JP7501866B2 - Method for decomposing fluorine atom-containing polymer and device for decomposing fluorine atom-containing polymer - Google Patents
Method for decomposing fluorine atom-containing polymer and device for decomposing fluorine atom-containing polymer Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims description 72
- 229910052731 fluorine Inorganic materials 0.000 title claims description 59
- 125000001153 fluoro group Chemical group F* 0.000 title claims description 44
- 238000000034 method Methods 0.000 title claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 29
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 24
- 239000011737 fluorine Substances 0.000 claims description 24
- 150000007514 bases Chemical class 0.000 claims description 19
- 238000000354 decomposition reaction Methods 0.000 claims description 17
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 8
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000000126 substance Substances 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000008346 aqueous phase Substances 0.000 description 15
- -1 fluoride ions Chemical class 0.000 description 15
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 238000004255 ion exchange chromatography Methods 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 229920002620 polyvinyl fluoride Polymers 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
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-containing polymer and an apparatus for decomposing a fluorine-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。特に、最近では環境保護の観点から太陽電池パネルを用いた発電が盛んに行われ、その規模も家屋の屋根に設置する小規模なものからメガソーラーと呼ばれる大規模なものまで幅広く存在するが、太陽電池パネルを構成する素子を保護するためのバックシート等の材料は、耐候性等の観点からフッ素原子を含んだポリマーが用いられている。これらを初めとして、フッ素原子含有ポリマーが幅広く用いられているのは周知の通りである。 Polymers containing fluorine atoms are valued for their properties such as chemical stability and high resistance to heat, and are used in a variety of fields, from physicochemical and medical equipment to various daily necessities. In particular, from the perspective of environmental protection, solar panels have recently become popular for generating electricity, and they come in a wide range of sizes, from small-scale systems installed on the roofs of houses to large-scale systems known as mega solar panels. Materials such as backsheets used to protect the elements that make up solar panels are made of polymers containing fluorine atoms, from the perspective of weather resistance. It is well known that fluorine-containing polymers are used in a wide range of applications, including these.
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。 On the other hand, these polymers, with their high chemical stability and heat resistance, tend to have problems with waste disposal. In other words, if these polymers are to be incinerated, not only will high temperature processing be necessary to break them down due to the presence of carbon-fluorine bonds, the strongest of all covalent bonds, but incineration will cause deterioration of the incinerator materials due to the hydrogen fluoride gas generated. For this reason, if these polymers are to be disposed of, they will need to be landfilled, but this is also problematic given the current situation where final waste disposal sites are under pressure. Therefore, a new waste disposal method for fluorine atom-containing polymers that is neither incinerated nor landfilled is required.
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。 In light of this background, for example, Non-Patent Document 1 proposes a treatment method in which a fluorine-containing polymer is brought into contact with subcritical water in the presence of hydrogen peroxide, thereby decomposing the polymer into carbon dioxide and fluoride ions. This treatment method not only makes it possible to mineralize a fluorine-containing polymer under relatively mild conditions, but also makes it possible to obtain calcium fluoride, which is a raw material for all fluorine-containing compounds, by reacting the fluoride ions produced by the treatment with calcium ions, making it an excellent method in terms of recycling resources.
また、特許文献１には、酸化剤である過マンガン酸塩の存在下で２００℃以上の亜臨界水中でフッ素原子含有ポリマーを処理することで、これを分解する方法が提案されている。この方法によれば、過酸化水素を酸化剤として亜臨界水でフッ素原子含有ポリマーを処理する場合に比べて、酸化剤の使用量を大幅に低減できるとされている。 Patent Document 1 also proposes a method for decomposing a fluorine atom-containing polymer by treating it in subcritical water at 200°C or higher in the presence of an oxidizing agent, permanganate. This method is said to enable a significant reduction in the amount of oxidizing agent used compared to treating a fluorine atom-containing polymer in subcritical water using hydrogen peroxide as an oxidizing agent.
本発明は、以上の状況に鑑みてなされたものであり、フッ素原子含有ポリマーの新しい分解方法を提供することを目的とする。 The present invention was made in consideration of the above circumstances, and aims to provide a new method for decomposing fluorine atom-containing polymers.
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、アルカリ金属水酸化物やアルカリ土類金属水酸化物のような塩基性化合物の存在下、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ることを見出し、本発明を完成するに至った。具体的には、本発明は、以下のようなものを提供する。 As a result of extensive research into solving the above problems, the present inventors discovered that a fluorine-containing polymer can be decomposed by contacting the fluorine-containing polymer to be decomposed with subcritical water at 200°C or higher in the presence of a basic compound such as an alkali metal hydroxide or an alkaline earth metal hydroxide, and thus completed the present invention. Specifically, the present invention provides the following:
（１）本発明は、アルカリ金属水酸化物及びアルカリ土類金属水酸化物からなる群より選択される少なくとも１種の塩基性化合物の存在下、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て上記ポリマーの分解物である黒色固体を生成させる工程を含み、この工程における上記塩基性化合物の濃度を０．５ｍｏｌ／Ｌ～６．０ｍｏｌ／Ｌとす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 provides a method for decomposing a fluorine-containing polymer, comprising a step of contacting a fluorine-containing polymer to be decomposed with subcritical water at 200° C. or higher in the presence of at least one basic compound selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides to generate a black solid, which is a decomposition product of the polymer, wherein the concentration of the basic compound in this step is 0.5 mol/L to 6.0 mol/L.
（２）上記亜臨界水の温度は、２５０℃以上であることが好ましい。 (2) The temperature of the subcritical water is preferably 250°C or higher.
（３）上記塩基性化合物は、水酸化ナトリウム及び／又は水酸化カリウムであることが好ましい。 (3) The basic compound is preferably sodium hydroxide and/or potassium hydroxide.
本発明によれば、フッ素原子含有ポリマーの新しい分解方法が提供される。 The present invention provides a new method for decomposing fluorine atom-containing polymers.
＜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、及びフッ素原子含有ポリマーの分解装置の一実施形態について説明する。なお本発明は、以下の実施態様及び実施形態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 and one embodiment of the device for decomposing a fluorine atom-containing polymer of the present invention will be described. Note that the present invention is not limited to the following embodiment and can be practiced by making 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、アルカリ金属水酸化物及びアルカリ土類金属水酸化物からなる群より選択される少なくとも１種の塩基性化合物の存在下、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含む。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-containing polymer of the present invention includes a step of contacting a fluorine-containing polymer to be decomposed with subcritical water at 200°C or higher in the presence of at least one basic compound selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides. The effects of the present invention can be obtained as long as this step is included in the scope of the present invention. Other steps include a pretreatment step in which the fluorine-containing polymer is finely chopped to increase the efficiency of the decomposition reaction, but such pretreatment is not essential. When performing pretreatment, it is desirable to reduce the particle size of the fluorine-containing polymer until it 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、耐熱性、耐候性等の特性が評価され、産業や医療等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（ＥＴＦＥ）、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリフッ化ビニル（ＰＶＦ）等を挙げることができる。 The fluorine-containing polymer to be decomposed in the present invention is a polymer containing fluorine atoms in the molecule, and if the molecule contains even one fluorine atom, it is the subject of decomposition in the present invention. Fluorine-containing polymers are valued for their high chemical resistance, heat resistance, weather resistance, and other properties, and are used in a variety of fields, including industry and medicine. On the other hand, these polymers tend to have problems with waste disposal, which is the flip side of their high chemical stability and high durability against heat. The present invention provides a method for chemically decomposing and treating these polymers that have become waste. Such fluorine-containing polymers may be homopolymers or copolymers, and examples of such polymers include ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), etc.
本発明では、塩基性化合物の存在下にて亜臨界水中でフッ素原子含有ポリマーを処理するが、このとき、塩基性化合物によりポリマー中からフッ化水素（ＨＦ）が引き抜かれることでポリマーの分解が生じると考えられる。このような機構によれば、ポリテトラフルオロエチレン（ＰＴＦＥ）のように、水素原子の存在しないポリマーでは本発明による分解は困難と考えられる。したがって、水素原子の存在しないポリマーは、本発明の適用除外とされることが好ましい。なお、ＥＴＦＥは、重合してポリマーを形成するときに、エチレンとテトラフルオロエチレンとが交互に重合することが知られており、必ずフッ素原子の隣に水素原子が存在することになる。したがって、本発明は、ＥＴＦＥにも好ましく適用可能である。 In the present invention, a fluorine-containing polymer is treated in subcritical water in the presence of a basic compound. At this time, it is believed that the basic compound extracts hydrogen fluoride (HF) from the polymer, causing the polymer to decompose. According to this mechanism, it is believed that decomposition by the present invention is difficult for polymers that do not contain hydrogen atoms, such as polytetrafluoroethylene (PTFE). Therefore, it is preferable that polymers that do not contain hydrogen atoms are excluded from the application of the present invention. It is known that ethylene and tetrafluoroethylene are polymerized alternately when ETFE is polymerized to form a polymer, and hydrogen atoms are always present next to fluorine atoms. Therefore, the present invention can also be preferably applied to ETFE.
また、本発明では、上記のように、ポリマーからＨＦが引き抜かれることにより分解を生じると考えられ、ポリマーからフッ素原子は取り除かれるものの、ポリマーが二酸化炭素まで完全に分解されるものではない。しかしながら、廃棄処理の際に問題となるフッ素原子をポリマーから取り除くことは実現されるので、本発明においては、このような二酸化炭素まで完全に分解されない分解であっても、ポリマーの分解として扱う。なお、ポリマー鎖中において水素原子とフッ素原子が取り除かれた箇所には二重結合を生じると考えられ、処理の完了したポリマーは、二重結合を有する元素状炭素、すなわち黒鉛のような化学構造を有するものになると考えられる。実際に、本発明の処理を受けたポリマーは、処理後に黒色を呈する固体となることが確認されており、こうした考えを支持している。このように元素状炭素まで分解されたポリマーは、容易に燃焼させることができ、最終的には二酸化炭素まで分解させることができる。 In addition, in the present invention, as described above, it is believed that decomposition occurs by the extraction of HF from the polymer, and although the fluorine atoms are removed from the polymer, the polymer is not completely decomposed to carbon dioxide. However, since it is possible to remove the fluorine atoms that are problematic during waste disposal from the polymer, in the present invention, even decomposition that does not completely decompose to carbon dioxide is treated as decomposition of the polymer. It is believed that double bonds are generated at the points in the polymer chain where hydrogen atoms and fluorine atoms are removed, and the polymer that has been treated is considered to have an elemental carbon with double bonds, that is, a chemical structure similar to graphite. In fact, it has been confirmed that the polymer that has been treated in the present invention becomes a black solid after treatment, which supports this idea. A polymer that has been decomposed to elemental carbon in this way can be easily burned and ultimately decomposed to carbon dioxide.
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２５０℃以上、より好ましくは３００℃以上の亜臨界水が用いられる。 Subcritical water is liquid water that is pressurized to a temperature range exceeding 100°C and lower than the critical temperature of 374°C. Subcritical water has different physical properties from water below 100°C. In particular, subcritical water in the range of 200°C to 300°C has a significantly reduced dielectric constant and exhibits almost the same lipid solubility as methanol or acetone at room temperature, and the ion product, which was 10 -14 mol/L at room temperature, becomes on the order of 10 -11 mol/L, and the concentration of hydrogen ions and hydroxide ions is 30 times higher than that of water at room temperature. For this reason, it is known that subcritical water, particularly at 200°C to 300°C, exhibits a different reactivity from water at room temperature. In the present invention, subcritical water at 200°C or higher is used, preferably subcritical water at 250°C or higher, more preferably subcritical water at 300°C or higher is 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 to prepare the subcritical water is not particularly limited, and any type of water can be used, such as tap water, ion-exchanged water, distilled water, or well water. However, from the viewpoint of suppressing side reactions caused by the influence of coexisting salts, etc., ion-exchanged water or distilled water is preferred. The amount of water used should be enough to fully immerse the fluorine atom-containing polymer to be treated, but care must be taken that if the amount of water introduced into the sealed container for pressurization is extremely small, it will all turn into water vapor after heating and will not become subcritical water.
本発明では、アルカリ金属水酸化物及びアルカリ土類金属水酸化物からなる群より選択される少なくとも１種の塩基性化合物が用いられる。既に述べたように、塩基性化合物は、フッ素原子含有ポリマーからＨＦを引き抜く反応を生じさせるために用いられる。 In the present invention, at least one basic compound selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides is used. As already mentioned, the basic compound is used to cause a reaction to abstract HF from the fluorine atom-containing polymer.
アルカリ金属水酸化物としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化セシウム等が挙げられ、これらの中でも、水酸化ナトリウムや水酸化カリウムが好ましく挙げられる。ここで、水酸化カリウムは、濃厚溶液において水酸化ナトリウムよりも活量が高く、塩基性が高いことが知られており、ＨＦの引き抜き反応では高い活性が見込まれる。実際に、本発明において、水酸化カリウムを用いてフッ素原子含有ポリマーの分解を行うと、水酸化ナトリウムを用いた場合よりも活性が高いことが確認されている。このような観点からは、水酸化カリウムが最も好ましいといえる。 Examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, etc., and among these, sodium hydroxide and potassium hydroxide are preferred. Here, potassium hydroxide is known to have a higher activity and higher basicity than sodium hydroxide in a concentrated solution, and is expected to have high activity in the HF abstraction reaction. In fact, it has been confirmed that when potassium hydroxide is used in the present invention to decompose a fluorine atom-containing polymer, the activity is higher than when sodium hydroxide is used. From this perspective, potassium hydroxide is the most preferred.
アルカリ土類金属水酸化物としては、水酸化カルシウム、水酸化バリウム等が挙げられる。 Examples of alkaline earth metal hydroxides include calcium hydroxide and barium hydroxide.
昇温して亜臨界水とする前の水中における塩基性化合物の濃度としては、０．５Ｍ～６．０Ｍ程度が挙げられる。なお、当業者にとって周知なように、単位の「Ｍ」はｍｏｌ／Ｌを意味する。昇温して亜臨界水とする前の水中における塩基性化合物の濃度として、より好ましくは１．０Ｍ～３．０Ｍが挙げられ、さらに好ましくは１．０Ｍ～２．０Ｍが挙げられる。 The concentration of the basic compound in the water before it is heated to turn it into subcritical water is, for example, about 0.5 M to 6.0 M. As is well known to those skilled in the art, the unit "M" means mol/L. The concentration of the basic compound in the water before it is heated to turn it into subcritical water is more preferably 1.0 M to 3.0 M, and even more preferably 1.0 M to 2.0 M.
次に、塩基性化合物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、塩基性化合物、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。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 of decomposing a fluorine atom-containing polymer by contacting it with subcritical water containing a basic compound will be described. Water, a basic compound, and the fluorine atom-containing polymer to be treated are added to a pressure vessel of a size according to the amount of the fluorine atom-containing polymer to be treated, and the inside of the pressure vessel is pressurized and sealed. To pressurize the inside of the pressure vessel, a gas may be enclosed. Examples of such gases include air, argon, and nitrogen. The degree of pressurization may 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、２５０℃以上であることが好ましく、３００℃以上であることがより好ましい。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 The pressure vessel that has undergone the above process is heated to initiate the decomposition reaction. The heating temperature is 200°C or higher, preferably 250°C or higher, and more preferably 300°C or higher. If the pressure vessel itself is equipped with a heating means, the heating means can be used to heat the vessel. If the pressure vessel itself does not have a heating means, the entire pressure vessel can be heated in an autoclave or oven. The reaction time can be around 6 to 24 hours.
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。 After the reaction is complete, the fluorine atoms contained in the fluorine-containing polymer are contained in the water in the form of fluoride ions. By reacting the fluoride ions with calcium ions, they can be converted into calcium fluoride, which is the raw material for all fluorine compounds. Therefore, by using the method of the present invention to treat waste fluorine-containing polymers, it becomes possible to make effective use of resources.
また、反応終了後の水中には、フッ化物イオンの他に、ＨＦを引き抜かれたあとのポリマー分解物が含まれている。既に述べたように、この分解物は、二重結合を備えた元素状炭素と考えられ、多くの場合黒色を呈する。これは固体なので容易に分離することができ、フッ素原子が除かれているので焼却処分するのも容易である。 In addition to fluoride ions, the water after the reaction also contains polymer decomposition products that remain after the HF has been extracted. As mentioned above, these decomposition products are thought to be elemental carbon with double bonds, and are often black in color. As they are solid, they can be easily separated, and as the fluorine atoms have been removed, they can also be easily disposed of by incineration.
＜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、アルカリ金属水酸化物及びアルカリ土類金属水酸化物からなる群より選択される少なくとも１種の塩基性化合物の存在下、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。
<Fluorine atom-containing polymer decomposition device>
The present invention also includes an apparatus capable of implementing the above-mentioned method for decomposing a fluorine atom-containing polymer of the present invention. The apparatus is characterized by comprising a reaction vessel for contacting a fluorine atom-containing polymer to be decomposed with subcritical water at 200° C. or higher in the presence of at least one basic compound selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides.
本発明の装置は、アルカリ金属水酸化物及びアルカリ土類金属水酸化物からなる群より選択される少なくとも１種の塩基性化合物を含む水と、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２５０℃以上であり、より好ましくは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 device of the present invention can introduce water containing at least one basic compound selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides, and a fluorine atom-containing polymer to be decomposed, into the inside of a pressure vessel, and can heat the inside of the vessel under pressure. The heating temperature is 200°C or higher, preferably 250°C or higher, and more preferably 300°C or higher. It is desirable to provide a stirring device for stirring the contents inside the pressure vessel. Other matters are as explained in the above-mentioned method for decomposing a fluorine atom-containing polymer, and therefore will not be explained 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。 The present invention will be explained in more detail below by showing examples, but the present invention is not limited to the following examples.
［ポリフッ化ビニリデン（ＰＶＤＦ）含有樹脂シートの亜臨界水を用いた分解反応］
（参考例１）
ＰＶＤＦを含む樹脂シート（燃焼イオンクロマトグラフィーで求めたフッ素原子含有率は３７質量％である。）３０．５ｍｇと、２００ｍＭ過マンガン酸カリウム水溶液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、２５０℃で６時間反応させた。反応時の圧力は、４．７ＭＰａである。なお、この樹脂シート３０．５ｍｇ中に含まれるフッ素原子物質量は、３０．５×１０－３×０．３７／１８．９９８＝５．９４×１０－４ｍｏｌ＝５９４μｍｏｌである。反応終了後、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、水相に生成したフッ化物イオン物質量は、５７０μｍｏｌ（収率９６％）だった。
[Decomposition reaction of polyvinylidene fluoride (PVDF)-containing resin sheet using subcritical water]
(Reference Example 1)
30.5 mg of a resin sheet containing PVDF (fluorine atom content determined by combustion ion chromatography is 37% by mass) and 10 mL of a 200 mM potassium permanganate aqueous solution were placed in a hot water reactor, pressurized to 0.5 MPa with argon gas, and reacted at 250° C. for 6 hours. The pressure during the reaction was 4.7 MPa. The amount of fluorine atom substance contained in 30.5 mg of this resin sheet was 30.5×10 −3 ×0.37/18.998=5.94×10 −4 mol=594 μmol. After the reaction was completed, the contents were cooled to room temperature, and the fluoride ions generated in the aqueous phase were quantified by ion chromatography. As a result, the amount of fluoride ion substance generated in the aqueous phase was 570 μmol (yield 96%).
（実施例１）
参考例１で用いたのと同じ樹脂シート２９．６ｍｇと、１．０Ｍ水酸化ナトリウム水溶液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、２５０℃で６時間反応させた。反応時の圧力は、４．５ＭＰａである。なお、この樹脂シート３０．５ｍｇ中に含まれるフッ素原子物質量は、５７７μｍｏｌである。反応終了後、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、水相に生成したフッ化物イオン物質量は、５６５μｍｏｌ（収率９８％）だった。
Example 1
29.6 mg of the same resin sheet as used in Reference Example 1 and 10 mL of 1.0 M sodium hydroxide aqueous solution were placed in a hot water reactor, pressurized to 0.5 MPa with argon gas, and reacted at 250° C. for 6 hours. The pressure during the reaction was 4.5 MPa. The amount of fluorine atom substance contained in 30.5 mg of this resin sheet was 577 μmol. After the reaction was completed, the contents were cooled to room temperature, and the fluoride ions generated in the aqueous phase were quantified by ion chromatography. As a result, the amount of fluoride ion substance generated in the aqueous phase was 565 μmol (yield 98%).
参考例１と実施例１とを比較すると、塩基性化合物を用いた本発明の方法は、酸化剤（過マンガン酸カリウム）を用いた方法（背景技術に記載した特許文献１記載の方法）と比べて、フッ化物イオン収率において遜色ない結果だった。 Comparing Reference Example 1 and Example 1, the method of the present invention using a basic compound had results comparable to the method using an oxidizing agent (potassium permanganate) (the method described in Patent Document 1 in the Background Art) in terms of fluoride ion yield.
［ＰＶＤＦ粉末の亜臨界水を用いた分解反応］
（実施例２）
試薬として市販されているＰＶＤＦ粉末（フッ素原子含有率：６０．７質量％）３０．０ｍｇと、１．０Ｍ水酸化ナトリウム水溶液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、２５０℃で６時間反応させた。反応時の圧力は、４．５ＭＰａである。なお、ＰＶＤＦ粉末３０．０ｍｇ中に含まれるフッ素原子物質量は、９５９μｍｏｌである。反応終了後、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、水相に生成したフッ化物イオン物質量は、８５８μｍｏｌ（収率８９％）だった。
[Decomposition reaction of PVDF powder using subcritical water]
Example 2
30.0 mg of PVDF powder (fluorine atom content: 60.7% by mass) commercially available as a reagent and 10 mL of 1.0 M sodium hydroxide aqueous solution were placed in a hot water reactor, pressurized to 0.5 MPa with argon gas, and reacted at 250° C. for 6 hours. The pressure during the reaction was 4.5 MPa. The amount of fluorine atom substance contained in 30.0 mg of PVDF powder was 959 μmol. After the reaction was completed, the contents were cooled to room temperature, and the fluoride ions generated in the aqueous phase were quantified by ion chromatography. As a result, the amount of fluoride ion substance generated in the aqueous phase was 858 μmol (yield 89%).
（実施例３）
１．０Ｍ水酸化ナトリウム水溶液に代えて、１．０Ｍ水酸化カリウム水溶液を用いたことを除いて、実施例２と同様の手順で実験を行った。その結果、水相に生成したフッ化物イオン物質量は、９３５μｍｏｌ（収率９７％）だった。
Example 3
Except for using a 1.0 M aqueous potassium hydroxide solution instead of the 1.0 M aqueous sodium hydroxide solution, an experiment was carried out in the same manner as in Example 2. As a result, the amount of fluoride ion substance produced in the aqueous phase was 935 μmol (yield 97%).
実施例２と実施例３とを比較すると、水酸化カリウム水溶液を用いた実施例３は、水酸化ナトリウム水溶液を用いた実施例２よりも収率が高いことがわかる。 Comparing Example 2 and Example 3, it can be seen that Example 3, which used an aqueous potassium hydroxide solution, had a higher yield than Example 2, which used an aqueous sodium hydroxide solution.
［エチレン－テトラフルオロエチレン共重合体（ＥＴＦＥ）の亜臨界水を用いた分解反応］
（実施例４）
試薬として市販されているＥＴＦＥビーズ（フッ素原子含有率：５４．６質量％）２９．６ｍｇと、１．０Ｍ水酸化ナトリウム水溶液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、２５０℃で６時間反応させた。反応時の圧力は、４．４ＭＰａである。なお、ＥＴＦＥビーズ２９．６ｍｇ中に含まれるフッ素原子物質量は、８５１μｍｏｌである。反応終了後、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、水相に生成したフッ化物イオン物質量は、１８０μｍｏｌ（収率２１％）だった。
[Decomposition reaction of ethylene-tetrafluoroethylene copolymer (ETFE) using subcritical water]
Example 4
29.6 mg of ETFE beads (fluorine atom content: 54.6 mass%) commercially available as a reagent and 10 mL of 1.0 M sodium hydroxide aqueous solution were placed in a hot water reactor, pressurized to 0.5 MPa with argon gas, and reacted at 250 ° C. for 6 hours. The pressure during the reaction was 4.4 MPa. The amount of fluorine atom substance contained in 29.6 mg of ETFE beads was 851 μmol. After the reaction was completed, the contents were cooled to room temperature, and the fluoride ions generated in the aqueous phase were quantified by ion chromatography. As a result, the amount of fluoride ion substance generated in the aqueous phase was 180 μmol (yield 21%).
（実施例５）
試薬として市販されているＥＴＦＥビーズ（フッ素原子含有率：５４．６質量％）３０．０ｍｇと、１．０Ｍ水酸化ナトリウム水溶液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、３００℃で６時間反応させた。反応時の圧力は、９．４ＭＰａである。なお、ＥＴＦＥビーズ３０．０ｍｇ中に含まれるフッ素原子物質量は、８６２μｍｏｌである。反応終了後、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、水相に生成したフッ化物イオン物質量は、８６８μｍｏｌ（収率１０１％）だった。
Example 5
30.0 mg of ETFE beads (fluorine atom content: 54.6% by mass) commercially available as a reagent and 10 mL of 1.0 M aqueous sodium hydroxide solution were placed in a hot water reactor, pressurized to 0.5 MPa with argon gas, and reacted at 300° C. for 6 hours. The pressure during the reaction was 9.4 MPa. The amount of fluorine atom substance contained in 30.0 mg of ETFE beads was 862 μmol. After the reaction was completed, the contents were cooled to room temperature, and the fluoride ions generated in the aqueous phase were quantified by ion chromatography. As a result, the amount of fluoride ion substance generated in the aqueous phase was 868 μmol (yield 101%).
実施例４と実施例５とを対比すると、分解対象がＥＴＦＥの場合、１．０Ｍ水酸化ナトリウム水溶液を用いて２５０℃で反応させた時の収率は２１％だったが、反応温度を３００℃に高めることで収率が大幅に改善されることがわかる。 Comparing Example 4 and Example 5, when the decomposition target was ETFE, the yield was 21% when reacted at 250°C using 1.0 M aqueous sodium hydroxide solution, but it can be seen that the yield was significantly improved by increasing the reaction temperature to 300°C.
［ポリフッ化ビニル（ＰＶＦ）含有樹脂シートの亜臨界水を用いた分解反応］
（実施例６）
ＰＶＦを含む樹脂シート（フッ素原子含有率：３１質量％）２９．６ｍｇと、１．０Ｍ水酸化ナトリウム水溶液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、２５０℃で６時間反応させた。反応時の圧力は、４．５ＭＰａである。なお、ＰＶＦ含有樹脂シート２９．６ｍｇ中に含まれるフッ素原子物質量は、４８３μｍｏｌである。反応終了後、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、水相に生成したフッ化物イオン物質量は、１４６μｍｏｌ（収率３０％）だった。
[Decomposition reaction of polyvinyl fluoride (PVF)-containing resin sheet using subcritical water]
Example 6
29.6 mg of a resin sheet containing PVF (fluorine atom content: 31% by mass) and 10 mL of a 1.0 M aqueous sodium hydroxide solution were placed in a hot water reactor, pressurized to 0.5 MPa with argon gas, and reacted at 250° C. for 6 hours. The pressure during the reaction was 4.5 MPa. The amount of fluorine atom substance contained in 29.6 mg of the PVF-containing resin sheet was 483 μmol. After the reaction was completed, the contents were cooled to room temperature, and the fluoride ions generated in the aqueous phase were quantified by ion chromatography. As a result, the amount of fluoride ion substance generated in the aqueous phase was 146 μmol (yield 30%).
（実施例７）
実施例６で用いたのと同じ樹脂シート２９．６ｍｇと、１．０Ｍ水酸化カリウム水溶液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、２５０℃で６時間反応させた。反応時の圧力は、４．５ＭＰａである。なお、ＰＶＦ含有樹脂シート２９．６ｍｇ中に含まれるフッ素原子物質量は、４８３μｍｏｌである。反応終了後、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、水相に生成したフッ化物イオン物質量は、２７４μｍｏｌ（収率５７％）だった。
(Example 7)
29.6 mg of the same resin sheet as used in Example 6 and 10 mL of 1.0 M potassium hydroxide aqueous solution were placed in a hot water reactor, pressurized to 0.5 MPa with argon gas, and reacted at 250° C. for 6 hours. The pressure during the reaction was 4.5 MPa. The amount of fluorine atom substance contained in 29.6 mg of the PVF-containing resin sheet was 483 μmol. After the reaction was completed, the contents were cooled to room temperature, and the fluoride ions generated in the aqueous phase were quantified by ion chromatography. As a result, the amount of fluoride ion substance generated in the aqueous phase was 274 μmol (yield 57%).
実施例６と実施例７とを比較すると、水酸化カリウムを用いた実施例７は、水酸化ナトリウム水溶液を用いた実施例６よりも収率が高いことがわかる。 Comparing Example 6 and Example 7, it can be seen that Example 7, which used potassium hydroxide, had a higher yield than Example 6, which used an aqueous solution of sodium hydroxide.
以上、各実施例にて示されるように、本発明によれば、フッ素原子含有ポリマーを良好に分解可能であることが理解できる。 As shown in the above examples, it can be seen that the present invention can effectively decompose fluorine-containing polymers.
Claims (3)
3. The method for decomposing a fluorine atom-containing polymer according to claim 1, wherein the basic compound is sodium hydroxide and/or potassium hydroxide.
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