JP6219165B2 - 炭素膜の製造方法 - Google Patents
炭素膜の製造方法 Download PDFInfo
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- JP6219165B2 JP6219165B2 JP2013530739A JP2013530739A JP6219165B2 JP 6219165 B2 JP6219165 B2 JP 6219165B2 JP 2013530739 A JP2013530739 A JP 2013530739A JP 2013530739 A JP2013530739 A JP 2013530739A JP 6219165 B2 JP6219165 B2 JP 6219165B2
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- ethylenically unsaturated
- carbon
- temperature
- porous
- pyrolysis
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Classifications
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- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
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- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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Description
[1] E. Fitzer、「ポリマーの元素状炭素への熱分解−未来の材料への道」、Angew. Chem., 92, 375−386 (1980)
[2] E. Fitzer、「ポリマーから高分子状炭素−いろいろな新規材料の製造方法」、Pure & Appl. Chem., 52, 1865−1882 (1980)
[3] H. Boder and E. Fitzer、「新しい形状の炭素」、Naturwissenschaften、57, 29−36 (1970).
[4] A. Gardziella、L. Pifato and A. Knop、2000
[5] W. Koros and D. Vu、San Ramon, United States, 2002
[6] P. Harris、University of Reasing、Whiteknights, UK、2001
[7] A. Softer、D. Rosen、S. Sagueeand J. Koresh、Germany, 1992
[8] S. Saufi and Ismail AF、「ガス分離用炭素膜の組み立て−総説」、Carbon, 42, 241−259 (2004)
[9] A. Fuertes、「吸着選択性炭素膜のガス分離特性への空気酸化の影響」、Carbon、39, 697−706 (2001)
[10] C.J. Anderson、S.J. Pas、G. Arora、S.E. Kentisch、A.J. Hill、S.I. Sandier and G.W. Stevens、「ナノ多孔性炭素膜の性能に対する熱分解温度と運転温度の影響]、Journal of Membrane Science、[322], 19−27 (2008)
水素透過選択性≧30
透過速度の定義:標準的な温度とガスの圧力条件(Nm3)下での膜面積と時間と圧力当りの流量(立方メートル)。なお、使用圧力(駆動力)は、相当するガスの供給/未透過流と透過流の間の分圧差である。
透過選択性の定義:次いで、透過選択性は求めた透過速度の比率で与えられる。
a)多孔性基材をエチレン性不飽和ポリエステルの溶液で塗布する工程と、
b)多孔性基材上のポリエステル塗膜から溶媒を除いて乾燥させる工程と、
c)多孔性基材上のポリエステル塗膜を熱分解してガス分離に適当な炭素膜を形成する工程とを含むガス分離に好適な炭素膜の製造方法により達成される。
例えば脱水素では、C1以上の炭化水素からの水素の分離。
ジオールを少なくとも一種の不飽和カルボン酸と反応させて不飽和ポリエステルとし、続いてオレフィンを添加して前駆体溶液を製造した。ある特定の場合には、250mlの二口フラスコ中に、19.98gの1,2−プロパンジオール(0.25mol、+5%過剰;VWR)と、12.26gの無水マレイン酸(0.125mol;VWR)、18.52gの無水フタル酸(0.125mol;VWR)を評量して投入した。次いで、急激な重合または架橋を防止するため、0.01gのヒドロキノン(VWR)を重合防止剤として加えた。窒素下でこれらの秤量原料を、オイルバスを使って反応温度の200℃まで加熱した。鎖成形を確認するため、定期的に酸価をKOH溶液での滴定により測定した。酸価が約50となった時点で、140℃にまで急冷して反応を停止させた。次いで、激しく攪拌しながら滴下ロートを用いて1分以内に50gのスチレンを架橋剤として添加した。加えたスチレンは、前もって50℃にまで加熱していた。急激なポリエステルスチレン混合物の重合を防ぐため、この不飽和ポリエステル樹脂溶液を水槽中で室温にまで冷却した。その後、このポリエステル−スチレン混合物に、フリーラジカル形成剤として1%過酸化ジベンゾイル(VWR)を加え、次いでこの混合物を室温で5分間攪拌した。
1.窒素下にて温度を0.5K/minの速度で室温から380℃に加熱
2.窒素下にて380℃で滞留時間が1時間
3.窒素下にて温度を0.6K/minの速度で380〜500℃に加熱、
4.窒素下にて500℃で滞留時間が10分
5.雰囲気を窒素からアルゴンに変更、
6.アルゴン下にて、温度を1K/minの速度で500℃〜最終熱分解温度に加熱
7.アルゴン下、最終熱分解温度で滞留時間が1時間
8.アルゴン下で5K/minの速度で最終熱分解温度から500℃に冷却
9.雰囲気をアルゴンから窒素に変更、
10.窒素下にて5K/minの速度で500℃から室温へ冷却
ポリエステルの組成と架橋剤の量、最終熱分解温度を、実施例4の結果の表に示す。
実施例1の方法を繰り返した。ただし、反応物の無水マレイン酸/無水フタル酸/1,2−プロパンジオールの比率を、0.2/0.05/0.25mol〜0.07/0.43/0.5molの範囲で変更した。
300℃と500℃と650℃で焼成したメソポーラスγ−Al2O3層を用いて、実施例1の方法を繰り返した。
実施例1と同様にして、以下の条件で実施した。前駆体溶液:(ポリエステル:25モル%の無水マレイン酸と25モル%の無水フタル酸と50モル%の1,2−プロパンジオール;溶液:50質量%のPESと50質量%のスチレン)、塗布に用いる支持体の製造:(最上層:500℃で焼成したベーマイトゾル)、前駆体溶液の塗布、乾燥:(空気下室温で24時間)、架橋:(空気下80℃で12時間)、最終の熱分解:(Ar下650℃で1時間)。
I:300℃で2.6〜10.2絶対barの間での供給/未透過流圧力の変化
II.供給/未透過流圧力が7.1絶対barでの200〜350℃の間での温度変動
これらの結果から、300℃の一定温度では、膜間圧力の増加(TMP=供給流圧力と未透過流圧力の算術平均−透過流圧力)により、水素透過速度の9.9から5.9Nm3/h/m2/barへの低下と透過選択性の930から400への低下が起こることがわかる。供給流/未透過流圧力が7.1絶対barで一定での温度増加から、水素の流速と透過速度だけでなく、水素対プロパンの透過選択性も増加することが分る。
Claims (10)
- a)多孔性基材をエチレン性不飽和ポリエステルの溶液で塗布する工程と、
b)多孔性基材をエチレン性不飽和ポリエステルの溶液で塗布して得られた、当該多孔性基材上のポリエステル塗膜を乾燥させ、溶媒を除去する工程と、
c)多孔性基材上のポリエステル塗膜を熱分解させて炭素膜を形成する工程と、を含み、
前記多孔性基材は、多孔性金属、多孔性セラミックス、多孔性ガラス及びこれらの多孔性複合物から選択され、
前記エチレン性不飽和ポリエステルが、脂肪族ジオールと芳香族ジカルボン酸とエチレン性不飽和ジカルボン酸の繰返し単位を有することを特徴とする、ガス分離用の炭素膜の製造方法。 - 上記脂肪族ジオールがC2−12−アルカンジオールである請求項1に記載の方法。
- 上記エチレン性不飽和ジカルボン酸がマレイン酸である請求項1または2に記載の方法。
- 上記エチレン性不飽和ポリエステルの溶液が、さらに架橋性エチレン性不飽和モノマーと、架橋開始剤としてのフリーラジカル形成剤を含む請求項1〜3のいずれか一項に記載の方法。
- 上記架橋性エチレン性不飽和モノマーがスチレンまたはα−メチルスチレンである請求項4に記載の方法。
- 上記多孔性基材が、TiO2かZrO2、Al2O3、SiO2、あるいはこれらの混合物のメソポーラスセラミック酸化物層を持ち、この酸化物層が上記エチレン性不飽和ポリエステルの溶液で被覆されている請求項1〜5のいずれか一項に記載の方法。
- 上記メソポーラスセラミック酸化物層がγ−Al2O3から形成されている請求項6に記載の方法。
- 上記メソポーラスセラミック酸化物層の工程c)での焼付温度がその熱分解温度より低い請求項6または7に記載の方法。
- 工程c)での熱分解が500〜900℃の範囲の温度で行われる請求項1〜8のいずれか一項に記載の方法。
- 上記熱分解が、窒素下にて最高で500℃の温度で、及びアルゴン下で500℃を超える温度で行われる請求項9に記載の方法。
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