JP5567211B2 - 空気分離のための高パーミアンスポリイミド膜 - Google Patents
空気分離のための高パーミアンスポリイミド膜 Download PDFInfo
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- JP5567211B2 JP5567211B2 JP2013512638A JP2013512638A JP5567211B2 JP 5567211 B2 JP5567211 B2 JP 5567211B2 JP 2013512638 A JP2013512638 A JP 2013512638A JP 2013512638 A JP2013512638 A JP 2013512638A JP 5567211 B2 JP5567211 B2 JP 5567211B2
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- hollow fiber
- membrane
- polyimide
- gas
- asymmetric
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
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- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 claims description 4
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
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Description
本出願は、2010年5月28日出願の米国特許出願第12/790,095号の優先権を主張するものである。
本発明は、ガス分離のための高パーミアンスを有する新しいタイプのポリイミド平板型および中空繊維膜、およびこれらの膜を作製する方法に関する。
いくつかの場合では、高パーミアンスを有する新しいポリイミド中空繊維膜は、化学もしくはUV架橋、または当業者に公知のその他の架橋プロセスによる追加の架橋工程を受ける。架橋ポリイミド中空繊維膜は、ポリイミド中空繊維膜をUV放射線を介してUV架橋することによって作製することができる。本発明で述べる高パーミアンスを有するポリイミド中空繊維膜の作製に用いられるいくつかのポリイミドポリマーは、ベンゾフェノン基などのUV架橋性官能基を有する。架橋ポリイミド中空繊維膜は、ポリマー鎖セグメントを含み、これらのポリマー鎖セグメントの少なくとも一部が、UV放射線への曝露によって、恐らくは直接の共有結合によって互いに架橋している。ポリイミド中空繊維膜の架橋により、対応する高パーミアンスを有する未架橋のポリイミド中空繊維膜と比較して、改善された選択性および僅かに低下したパーミアンスを有する膜が提供される。
本発明で述べる高パーミアンスを有する非対称ポリイミド膜の作製に用いられるポリイミドポリマーのいくつかの例としては、これらに限定されないが:3,3’,4,4’−ジフェニルスルホンテトラカルボン酸二無水物(DSDA)および3,3’,5,5’−テトラメチル−4,4’−メチレンジアニリン(TMMDA)の縮合反応から誘導され、ポリ(DSDA−TMMDA)と称するポリ(3,3’,4,4’−ジフェニルスルホンテトラカルボン酸二無水物−3,3’,5,5’‐テトラメチル−4,4’−メチレンジアニリン);3,3’,4,4’−ジフェニルスルホンテトラカルボン酸二無水物(DSDA、80モル%)およびピロメリット酸二無水物(PMDA、20モル%)の、3,3’,5,5’−テトラメチル−4,4’−メチレンジアニリン(TMMDA、100モル%)との縮合反応から誘導され、ポリ(DSDA−PMDA−TMMDA)と称するポリ(3,3’,4,4’−ジフェニルスルホンテトラカルボン酸二無水物−ピロメリット酸二無水物−3,3’,5,5’−テトラメチル−4,4’−メチレンジアニリン);3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物(BTDA、25モル%)、ピロメリット酸二無水物(PMDA、50モル%)、および4,4’−オキシジフタル酸無水物(ODPA、25モル%)の、3,3’,5,5’−テトラメチル−4,4’−メチレンジアニリン(TMMDA、100モル%)との縮合反応から誘導され、ポリ(BTDA−PMDA−ODPA−TMMDA)と称するポリ(3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物−ピロメリット酸二無水物−4,4’−オキシジフタル酸無水物−3,3’,5,5’−テトラメチル−4,4’−メチレンジアニリン)、または、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物(BTDA、50モル%)およびピロメリット酸二無水物(PMDA、50モル%)の、3,3’,5,5’−テトラメチル−4,4’−メチレンジアニリン(TMMDA、100モル%)との縮合反応から誘導され、ポリ(BTDA−PMDA−TMMDA)と称するポリ(3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物−ピロメリット酸二無水物−3,3’,5,5’−テトラメチル−4,4’−メチレンジアニリン);ならびに、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物(BTDA、100モル%)と3,3’,5,5’−テトラメチル−4,4’−メチレンジアニリン(TMMDA、100モル%)との縮合反応から誘導され、ポリ(BTDA−TMMDA)と称するポリ(3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物−3,3’,5,5’−テトラメチル−4,4’−メチレンジアニリン)を挙げることができる。
3,3’,4,4’−ジフェニルスルホンテトラカルボン酸二無水物(DSDA、80モル%)およびピロメリット酸二無水物(PMDA、20モル%)の、3,3’,5,5’−テトラメチル−4,4’−メチレンジアニリン(TMMDA、100モル%)との縮合反応から誘導されるポリ(3,3’,4,4’−ジフェニルスルホンテトラカルボン酸二無水物−ピロメリット酸二無水物−3,3’,5,5’−テトラメチル−4,4’−メチレンジアニリン)(ポリ(DSDA−PMDA−TMMDA)と略す)を用いたポリイミド中空繊維膜の作製(PI−p)
29.0重量%のポリ(DSDA−PMDA−TMMDA)ポリイミド、65.0重量%のNMP、および6.0重量%の1,3−ジオキソランを含有する中空繊維紡糸ドープを調製した。この紡糸ドープを、50℃の紡糸温度にて、紡糸口金を通して流速0.7mL/分で押出した。紡糸ドープを押出すと同時に、NMP中に10重量%の水を含有するボア液を、流速0.4mL/分にて繊維のボアへ注入した。初期繊維を、湿度45%の室温にてエアギャップ長さ3cmに通し、次に、21℃にて凝固水浴中に浸漬し、8.0m/分の速度で巻き取った。水湿潤繊維を85℃の熱水浴中にて30分間アニーリングした。アニーリングした水湿潤繊維を、次に、メタノールおよびヘキサンによる溶媒交換を連続的に3回、各々30分間ずつ行い、続いてオーブン中、100℃にて1時間の乾燥を行い、PI−p中空繊維膜を形成した。
ポリ(DSDA−PMDA−TMMDA)ポリマーを用いたポリイミド中空繊維膜(PI−g)の作製
PI−gポリイミド中空繊維膜を、繊維の巻き取り速度を23.5m/分とし、繊維を通したエアギャップ長さを15cmとした以外は実施例1に記載のものと同じ紡糸ドープおよび紡糸条件を用いて作製した。繊維のアニーリングおよび乾燥を、実施例1に記載の手順で行った。
ポリ(DSDA−PMDA−TMMDA)ポリマーを用いたポリイミド中空繊維膜(PI−wy)の作製
PI−wyポリイミド中空繊維膜を、初期繊維をエアギャップ長さ10cmに室温で通し、8℃の凝固水浴に浸漬し、18.1m/分で巻き取った以外は実施例1に記載のものと同じ紡糸ドープおよび紡糸条件を用いて作製した。繊維のアニーリングおよび乾燥を、実施例1に記載の手順で行った。
PI−p、PI−g、およびPI−wy中空繊維膜のO2/N2分離性能の評価
PI−p、PI−g、およびPI−wy中空繊維を、60℃、フィードガス圧308kPa(30psig)にて、中空繊維のボア側にフィードすることで、O2/N2分離について試験した。結果を以下の表に示す。表より、本発明で述べる中空繊維膜はすべて、400GPU超のO2パーミアンスおよび3超のO2/N2選択性を示したことが分かる。
Claims (9)
- 前記ポリイミドが、3,3’,4,4’−ジフェニルスルホンテトラカルボン酸二無水物(DSDA)、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物(BTDA)、およびピロメリット酸二無水物(PMDA)の、3,3’,5,5’−テトラメチル−4,4’−メチレンジアニリン(TMMDA)との縮合反応から誘導されるポリ(3,3’,4,4’−ジフェニルスルホンテトラカルボン酸二無水物−3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物−ピロメリット酸二無水物−3,3’,5,5’−テトラメチル−4,4’−メチレンジアニリン)であり、ここで、前記TMMDAの前記DSDAと前記BTDAと前記PMDAとの混合物に対するモル比は、100:100である、請求項1に記載の非対称中空繊維膜。
- 前記ポリイミドが、3,3’,4,4’−ジフェニルスルホンテトラカルボン酸二無水物(DSDA)、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物(BTDA)、および4,4’−オキシジフタル酸無水物(ODPA)の、3,3’,5,5’−テトラメチル−4,4’−メチレンジアニリン(TMMDA)との縮合反応から誘導されるポリ(3,3’,4,4’−ジフェニルスルホンテトラカルボン酸二無水物−3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物−4,4’−オキシジフタル酸無水物−3,3’,5,5’−テトラメチル−4,4’−メチレンジアニリン)であり、ここで、前記TMMDAの前記DSDAと前記BTDAと前記ODPAとの混合物に対するモル比は、100:100である、請求項1に記載の非対称中空繊維膜。
- a)式(I):
の繰り返し単位を複数含むポリイミドを、溶媒の混合物中に溶解して中空繊維紡糸ドープを形成すること;
b)前記中空繊維紡糸ドープおよびボア液を、環状紡糸口金から同時に紡糸して、初期中空繊維を形成すること、
c)前記初期中空繊維を、凝固浴に浸漬して、湿潤中空繊維を作製すること、
d)前記湿潤中空繊維を、70℃から100℃の範囲の温度である熱水浴中、10分から3時間の範囲の特定の時間にわたってアニーリングすること、
e)前記湿潤中空繊維を、連続する溶媒交換によって洗浄すること、ならびに
f)前記湿潤中空繊維を乾燥させて、ポリイミド中空繊維膜を作製すること、
を含む、ポリイミド中空繊維膜を作製するための方法。 - 前記中空繊維紡糸ドープが、N−メチルピロリドンおよび1,3−ジオキソランの、重量比99:1から50:50での混合物を含む、請求項4に記載の方法。
- ガスの混合物から少なくとも1つのガスを分離する方法であって:
a)前記少なくとも1つのガスに対して透過性である非対称ポリイミド中空繊維膜を前記ガスの混合物と接触させること、ここで、前記非対称ポリイミド膜は、式(I):
の繰り返し単位を複数含むポリイミドから形成される;
b)前記非対称ポリイミド膜の一方の側に前記ガスの混合物を接触させて、前記少なくとも1つのガスを前記膜に透過させること;ならびに、
c)前記非対称ポリイミド膜の反対側から、前記非対称ポリイミド膜を透過した前記少なくとも1つのガスの一部を含む透過物ガス組成物を除去すること、
を含む、方法。 - 前記ガス混合物が、CO2/CH4、CO2/N2、H2/CH4、O2/N2、H2S/CH4、オレフィン/パラフィン、およびイソパラフィン/ノルマルパラフィンから成る群より選択される、請求項6に記載の方法。
- 前記ガス混合物が、アンモニアパージ流中の水素、窒素、メタン、およびアルゴンの混合物を含む、請求項6に記載の方法。
- 前記ガス混合物が、メタン、ならびに二酸化炭素、酸素、窒素、水蒸気、硫化水素、ヘリウム、およびその他の微量ガスから成る群より選択される少なくとも1つのガス成分を含む天然ガスを含む、請求項6に記載の方法。
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PCT/US2011/035863 WO2011149654A2 (en) | 2010-05-28 | 2011-05-10 | High permeance polyimide membranes for air separation |
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