ポリマーについての、焼却でもなく埋め立てでもない、新たな廃棄物処理法が求められている。 Polymers containing fluorine atoms have been evaluated for properties such as chemical stability and high durability against heat, and have been applied to various fields ranging from physics and chemistry medical devices to various daily necessities. On the other hand, these polymers are prone to waste disposal problems as the reverse of such chemical stability and high durability against heat. That is, if these polymers are to be incinerated, the presence of carbon / fluorine bonds, which are the strongest of the covalent bonds, requires not only high-temperature treatment for decomposition, but also hydrogen fluoride generated by incineration. It will cause deterioration of the incinerator material due to gas. For this reason, if these polymers are to be disposed of, landfill processing is required, but this is also a problem in the current situation where the final disposal site for waste is tight. Therefore, there is a need for a new waste treatment method for fluorine atom-containing polymers that is neither incinerated nor landfilled.
そのような背景から、例えば非特許文献１には、過酸化水素の存在下、亜臨界水にフッ素原子含有ポリマーを接触させることにより、このポリマーを二酸化炭素とフッ化物イオンまで分解する処理方法が提案されている。このような処理法であれば、比較的穏和な条件でフッ素原子含有ポリマーを無機化することができるばかりか、その処理で生じたフッ化物イオンをカルシウムイオンと反応させることにより、あらゆるフッ素含有化合物の原料になるフッ化カルシウムを得ることができ、資源のリサイクル面からも優れるということができる。 From such a background, for example, Non-Patent Document 1 discloses a treatment method for decomposing this polymer into carbon dioxide and fluoride ions by bringing the fluorine atom-containing polymer into contact with subcritical water in the presence of hydrogen peroxide. Proposed. With such a treatment method, not only can the fluorine atom-containing polymer be mineralized under relatively mild conditions, but any fluorine-containing compound can be obtained by reacting the fluoride ions generated by the treatment with calcium ions. It can be said that calcium fluoride as a raw material can be obtained, which is also excellent in terms of resource recycling.
上記の通り、非特許文献１に記載された処理方法によれば、焼却でも埋め立てでもなく、さらには資源リサイクルすら可能なフッ素原子含有ポリマーの分解方法が提供される。しかしながら、上記の分解方法は、フッ素原子含有ポリマーの種類によっては分解効率が十分でなく、酸化剤となる過酸化水素の量が多量に必要になる等の面で、改善の余地があるのも実情であった。 As described above, according to the treatment method described in Non-Patent Document 1, there is provided a method for decomposing a fluorine atom-containing polymer that is neither incinerated nor landfilled, and even capable of resource recycling. However, the above-described decomposition method has room for improvement in that the decomposition efficiency is not sufficient depending on the type of the fluorine atom-containing polymer, and a large amount of hydrogen peroxide as an oxidizing agent is required. It was a fact.
本発明は、以上の状況に鑑みてなされたものであり、焼却でも埋め立てでもなく、比較的穏和な条件で実現可能なフッ素原子含有ポリマーの分解方法、及びそのような分解方法に適用可能な分解装置を提供することを目的とする。 The present invention has been made in view of the above circumstances, and is a method for decomposing a fluorine atom-containing polymer that can be realized under relatively mild conditions, neither incineration nor landfill, and decomposition applicable to such a decomposing method. An object is to provide an apparatus.
本発明者は、上記の課題を解決するために鋭意検討を重ねた結果、過マンガン酸塩の存在下、分解対象であるフッ素原子含有ポリマーを２００℃以上の亜臨界水に接触させることにより、フッ素原子含有ポリマーを分解でき、その分解効率は過酸化水素を用いた上記非特許文献１の手法に比べて著しく向上することを見出した。本発明は、このような知見に基づいてなされたものであり、以下のようなものを提供する。 As a result of intensive studies to solve the above problems, the present inventor brought the fluorine atom-containing polymer to be decomposed into contact with subcritical water at 200 ° C. or higher in the presence of permanganate, It has been found that a fluorine atom-containing polymer can be decomposed, and the decomposition efficiency is remarkably improved as compared with the method of Non-Patent Document 1 using hydrogen peroxide. The present invention has been made based on such findings, and provides the following.
（１）本発明は、過マンガン酸塩の存在下、分解対象であるフッ素原子含有ポリマーを２００℃以上の亜臨界水に接触させる工程を備えることを特徴とするフッ素原子含有ポリマーの分解方法である。 (1) The present invention is a method for decomposing a fluorine atom-containing polymer, comprising the step of bringing a fluorine atom-containing polymer to be decomposed into contact with subcritical water at 200 ° C. or higher in the presence of a permanganate. is there.
（２）上記亜臨界水の温度は、３００℃以上であることが好ましい。 (2) The temperature of the subcritical water is preferably 300 ° C. or higher.
（３）また本発明は、過マンガン酸塩の存在下、分解対象であるフッ素原子含有ポリマーを２００℃以上の亜臨界水に接触させるための反応容器を備えることを特徴とするフッ素原子含有ポリマーの分解装置でもある。 (3) Moreover, this invention is equipped with the reaction container for making the fluorine atom containing polymer which is a decomposition | disassembly object contact 200 degreeC or more subcritical water in presence of permanganate, The fluorine atom containing polymer characterized by the above-mentioned. It is also a decomposition device.
本発明によれば、焼却でも埋め立てでもなく、比較的穏和な条件で実現可能なフッ素原子含有ポリマーの分解方法、及びそのような分解方法に適用可能な分解装置が提供される。 According to the present invention, there is provided a method for decomposing a fluorine atom-containing polymer that can be realized under relatively mild conditions, not incineration or landfill, and a decomposing apparatus applicable to such a decomposing method.
＜フッ素原子含有ポリマーの分解方法＞
以下、本発明のフッ素原子含有ポリマーの分解方法の一実施態様について説明する。なお本発明は、以下の実施態様に何ら限定されるものでなく、本発明の範囲において適宜変更を加えて実施することが可能である。
<Method for Decomposing Fluorine Atom-Containing Polymer>
Hereinafter, one embodiment of the method for decomposing a fluorine atom-containing polymer of the present invention will be described. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the present invention.
本発明のフッ素原子含有ポリマーの分解方法は、過マンガン酸塩の存在下、分解対象であるフッ素原子含有ポリマーを２００℃以上の亜臨界水に接触させる工程を備える。本工程を備えさえすれば本発明の効果を得ることができ、本発明の範囲に含まれることになる。その他の工程としては、分解反応の効率を高めるためにフッ素原子含有ポリマーを細かく裁断する前処理工程を挙げることができるが、このような前処理は必須ではない。前処理を行う場合、フッ素原子含有ポリマーが粉末状になるまで小粒径化させておくことが望ましい。 The method for decomposing a fluorine atom-containing polymer of the present invention comprises a step of bringing a fluorine atom-containing polymer to be decomposed into contact with subcritical water at 200 ° C. or higher in the presence of a permanganate. As long as this step is provided, the effect of the present invention can be obtained and included in the scope of the present invention. Examples of the other steps include a pretreatment step of finely cutting the fluorine atom-containing polymer in order to increase the efficiency of the decomposition reaction, but such pretreatment is not essential. When the pretreatment is performed, it is desirable to reduce the particle size until the fluorine atom-containing polymer becomes powdery.
本発明における分解対象のフッ素原子含有ポリマーは、分子中にフッ素原子を含むポリマーであり、分子中に１原子でもフッ素原子を含めば本発明の分解対象となる。フッ素原子含有ポリマーは、その高い耐薬品性や耐熱性等の特性が評価され、産業や医療などを初めとしたあらゆる場面で応用されている。その反面、これらのポリマーは、こうした化学的安定性や熱に対する耐久性の高さなどの裏返しとして、廃棄物処理の問題を抱えがちである。本発明は、廃棄物となったこれらのポリマーを化学的に分解処理する方法を提供するものである。このようなフッ素原子含有ポリマーとしては、ホモポリマーでもコポリマーでもよく、そのようなものの例として、エチレン−テトラフルオロエチレン共重合体、フッ化ビニリデン−ヘキサフルオロプロピレン−テトラフルオロエチレン共重合体、ポリフッ化ビニリデンや、フッ化ビニリデンと他のモノマーとの共重合体等を挙げることができる。 The fluorine atom-containing polymer to be decomposed in the present invention is a polymer containing a fluorine atom in the molecule, and if even one atom in the molecule includes a fluorine atom, it becomes the decomposition object of the present invention. Fluorine atom-containing polymers are evaluated for their high chemical resistance and heat resistance, and are applied in various fields including industry and medicine. On the other hand, these polymers are prone to waste disposal problems as the reverse of such chemical stability and high durability against heat. The present invention provides a method for chemically decomposing these polymers as waste. Such a fluorine atom-containing polymer may be a homopolymer or a copolymer, and examples of such a polymer include ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, polyfluoride. Examples thereof include vinylidene and copolymers of vinylidene fluoride and other monomers.
亜臨界水は、加圧されることにより、１００℃を超え、臨界温度である３７４℃よりも低い温度範囲にある液体状態の水である。亜臨界水は、１００℃以下の水とは物性面で異なる性質を備えており、特に２００℃〜３００℃の範囲にある亜臨界水では、比誘電率が大きく低下して室温におけるメタノールやアセトンとほぼ同等の脂溶性を示したり、室温で１０−１４ｍｏｌ／Ｌだったイオン積が１０−１１ｍｏｌ／Ｌのオーダーとなって、水素イオン及び水酸化物イオンの濃度が室温の水よりも３０倍高くなったりする。このため、特に２００℃〜３００℃の亜臨界水では、室温の水とは異なる反応性を示すことが知られている。本発明では、２００℃以上の亜臨界水が用いられ、好ましくは３００℃、又はそれ以上の温度の亜臨界水が用いられる。 Subcritical water is water in a liquid state in a temperature range exceeding 100 ° C. and lower than the critical temperature of 374 ° C. by being pressurized. Subcritical water has properties different from those of water at 100 ° C. or lower, and particularly in subcritical water in the range of 200 ° C. to 300 ° C., the relative permittivity is greatly reduced, and methanol or acetone at room temperature. And the ion product that was 10-14 mol / L at room temperature is on the order of 10-11 mol / L, and the concentration of hydrogen ions and hydroxide ions is higher than that of water at room temperature. 30 times higher. For this reason, it is known that subcritical water at 200 ° C. to 300 ° C. exhibits reactivity different from that at room temperature. In the present invention, subcritical water having a temperature of 200 ° C. or higher is preferably used, and subcritical water having a temperature of 300 ° C. or higher is preferably used.
亜臨界水の調製に用いられる水としては特に限定されず、水道水、イオン交換水、蒸留水、井戸水等、どのようなものを用いてもよいが、共存する塩等の影響による副反応を抑制するとの観点からはイオン交換水や蒸留水が好ましく挙げられる。用いる水の量については、処理対象であるフッ素原子含有ポリマーが十分に浸る程度であればよいが、加圧のための密閉容器へ導入する水の量が極端に少ないと加熱後すべて水蒸気になり亜臨界水の状態にならないため注意が必要である。 The water used for the preparation of subcritical water is not particularly limited, and any water such as tap water, ion exchange water, distilled water, well water, etc. may be used, but side reactions due to the influence of coexisting salts etc. From the viewpoint of suppression, ion-exchanged water and distilled water are preferable. The amount of water used may be sufficient if the fluorine atom-containing polymer to be treated is sufficiently immersed, but if the amount of water introduced into the sealed container for pressurization is extremely small, all of the water will become water vapor after heating. Care must be taken because it is not subcritical water.
過マンガン酸塩は、酸化数＋７のマンガンのオキソ酸の塩であり、フッ素原子含有ポリマーを分解するための酸化力を付与するために用いられる。このような過マンガン酸塩としては、過マンガン酸カリウム、過マンガン酸ナトリウム、過マンガン酸バリウム、過マンガン酸カルシウム等が挙げられるが、これらの中でも過マンガン酸カリウムが好ましく挙げられる。昇温して亜臨界水とする前の水中における過マンガン酸塩の濃度としては、１０〜１０００ｍｍｏｌ／Ｌ（ｍＭ）程度が挙げられる。昇温して亜臨界水とする前の水中における過マンガン酸塩の濃度の下限としては、２５ｍＭがより好ましく挙げられ、３０ｍＭがさらに好ましく挙げられる。過マンガン酸塩の濃度が大きくなればなるほどフッ素原子含有ポリマーの分解速度を高めることができるが、本発明者の調査によれば、２００ｍＭ程度で十分な分解速度を得られることが判明している。そのため、昇温して亜臨界水とする前の水中における過マンガン酸塩の濃度の上限としては、２００ｍＭが好ましく挙げられる。 The permanganate is a salt of manganese oxo acid having an oxidation number of +7, and is used to impart an oxidizing power for decomposing the fluorine atom-containing polymer. Examples of such a permanganate include potassium permanganate, sodium permanganate, barium permanganate, and calcium permanganate. Among these, potassium permanganate is preferable. The concentration of permanganate in the water before being heated to subcritical water is about 10 to 1000 mmol / L (mM). The lower limit of the concentration of permanganate in the water before being heated to subcritical water is more preferably 25 mM, and more preferably 30 mM. As the concentration of permanganate increases, the decomposition rate of the fluorine atom-containing polymer can be increased. However, according to the present inventors' investigation, it has been found that a sufficient decomposition rate can be obtained at about 200 mM. . Therefore, the upper limit of the concentration of permanganate in the water before raising the temperature to subcritical water is preferably 200 mM.
なお、上述の非特許文献１にも示されるように、過酸化水素を含有する亜臨界水中でフッ素原子含有ポリマーを分解する例はあった。しかしながら、その場合、昇温して亜臨界水とする前の水中における過酸化水素の濃度を３０００ｍＭ以上としても十分に分解を行うことはできず、分解により回収されるフッ化物イオンの収率はあまり高いものではなかった。しかしながら、本発明者が、過マンガン酸塩を酸化剤として亜臨界水中でフッ素原子含有ポリマーの分解を試みたところ、意外にも、数十ｍＭ程度の過マンガン酸塩が存在するだけで、分解により回収されるフッ化物イオンの収率が劇的に向上することが見出された。一般に、過酸化水素は過マンガン酸塩よりも高い酸化力を備えているとされていることに鑑みればこのような結果は意外であるが、過酸化水素分子の一部が高温では酸素分子と水分子に分解するためと考えられる。また、過マンガン酸塩を用いた場合にフッ素原子含有ポリマーの分解がこれほど進む理由は明らかではないが、過マンガン酸塩から生じる二酸化マンガンが何らかの促進作用を示している可能性がある。 In addition, as shown in the above-mentioned Non-Patent Document 1, there has been an example in which a fluorine atom-containing polymer is decomposed in subcritical water containing hydrogen peroxide. However, in that case, even if the concentration of hydrogen peroxide in the water before raising the temperature to subcritical water is 3000 mM or more, it cannot be sufficiently decomposed, and the yield of fluoride ions recovered by decomposition is It was not very expensive. However, the present inventor tried to decompose the fluorine atom-containing polymer in subcritical water using permanganate as an oxidizing agent. It has been found that the yield of fluoride ions recovered by is dramatically improved. In general, these results are surprising in view of the fact that hydrogen peroxide has higher oxidizing power than permanganate, but some of the hydrogen peroxide molecules are separated from oxygen molecules at high temperatures. This is thought to be due to decomposition into water molecules. Further, when permanganate is used, the reason why the decomposition of the fluorine atom-containing polymer proceeds so much is not clear, but manganese dioxide generated from the permanganate may show some promoting action.
次に、過マンガン酸塩を含んだ亜臨界水にフッ素原子含有ポリマーを接触させて分解を行う方法について説明する。処理対象であるフッ素原子含有ポリマーの量に応じたサイズの圧力容器に水、過マンガン酸塩、及び処理対象であるフッ素原子含有ポリマーを加え、圧力容器内部を加圧して密閉する。圧力容器内部を加圧するには、気体を封入すればよい。このような気体としては、空気、アルゴン、窒素等を挙げることができるが、酸素による酸化作用を期待できる点からは空気を用いることが好ましい。加圧の程度としては０．５ＭＰａ程度を挙げることができるが、特に限定されない。 Next, a method for performing decomposition by bringing a fluorine atom-containing polymer into contact with subcritical water containing permanganate will be described. Water, permanganate, and the fluorine atom-containing polymer to be treated are added to a pressure vessel having a size corresponding to the amount of the fluorine atom-containing polymer to be treated, and the inside of the pressure vessel is pressurized and sealed. In order to pressurize the inside of the pressure vessel, gas may be enclosed. Examples of such a gas include air, argon, nitrogen, and the like, but it is preferable to use air from the viewpoint that an oxidizing action by oxygen can be expected. The degree of pressurization can be about 0.5 MPa, but is not particularly limited.
上記の過程を経た圧力容器を加熱して分解反応を開始させる。加熱の温度は２００℃以上であるが、３００℃以上であることが望ましい。圧力容器自体が加熱手段を備える場合には、その加熱手段を用いて加熱すればよく、圧力容器自体が加熱手段を備えない場合には、圧力容器全体をオートクレーブやオーブン中で加熱すればよい。反応時間としては６時間〜２４時間程度を挙げることができる。反応中は、内容物の撹拌を行うことが好ましい。このような撹拌手段としてはマグネチックスターラー、撹拌羽根等を挙げることができるが、圧力容器の大きさや内容物の量等に鑑みて適切なものを選択すればよい。 The pressure vessel that has undergone the above process is heated to initiate the decomposition reaction. The heating temperature is 200 ° C. or higher, but is desirably 300 ° C. or higher. When the pressure vessel itself is provided with heating means, the heating means may be used for heating. When the pressure vessel itself is not provided with heating means, the entire pressure vessel may be heated in an autoclave or an oven. The reaction time can be about 6 to 24 hours. During the reaction, it is preferable to stir the contents. Examples of such a stirring means include a magnetic stirrer, a stirring blade, and the like, but an appropriate one may be selected in view of the size of the pressure vessel, the amount of contents, and the like.
反応終了後の水中には、フッ素原子含有ポリマーに含まれていたフッ素原子がフッ化物イオンとなって含まれている。フッ化物イオンは、カルシウムイオンと反応させることにより、あらゆるフッ素化合物の原料となるフッ化カルシウムに転換させることができる。このため、本発明の方法を用いてフッ素原子含有ポリマーの廃棄物処理を行うことにより、資源の有効活用を行うことが可能になる。 In the water after completion of the reaction, fluorine atoms contained in the fluorine atom-containing polymer are contained as fluoride ions. Fluoride ions can be converted to calcium fluoride as a raw material for any fluorine compound by reacting with calcium ions. For this reason, it is possible to effectively utilize resources by performing waste treatment of fluorine atom-containing polymers using the method of the present invention.
＜フッ素原子含有ポリマーの分解装置＞
上記本発明のフッ素原子含有ポリマーの分解方法を実現することのできる装置も本発明の一つである。この装置は、過マンガン酸塩の存在下、分解対象であるフッ素原子含有ポリマーを２００℃以上の亜臨界水に接触させるための反応容器を備えることを特徴とする。
<Decomposition device for fluorine atom-containing polymer>
The apparatus which can implement | achieve the decomposition | disassembly method of the said fluorine atom containing polymer of this invention is also one of this invention. This apparatus is provided with a reaction vessel for bringing a fluorine atom-containing polymer to be decomposed into contact with subcritical water at 200 ° C. or higher in the presence of permanganate.
本発明の装置は、過マンガン酸塩を含む水と、分解対処であるフッ素原子含有ポリマーとを圧力容器の内部に導入することができ、その内部を加圧状態で加熱することが可能である。その際の加熱温度は、２００℃以上であり、好ましくは３００℃以上である。圧力容器の内部には、その内容物を撹拌するための撹拌装置を備えることが望ましい。その他の事項については、上記フッ素原子含有ポリマーの分解方法で説明した通りであるので、ここでの説明を省略する。 The apparatus of the present invention can introduce water containing permanganate and a fluorine atom-containing polymer that is a countermeasure against decomposition into the inside of the pressure vessel, and can heat the inside in a pressurized state. . The heating temperature in that case is 200 degreeC or more, Preferably it is 300 degreeC or more. It is desirable to provide a stirring device for stirring the contents inside the pressure vessel. Since other matters are as described in the method for decomposing a fluorine atom-containing polymer, description thereof is omitted here.
以下、実施例を示すことにより本発明をさらに具体的に説明するが、本発明は以下の実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.
［エチレン−テトラフルオロエチレン共重合体（ＥＴＦＥ共重合体）の亜臨界水を用いた分解反応］
ＥＴＦＥ共重合体（フッ素原子含有率５４．６ｗｔ％、炭素原子含有率４１．４ｗｔ％；一般式−（ＣＨ２ＣＨ２）ｍ−（ＣＦ２ＣＦ２）ｎ−）の粉末３０ｍｇと、酸化剤（過マンガン酸カリウム又は過酸化水素）の水溶液３０ｍＬを撹拌機付き熱水リアクターに入れ、アルゴンガスで０．５ＭＰａまで加圧した後、所定の温度で一定時間反応させた（温度及び時間は表１を参照）。その後、内容物を室温まで冷却し、水相に生成したフッ化物イオンをイオンクロマトグラフィーで定量した。その結果を表１に示す。なお、フッ化物イオンの収率（Ｆ−収率）は、反応に使用したＥＴＦＥ共重合体に含まれるフッ素原子の物質量をもとに計算して求めた。
[Decomposition reaction of ethylene-tetrafluoroethylene copolymer (ETFE copolymer) using subcritical water]
ETFE copolymer (fluorine atom content 54.6 wt%, carbon atom content 41.4 wt%; general formula — (CH 2 CH 2 ) m — (CF 2 CF 2 ) n —) powder 30 mg, and oxidizing agent 30 mL of an aqueous solution of (potassium permanganate or hydrogen peroxide) was placed in a hot water reactor equipped with a stirrer, pressurized with argon gas to 0.5 MPa, and then reacted at a predetermined temperature for a certain period of time (temperatures and times are shown in the table). 1). Thereafter, the contents were cooled to room temperature, and fluoride ions generated in the aqueous phase were quantified by ion chromatography. The results are shown in Table 1. The fluoride ion yield (F - yield) was determined by calculation based on the amount of fluorine atoms contained in the ETFE copolymer used in the reaction.
表１に示すように、過マンガン酸カリウムを酸化剤として用いた実施例１〜５では、過酸化水素を酸化剤として用いた比較例２〜５に比べて少ない酸化剤の量でフッ素原子含有ポリマーの分解を行えることがわかる。特に、反応温度を３００℃とし、酸化剤の量を３０ｍＭ以上とした実施例２〜４では、その他の実施例に比べて高いＦ−収率となり、フッ素原子含有ポリマーの分解が高度に行われたことがわかる。 As shown in Table 1, in Examples 1 to 5 using potassium permanganate as an oxidizing agent, fluorine atoms are contained in a smaller amount of oxidizing agent than in Comparative Examples 2 to 5 using hydrogen peroxide as an oxidizing agent. It can be seen that the polymer can be decomposed. In particular, the reaction temperature was 300 ° C., in Examples 2-4 the amount of the oxidizing agent was more 30 mM, higher F in comparison with the other embodiments - be yield, decomposition of the fluorine atom-containing polymer is carried out highly I understand that.
［フッ化ビニリデン−ヘキサフルオロプロピレン−テトラフルオロエチレン共重合体（ＶＤＦ−ＨＦＰ−ＴＦＥ共重合体）の亜臨界水を用いた分解反応］
ＶＤＦ−ＨＦＰ−ＴＦＥ共重合体（フッ素原子含有率６７．７ｗｔ％、炭素原子含有率２９．９ｗｔ％；一般式−（ＣＦ２ＣＨ２）ｍ−（ＣＦ２ＣＦ（ＣＦ３））ｎ−（ＣＦ２ＣＦ２）ｏ−）の粉末３０ｍｇと、酸化剤（過マンガン酸カリウム又は過酸化水素）の水溶液１０ｍＬを熱水リアクターに入れ、アルゴンガスで０．５ＭＰａまで加圧した後、所定の温度で一定時間反応させた（温度及び時間は表２を参照）。その後、内容物を室温まで冷却し、水相に生成したフッ化物イオンをイオンクロマトグラフィーで定量した。その結果を表２に示す。なお、フッ化物イオンの収率（Ｆ−収率）は、反応に使用したＶＤＦ−ＨＦＰ−ＴＦＥ共重合体に含まれるフッ素原子の物質量をもとに計算して求めた。
[Decomposition reaction of vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer (VDF-HFP-TFE copolymer) using subcritical water]
VDF-HFP-TFE copolymer (fluorine atom content 67.7 wt%, carbon atom content 29.9 wt%; general formula-(CF 2 CH 2 ) m- (CF 2 CF (CF 3 )) n- ( A powder of 30 mg of CF 2 CF 2 ) o- ) and 10 mL of an oxidizing agent (potassium permanganate or hydrogen peroxide) aqueous solution were placed in a hot water reactor and pressurized to 0.5 MPa with argon gas, and then at a predetermined temperature. For a certain period of time (see Table 2 for temperature and time). Thereafter, the contents were cooled to room temperature, and fluoride ions generated in the aqueous phase were quantified by ion chromatography. The results are shown in Table 2. Incidentally, the yield fluoride ions (F - yield), the amount of substance of the fluorine atoms contained in the VDF-HFP-TFE copolymer used in the reaction was calculated based on.
先のＥＴＦＥ共重合体の場合と同様に、ＶＤＦ−ＨＦＰ−ＴＦＥ共重合体の場合も表２に示すように、過マンガン酸カリウムを酸化剤として用いた実施例６〜９では、過酸化水素を酸化剤として用いた比較例７〜１１に比べて少ない酸化剤の量でフッ素原子含有ポリマーの分解を行えることがわかる。特に、反応温度を３００℃とし、酸化剤の量を２５ｍＭ以上とした実施６〜８では、実施例９に比べて高いＦ−収率となり、フッ素原子含有ポリマーの分解が高度に行われたことがわかる。 As in the case of the previous ETFE copolymer, in the case of the VDF-HFP-TFE copolymer, as shown in Table 2, in Examples 6 to 9 using potassium permanganate as an oxidizing agent, hydrogen peroxide It can be seen that the fluorine atom-containing polymer can be decomposed with a smaller amount of the oxidizing agent than in Comparative Examples 7 to 11 using as an oxidizing agent. In particular, the reaction temperature was 300 ° C., the embodiment 6-8 the amount of the oxidizing agent was 25mM or more, higher F compared to Example 9 - that becomes yields, decomposition of the fluorine atom-containing polymer is performed highly I understand.
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| WO2022190835A1 (en) | 2021-03-11 | 2022-09-15 | 学校法人帝京大学 | Method for producing alkali metal halide and method for producing halide |
| WO2023074550A1 (en) | 2021-10-29 | 2023-05-04 | 学校法人神奈川大学 | Method and apparatus for decomposing fluorine atom-containing polymer |
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| WO2013031849A1 (en) * | 2011-09-02 | 2013-03-07 | 旭硝子株式会社 | Method for producing organic compound having sulfo group, method for producing liquid composition, and method for hydrolytically treating organic compound having fluorosulfonyl group |
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| WO2013031849A1 (en) * | 2011-09-02 | 2013-03-07 | 旭硝子株式会社 | Method for producing organic compound having sulfo group, method for producing liquid composition, and method for hydrolytically treating organic compound having fluorosulfonyl group |
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| JP7501866B2 (en) | 2020-03-25 | 2024-06-18 | 学校法人神奈川大学 | Method for decomposing fluorine atom-containing polymer and device for decomposing fluorine atom-containing polymer |
| WO2022190835A1 (en) | 2021-03-11 | 2022-09-15 | 学校法人帝京大学 | Method for producing alkali metal halide and method for producing halide |
| WO2023074550A1 (en) | 2021-10-29 | 2023-05-04 | 学校法人神奈川大学 | Method and apparatus for decomposing fluorine atom-containing polymer |
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