JP2018507098A - フッ化ビニリデンポリマーおよび吸着性炭素材料を含む組成物 - Google Patents
フッ化ビニリデンポリマーおよび吸着性炭素材料を含む組成物 Download PDFInfo
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Abstract
Description
本出願は、2014年12月24日出願の欧州特許出願公開第14307180.1号に対する優先権を主張するものであり、この出願の全内容は、あらゆる目的のために参照により本明細書に援用される。
本発明の第1の目的は、フッ素化ポリマーと、前記フッ素化ポリマーのマトリックス中に埋め込まれた炭素材料とを含むある種の組成物であって、吸着法によるガス分離またはガス精製のために使用されてもよい組成物を提供することである。
(式中、同じまたは異なるものであってよいR1〜R3が、独立して、水素原子またはC1〜C6、好ましくはC1〜C3アルキル基であり、およびR4が、水素原子または少なくとも1個のヒドロキシル基を含むC1〜C6炭化水素部分である)
の親水性モノマーである。
5〜20℃/分(例えば10℃/分)の昇温速度で室温から160〜190℃の範囲の温度(例えば175℃)まで加熱し、および6〜48時間(例えば約16時間)にわたりこの温度に保持し、その後、5〜20℃/分(例えば10℃/分)の昇温速度で175℃から600℃まで加熱し、および約30分〜6時間(例えば1時間)にわたり600℃に保持すること。
r=2σcosθ/P
に従って計算されるrとr−Δrとの間の半径を有する細孔の容積に等しいであろう。
実施例に使用される活性炭材料は、200ミクロンの粒度を有する手を加えていない材料を7ミクロンの粒度へすり潰すことによって得られたATMIによって供給されるBrightblack(登録商標)炭素であった。生成物は、1050m2/gのBET比表面積、0.40ml/gの細孔容積を有し、細孔容積は、2nm以下の半径を有する細孔から定量的に(99%超)なった。
C 888g/kg
H 8g/kg
N 5g/kg未満
O 30g/kg
をもたらした。
アクリレート基を含む、および国際公開第2008/129041号パンフレットの実施例1に記載されているように得られたフッ化ビニリデンポリマーの10gの5重量%溶液に、実施例1に記載された4.5gの吸着性炭素材料を室温で磁気攪拌下において添加した。2mlのNMPを、粘度を調整するために添加した。フッ化ビニリデンポリマーと吸着性炭素材料とを10:90の重量比で含む、キャスティングのための良好な粘度を有するスラリーが得られた。
実施例2を繰り返したが、20:80のフッ化ビニリデンポリマー対吸着性炭素材料の重量比で繰り返した、すなわち、吸着性炭素材料の量は、4.5gの代わりに2gであった。
得られたスラリーを、250マイクロメートルのギャップ開口部のドクターブレードを用いて(SGL Carbonから入手した)Sigracet(登録商標)GDL25BC支持体の灰色側上にキャストした。結果として生じるフィルムを一晩110℃で乾燥させてNMPを蒸発させた。20:80重量比のスラリーは、10:90重量比のスラリーよりも良好な接着性を示し、さらなる性能研究のために使用された。
基材キャラクタリゼーション用のプロトタイプは、基材がその中に平行に組み立てられている透明セルを使って製造した(図1に示されるアセンブリ)。ガス循環のために用いられる2つの基材間のスペースは、透明セルにおける層流条件を前提とするように適合させた。
N2フローを、活性炭粒子上に以前に吸着された分子を潜在的に脱着させるために60秒間基材層を含有するセル中へ注入した。
フル要因計画を、18の実験(コーティングされた基材の9つの実験およびガラスマイクロビーズを含有するブランクの9つの実験)の実現をもたらす3つのレベルのCO2濃度および3つのレベルのガス流量で作成した。各実験について、CO2ピーク強度とArピーク強度との間の比を計算した。ブランクに対応するCO2/Ar強度比と、試料に対応するCO2/Ar強度比との間の差は、吸着されたCO2の量に関連している。流量値、ガス入口におけるCO2の百分率および2秒の注入時間を考えて、本発明者らは吸着されたCO2の全量を計算することができ、最終的に、吸着能(%)を各実験について見積もることができた(表1)。
Claims (15)
- a)フッ化ビニリデンモノマーと、カルボキシル基、エステル基およびヒドロキシル基から選択される少なくとも1個の官能基を有する少なくとも1つのモノマーとに由来する繰り返し単位を含むポリマーと、
b)少なくとも700m2/gの比表面積(BET)、0.1〜0.7ml/gの範囲の細孔容積を有するマイクロ孔性の吸着性炭素材料であって、前記細孔容積の少なくとも60%が、2nm以下の細孔半径を有するマイクロ孔によって形成されている、マイクロ孔性の吸着性炭素材料と
を含む組成物。 - 前記ポリマーが、カルボキシル基、エステル基およびヒドロキシル基から選択される少なくとも1個の官能基を有する前記モノマーに由来する0.02〜20モル%の繰り返し単位を含む、請求項1に記載の組成物。
- カルボキシル基、エステル基およびヒドロキシル基から選択される少なくとも1個の官能基を有する前記モノマーに由来する少なくとも40モル%の前記繰り返し単位がランダムに分布している、請求項1または2に記載の組成物。
- 少なくとも1個の官能基を有する前記モノマーが、式1
(式中、同じまたは異なるものであってよいR1、R2、およびR3のそれぞれが、独立して、水素原子またはC1〜C3炭化水素基を表し、およびR4が、水素または少なくとも1個のヒドロキシル基を含むC1〜C5炭化水素部分である)
の(メタ)アクリル酸モノマーから選択される、請求項1〜3のいずれか一項に記載の組成物。 - 前記マイクロ孔性の吸着性炭素材料が少なくとも900m2/gの比表面積(BET)を有する、請求項1〜4のいずれか一項に記載の組成物。
- 前記マイクロ孔性の吸着性炭素材料が塩化ビニリデンポリマーの熱分解物である、請求項1〜5のいずれか一項に記載の組成物。
- 請求項1〜6のいずれか一項に記載の組成物を含むスラリーまたは液体分散系。
- 水性溶媒もしくは有機溶媒またはそれらの混合物を含む、請求項7に記載のスラリーまたは分散系。
- 請求項7または8に記載のスラリーまたは分散系を含むキャスティング組成物。
- 表面コーティングを含む基材材料を含む吸着システムであって、前記表面コーティングが、請求項9に記載のキャスティング組成物を前記基材材料の表面上へキャストすることおよびその後の前記溶媒の除去によって得られる、吸着システム。
- 流体混合物の成分を前記流体混合物の他の成分から分離するための方法での、請求項1〜6のいずれか一項に記載のコーティング組成物または請求項7もしくは8に記載のスラリーもしくは分散系の使用。
- 分離される前記成分が二酸化炭素である、請求項11に記載の使用。
- 請求項1〜6のいずれか一項に記載の組成物または請求項10に記載の吸着システムを含む、二酸化炭素回収システム。
- 圧力スイング、温度スイング、真空スイングシステムまたは移動床接触システムを含む、請求項13に記載の二酸化炭素回収システム。
- 流体混合物の1つまたは複数の成分を前記流体混合物から分離する方法であって、温度T1での前記流体混合物の少なくとも1つの成分の吸着と、T1よりも高い温度T2での再生工程とを含み、T1からT2への加熱が抵抗損、容量損失または誘導電流損失によって達成され、表面コーティングを含む基材材料を含む吸着システムであって、前記表面コーティングが、請求項9に記載のキャスティング組成物を前記基材の表面上へキャストし、およびその後、前記溶媒を除去することによって得られる、吸着システムが使用される、方法。
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Application Number | Priority Date | Filing Date | Title |
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EP14307180.1A EP3037473B1 (en) | 2014-12-24 | 2014-12-24 | Compositions comprising vinylidene fluoride polymers and adsorbent carbon materials |
EP14307180.1 | 2014-12-24 | ||
PCT/EP2015/080709 WO2016102418A1 (en) | 2014-12-24 | 2015-12-21 | Compositions comprising vinylidene fluoride polymers and adsorbent carbon materials |
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CN107278218A (zh) | 2017-10-20 |
JP7079603B2 (ja) | 2022-06-02 |
EP3037473A1 (en) | 2016-06-29 |
CN107278218B (zh) | 2020-08-21 |
EP3037473B1 (en) | 2017-11-08 |
US20180085704A1 (en) | 2018-03-29 |
WO2016102418A1 (en) | 2016-06-30 |
PL3037473T3 (pl) | 2018-04-30 |
US11421096B2 (en) | 2022-08-23 |
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