JP4016645B2 - Method for extracting and purifying perfluoroalkanoic acid - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、低毒性で、化学的に安定である媒体を用いるペルフルオロアルカン酸の抽出方法及び精製方法に関する。
【０００２】
【従来の技術】
ペルフルオロアルカン酸のアンモニウム塩やＮａ塩等は、水性媒体中で含フッ素モノマーを重合し含フッ素ポリマーを製造する工程で、乳化剤として広く利用されている。近年、含フッ素ポリマーの製造量の増大にともない、使用されたペルフルオロアルカン酸を回収し再使用することが要請されている。含フッ素ポリマーの製造工程で広く使用されているペルフルオロアルカン酸（以下、ＰＦＡＡという。）は、ペルフルオロオクタン酸（以下、ＰＦＯＡという。）又はそのアンモニウム塩（以下、ＡＰＦＯという。）であり、含フッ素モノマーを重合し、含フッ素ポリマーを凝集した後の排水にＰＦＯＡ又はＡＰＦＯ（以下、まとめてＰＦＯＡ類という場合がある。）が含有される。ＡＰＦＯ類の濃度は、１重量％未満であり、このような低濃度の排水からＰＦＯＡ又はＡＰＦＯを回収する方法が種々提案されている。
【０００３】
例えば、アルミナ等の吸着剤又は陰イオン交換樹脂にＰＦＯＡ類を吸着させた後、溶出液を用いて回収する方法がある。この溶出液としては、アンモニア水、アルキルアミン水溶液、アルカリ金属の水酸化物の水溶液、鉱酸等が用いられる。しかし、アンモニア水やアルキルアミン水溶液では、吸着剤に残留するアンモニアやアルキルアミンの後処理が必要となる。また、アルカリ金属の水酸化物や鉱酸では、溶出されるＰＦＯＡ類の濃度が数質量％と低く、その後に濃縮が必要である。
【０００４】
特開昭５５−１０４６５１、特開２００１−６２３１３には、水と混和しうる有機溶剤を溶出液に添加する方法が開示されている。溶出液中のＰＦＯＡ類の濃度は１０質量％以上にできるが、使用された有機媒体は可燃性で、ＣＯＤの増加原因にもなる。したがって、有機媒体の後処理が必要で、このＰＦＯＡ回収方法は経済面や安全面で充分でない。
【０００５】
特開昭６１−２１５３４６、特開昭６１−２１５３４７、特開昭６１−２１５３４８、ＥＰ０１９４６８１には、ジクロロメタンやクロロホルム等の塩素化炭化水素を用いる、希薄な水溶液からＰＦＯＡ類を抽出・回収方法が開示されている。これらの塩素化炭化水素は不燃性、沸点及び揮発性に優れ、抽出操作及びその後の濃縮操作が容易である。しかし、これらの塩素化炭化水素へのＰＦＯＡの溶解度は低く、抽出に際して大量の溶剤を使用する必要がある。また、発ガン性の懸念物質であり、作業従事者の健康や衛生性上に問題がある。
【０００６】
特開平１−１１７８４０には、クロロホルムを用いて、種々のＡＰＦＯ構造異性体の混合物から直鎖ＡＰＦＯを分離するために、再結晶する方法が開示されているが、上記同様に作業従事者の健康への影響の点で問題がある。
【０００７】
【発明が解決しようとする課題】
本発明の目的は、ＰＦＡＡを含有する水性媒体と特定の含フッ素炭化水素とを接触させてＰＦＡＡを抽出することを特徴とするＰＦＡＡの抽出方法、及び抽出されたＰＦＡＡを再結晶する精製方法を提供することである。
【０００８】
【課題を解決するための手段】
本発明は、ＰＦＡＡを含有する水性媒体と特定の含フッ素炭化水素とを接触させてＰＦＡＡを抽出することを特徴とするＰＦＡＡの抽出方法を提供する。
また、本発明は、前記抽出方法で抽出されたＰＦＡＡを、特定の含フッ素炭化水素を媒体として再結晶することを特徴とするＰＦＡＡの精製方法を提供する。
【０００９】
【発明の実施の形態】
本発明におけるＰＦＡＡとしては、炭素数３〜１８のペルフルオロアルカン酸が好ましい。ＰＦＡＡは、直鎖状でも、分岐状でもよい。また、炭素鎖内にエーテル性の酸素原子を有してもよい。また、ω位の末端に水素原子を有してもよい。ＰＦＡＡとしては、炭素数６〜１２のペルフルオロアルカン酸がより好ましく、ＰＦＯＡが最も好ましい。
【００１０】
ＰＦＡＡの具体例としては、Ｃ２Ｆ５ＣＯＯＨ、ＣＦ３ＣＦ２ＣＦ２ＣＯＯＨ、ＣＦ３ＣＦ（ＣＦ３）ＣＯＯＨ、ＣＦ３（ＣＦ２）３ＣＯＯＨ、ＣＦ３ＣＦ（ＣＦ３）ＣＦ２ＣＯＯＨ、ＣＦ３ＣＦ２ＣＦ（ＣＦ３）ＣＯＯＨ、ＣＦ３（ＣＦ２）４ＣＯＯＨ、（ＣＦ３）３ＣＣＦ２ＣＦ２ＣＯＯＨ、ＣＦ３（ＣＦ２）５ＣＯＯＨ、ＣＦ３（ＣＦ２）３ＣＦ（Ｃ２Ｆ５）ＣＯＯＨ、ＣＦ３ＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＯＯＨ、ＣＦ３（ＣＦ２）４ＣＦ（ＣＦ３）ＣＯＯＨ、ＣＦ３（ＣＦ２）６ＣＯＯＨ、ＣＦ２Ｈ（ＣＦ２）６ＣＯＯＨ、ＣＦ３ＣＦ（ＣＦ３）（ＣＦ２）４ＣＯＯＨ、ＣＦ３ＣＦ（ＣＦ３）（ＣＦ２）５ＣＯＯＨ、ＣＦ３ＣＦ（ＣＦ３）（ＣＦ２）６ＣＯＯＨ、ＣＦ３（ＣＦ２）６ＣＦ（ＣＦ３）ＣＯＯＨ、ＣＦ３（ＣＦ２）７ＣＯＯＨ、ＣＦ２Ｈ（ＣＦ２）７ＣＯＯＨ、ＣＦ３（ＣＦ２）８ＣＯＯＨ、ＣＦ２Ｈ（ＣＦ２）８ＣＯＯＨ、ＣＦ３ＣＦ（ＣＦ３）（ＣＦ２）７ＣＯＯＨ、ＣＦ３（ＣＦ２）９ＣＯＯＨ、ＣＦ３（ＣＦ２）１０ＣＯＯＨ、ＣＦ３ＣＦ（ＣＦ３）（ＣＦ２）８ＣＯＯＨ、ＣＦ３（ＣＦ２）１１ＣＯＯＨ、ＣＦ３ＣＦ（ＣＦ３）（ＣＦ２）９ＣＯＯＨ、ＣＦ３（ＣＦ２）１２ＣＯＯＨ、ＣＦ３（ＣＦ２）１３ＣＯＯＨ、ＣＦ３（ＣＦ２）１４ＣＯＯＨ、ＣＦ３（ＣＦ２）１５ＣＯＯＨ、ＣＦ３（ＣＦ２）１６ＣＯＯＨ、ＣＦ３（ＣＦ２）２ＯＣＦ（ＣＦ３）ＣＯＯＨ、ＣＦ３（ＣＦ２）２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）ＣＯＯＨ、ＣＦ３（ＣＦ２）２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）ＣＯＯＨが挙げられる。また、それらの、アンモニウム塩、Ｌｉ塩、Ｎａ塩、Ｋ塩及びＣｓ塩も挙げられる。
【００１１】
より好ましくは、ＣＦ３（ＣＦ２）４ＣＯＯＨ、（ＣＦ３）３ＣＣＦ２ＣＦ２ＣＯＯＨ、ＣＦ３（ＣＦ２）５ＣＯＯＨ、ＣＦ３（ＣＦ２）３ＣＦ（Ｃ２Ｆ５）ＣＯＯＨ、ＣＦ３ＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＯＯＨ、ＣＦ３（ＣＦ２）４ＣＦ（ＣＦ３）ＣＯＯＨ、ＣＦ３（ＣＦ２）６ＣＯＯＨ、ＨＣＦ２（ＣＦ２）６ＣＯＯＨ、ＣＦ３ＣＦ（ＣＦ３）（ＣＦ２）４ＣＯＯＨ、ＣＦ３ＣＦ（ＣＦ３）（ＣＦ２）５ＣＯＯＨ、ＣＦ３ＣＦ（ＣＦ３）（ＣＦ２）６ＣＯＯＨ、ＣＦ３（ＣＦ２）６ＣＦ（ＣＦ３）ＣＯＯＨ、ＣＦ３（ＣＦ２）７ＣＯＯＨ、ＨＣＦ２（ＣＦ２）７ＣＯＯＨ、ＣＦ３（ＣＦ２）８ＣＯＯＨ、ＨＣＦ２（ＣＦ２）８ＣＯＯＨ、ＣＦ３ＣＦ（ＣＦ３）（ＣＦ２）７ＣＯＯＨ、ＣＦ３（ＣＦ２）９ＣＯＯＨ、ＣＦ３（ＣＦ２）１０ＣＯＯＨ、ＣＦ３ＣＦ（ＣＦ３）（ＣＦ２）８ＣＯＯＨ、ＣＦ３（ＣＦ２）２ＯＣＦ（ＣＦ３）ＣＯＯＨ、ＣＦ３（ＣＦ２）２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）ＣＯＯＨ、ＣＦ３（ＣＦ２）２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）ＣＯＯＨ及びそれらの、アンモニウム塩、Ｎａ塩及びＫ塩である。
【００１２】
最も好もしくは、ＣＦ３（ＣＦ２）６ＣＯＯＨ及びそのアンモニウム塩である。
【００１５】
本発明における含フッ素炭化水素は、Ｃ３ＨＣｌ２Ｆ５及びＣ３Ｈ３Ｆ５からなる群から選ばれる１種以上である。
【００１６】
Ｃ３ＨＣｌ２Ｆ５としては、ＣＦ３ＣＦ２ＣＨＣｌ２、ＣＣｌＦ２ＣＦ２ＣＨＣｌＦ、ＣＣｌＦ２ＣＨＦＣＣｌＦ２，ＣＦ３ＣＨＦＣＣｌ２Ｆ、ＣＦ３ＣＨＣｌＣＣｌＦ２が挙げられ、ＣＦ３ＣＦ２ＣＨＣｌ２、ＣＣｌＦ２ＣＦ２ＣＨＣｌＦが最も好ましい。
【００１７】
Ｃ３Ｈ３Ｆ５としては、ＣＦ３ＣＨ２ＣＨＦ２、ＣＦ３ＣＨＦＣＨ２Ｆ、ＣＨＦ２ＣＨＦＣＨＦ２が挙げられ、ＣＦ３ＣＨ２ＣＨＦ２が最も好ましい。
【００１８】
すなわち、含フッ素炭化水素としては、ＣＦ３ＣＦ２ＣＨＣｌ２、ＣＣｌＦ２ＣＦ２ＣＨＣｌＦ及びＣＦ３ＣＨ２ＣＨＦ２からなる群から選ばれる１種以上であることが最も好ましい。
【００１９】
Ｃ３ＨＣｌ２Ｆ５及びＣ３Ｈ３Ｆ５に対するＰＦＡＡの溶解度はジクロロメタン、クロロホルムよりも大きく、より少量の媒体でＰＦＡＡを抽出できる。また、Ｃ３ＨＣｌ２Ｆ５及びＣ３Ｈ３Ｆ５は不燃性であり、かつ従来の塩素化炭化水素に比べて低毒性であり、その沸点、蒸発潜熱が濃縮や回収操作に適するので好ましい。また、従来の塩素化炭化水素に比べて化学的に安定であり、多数回にわたり反復して濃縮及び回収に使用できる。さらに、ＰＦＡＡの抽出に従来の塩素化炭化水素を用いた場合水相に溶解する塩素化炭化水素の処理が必要になるのに対し、含フッ素炭化水素の水への溶解度は従来の塩素化炭化水素よりも低いのでこのような処理は不要である。また、抽出操作後に従来の塩素化炭化水素の場合よりも速やかに水相と含フッ素炭化水素相との間に明瞭な液・液界面が形成されるという利点がある。
【００２０】
本発明における抽出方法としては、ＰＦＡＡの塩を含有する水性媒体に無機酸を添加して、遊離させたＰＦＡＡを、含フッ素炭化水素と接触させて抽出することが好ましい。無機酸としては、ＨＣｌ、Ｈ２ＳＯ４、ＨＮＯ３が挙げられる。特に、ＨＣｌが好ましい。ＨＣｌは沸点が−８５℃の酸であり、抽出液に混入するＨＣｌは後の濃縮操作により容易に抽出液から除去できる。
【００２１】
本発明のＰＦＡＡの精製方法において、上記の抽出方法で抽出したＰＦＡＡを、前記含フッ素炭化水素を媒体として再結晶する。
【００２２】
本発明において、上記のＰＦＡＡの抽出又は精製操作には、従来用いられている装置、設備が利用できる。抽出装置としては回分式抽出装置、並流多回抽出装置、向流多段抽出装置、連続向流抽出装置が挙げられる。また、精製装置としてはタンク式晶析器、Ｓｗｅｎｓｏｎ−Ｗａｌｋｅｒ晶析器、Ｈｏｗａｒｄ晶析装置、蒸発式晶析装置が挙げられる。
【００２３】
抽出条件としては、溶剤の沸点未満の温度においてＰＦＡＡを含有する水性媒体と抽出溶剤とを混合する。通常水性媒体に対して２０〜１００質量％、好ましくは３０〜５０質量％の抽出溶剤を添加する。より大量の抽出溶剤を用いることによりＰＦＡＡの抽出率は向上するが濃縮等の工程での溶剤の処理量は増大する。混合に際しては撹拌、流動、震盪などにより水性媒体中に抽出媒体を分散させる。抽出媒体の液滴の直径が０．１ｍｍ以下となるように分散を行った場合１０分未満の混合時間で抽出が完了する。抽出完了後静置して水相と媒体相を分離させる。両相の界面が明瞭になるまで分離させることが要求されるがこれは通常１０分未満の静置時間で達成される。
【００２４】
再結晶による精製条件としては、晶析を行う温度において精製に供するＰＦＡＡの１０〜４０％、好ましくは１０〜２０％を溶解し得る量の媒体を加え、媒体が沸騰するまで加熱してＰＦＡＡを溶解させる。ＰＦＡＡが直鎖体と分岐鎖体の混合物である場合には、より多くの媒体を使用することにより得られるＰＦＡＡ中の直鎖体の比率は向上するが再結晶の収率は低下する。次いでこの溶液を０〜１０℃まで冷却し、析出したＰＦＡＡを回収する。
【００２５】
本発明の抽出方法は、炭素原子数３〜１８のＰＦＡＡの抽出に好ましく適用される。されに、炭素原子数３〜１８のペルフルオロアルカンスルホン酸及び／又はその塩、炭素原子数２のＰＦＡＡ及び／又はその塩、炭素原子数２のペルフルオロアルカンスルホン酸及び／又はその塩、にも好ましく適用できる。
【００２６】
【実施例】
本発明を以下実施例で詳細に説明するが本発明はこれらに限定されない。
なお、実施例中、ＡＰＦＯ類の定量には液体クロマトグラフ−質量スペクトル法を、直鎖体／分岐体比率の測定には誘導体化ガスクロマトグラフ−質量スペクトル法を用いた。
【００２７】
［実施例１］
ＰＦＯＡを０．１１質量％含有する、ｐＨ３．０の水溶液の１８０ｇに、抽出媒体としてＣＦ２ＣｌＣＦ２ＣＨＣｌＦ／ＣＦ３ＣＦ２ＣＨＣｌ２混合媒体（モル比５５／４５、旭硝子社製アサヒクリン２２５、以下、ＡＫ２２５という。）の８０ｇを加え、１０分間激しく振盪した。この液を静置して２相に分離した後の上層の水相には０．０２質量％のＰＦＯＡ、下層のＡＫ２２５相には０．２０質量％のＰＦＯＡが含有された。ＰＦＯＡ抽出率は、８０．０％と計算された。
【００２８】
［実施例２］
抽出媒体としてＡＫ２２５に代えて、ＣＨＦ２ＣＨ２ＣＦ３の８０ｇを用いる以外は実施例１と同様に操作した。上層の水相には０．０３質量％、下層のＣＨＦ２ＣＨ２ＣＦ３相には０．１７質量％のＰＦＯＡが含有された。ＰＦＯＡ抽出率は、６８．４％と計算された。
【００２９】
［比較例１］
抽出媒体としてＡＫ２２５に代えて、クロロホルムの８０ｇを用いる以外は実施例１と同様に操作した。上層の水相には０．０３質量％、下層のクロロホルム相には０．１９質量％のＰＦＯＡが含有された。ＰＦＯＡ抽出率は、７６．０％と計算された。
【００３０】
［比較例２］
抽出媒体としてＡＫ２２５に代えて、ジクロロメタンの８０ｇを用いる以外は実施例１と同様に操作した。上層の水相には０．０３質量％、下層のジクロロメタン相には０．１７質量％のＰＦＯＡが含有された。ＰＦＯＡ抽出率は、６８．２％と計算された。
【００３１】
［比較例３］
抽出媒体としてＡＫ２２５に代えて、ジエチルエーテルの８０ｇを用いる以外は実施例１と同様に操作した。下層の水相には０．０６質量％、上層のジエチルエーテル相には０．１１質量％のＰＦＯＡが含有された。ＰＦＯＡ抽出率は、４４．２％と計算された。
【００３２】
［実施例３］
ＡＰＦＯを２．０質量％含有する水溶液の２００ｇに３５．０質量％の濃塩酸の１．０ｇを加えた後ＡＫ２２５の８０ｇを加え、１０分間激しく振盪した。この液を静置して２相に分離した後の上層の水相には０．４１質量％、下層のＡＫ２２５相には３．８５質量％のＰＦＯＡが含有された。ＰＦＯＡ抽出率は、８０．３％と計算された。
【００３３】
［実施例４］
抽出媒体としてＡＫ２２５に代えて、ＣＨＦ２ＣＨ２ＣＦ３を用いる以外は実施例３と同様と同様に操作した。上層の水相には０．６３質量％、下層のＣＨＦ２ＣＨ２ＣＦ３相には３．３２質量％のＰＦＯＡが含有されていた。ＰＦＯＡ抽出率は、６８．５％と計算された。
【００３４】
［比較例４］
抽出媒体としてＡＫ２２５に代えて、クロロホルムを用いる以外は実施例３と同様と同様に操作した。上層の水相には０．５６質量％、下層のクロロホルム相には１．０３質量％のＰＦＯＡが含有されていた。二相の界面付近にはＰＦＯＡの沈殿が認められ、その質量は２．０１ｇであった。ＰＦＯＡ抽出率は、２０．８％と計算された。
【００３５】
［実施例５］
直鎖体／分岐体のモル比が８４．６／１５．４であるＡＰＦＯを２．０質量％含有する水溶液の２０００ｇに３５．０質量％の濃塩酸の１０．０ｇを加えた後、ＡＫ２２５の８００ｇを加え、１０分間激しく振盪した。この液を静置して２相に分離した後の上層の水相には０．４０質量％、下層のＡＫ２２５相には３．８６質量％のＰＦＯＡが含有された。ＰＦＯＡの抽出率は７７．２％と計算された。
【００３６】
このＡＫ２２５相を分離し、絶対圧０．０３ＭＰａの減圧下でＡＫ２２５を留去し、得られた固体にＡＫ２２５の１００ｇを加えた。ついで、ＡＫ２２５が沸騰するまで加熱した後、ＡＫ２２５溶液を１０℃まで冷却した。２３．１ｇのＰＦＯＡが固体として析出した。その直鎖体／分岐体のモル比は９９．８／０．２であった。
【００３７】
［実施例６］
ＡＫ２２５に代えて、ＣＨＦ２ＣＨ２ＣＦ３を用いる以外は実施例５と同様に操作した。上層の水相には０．６４質量％、下層のＣＨＦ２ＣＨ２ＣＦ３相には３．３１質量％のＰＦＯＡが含有された。ＰＦＯＡの抽出率は６６．２％と計算された。
【００３８】
このＣＨＦ２ＣＨ２ＣＦ３相を分離し、絶対圧０．０８ＭＰａの減圧下でＣＨＦ２ＣＨ２ＣＦ３を留去し、得られた固体にＣＨＦ２ＣＨ２ＣＦ３の１１０ｇを加えた。ついで、ＣＨＦ２ＣＨ２ＣＦ３が沸騰するまで加熱した後、ＣＨＦ２ＣＨ２ＣＦ３溶液を０℃まで冷却した。２１．２ｇのＰＦＯＡが固体として析出した。その直鎖体／分岐体のモル比は９９．９／０．１であった。
【００３９】
［比較例５］
直鎖体／分岐体のモル比が８４．６／１５．４であるＡＰＦＯを２．０質量％含有する水溶液の２０００ｇに３５．０質量％の濃塩酸の１０．０ｇを加えた後、ＡＫ２２５の８００ｇを加え、１０分間激しく振盪した。この液を静置して２相に分離した後の上層の水相には０．４１質量％、下層のＡＫ２２５相には３．８３質量％のＰＦＯＡが含有された。ＰＦＯＡの抽出率は７９．８％と計算された。
【００４０】
このＡＫ２２５相を分離し、絶対圧０．０３ＭＰａの減圧下でＡＫ２２５を留去し、得られた固体にクロロホルムの９６０ｇを加えた。ついで、クロロホルムが沸騰するまで加熱した後、クロロホルム溶液を１０℃まで冷却した。２４．７ｇのＰＦＯＡが固体として析出した。その直鎖体／分岐体のモル比は９９．８／０．２であった。
【００４１】
［実施例７］
ＡＰＦＯを乳化剤として使用して得たＰＴＦＥの水性分散液からＰＴＦＥを凝集分離した後の凝集排水には、ＰＦＯＡが０．０５質量％含有された。該排水の１８０ｇに塩酸を加えｐＨ３．０とした後、抽出媒体としてＡＫ２２５の８０ｇを加え、１０分間激しく振盪した。ついで、分散していた少量のＰＴＦＥが析出したので、ろ過で除去した後、ろ液を静置したところ、ろ液が２相に分離した。上層の水相には０．０１５質量％のＰＦＯＡが、下層のＡＫ２２５相には０．０７９質量％のＰＦＯＡが、含有された。ＰＦＯＡ抽出率は、７０．１％と計算された。
【００４２】
【発明の効果】
本発明の抽出方法及び精製方法によれば、従来の塩素化炭化水素に比べて低毒性で、化学的に安定である含フッ素炭化水素媒体を用いるので、多数回にわたり反復して濃縮、回収、再結晶操作に使用できる。さらに、含フッ素炭化水素は水相にほとんど溶解しないので水相の後処理が不要である。また、抽出操作後に速やかに水相と含フッ素炭化水素相とが分離する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for extracting and purifying perfluoroalkanoic acid using a low-toxic and chemically stable medium.
[0002]
[Prior art]
Ammonium salts, Na salts, and the like of perfluoroalkanoic acid are widely used as emulsifiers in the step of producing a fluorine-containing polymer by polymerizing a fluorine-containing monomer in an aqueous medium. In recent years, it has been demanded to recover and reuse the used perfluoroalkanoic acid as the production amount of the fluoropolymer increases. Perfluoroalkanoic acid (hereinafter referred to as PFAA) widely used in the production process of a fluorine-containing polymer is perfluorooctanoic acid (hereinafter referred to as PFOA) or an ammonium salt thereof (hereinafter referred to as APFO). PFOA or APFO (hereinafter sometimes collectively referred to as PFOAs) is contained in the waste water after the monomers are polymerized and the fluorine-containing polymer is aggregated. The concentration of APFOs is less than 1% by weight, and various methods for recovering PFOA or APFO from such low-concentration wastewater have been proposed.
[0003]
For example, there is a method in which PFOAs are adsorbed on an adsorbent such as alumina or an anion exchange resin and then recovered using an eluate. As the eluent, ammonia water, an aqueous alkylamine solution, an aqueous solution of an alkali metal hydroxide, a mineral acid, or the like is used. However, ammonia water or an alkylamine aqueous solution requires post-treatment of ammonia or alkylamine remaining in the adsorbent. Further, in the case of alkali metal hydroxides and mineral acids, the concentration of eluted PFOAs is as low as several mass%, and it is necessary to concentrate thereafter.
[0004]
JP-A-55-104651 and JP-A-2001-62313 disclose a method of adding an organic solvent miscible with water to the eluate. The concentration of PFOAs in the eluate can be increased to 10% by mass or more, but the organic medium used is flammable and causes an increase in COD. Accordingly, post-treatment of the organic medium is necessary, and this PFOA recovery method is not sufficient in terms of economy and safety.
[0005]
JP-A-61-215346, JP-A-61-215347, JP-A-61-215348, and EP0194681 disclose a method for extracting and recovering PFOAs from dilute aqueous solutions using chlorinated hydrocarbons such as dichloromethane and chloroform. Has been. These chlorinated hydrocarbons are excellent in nonflammability, boiling point and volatility, and can be easily extracted and subsequently concentrated. However, the solubility of PFOA in these chlorinated hydrocarbons is low, and it is necessary to use a large amount of solvent for extraction. In addition, it is a carcinogenic substance and has problems in the health and hygiene of workers.
[0006]
Japanese Laid-Open Patent Publication No. 1-1117840 discloses a method of recrystallization in order to separate linear APFO from a mixture of various APFO structural isomers using chloroform. There is a problem in terms of impact.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for extracting PFAA characterized by bringing PFAA into contact with an aqueous medium containing PFAA and a specific fluorinated hydrocarbon, and a purification method for recrystallizing the extracted PFAA. Is to provide.
[0008]
[Means for Solving the Problems]
The present invention provides a method for extracting PFAA, wherein PFAA is extracted by bringing an aqueous medium containing PFAA into contact with a specific fluorine-containing hydrocarbon.
The present invention also provides a method for purifying PFAA, wherein the PFAA extracted by the extraction method is recrystallized using a specific fluorine-containing hydrocarbon as a medium.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
As PFAA in this invention, C3-C18 perfluoroalkanoic acid is preferable. PFAA may be linear or branched. Moreover, you may have an etheric oxygen atom in a carbon chain. Moreover, you may have a hydrogen atom in the terminal of omega position. As PFAA, a C6-C12 perfluoroalkanoic acid is more preferable, and PFOA is the most preferable.
[0010]
Specific examples of PFAA include C 2 F 5 COOH, CF 3 CF 2 CF 2 COOH, CF 3 CF (CF 3 ) COOH, CF 3 (CF 2 ) 3 COOH, CF 3 CF (CF 3 ) CF 2 COOH, CF 3 CF 2 CF (CF 3 ) COOH, CF 3 (CF 2 ) 4 COOH, (CF 3 ) 3 CCF 2 CF 2 COOH, CF 3 (CF 2 ) 5 COOH, CF 3 (CF 2 ) 3 CF (C 2 F 5) COOH, CF 3 CF (CF 3) CF 2 CF 2 CF 2 CF 2 COOH, CF 3 (CF 2) 4 CF (CF 3) COOH, CF 3 (CF 2) 6 COOH, CF 2 H ( CF 2 ) 6 COOH, CF 3 CF (CF 3 ) (CF 2 ) 4 COOH, CF 3 CF (CF 3 ) (CF 2 ) 5 COOH, CF 3 CF (CF 3) (CF 2) 6 COOH , CF 3 (CF 2) 6 CF (CF 3) COOH, CF 3 (CF 2) 7 COOH, CF 2 H (CF 2) 7 COOH, CF 3 (CF 2) 8 COOH , CF 2 H (CF 2 ) 8 COOH, CF 3 CF (CF 3 ) (CF 2 ) 7 COOH, CF 3 (CF 2 ) 9 COOH, CF 3 (CF 2 ) 10 COOH, CF 3 CF (CF 3 ) (CF 2 ) 8 COOH, CF 3 (CF 2 ) 11 COOH, CF 3 CF (CF 3 ) (CF 2 ) 9 COOH, CF 3 (CF 2 ) 12 COOH, CF 3 (CF 2 ) 13 COOH, CF 3 (CF 2 ) 14 COOH, CF 3 (CF 2 ) 15 COOH, CF 3 (CF 2 ) 16 COOH, CF 3 (CF 2 ) 2 OCF (CF 3 ) COO H, CF 3 (CF 2) 2 OCF (CF 3) CF 2 OCF (CF 3) COOH, CF 3 (CF 2) 2 OCF (CF 3) CF 2 OCF (CF 3) CF 2 OCF (CF 3) COOH Is mentioned. Moreover, those ammonium salt, Li salt, Na salt, K salt, and Cs salt are also mentioned.
[0011]
More preferably, CF 3 (CF 2 ) 4 COOH, (CF 3 ) 3 CCF 2 CF 2 COOH, CF 3 (CF 2 ) 5 COOH, CF 3 (CF 2 ) 3 CF (C 2 F 5 ) COOH, CF 3 CF (CF 3 ) CF 2 CF 2 CF 2 CF 2 COOH, CF 3 (CF 2 ) 4 CF (CF 3 ) COOH, CF 3 (CF 2 ) 6 COOH, HCF 2 (CF 2 ) 6 COOH, CF 3 CF (CF 3 ) (CF 2 ) 4 COOH, CF 3 CF (CF 3 ) (CF 2 ) 5 COOH, CF 3 CF (CF 3 ) (CF 2 ) 6 COOH, CF 3 (CF 2 ) 6 CF (CF 3) COOH, CF 3 (CF 2) 7 COOH, HCF 2 (CF 2) 7 COOH, CF 3 (CF 2) 8 COOH, HCF 2 (CF 2) 8 COOH , CF 3 CF (CF 3 ) (CF 2 ) 7 COOH, CF 3 (CF 2 ) 9 COOH, CF 3 (CF 2 ) 10 COOH, CF 3 CF (CF 3 ) (CF 2 ) 8 COOH, CF 3 ( CF 2 ) 2 OCF (CF 3 ) COOH, CF 3 (CF 2 ) 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) COOH, CF 3 (CF 2 ) 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) COOH and their ammonium, Na and K salts.
[0012]
Most preferred is CF 3 (CF 2 ) 6 COOH and its ammonium salt.
[0015]
Fluorinated hydrocarbon in the present invention, Ru der least one member selected from the group consisting of C 3 HCl 2 F 5 and C 3 H 3 F 5.
[0016]
C 3 The HCl 2 F 5, CF 3 CF 2 CHCl 2, CClF 2 CF 2 CHClF, CClF 2 CHFCClF 2, CF 3 CHFCCl 2 F, CF 3 CHClCClF 2 can be mentioned, CF 3 CF 2 CHCl 2, CClF 2 Most preferred is CF 2 CHClF.
[0017]
Examples of C 3 H 3 F 5 include CF 3 CH 2 CHF 2 , CF 3 CHFCH 2 F, and CHF 2 CHFCHF 2 , and CF 3 CH 2 CHF 2 is most preferable.
[0018]
That is, the fluorine-containing hydrocarbon is most preferably at least one selected from the group consisting of CF 3 CF 2 CHCl 2 , CClF 2 CF 2 CHClF, and CF 3 CH 2 CHF 2 .
[0019]
The solubility of PFAA in C 3 HCl 2 F 5 and C 3 H 3 F 5 is greater than that in dichloromethane and chloroform, and PFAA can be extracted with a smaller amount of medium. C 3 HCl 2 F 5 and C 3 H 3 F 5 are nonflammable and are less toxic than conventional chlorinated hydrocarbons, and their boiling point and latent heat of vaporization are suitable for concentration and recovery operations. . In addition, it is chemically stable compared to conventional chlorinated hydrocarbons, and can be used repeatedly for concentration and recovery many times. Furthermore, when conventional chlorinated hydrocarbons are used for extraction of PFAA, treatment of chlorinated hydrocarbons dissolved in the aqueous phase is required, whereas the solubility of fluorine-containing hydrocarbons in water is the same as conventional chlorinated carbonization. Such treatment is unnecessary because it is lower than hydrogen. Further, there is an advantage that a clear liquid / liquid interface is formed between the aqueous phase and the fluorinated hydrocarbon phase more rapidly than in the case of the conventional chlorinated hydrocarbon after the extraction operation.
[0020]
As the extraction method in the present invention, it is preferable to extract the PFAA released by adding an inorganic acid to an aqueous medium containing a salt of PFAA and then contacting with the fluorinated hydrocarbon. Examples of inorganic acids include HCl, H 2 SO 4 , and HNO 3 . In particular, HCl is preferred. HCl is an acid having a boiling point of −85 ° C., and HCl mixed in the extract can be easily removed from the extract by a subsequent concentration operation.
[0021]
In the method for purifying PFAA of the present invention, PFAA extracted by the above extraction method is recrystallized using the fluorinated hydrocarbon as a medium.
[0022]
In the present invention, conventionally used apparatus and equipment can be used for the above-described extraction or purification operation of PFAA. Examples of the extraction device include a batch type extraction device, a cocurrent multiple extraction device, a countercurrent multistage extraction device, and a continuous countercurrent extraction device. Examples of the refining device include a tank crystallizer, a Swenson-Walker crystallizer, a Howard crystallizer, and an evaporation crystallizer.
[0023]
As extraction conditions, an aqueous medium containing PFAA and the extraction solvent are mixed at a temperature lower than the boiling point of the solvent. Usually, 20 to 100% by mass, preferably 30 to 50% by mass of an extraction solvent is added to the aqueous medium. By using a larger amount of extraction solvent, the extraction rate of PFAA is improved, but the amount of solvent treated in the steps such as concentration is increased. During mixing, the extraction medium is dispersed in the aqueous medium by stirring, fluidization, shaking, or the like. When the dispersion is performed so that the diameter of the droplet of the extraction medium is 0.1 mm or less, the extraction is completed in a mixing time of less than 10 minutes. Allow to stand after extraction to separate the aqueous and media phases. Separation is required until the interface between the two phases is clear, which is usually achieved with a standing time of less than 10 minutes.
[0024]
As the purification conditions by recrystallization, an amount of a medium capable of dissolving 10 to 40%, preferably 10 to 20%, of PFAA used for purification is added at a temperature at which crystallization is performed, and the PFAA is heated until the medium boils. Dissolve. When PFAA is a mixture of a linear chain and a branched chain, the ratio of the linear chain in PFAA obtained by using more media improves, but the recrystallization yield decreases. The solution is then cooled to 0-10 ° C. and the precipitated PFAA is recovered.
[0025]
The extraction method of the present invention is preferably applied to the extraction of PFAA having 3 to 18 carbon atoms. In addition, it is also preferable for C 3-18 perfluoroalkanesulfonic acid and / or salt thereof, PFAA of carbon number 2 and / or salt thereof, C 2 perfluoroalkanesulfonic acid and / or salt thereof. Applicable.
[0026]
【Example】
The present invention will be described in detail in the following examples, but the present invention is not limited thereto.
In Examples, liquid chromatography-mass spectrometry was used for quantification of APFOs, and derivatization gas chromatography-mass spectrometry was used for measurement of the linear / branched body ratio.
[0027]
[Example 1]
180 g of an aqueous solution containing 0.11% by mass of PFOA and having a pH of 3.0 is mixed with a CF 2 ClCF 2 CHClF / CF 3 CF 2 CHCl 2 mixed medium (molar ratio 55/45, Asahi Clin 225 manufactured by Asahi Glass Co., Ltd.). Hereinafter, 80 g of AK225) was added and shaken vigorously for 10 minutes. After the liquid was allowed to stand and separated into two phases, the upper aqueous phase contained 0.02% by mass of PFOA, and the lower AK225 phase contained 0.20% by mass of PFOA. The PFOA extraction rate was calculated as 80.0%.
[0028]
[Example 2]
The same operation as in Example 1 was performed except that 80 g of CHF 2 CH 2 CF 3 was used instead of AK225 as the extraction medium. The upper aqueous phase contained 0.03% by mass, and the lower CHF 2 CH 2 CF 3 phase contained 0.17% by mass of PFOA. The PFOA extraction rate was calculated to be 68.4%.
[0029]
[Comparative Example 1]
The same operation as in Example 1 was performed except that 80 g of chloroform was used instead of AK225 as the extraction medium. The upper aqueous phase contained 0.03% by mass, and the lower chloroform phase contained 0.19% by mass of PFOA. The PFOA extraction rate was calculated to be 76.0%.
[0030]
[Comparative Example 2]
The same operation as in Example 1 was performed except that 80 g of dichloromethane was used instead of AK225 as the extraction medium. The upper aqueous phase contained 0.03% by mass, and the lower dichloromethane phase contained 0.17% by mass of PFOA. The PFOA extraction rate was calculated as 68.2%.
[0031]
[Comparative Example 3]
The same operation as in Example 1 was performed except that 80 g of diethyl ether was used instead of AK225 as the extraction medium. The lower aqueous phase contained 0.06% by mass, and the upper diethyl ether phase contained 0.11% by mass of PFOA. The PFOA extraction rate was calculated to be 44.2%.
[0032]
[Example 3]
To 200 g of an aqueous solution containing 2.0% by mass of APFO, 1.0 g of 35.0% by mass concentrated hydrochloric acid was added, and then 80 g of AK225 was added and shaken vigorously for 10 minutes. This liquid was allowed to stand and separated into two phases. The upper aqueous phase contained 0.41% by mass, and the lower AK225 phase contained 3.85% by mass of PFOA. The PFOA extraction rate was calculated as 80.3%.
[0033]
[Example 4]
The same operation as in Example 3 was performed except that CHF 2 CH 2 CF 3 was used instead of AK225 as the extraction medium. The upper aqueous phase contained 0.63% by mass, and the lower CHF 2 CH 2 CF 3 phase contained 3.32% by mass of PFOA. The PFOA extraction rate was calculated to be 68.5%.
[0034]
[Comparative Example 4]
The same operation as in Example 3 was performed except that chloroform was used instead of AK225 as the extraction medium. The upper aqueous phase contained 0.56% by mass and the lower chloroform phase contained 1.03% by mass of PFOA. Precipitation of PFOA was observed near the two-phase interface, and its mass was 2.01 g. The PFOA extraction rate was calculated as 20.8%.
[0035]
[Example 5]
After adding 10.0 g of 35.0 mass% concentrated hydrochloric acid to 2000 g of an aqueous solution containing 2.0 mass% of APFO having a linear / branched molar ratio of 84.6 / 15.4, AK225 Was added and shaken vigorously for 10 minutes. This liquid was allowed to stand and separated into two phases. The upper aqueous phase contained 0.40% by mass, and the lower AK225 phase contained 3.86% by mass of PFOA. The extraction rate of PFOA was calculated as 77.2%.
[0036]
This AK225 phase was separated, AK225 was distilled off under a reduced pressure of 0.03 MPa in absolute pressure, and 100 g of AK225 was added to the obtained solid. Subsequently, after heating until AK225 boiled, the AK225 solution was cooled to 10 degreeC. 23.1 g of PFOA precipitated as a solid. The linear / branched molar ratio was 99.8 / 0.2.
[0037]
[Example 6]
The same operation as in Example 5 was performed except that CHF 2 CH 2 CF 3 was used instead of AK225. The upper aqueous phase contained 0.64% by mass, and the lower CHF 2 CH 2 CF 3 phase contained 3.31% by mass of PFOA. The extraction rate of PFOA was calculated to be 66.2%.
[0038]
This CHF 2 CH 2 CF 3 phase was separated, CHF 2 CH 2 CF 3 was distilled off under a reduced pressure of 0.08 MPa in absolute pressure, and 110 g of CHF 2 CH 2 CF 3 was added to the obtained solid. Then, after heating to CHF 2 CH 2 CF 3 boils was cooled CHF 2 CH 2 CF 3 solution until 0 ° C.. 21.2 g of PFOA precipitated as a solid. The linear / branched molar ratio was 99.9 / 0.1.
[0039]
[Comparative Example 5]
After adding 10.0 g of 35.0 mass% concentrated hydrochloric acid to 2000 g of an aqueous solution containing 2.0 mass% of APFO having a linear / branched molar ratio of 84.6 / 15.4, AK225 Was added and shaken vigorously for 10 minutes. This liquid was allowed to stand and separated into two phases. The upper aqueous phase contained 0.41% by mass, and the lower AK225 phase contained 3.83% by mass of PFOA. The extraction rate of PFOA was calculated to be 79.8%.
[0040]
This AK225 phase was separated, AK225 was distilled off under a reduced pressure of 0.03 MPa in absolute pressure, and 960 g of chloroform was added to the obtained solid. Subsequently, after heating until chloroform boiled, the chloroform solution was cooled to 10 degreeC. 24.7 g of PFOA precipitated as a solid. The linear / branched molar ratio was 99.8 / 0.2.
[0041]
[Example 7]
The aggregated effluent after coagulating and separating PTFE from the aqueous PTFE dispersion obtained by using APFO as an emulsifier contained 0.05 mass% of PFOA. After adding hydrochloric acid to 180 g of the waste water to adjust the pH to 3.0, 80 g of AK225 was added as an extraction medium and shaken vigorously for 10 minutes. Subsequently, since a small amount of PTFE that had been dispersed was deposited, the filtrate was allowed to stand after removing by filtration, and the filtrate separated into two phases. The upper aqueous phase contained 0.015% by mass of PFOA, and the lower AK225 phase contained 0.079% by mass of PFOA. The PFOA extraction rate was calculated to be 70.1%.
[0042]
【The invention's effect】
According to the extraction method and the purification method of the present invention, since a fluorine-containing hydrocarbon medium that is less toxic and chemically stable than conventional chlorinated hydrocarbons is used, it is repeatedly concentrated and recovered many times. Can be used for recrystallization operations. Furthermore, since the fluorine-containing hydrocarbon hardly dissolves in the aqueous phase, no post-treatment of the aqueous phase is necessary. Further, the aqueous phase and the fluorinated hydrocarbon phase are separated immediately after the extraction operation.
Claims (4)
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| CN100381366C (en) * | 2002-06-19 | 2008-04-16 | 笹仓机械工程有限公司 | Method for recovering fluorine-containing emulsifier |
| RU2388537C2 (en) * | 2005-10-14 | 2010-05-10 | Асахи Гласс Компани, Лимитед | Method of regenerating basic ion exchange resin |
| CN101792383B (en) * | 2010-03-12 | 2012-08-29 | 浙江大学 | Method for extracting low concentration perfluorooctanoic acid from fatty substances |
| CN112028765B (en) * | 2020-08-31 | 2022-12-13 | 上海沃凯生物技术有限公司 | Separation method of mixture of linear perfluorooctanoic acid and branched perfluorooctanoic acid |
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