JP5981989B2 - ポリイミド気体分離膜 - Google Patents
ポリイミド気体分離膜 Download PDFInfo
- Publication number
- JP5981989B2 JP5981989B2 JP2014515849A JP2014515849A JP5981989B2 JP 5981989 B2 JP5981989 B2 JP 5981989B2 JP 2014515849 A JP2014515849 A JP 2014515849A JP 2014515849 A JP2014515849 A JP 2014515849A JP 5981989 B2 JP5981989 B2 JP 5981989B2
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- Japan
- Prior art keywords
- membrane
- polyimide
- npi
- gas
- separation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000002184 metal Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
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- 239000004814 polyurethane Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- AIISZVRFZVBASR-UHFFFAOYSA-N propan-1-ol;propyl acetate Chemical compound CCCO.CCCOC(C)=O AIISZVRFZVBASR-UHFFFAOYSA-N 0.000 description 1
- SAALQYKUFCIMHR-UHFFFAOYSA-N propan-2-ol;2-propan-2-yloxypropane Chemical compound CC(C)O.CC(C)OC(C)C SAALQYKUFCIMHR-UHFFFAOYSA-N 0.000 description 1
- AAZYNPCMLRQUHI-UHFFFAOYSA-N propan-2-one;2-propan-2-yloxypropane Chemical compound CC(C)=O.CC(C)OC(C)C AAZYNPCMLRQUHI-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- DCGLONGLPGISNX-UHFFFAOYSA-N trimethyl(prop-1-ynyl)silane Chemical compound CC#C[Si](C)(C)C DCGLONGLPGISNX-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Description
[0002]本発明は、気体分離のため、より詳しくは天然ガスの改質及び水素精製において用いるための高い透過度及び高い選択性を有する新しいタイプのポリイミド膜に関する。
[0009]本発明は、概して気体分離膜、より詳しくは気体分離用の高い透過度及び高い選択性のポリイミド膜に関する。本発明において記載する高い透過度及び高い選択性を有するポリイミド膜は、50℃において、791kPaの供給圧力下で少なくとも50バーラー(1バーラー=10−10cm3(STP)cm/cm2秒(cmHg))のCO2透過係数及び少なくとも15の単一気体CO2/CH4選択率を有する。
[0029]本発明において記載する高い透過度及び高い選択性を有するポリイミド膜を製造するために用いるポリイミドポリマーは、50,000〜1,000,000ダルトンの範囲、好ましくは70,000〜500,000ダルトンの間の重量平均分子量を有する。
[0032]本発明はまた、本発明において記載する高い透過度及び高い選択性を有するポリイミド膜を製造するために用いるポリイミドポリマーを含むブレンドポリマー膜も包含する。本発明の幾つかの態様においては、本発明において記載する高い透過度及び高い選択性を有するポリイミド膜を製造するために用いるポリイミドポリマーを含むブレンドポリマー膜は、更なる架橋工程にかけて膜の選択性を増加させることができる。
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−2,4,6−トリメチル−m−フェニレンジアミン)ポリイミド(NPI−1)を用いたポリイミドの緻密フィルム膜の製造:
[0043]ポリ(アミド酸)を形成し、次に溶液イミド化プロセスを行うことを含む2段階プロセスにより、DMAc極性溶媒中において、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)と2,4,6−トリメチル−m−フェニレンジアミン(TMPDA)から、UV架橋性のスルホン基を含む芳香族ポリ(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−2,4,6−トリメチル−m−フェニレンジアミン)ポリイミド(NPI−1と略称する)を合成した。脱水剤として無水酢酸を用い、溶液イミド化反応のためのイミド化触媒としてピリジンを用いた。例えば、窒素入口及びメカニカルスターラーを装備した250mLの3つ口丸底フラスコに、10.5gのTMPDA、及び42gのDMAcを充填した。TMPDAが完全に溶解したら、フラスコ内において撹拌下で、25.8gのDSDA固体粉末をTMPDAの溶液に段階的に加えた。TMPDA粉末を加えた後に、50gのジメチルアセトアミド(DMAc)を溶液に加えた。反応混合物を雰囲気温度において24時間機械撹拌して、粘稠なポリ(アミド酸)溶液を与えた。次に、14.7gの無水酢酸を、撹拌下で反応混合物にゆっくりと加え、次に22.8gのピリジンを反応混合物に加えた。反応混合物を90℃において更に2.0時間機械撹拌して、本出願の目的のためにNPI−1と表すポリイミドを得た。1:1の体積比を有する多量のメタノール及びアセトンの混合物中に反応混合物をゆっくりと沈殿させることによって、微細繊維形態のNPI−1生成物を回収した。次に、得られたNPI−1ポリイミド繊維をメタノールで十分にすすぎ、100℃の真空オーブン内において24時間乾燥した。
実施例1において製造したNPI−1膜のCO2/CH4及びH2/CH4分離性能の評価:
[0045]緻密なフィルムの形態のNPI−1膜を、50℃において、791kPa(100psig)の純粋気体供給圧下でCO2/CH4及びH2/CH4の分離に関して試験した。結果は、この新規なNPI−1膜は、CO2/CH4分離に関して、50℃、791kPaにおいて73.4バーラー(1バーラー=10−10cm3(STP)cm/cm2秒(cmHg))の固有CO2透過係数及び25.3の単一気体CO2/CH4選択率を有することを示す。この膜はまた、H2/CH4分離に関して、50℃、791kPaにおいて136.6バーラーの固有H2透過係数及び47.1の単一気体H2/CH4選択率を有する。
実施例1において製造したNPI−1ポリイミドを用いるNPI−1ポリイミド中空繊維膜の製造;
[0046]29.7gの実施例1からのNPI−1ポリイミド、62.86gのNMP、8.48gの1,3−ジオキソラン、2.51gのイソプロパノール、及び2.51gのアセトンを含む中空繊維紡糸ドープを製造した。紡糸ドープを、50℃の紡糸温度において紡糸口金を通して2.6mL/分の流速で押出した。紡糸ドープを押出すのと同時に、NMP中の10重量%の水を含むボア流体を0.8mL/分の流速で繊維のボアに注入した。発生期の繊維を、室温において25%の湿度で5cmの空隙長さを通して送り、次に21℃の水凝固剤浴中に浸漬し、8.0m/分の速度で巻き取った。水で湿潤している繊維を85℃の湯浴中で30分間アニールした。次に、アニールした水で湿潤している繊維を、順次メタノール及びヘキサンで3回、それぞれ30分間交換し、次にオーブン中100℃において1時間乾燥してNPI−1中空繊維膜を形成した。
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’−ビフェニルテトラカルボン酸二無水物−2,4,6−トリメチル−m−フェニレンジアミン−3,3’,5,5’−テトラメチル−4,4’−メチレンジアニリン(NPI−2と呼ぶ)の合成:
[0047]DMAc極性溶媒中におけるDSDA及び3,3’,4,4’−ビフェニルテトラカルボン酸二無水物(BPDA)と3,3’,5,5’−テトラメチル−4,4’−メチレンジアニリン(TMMDA)及びTMPDA(DSDA:BPDA:TMMDA:TMPDA=3.06:1.02:2.00:2.00(モル比))の重縮合反応によって、UV架橋性のスルホン基を含む芳香族ポリイミドであるポリ(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’−ビフェニルテトラカルボン酸二無水物−2,4,6−トリメチル−m−フェニレンジアミン−3,3’,5,5’−テトラメチル−4,4’−メチレンジアニリン)(NPI−2と略称する)を合成した。窒素入口及びメカニカルスターラーを装備した500mLの3つ口丸底フラスコに、17.8gのTMMDA、10.5gのTMPDA、及び60gのDMAcを充填した。TMMDA及びTMPDAが完全に溶解したら、フラスコ内において撹拌下で、38.3gのDSDA及び10.5gのBPDA固体粉末を、TMMDA及びTMPDAの溶液に段階的に加えた。DSDA及びBPDA粉末を加えた後に、40gのDMAcを溶液に加えた。10分後に更に30gのDMAcを加えた。次に、反応混合物を70℃に加熱して粉末を完全に溶解させた。70℃において0.5時間加熱した後に、更に130gのDMAcを反応混合物に加えた。次に、反応混合物を雰囲気温度に冷却し、雰囲気温度において24時間機械撹拌して、粘稠なポリ(アミド酸)溶液を与えた。次に、31.4gの無水酢酸を、撹拌下で反応混合物にゆっくりと加え、次に48.7gのピリジンを反応混合物に加えた。反応混合物を90℃において更に2時間機械撹拌してNPI−2を得た。多量のメタノール中に反応混合物をゆっくりと沈殿させることによって、微細繊維形態のポリイミドNPI−2生成物を回収した。次に、得られたポリイミドNPI−2繊維をメタノールで十分にすすぎ、100℃の真空オーブン内において24時間乾燥した。
NPI−2の緻密フィルム膜の製造:
[0048]次のようにしてNPI−2緻密フィルム膜を製造した。7.0gのポリイミドNPI−2を、15.5gのNMPと12.5gの1,3−ジオキソランの溶媒混合物中に溶解した。混合物を2時間機械撹拌して、均一なキャスティングドープを形成した。得られた均一なキャスティングドープを濾過し、一晩脱気させた。20ミルの間隙でドクターナイフを用い、泡を含まないキャスティングドープから清浄なガラスプレート上においてNPI−2の緻密フィルム膜を製造した。次に、緻密なフィルムをガラスプレートと共に真空オーブン中に入れた。真空オーブンの真空度及び温度をゆっくりと上昇させることによって溶媒を除去した。最後に、緻密なフィルムを真空下200℃において少なくとも48時間乾燥して残留溶媒を完全に除去して、NPI−2の緻密フィルム膜を形成した。
UV架橋NPI−2緻密フィルム膜の製造:
[0049]1.9cm(0.75インチ)のNPI−3緻密フィルム膜の表面からUVランプまでの距離のUVランプから生成させた254nmの波長のUV光、及び10分間の照射時間を用いて50℃においてUV放射線に曝露することによって、実施例5において製造したNPI−2緻密フィルム膜を更にUV架橋した。ここで記載するUVランプは、Ace Glass Incorporatedからの12Wの電源装置を用いる低圧水銀アーク液浸UV石英12Wランプである。
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−2,4,6−トリメチル−m−フェニレンジアミン)(NPI−3と略称する)の合成:
[0050]NMP極性溶媒中における3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物(BTDA)及びピロメリット酸二無水物(PMDA)とTMPDA(BTDA:PMDA:TMPDA=2.04:2.04:4.00(モル比))の重縮合反応によって、UV架橋性カルボニル基を含む芳香族ポリイミドであるポリ(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−2,4,6−トリメチル−m−フェニレンジアミン)(NPI−3と略称する)を合成した。NPI−3に関する合成手順は、NPI−3の合成に関しては異なるモノマー及び溶媒を用いた他は、NPI−2に関して実施例4において記載したものと同じであった。
NPI−3緻密フィルム膜の製造:
[0051]緻密フィルム膜を製造するために用いたポリマーがNPI−3である他は、実施例5に記載したものと同様の手順を用いてNPI−3緻密フィルム膜を製造した。
UV架橋NPI−3緻密フィルム膜の製造:
[0052]1.9cm(0.75インチ)のNPI−3緻密フィルムの表面からUVランプまでの距離のUVランプから生成させた254nmの波長のUV光、及び10分間の照射時間を用いて50℃においてUV放射線に曝露することによって、実施例8において製造したNPI−3緻密フィルム膜を更にUV架橋した。ここで記載するUVランプは、Ace Glass Incorporatedからの12Wの電源装置を用いる低圧水銀アーク液浸UV石英12Wランプである。
緻密フィルム膜のCO2/CH4及びH2/CH4分離特性:
[0053]それぞれ実施例5、6、8、及び9において製造した緻密フィルム膜のCO2、H2、及びCH4の透過係数(PCO2、PH2、及びPCH4)、並びにCO2/CH4の選択率(αCO2/CH4)及びH2/CH4の選択率(αH2/CH4)を、50℃、790kPa(100psig)の圧力における純粋気体測定によって測定した。結果を表1に示す。
NPI−2中空繊維膜の製造:
[0054]52.1gのn−メチルピロリジノン(NMP)、7.0gの1,3−ジオキソラン、2.1gの2−プロパノール、2.1gのアセトン、及び23.4gの実施例4において合成したNPI−2ポリイミドから構成されるポリマードープを、均一になるまで混合した。このドープの粘度は30℃において280,000cPであった。このドープを、中空繊維膜紡糸口金の円環部から0.7〜3.0mL/分の範囲の流速で押出した。同時に、10重量%H2O/90重量%NMPのボア溶液を、紡糸口金の内側流路から0.4〜0.8mL/分で流して、発生期の繊維が崩壊しないようにした。押出中においては、ドープ及び紡糸口金を50℃に制御した。発生期の繊維を3〜10cmの空隙に通し、次に4℃の水凝固浴に入れて、液液偏析及び中空繊維膜の非対称の多孔質部分の形成を行った。最後に、固化した中空繊維膜を、室温水中に部分的に浸漬した巻き取りドラム上に8〜37m/分で巻き取った。得られたNPI−2中空繊維膜は、繊維の外表面上に緻密な選択性の層を有していた。
NPI−3中空繊維膜の製造:
[0056]62.6gのNMP、8.5gの1,3−ジオキソラン、2.5gの2−プロパノール、2.5gのアセトン、及び24.0gの実施例7において合成したNPI−3ポリイミドから構成されるポリマードープを、均一になるまで混合した。このドープの粘度は30℃において300,000cPであった。このドープを、中空繊維膜紡糸口金の円環部から0.7〜3.0mL/分の範囲の流速で押出した。同時に、10重量%H2O/90重量%NMPのボア溶液を、紡糸口金の内側流路から0.4〜0.8mL/分で流して、発生期の繊維が崩壊しないようにした。押出中においては、ドープ及び紡糸口金を50℃に制御した。発生期の繊維を3〜10cmの空隙に通し、次に3℃の水凝固浴に入れた。最後に、固化した中空繊維膜を、室温水中に部分的に浸漬した巻き取りドラム上に8〜30m/分で巻き取った。得られた膜は、繊維の外表面上に緻密な選択性の層を有していた。中空繊維NPI−3膜のそれぞれに関して用いた具体的な条件の詳細を表3に示す。
NPI−2ポリイミド中空繊維膜のCO2/CH4分離特性:
[0059]実施例11においてNPI−2ポリイミドから製造したポリイミド中空繊維膜を、790kPa(100psig)の供給流及び101kPa(0psig)の透過流で、50℃においてCO2及びCH4の単一気体透過に関して試験した。これらの膜の性能を、それぞれの膜に関する固有の製造条件と共に表2に示す。これらの膜に関する他の製造条件は実施例11において記載した。表2に示すNPI−2ポリイミド中空繊維膜は全て、欠陥をほぼ含まず、NPI−2の緻密フィルム膜の固有選択率の付近か又はこれよりも高いCO2/CH4選択率を有していた。
NPI−3中空繊維膜のCO2/CH4分離特性:
[0060]実施例12においてNPI−3から製造したポリイミド中空繊維膜を、790kPa(100psig)の供給流及び101kPa(0psig)の透過流で、50℃においてCO2及びCH4の単一気体透過に関して試験した。実施例12において記載したようにして、異なるドープ配合物を用いてNPI−3中空繊維膜の2つの異なる組を製造した。これらの膜の性能を、それぞれの膜に関する固有の製造条件と共に表3及び4に示す。これらの膜に関する他の製造条件は実施例12において記載した。表3及び4に示すポリイミドNPI−3中空繊維膜は全て、欠陥をほぼ含まず、NPI−2中空繊維膜の固有選択率よりも高いCO2/CH4選択率を有していた。
NPI−2/PESのブレンド緻密フィルム膜の製造:
[0061]以下のようにして、NPI−2ポリイミドとポリエーテルスルホン(PES)のブレンドポリマー緻密フィルム膜を製造した。3.5gのポリイミドNPI−2及び3.5gのPESを、15.5gのNMP及び12.5gの1,3−ジオキソランの溶媒混合物中に溶解した。この混合物を2時間機械撹拌して均一なキャスティングドープを形成した。得られた均一なキャスティングドープを濾過し、一晩脱気させた。20ミルの間隙でドクターナイフを用いて、清浄なガラスプレート上において泡を含まないキャスティングドープからNPI−1/PESブレンドの緻密フィルム膜を製造した。次に、緻密フィルムをガラスプレートと共に真空オーブン中に入れた。真空オーブンの真空度及び温度をゆっくりと上昇させることによって溶媒を除去した。最後に、緻密フィルムを真空下200℃において少なくとも48時間乾燥して残留溶媒を完全に除去して、NPI−2/PESブレンドの緻密フィルム膜を形成した。
Claims (9)
- ポリエーテルスルホンを更に含む、請求項1に記載のポリイミド膜。
- 請求項1または2に記載のポリイミド膜を用いて2種類以上の物質を分離する分離方法。
- 分離方法が水から1種類以上の有機化合物を分離する、請求項3に記載の方法。
- 分離方法がガソリン又はディーゼル燃料からイオウを除去するためのパーベーパレーション法である、請求項3に記載の方法。
- 分離方法が少なくとも第1の有機化合物を第2の有機化合物から分離する、請求項3に記載の方法。
- 分離方法が逆浸透による水の脱塩である、請求項3に記載の方法。
- 2種類以上の物質が気体の混合物を含む、請求項3に記載の方法。
- 気体の混合物が、メタンと混合している二酸化炭素及び硫化水素から選択される少なくとも1種類の気体を含む、請求項8に記載の方法。
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WO2012173776A3 (en) | 2013-05-23 |
KR101526096B1 (ko) | 2015-06-04 |
CA2836127C (en) | 2016-02-23 |
RU2013149276A (ru) | 2015-05-10 |
KR20130137238A (ko) | 2013-12-16 |
AU2012271128B2 (en) | 2015-05-07 |
EP2720782B1 (en) | 2018-04-18 |
EP2720782A2 (en) | 2014-04-23 |
US20120322911A1 (en) | 2012-12-20 |
JP2014523338A (ja) | 2014-09-11 |
AU2012271128A1 (en) | 2013-10-03 |
WO2012173776A2 (en) | 2012-12-20 |
CA2836127A1 (en) | 2012-12-20 |
BR112013024956B1 (pt) | 2020-11-17 |
RU2556666C2 (ru) | 2015-07-10 |
CN103608094A (zh) | 2014-02-26 |
CN103608094B (zh) | 2015-11-25 |
EP2720782A4 (en) | 2015-01-14 |
MY161235A (en) | 2017-04-14 |
BR112013024956A2 (pt) | 2016-12-20 |
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