JP6911757B2 - 流体分離膜、流体分離膜モジュールおよび多孔質炭素繊維 - Google Patents
流体分離膜、流体分離膜モジュールおよび多孔質炭素繊維 Download PDFInfo
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- JP6911757B2 JP6911757B2 JP2017505878A JP2017505878A JP6911757B2 JP 6911757 B2 JP6911757 B2 JP 6911757B2 JP 2017505878 A JP2017505878 A JP 2017505878A JP 2017505878 A JP2017505878 A JP 2017505878A JP 6911757 B2 JP6911757 B2 JP 6911757B2
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Description
<1>共連続多孔構造を有する多孔質炭素繊維の表面に、有機高分子層が形成されてなる流体分離膜。
<2>前記多孔質炭素繊維の全体に前記共連続多孔構造を有する、<1>に記載の流体分離膜。
<3>水銀圧入法により測定される前記多孔質炭素繊維の全体の平均細孔直径が30〜5,000nmである、<1>または<2>に記載の流体分離膜。
<4>走査型電子顕微鏡による表面観察によって測定される前記多孔質炭素繊維の表面の平均細孔直径が2〜500nmである、<1>〜<3>のいずれか1つに記載の流体分離膜。
<5>前記共連続多孔構造の構造周期が10〜10,000nmである、<1>〜<4>のいずれか1つに記載の流体分離膜。
<6>前記多孔質炭素繊維のX線散乱の強度ピークの半値幅が5°以下である、<1>〜<5>のいずれか1つに記載の流体分離膜。
<7>前記有機高分子層が、芳香族ポリイミド、酢酸セルロース、ポリスルホン、芳香族ポリアミド、ポリエーテルイミド、ポリエーテルスルホン、ポリアクリロニトリル、ポリフェニレンスルフィド、ポリエーテルエーテルケトン、ポリテトラフルオロエチレン、ポリフッ化ビニリデンおよびこれらの誘導体からなる群より選択される1種または2種以上の有機高分子を含む層である、<1>〜<6>のいずれか1つに記載の流体分離膜。
<8>前記有機高分子層が、芳香族ポリイミド、芳香族ポリアミドおよびこれらの誘導体からなる群より選択される1種または2種以上の有機高分子を含む層である、<1>〜<7>のいずれか1つに記載の流体分離膜。
<9>ケーシング内に<1>〜<8>のいずれか1つに記載の流体分離膜を複数本収容してなる流体分離膜モジュール。
<10>全体に共連続多孔構造を有する多孔質炭素繊維。
<11>水銀圧入法により測定される全体の平均細孔直径が30nm〜5,000nmである、<10>に記載の多孔質炭素繊維。
<12>走査型電子顕微鏡による表面観察によって測定される表面の平均細孔直径が2〜500nmである、<10>または<11>に記載の多孔質炭素繊維。
<13>前記共連続多孔構造の構造周期が10〜10,000nmである、<10>〜<12>のいずれか1つに記載の多孔質炭素繊維。
<14>X線散乱の強度ピークの半値幅が5°以下である、<10>〜<13>のいずれか1つに記載の多孔質炭素繊維。
〔多孔質炭素繊維〕
本発明の流体分離膜(以下、単に「流体分離膜」または「分離膜」ということがある。)は、共連続多孔構造を有する多孔質炭素繊維を基材とする。
ただし、構造周期が大きくて小角での散乱が観測できない場合がある。その場合はX線コンピュータ断層撮影(X線CT)によって構造周期を得る。具体的には、X線CTによって撮影した三次元画像をフーリエ変換した後に、その二次元スペクトルの円環平均を取り、一次元スペクトルを得る。その一次元スペクトルにおけるピークトップの位置に対応する特性波長を求め、その逆数として構造周期を算出する。
平均空隙率とは、包埋した試料をクロスセクションポリッシャー法(CP法)により精密に形成させた多孔質炭素繊維の断面を、1±0.1(nm/画素)となる倍率にて70万画素以上で観察し、その画像から計算に必要な着目領域を512画素四方で設定し、細孔部分の面積をA、炭素部分の面積をBとして以下の式で算出し、任意の断面20箇所の算術平均値により算出した値である。ここで、多孔質炭素繊維が中空部を有する場合、中空部分の面積は細孔の面積には含めない。
平均空隙率(%)=A/B×100
また、圧縮比強度が高いほど軽くて強度が高い材料であるため、圧縮比強度は一例として10N・m/kg以上が好ましく、20N・m/kg以上がより好ましい。ここで、圧縮比強度は圧縮強度を平均かさ密度で除して算出する。
本発明の流体分離膜は多孔質炭素繊維を基材とするが、ここで、繊維とは繊維直径dに対する繊維長さl(アスペクト比l/d)が100以上のものを指す。多孔質炭素繊維および流体分離膜の断面の形状は制限されず、丸断面、多角形断面、多葉断面、扁平断面など任意の形状とすることが可能であるが、丸断面であると断面内の強度分布が均一になり、繊維断面方向の圧縮強度および圧縮比強度がより向上するため好ましい。
本発明の流体分離膜は、上記の多孔質炭素繊維の表面に有機高分子層が形成されてなる。多孔質炭素繊維が中空部を有する中空糸である場合は、内表面に有機高分子層が形成されていてもよい。
本発明の流体分離膜は、一例として、炭化可能樹脂と消失樹脂とを相溶させて樹脂混合物とする工程(工程1)と、相溶した状態の樹脂混合物を紡糸し、相分離させる工程(工程2)と、加熱焼成により炭化する工程(工程3)と、表面に有機高分子層を形成する工程(工程4)とを有する製造方法により製造することができる。
工程1は、炭化可能樹脂10〜90重量%と消失樹脂90〜10重量%を相溶させ、樹脂混合物とする工程である。
工程2は、工程1において相溶させた状態の樹脂混合物を紡糸し、微細な相分離構造を形成する工程である。
工程2において得られた多孔質炭素繊維の前駆体は、炭化工程(工程3)に供される前、または炭化工程(工程3)と同時、またはその両方で消失樹脂の除去処理を行うことが好ましい。
工程2において得られた多孔質炭素繊維の前駆体は、炭化工程(工程3)に供される前に不融化処理を行うことが好ましい。
工程3は、工程2において得られた多孔質炭素繊維の前駆体、あるいは必要に応じて消失樹脂の除去および/または不融化処理に供された前駆体を焼成し、炭化して多孔質炭素繊維を得る工程である。
工程4は、工程3により製造した多孔質炭素繊維の表面に有機高分子層を形成する工程である。
本発明の流体分離膜モジュールは、ケーシング内に本発明の流体分離膜を複数本収容してなる。
本発明の流体分離膜を用いて実際に流体分離を行う際には、複数本の流体分離膜を接続しケーシング内に収納して流体分離膜モジュールとして使用する。
(共連続多孔構造の有無)
流体分離膜または多孔質炭素繊維を液体窒素中で充分に冷却後、ピンセットで割断して形成した断面の多孔質炭素繊維部分を走査型電子顕微鏡で表面観察し、炭素骨格の枝部と細孔部(空隙部)がそれぞれ連続しつつ三次元的に規則的に絡み合った構造であった場合、共連続多孔構造を有していると判定した。
流体分離膜の圧縮強度の測定は、株式会社島津製作所製の微小圧縮試験機MCTW−500を用い、多孔質炭素繊維1本を治具で挟み、φ500μmのダイヤモンド製平面圧子を用い、負荷速度41.482mN/sの負荷速度一定方式にて繊維断面方向に圧縮して圧縮変位と荷重を測定し、圧縮強度σを下記の式により算出した。
多孔質炭素繊維を試料プレートに固定し、CuKα線光源から得られたX線源から散乱角度10°未満の情報が得られるように、光源、試料および二次元検出器の位置を調整した。二次元検出器から得られた画像データ(輝度情報)から、ビームストッパーの影響を受けている中心部分を除外して、ビーム中心から動径を設け、角度1°毎に360°の輝度値を合算して散乱角度2θに対する散乱強度分布曲線を得た。得られた曲線においてピークを持つ位置の散乱角度2θより、連続構造部分の構造周期を下記の式によって得た。
上記のX線散乱より得られた散乱角度2θ(横軸)と散乱強度(縦軸)からなる散乱強度分布曲線において、散乱強度のピークの頂点を点Aとし、点Aからグラフの縦軸に平行な直線を引き、該直線とスペクトルのベースラインとの交点を点Bとしたとき、点Aと点Bを結ぶ線分の中点Cにおけるピークの幅をX線散乱の強度ピーク半値幅とした。
多孔質炭素繊維を樹脂中に包埋し、その後カミソリで繊維断面を露出させ、日本電子株式会社製クロスセクションポリッシャー装置SM−09010を用いて加速電圧5.5kVにて試料表面にアルゴンイオンビームを照射、エッチングを施す。
平均空隙率(%)=A/B×100
多孔質炭素繊維を300℃、5時間の条件で真空乾燥を行うことで吸着したガス成分を除去した。その後、株式会社島津製作所製の自動ポロシメータ(オートポアIV9500)を用いて水銀圧入法にて細孔直径分布曲線を取得した。
多孔質炭素繊維20本をマイクロメーターで測定し、その算術平均値を繊維直径dとした。
株式会社日立ハイテクノロジーズ製の走査型電子顕微鏡S−5500を用い、多孔質炭素繊維表面を1±0.1(nm/画素)となる倍率にて70万画素以上で観察して取得した画像を画像解析ソフト“ImageJ”によって繊維表面を枝部(炭素部)および細孔部(空隙部)に分離した。
流体分離膜を種々の直径の円柱に180°以上巻きつけて、膜が破断するかどうかを観測した。曲げ半径は、膜が破断しない円柱において最小の半径を有する円柱を求め、その円柱の半径の値で示した。
長さ10cmの流体分離膜を20本束ねて外径φ6mm、肉厚1mmのステンレス製のケーシング内に収容し、束ねた流体分離膜の端をエポキシ樹脂系接着剤でケーシング内面に固定するとともにケーシングの両端を封止して、流体分離膜モジュールを作製し、ガス透過速度を測定した。
透過速度Q=[ガス透過流量(cm3・STP)]/[膜面積(cm2)×時間(s)×圧力差(cmHg)
芳香族ポリイミド“Matrimid(登録商標)”5218をN−メチルピロリドン(NMP)に溶解させて10.0重量%の芳香族ポリイミド溶液を作製した。
芳香族ポリイミド“Matrimid(登録商標)”5218をN−メチルピロリドン(NMP)に溶解させて25.0重量%の芳香族ポリイミド溶液を作製した。
70gのポリサイエンス社製ポリアクリロニトリル(Mw15万)と70gのシグマ・アルドリッチ社製ポリビニルピロリドン(Mw4万)、及び、溶媒として400gの和研薬製ジメチルスルホキシド(DMSO)をセパラブルフラスコに投入し、3時間攪拌および還流を行いながら150℃で均一かつ透明な溶液を調製した。このときポリアクリロニトリルの濃度、ポリビニルピロリドンの濃度はそれぞれ10重量%であった。
ポリアクリロニトリルおよびポリビニルピロリドンの濃度がそれぞれ11.5重量%のポリマー溶液を用いて紡糸を行った以外は実施例1と同様の手法で多孔質炭素繊維を作製した。
ポリアクリロニトリルおよびポリビニルピロリドンの濃度がそれぞれ13重量%のポリマー溶液を用いて紡糸を行い、到達温度を700℃とした以外は実施例1と同様の手法で多孔質炭素繊維を作製した。
芯鞘型の二重口金の内管から5mL/分で溶液を吐出し、外管からDMSO90重量%水溶液を8.8mL/分で同時に吐出して紡糸を行った以外は実施例1と同様の手法で多孔質炭素繊維を作製した。
芯鞘型の三重口金を用い、内管からDMSO85重量%水溶液を1mL/分で吐出し、中管からポリマー溶液を3mL/分で吐出し、外管からDMSO90重量%水溶液を5.3mL/分で同時に吐出した中空糸状の多孔質炭素繊維を作製した以外は実施例1と同様の手法で多孔質炭素繊維を作製した。
φ0.6mmの一穴の口金を用いてポリアクリロニトリルおよびポリビニルピロリドンの濃度がそれぞれ10重量%のポリマー溶液を用いて紡糸を行った以外は実施例1と同様の手法で多孔質炭素繊維を作製した。得られた多孔質炭素繊維の表面には緻密な層が形成されており、細孔は確認されなかった。
シクロヘキサノンパーオキシド(パーオキサH、日本油脂株式会社製)1部を、メチルメタクリレート(以下MMAと略記する)100部に溶かし、純水800部と乳化剤としてペレックスOTP(日本油脂株式会社製)1部を反応釜に加えて、不活性ガスで十分に置換した後、40℃に保持し、ロンガリット0.76部と硫酸水溶液でpH3とした後、重合を開始した。そのまま攪拌を続け、150分で第一段目の乳化重合を完結させた。
調製例2で作製した芳香族ポリイミド溶液を50℃に加温し、芯鞘型の二重口金の内管からは純水を4mL/分で吐出し、外管からは前記芳香族ポリイミドを8mL/分で同時に吐出した後、25℃の純水からなる凝固浴へ導き、ローラーに巻き取ることで原糸を得た。
2:多孔質炭素繊維
3:有機高分子層
Claims (8)
- 共連続多孔構造を有する多孔質炭素繊維の表面に、有機高分子層が形成されてなり、
水銀圧入法により測定される前記多孔質炭素繊維の全体の平均細孔直径が30〜5,000nmである、流体分離膜。 - 前記多孔質炭素繊維の全体に前記共連続多孔構造を有する、請求項1に記載の流体分離膜。
- 走査型電子顕微鏡による表面観察によって測定される前記多孔質炭素繊維の表面の平均細孔直径が2〜500nmである、請求項1又は2に記載の流体分離膜。
- 前記共連続多孔構造の構造周期が10〜10,000nmである、請求項1〜3のいずれか1項に記載の流体分離膜。
- 前記多孔質炭素繊維のX線散乱の強度ピークの半値幅が5°以下である、請求項1〜4のいずれか1項に記載の流体分離膜。
- 前記有機高分子層が、芳香族ポリイミド、酢酸セルロース、ポリスルホン、芳香族ポリアミド、ポリエーテルイミド、ポリエーテルスルホン、ポリアクリロニトリル、ポリフェニレンスルフィド、ポリエーテルエーテルケトン、ポリテトラフルオロエチレン、ポリフッ化ビニリデンおよびこれらの誘導体からなる群より選択される1種または2種以上の有機高分子を含む層である、請求項1〜5のいずれか1項に記載の流体分離膜。
- 前記有機高分子層が、芳香族ポリイミド、芳香族ポリアミドおよびこれらの誘導体からなる群より選択される1種または2種以上の有機高分子を含む層である、請求項1〜6のいずれか1項に記載の流体分離膜。
- ケーシング内に請求項1〜7のいずれか1項に記載の流体分離膜を複数本収容してなる流体分離膜モジュール。
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