有機物/水混合液の分離に向けた高性能silicalite-1膜の合成

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Title

有機物/水混合液の分離に向けた高性能silicalite-1膜の合成(

_{本文(Fulltext) )}

Author(s)

上野, 恭平

Report No.(Doctoral

Degree)

博士(工学) 工博甲第541号

Issue Date

2018-09-30

Type

博士論文

Version

ETD

URL

http://hdl.handle.net/20.500.12099/77253

※この資料の著作権は、各資料の著者・学協会・出版社等に帰属します。

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᭷ᶵ≀

_{/Ỉΰྜᾮࡢศ㞳࡟ྥࡅࡓ}

㧗ᛶ⬟

_{silicalite-1 ⭷ࡢྜᡂ}

Preparation of high-performance silicalite-1 membranes

for the separation of organic/water mixtures

㸰㸮㸯㸶ᖺ㸷᭶

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1 ┠ḟ

➨

1 ❶ ᗎㄽ ... 1

1.1. ◊✲⫼ᬒ ... 1 1.2. ศ㞳⭷ࡢ✀㢮 ... 3 1.3. ↓ᶵ⭷ࡢ✀㢮 ... 3 1.4. ࢮ࢜ࣛ࢖ࢺ ... 5 1.4.1. ࢮ࢜ࣛ࢖ࢺࡢᵓ㐀ⓗ≉ᚩ ... 5 1.4.2. ࢮ࢜ࣛ࢖ࢺࡢྜᡂ ... 7 1.5. ࢮ࢜ࣛ࢖ࢺ⭷ ... 10 1.5.1. ࢮ࢜ࣛ࢖ࢺ⭷ࡢᵓ㐀 ... 10 1.5.2. ࢮ࢜ࣛ࢖ࢺ⭷ࡢྜᡂ ... 10 1.5.3. ᨭᣢయ≉ᛶࡢᙳ㡪 ... 11 1.5.4. ࢮ࢜ࣛ࢖ࢺ⭷ࡢศ㞳ᶵᵓ ... 12 1.5.5. MFI ᆺࢮ࢜ࣛ࢖ࢺ⭷ ... 13 1.5.6. silicalite-1 ⭷ ... 14 1.5.6.1. silicalite-1 ⭷ࡢ≉ᚩ ... 14 1.5.6.2. silicalite-1 ⭷ࢆ⏝࠸ࡓᾐ㏱Ẽ໬ἲ࡟ࡼࡿ᭷ᶵ≀/Ỉΰྜᾮࡢศ㞳 ... 14 1.6. ᮏ◊✲ࡢ┠ⓗ࡜ㄽᩥᵓᡂ ... 15 1.7. ཧ⪃ᩥ⊩ ... 16

➨

2 ❶ silicalite-1 ⭷ྜᡂ࡟࠾ࡅࡿ✀⤖ᬗࡢ Si/Al ẚࡢᙳ㡪 ... 21

2.1. ⥴ゝ ... 21 2.2. ᐇ㦂᪉ἲ ... 22 2.2.1. ␗࡞ࡿ Si/Al ẚࢆ᭷ࡍࡿ MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗࡢྜᡂ ... 22 2.2.2. ✀⤖ᬗሬᕸᨭᣢయࡢㄪ〇 ... 23 2.2.3. silicalite-1 ⭷ࡢㄪ〇 ... 24 2.2.4. ࢟ࣕࣛࢡࢱࣜࢮ࣮ࢩࣙࣥ ... 25 2.2.5. ᾐ㏱Ẽ໬㸦PV㸧ヨ㦂 ... 25 2.3. ⤖ᯝ࡜⪃ᐹ ... 27 2.3.1. MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗࡢྜᡂ ... 27 2.3.2. silicalite-1 ⭷ࡢㄪ〇 ... 29 2.3.3. PV ᛶ⬟ ... 31 2.3.3.1. ࢚ࢱࣀ࣮ࣝ/Ỉΰྜᾮࡢศ㞳 ... 31 2.3.3.2. ࢚ࢱࣀ࣮ࣝ/Ỉศ㞳࡟࠾ࡅࡿࢥࣁࢡ㓟ῧຍࡢᙳ㡪 ... 36 2.4. ⤖ゝ ... 40 2.5. ཧ⪃ᩥ⊩ ... 41

➨

3 ❶ silicalite-1 ⭷ྜᡂ࡟࠾ࡅࡿ✀⤖ᬗሬᕸ㔞ࡢᙳ㡪... 44

3.1. ⥴ゝ ... 44 3.2. ᐇ㦂᪉ἲ ... 45 3.2.1. silicalite-1 ✀⤖ᬗࡢㄪ〇 ... 45 3.2.2. ✀⤖ᬗሬᕸᨭᣢయࡢㄪ〇 ... 45 3.2.3. silicalite-1 ⭷ࡢㄪ〇 ... 46

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2

3.2.4. ࢟ࣕࣛࢡࢱࣜࢮ࣮ࢩࣙࣥ ... 46 3.2.5. ᾐ㏱Ẽ໬㸦PV㸧ヨ㦂... 47 3.3. ⤖ᯝ࡜⪃ᐹ ... 47 3.3.1. silicalite-1 ✀⤖ᬗࡢㄪ〇 ... 47 3.3.2. ✀⤖ᬗሬᕸᨭᣢయࡢㄪ〇 ... 49 3.3.3. silicalite-1 ⭷ࡢㄪ〇 ... 51 3.3.3.1. ✀⤖ᬗሬᕸ㔞ࡢᙳ㡪 ... 51 3.3.3.2. ౪⤥ᾮ ᗘࡢᙳ㡪 ... 55 3.3.3.3. ⭷ྜᡂ⁐ᾮ⤌ᡂࡢᙳ㡪 ... 56 3.3.3.4. 㓑㓟/Ỉศ㞳࡬ࡢᛂ⏝... 59 3.3.3.5. ᪤ሗ࡜ࡢẚ㍑ ... 61 3.4. ⤖ゝ ... 62 3.5. ཧ⪃ᩥ⊩ ... 63

➨

4 ❶ ࢩࣜ࢝ᨭᣢయୖ࡬ࡢ㧗ᛶ⬟ silicalite-1 ⭷ࡢྜᡂ ... 67

4.1. ⥴ゝ ... 67 4.2. ᐇ㦂᪉ἲ ... 68 4.2.1. silicalite-1 ✀⤖ᬗࡢㄪ〇 ... 68 4.2.2. ✀⤖ᬗሬᕸᨭᣢయࡢㄪ〇 ... 68 4.2.3. silicalite-1 ⭷ࡢㄪ〇 ... 69 4.2.4. ࢟ࣕࣛࢡࢱࣜࢮ࣮ࢩࣙࣥ ... 70 4.2.5. ᾐ㏱Ẽ໬㸦PV㸧ヨ㦂... 70 4.3. ⤖ᯝ࡜⪃ᐹ ... 71 4.3.1. silicalite-1 ✀⤖ᬗࡢㄪ〇 ... 71 4.3.2. ✀⤖ᬗሬᕸ㔞ࡢᙳ㡪 ... 71

4.3.3. TPABr ⃰ᗘ㸦TPA+_{/Si ẚ㸧ࡢᙳ㡪 ... 75}

4.3.4. NaOH ⃰ᗘ㸦OH-_{/Si ẚ㸧ࡢᙳ㡪 ... 80}

4.3.5. ྜᡂ᫬㛫ࡢᙳ㡪 ... 82 4.3.6. ᨭᣢయ≉ᛶࡢᙳ㡪 ... 86 4.3.7. ⭷ᙧែࡀ PV ᛶ⬟࡟୚࠼ࡿᙳ㡪 ... 87 4.3.8. ᪤ሗ࡜ࡢẚ㍑ ... 88 4.4. ⤖ゝ ... 91 4.5. ཧ⪃ᩥ⊩ ... 92

➨

5 ❶ Gel-free steam-assisted conversion ἲ࡟ࡼࡿ silicalite-1 ⭷ࡢྜᡂ ... 95

5.1. ⥴ゝ ... 95 5.2. ᐇ㦂᪉ἲ ... 97 5.2.1. silicalite-1 ✀⤖ᬗࡢㄪ〇 ... 97 5.2.2. ✀⤖ᬗሬᕸᨭᣢయࡢㄪ〇 ... 97 5.2.3. silicalite-1 ⭷ࡢㄪ〇 ... 97 5.2.4. ࢟ࣕࣛࢡࢱࣜࢮ࣮ࢩࣙࣥ ... 98 5.2.5. ᾐ㏱Ẽ໬㸦PV㸧ヨ㦂... 99 5.3. ⤖ᯝ࡜⪃ᐹ ... 100 5.3.1. silicalite-1 ✀⤖ᬗࡢㄪ〇 ... 100 5.3.2. ✀⤖ᬗሬᕸᨭᣢయࡢㄪ〇 ... 100

5.3.3. Gel-free SAC ἲ࡟ࡼࡿ silicalite-1 ⭷ࡢㄪ〇 ... 101

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3

5.3.3.2. TPAOH Ỉ⁐ᾮ⃰ᗘࡢᙳ㡪 ... 107 5.3.3.3. ྜᡂ᫬㛫ࡢᙳ㡪 ... 109 5.3.3.4. PV ᛶ⬟࠾ࡼࡧ〇⭷ཎᩱࢥࢫࢺࡢẚ㍑ ... 114 5.4. ⤖ゝ ... 116 5.5. ཧ⪃ᩥ⊩ ... 117

➨

6 ❶ ࢮ࢜ࣛ࢖ࢺศᩓࣇ࢕࣒ࣝࢆ⏝࠸ࡓ᪂つ✀⤖ᬗሬᕸ᪉ἲࡢ㛤Ⓨ ... 120

6.1. ⥴ゝ ... 120 6.2. ᐇ㦂᪉ἲ ... 121 6.2.1. silicalite-1 ✀⤖ᬗࡢㄪ〇 ... 121 6.2.2. ࢮ࢜ࣛ࢖ࢺศᩓࣇ࢕࣒ࣝࡢㄪ〇 ... 121 6.2.3. ✀⤖ᬗሬᕸᨭᣢయࡢㄪ〇 ... 123 6.2.4. silicalite-1 ⭷ࡢㄪ〇 ... 123 6.2.5. ࢟ࣕࣛࢡࢱࣜࢮ࣮ࢩࣙࣥ ... 124 6.2.6. ᾐ㏱Ẽ໬㸦PV㸧ヨ㦂... 124 6.3. ⤖ᯝ࡜⪃ᐹ ... 125 6.3.1. ࢮ࢜ࣛ࢖ࢺศᩓࣇ࢕࣒ࣝࡢㄪ〇 ... 125 6.3.2. ✀⤖ᬗሬᕸᨭᣢయࡢㄪ〇 ... 125 6.3.3. silicalite-1 ⭷ࡢㄪ〇 ... 126 6.3.4. PV ᛶ⬟ ... 129 6.3.5. film seeding ࡢ෌⌧ᛶ࡜᭷⏝ᛶ ... 130 6.4. ⤖ゝ ... 132 6.5. ཧ⪃ᩥ⊩ ... 133

➨

7 ❶ ⥲ᣓ ... 136

ཧ⪃

... 140

ㅰ㎡

... 143

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1 ➨

➨

1 ❶ ᗎㄽ

1.1. ◊✲⫼ᬒ

2015 ᖺ 12 ᭶࡟ࣃ࡛ࣜ㛤ദࡉࢀࡓᅜ㐃Ẽೃኚືᯟ⤌᮲⣙㸦United Nations Framework Convention on Climate Change; UNFCCC㸧➨ 21 ᅇ⥾⣙ᅜ఍㆟㸦Conference of Parties 21; COP21㸧

࡟࠾࠸࡚ࠊ2020 ᖺ௨㝆ࡢ ᐊຠᯝ࢞ࢫࡢ᤼ฟ๐ῶࡢࡓࡵࡢ᪂ࡓ࡞ᅜ㝿ᯟ⤌ࡳ࡜࡞ࡿࣃࣜ༠

ᐃࡀி㒔㆟ᐃ᭩࡟௦ࢃࡿ఩⨨࡙ࡅ࡜ࡋ࡚᥇ᢥࡉࢀࡓࠋࣃࣜ༠ᐃ࡟ࡣࠊඛ㐍ᅜ࣭㏵ୖᅜ࡯ࡰ ඲࡚ࡢᅜ࡟ᑐࡋ࡚ ᐊຠᯝ࢞ࢫ๐ῶ࡟ྲྀࡾ⤌ࡴἲⓗᣊ᮰ຊࢆ᭷ࡋࠊᆅ⌫ ᬮ໬ࡢཎᅉ≀㉁

࡛࠶ࡿ஧㓟໬Ⅳ⣲㸦CO2㸧ࡢ᤼ฟ๐ῶࢆࠊୡ⏺つᶍ࡛ྲྀࡾ⤌ࡲ࡞ࡅࢀࡤ࡞ࡽ࡞࠸ㄢ㢟࡜ࡋ࡚

࠸ࡿࠋࡋ࠿ࡋࠊᅜ㝿࢚ࢿࣝࢠ࣮ᶵ㛵㸦International Energy Agency; IEA㸧ࡢሗ࿌࡟ࡼࡿ࡜ࠊୡ

⏺ࡢ࢚ࢿࣝࢠ࣮ᾘ㈝࡟ࡼࡿ2017 ᖺࡢ CO2᤼ฟ㔞ࡣࠊ๓ᖺ࡜ẚ࡭࡚1.4%ቑ࠼࡚ 325 ൨ࢺࣥ࡟

㐩ࡋࡓࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓ[1]_ࠋ_{14㹼16 ᖺࡣᶓࡤ࠸≧ែࡔࡗࡓࡀ୍㌿ቑຍ࡟㌿ࡌࠊIEA ࡣࠕࣃ}

ࣜ༠ᐃࠖࡢ┠ᶆࢆ㐩ᡂࡍࡿࡓࡵ࡟ࡣࠊ⌧≧ࡢྲྀࡾ⤌ࡳࡣ୙༑ศ࡛࠶ࡿࠊ࡜ࡋ࡚࠸ࡿࠋ

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2

᪥ᮏࡢᴗ✀ู࢚ࢿࣝࢠ࣮ᾘ㈝࡟ࡼࡿ CO2᤼ฟ㔞࡟╔┠ࡍࡿ࡜ࠊ᪥ᮏࡢࣔࣀ࡙ࡃࡾࢆᨭ࠼

ࡿ㕲㗰ࡸ໬Ꮫ࡜࠸ࡗࡓ⣲ᮦ⏘ᴗࡣࠊ㕲㗰ࡢ 53%ࢆ➹㢌࡟ࠊ໬Ꮫ⏘ᴗࡣ 20%ᙉࢆ༨ࡵࠊ኱ࡁ

࡞࢚ࢿࣝࢠ࣮ࢆᾘ㈝ࡍࡿ⏘ᴗ࡛࠶ࡿ㸦Fig. 1.2㸧[2]_{ࠋ1970 ᖺ௦࠿ࡽ௒᪥ࡲ࡛᪥ᮏࡢᅜෆ⥲⏕}

⏘㸦Gross Domestic Product; GDP㸧ࡣ኱ࡁࡃఙࡧ࡚ࡁࡓࡀࠊ࢚ࢿࣝࢠ࣮ᾘ㈝㔞ࡢ኱ࡁ࠸㕲㗰

ࡸ໬Ꮫࡢศ㔝࡟࠾࠸࡚ࠊᚭᗏࡋࡓ┬࢚ࢿࣝࢠ࣮໬ࡀᅗࡽࢀ࡚࠸ࡓࡓࡵࠊ⏘ᴗศ㔝ࡢ࢚ࢿࣝ ࢠ࣮ᾘ㈝㔞ࡣ࡯࡜ࢇ࡝ኚࢃࡗ࡚࠸࡞࠸ࠋࡋ࠿ࡋࠊ㏆ᖺࡢCOP21 ࡟௦⾲ࡉࢀࡿࡼ࠺࡟ CO2᤼ ฟ๐ῶ࡟ᑐࡍࡿᅜ㝿ⓗ࡞ᙉ࠸せㄳ࠿ࡽࠊ⏘ᴗ⏺ࡣ୍ᒙࡢ࢚ࢿࣝࢠ࣮๐ῶࢆ㏕ࡽࢀ࡚࠾ࡾࠊ ᪤ ࡢᢏ⾡ࡢᘏ㛗ୖ࡟࠶ࡿᢏ⾡࡛ࡣᑐᛂࡀᴟࡵ࡚㞴ࡋࡃ࡞ࡗ࡚࠸ࡿࠋ ໬Ꮫ⏘ᴗ࡟࠾࠸࡚ࠊศ㞳࣭⢭〇ࢆ┠ⓗ࡜ࡍࡿ⵨␃ᕤ⛬࡛ࠊ⣙ 40%࡜࠸࠺኱㔞ࡢ࢚ࢿࣝࢠ ࣮ࢆᾘ㈝ࡋ࡚࠾ࡾ㸦Fig. 1.2㸧ࠊ⏘ᴗศ㔝ࡢ࢚ࢿࣝࢠ࣮ᾘ㈝㔞ࡢ⣙ 8%ࢆ༨ࡵ࡚࠸ࡿࠋ᪥ᮏࡣ COP21 ࡟࠾࠸࡚ࠊ2030 ᖺࡲ࡛࡟ 2013 ᖺẚ࡛ 26%ࡢ CO2᤼ฟ๐ῶࢆ⣙᮰ࡋ࡚࠾ࡾࠊ኱つᶍ ࡞┬࢚ࢿ໬ࢆ㐩ᡂࡍࡿࡓࡵ࡟ࡣࠊࡇ࠺ࡋࡓᕤ⛬⮬యࡢ㌿᥮ࡀᚲせ࡜࡞ࡗ࡚࠸ࡿࠋ໬Ꮫ⏘ᴗ ࡟࠾࠸࡚⣙ 40%ࡢ࢚ࢿࣝࢠ࣮ࢆ⵨␃ᕤ⛬࡛ᾘ㈝ࡋ࡚࠸ࡿࡇ࡜ࡣࠊྛᅜࡢ໬Ꮫ⏘ᴗࡶྠࡌ࡛ ࠶ࡾࠊ⵨␃ᕤ⛬࡛౑⏝ࡋ࡚࠸ࡿ࢚ࢿࣝࢠ࣮㔞ࡢ๐ῶࡣࠊCO2๐ῶ࡟ྥࡅࡓ໬Ꮫ⏘ᴗඹ㏻ࡢㄢ㢟࡛࠶ࡿࠋ ࡑࡇ࡛㏆ᖺࠊ࢚ࢿࣝࢠ࣮኱㔞ᾘ㈝ᆺࡢ⵨␃࡟௦ࢃࡿ┬࢚ࢿࣝࢠ࣮࡞ศ㞳ᢏ⾡࡜ࡋ࡚ࠊ⭷ ศ㞳ἲࡀὀ┠ࡉࢀ࡚࠸ࡿࠋ⭷ศ㞳ἲࡣࠊ┬࢚ࢿࣝࢠ࣮࡛⿦⨨ࡀࢥࣥࣃࢡࢺࠊᖖ ᖖᅽ࡟㏆ ࠸ ࿴࡞᮲௳࡛᧯స࡛ࡁࠊ⎔ቃởᰁ≀㉁※࡜࡞ࡿ๪⏕ࡋ࡞࠸⎔ቃㄪ࿴ᆺࣉࣟࢭࢫ࡛࠶ࡿࠋ ࡇࡢࡓࡵࠊ⭷ศ㞳ἲࡣࠊ⵨␃ἲࠊ྾཰ἲࠊ྾╔ἲ࡟ḟࡄ 4 ␒ᡭࡢ㠉᪂ⓗศ㞳ᢏ⾡࡜ࡋ࡚ᮇ ᚅࡉࢀ࡚࠸ࡿࠋ Fig. 1.2. ᪥ᮏࡢ⏘ᴗู CO2᤼ฟ㔞

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3 1.2. ศ㞳⭷ࡢ✀㢮

ศ㞳⭷ࡢ✀㢮ࢆ⭷⣲ᮦ࡛኱ูࡍࡿ࡜ࠊ᭷ᶵ㧗ศᏊ⭷ࠊ↓ᶵ⭷ࡢ 2 ࡘ࡟ศ㢮ࡉࢀࡿࠋ㧗ศ Ꮚ⭷ࡣࠊᏳ౯࡞ᮦᩱ㈝ࡸ〇⭷ᛶࡢⰋࡉࠊ⭷ࣔࢪ࣮ࣗࣝ໬ࡢᐜ᫆ࡉ࡞࡝ࡢほⅬ࡛ၟᴗ໬ࡀẚ ㍑ⓗ⡆༢࡛࠶ࡾ[3],[4]_{ࠊࡇࢀࡲ࡛࡟ᾏỈῐỈ໬㸦㝈እℐ㐣⭷㸧ࡸỈ⣲ࡢศ㞳⢭〇㸦࢞ࢫศ㞳㸧} ࡟ᑐࡋ࡚኱つᶍ࡟ᐇ⏝໬ࡉࢀ࡚ࡁࡓࠋࡋ࠿ࡋࠊᐇ⏝ୖࡢㄢ㢟ࡶᣦ᦬ࡉࢀ࡚࠸ࡿࠋࡍ࡞ࢃࡕࠊ 㧗ศᏊ⭷ࡢ࢞ࢫ㏱㐣ᛶ࡜ศ㞳ᛶࡣtrade-off ࡢ㛵ಀ࡟࠶ࡾ[5],[6]_{ࠊᛶ⬟ᨵၿ࡟ࡣ㝈⏺ࡀ࠶ࡿࡇ࡜ࠊ} ⪏⇕ᛶࡸ⪏⸆ရᛶࡀ༑ศ࡛ࡣ࡞ࡃࠊ㐠㌿᮲௳ࡀไ㝈ࡉࢀࡿࡇ࡜[7]_{ࠋࡲࡓࠊศ㞳ᑐ㇟࡟㧗⃰ᗘ} ࡢCO2 ࡸ᭷ᶵ໬ྜ≀ࡀྵࡲࢀࡿሙྜ࡟ࡣࠊ㧗ศᏊࡢྍረ໬ࡸ⭾₶ࡀ㉳ࡇࡾࠊ࢞ࢫศ㞳ᛶ⬟ ࡀኻࢃࢀࡿࡇ࡜࡞࡝࡛࠶ࡿ[8],[9]_{ࠋࡑࡢࡓࡵࠊ㏆ᖺࠊ㧗ศᏊ⭷࡟௦ࢃࡾࠊ㔠ᒓࠊࢩࣜ࢝ࠊ࣮࢝} ࣎ࣥࠊࢮ࢜ࣛ࢖ࢺࠊ᭷ᶵ㔠ᒓᵓ㐀య࡟௦⾲ࡉࢀࡿ↓ᶵ≀㉁ࢆ⏝࠸ࡓ↓ᶵ⭷ࡀὀ┠ࡉࢀ࡚࠸ ࡿࠋࡇࢀࡽࡢ↓ᶵ⭷ࡣࠊ⪏⇕ᛶࡀ㧗ࡃࠊࢼࣀࣞ࣋ࣝࡢᚤ⣽Ꮝᵓ㐀ࡢไᚚࡀྍ⬟ࠊ≉␗࡞㏱㐣ศ㞳ᶵ⬟ࢆ฼⏝࡛ࡁࡿ࡞࡝ࡢ≉ᚩࢆ᭷ࡋࠊ㧗ศᏊ⭷࡟ẚ࡭࡚ඃࢀࡓ㏱㐣ᛶ࡜ศ㞳ᛶࢆⓎ ᥹ࡍࡿ[7]_ࠋ

1.3. ↓ᶵ⭷ࡢ✀㢮

↓ᶵ⭷ࢆ⭷ᮦᩱ࡛኱ูࡍࡿ࡜኱ࡁࡃ 2 ࡘ࡟ศ㢮ࡉࢀࠊ㔠ᒓ࡞࡝ࡢ↓Ꮝ⭷ࠊࢩࣜ࢝ࠊ࣮࢝ ࣎ࣥࠊ᭷ᶵ㔠ᒓᵓ㐀యࠊࢮ࢜ࣛ࢖ࢺ࡞࡝ࡢከᏍ⭷ࡀ◊✲ࡉࢀ࡚࠸ࡿࠋከᏍ⭷࡟ࡣࠊࢮ࢜ࣛ ࢖ࢺࡸ᭷ᶵ㔠ᒓᵓ㐀యࡢࡼ࠺࡟ࠊᅛ᭷ࡢᚤ⣽Ꮝࢆ᭷ࡍࡿ⤖ᬗ⢏Ꮚࢆᡂ㛗ࡉࡏ࡚⭷࡜ࡍࡿࡶ ࡢ࡜ࠊࢩࣜ࢝ࡸ࣮࢝࣎ࣥࡢࡼ࠺࡟┠ⓗ≀ᚤ⢏Ꮚࢆ⭷≧࡟✚ᒙࡋࠊ⢏Ꮚ㛫ࢆ⣽Ꮝ࡜ࡍࡿࡶࡢ ࡀ࠶ࡿࠋྛ✀↓ᶵ⭷ࡢ≉ᚩࢆୗグ࡟ࡲ࡜ࡵࡿࠋ 㸦a㸧㔠ᒓ⭷ ⣽Ꮝࢆࡶࡓ࡞࠸⦓ᐦ࡞⭷࡛࠶ࡾࠊศ㞳ᶵᵓࡣ⁐ゎᣑᩓᶵᵓ࡛࠶ࡿࠋ୍⯡ⓗ࡞㔠ᒓ⭷࡜ࡋ ࡚ࠊࣃࣛࢪ࣒࢘⭷࣭ࣃࣛࢪ࣒࢘ྜ㔠⭷ࡀ࠶ࡾࠊඃࢀࡓỈ⣲ศ㞳ᛶ⬟ࢆ♧ࡍ[10]_{ࠋẼయࡢỈ⣲} ࡀ⭷⾲㠃࡛ゎ㞳ࡋࠊཎᏊ≧Ỉ⣲ࡀ⭷ෆ㒊ࢆᣑᩓࡋ࡚㏱㐣ࡍࡿࡓࡵࠊ㧗⣧ᗘ࡞Ỉ⣲ࡀᚓࡽࢀ ࡿࠋࡋ࠿ࡋࠊ౑⏝ ᗘ㡿ᇦࡢไ㝈࣭Ỉ⣲⬤໬ࡸ◲㯤⿕ẘ࡟ࡼࡿ≉ᛶຎ໬ࠊࡉࡽ࡟ࠊᕼᑡ㔠 ᒓ࡛࠶ࡿࡀᨾࡢ㧗ࢥࢫࢺࡀᐇ⏝໬࡟ྥࡅ࡚ࡢ኱ࡁ࡞ㄢ㢟࡜࡞ࡗ࡚࠸ࡿ[10]_ࠋ 㸦b㸧ࢩࣜ࢝⭷ ࢩࣜ࢝⭷ࡣ࢔ࣔࣝࣇ࢓ࢫᵓ㐀࡛࠶ࡾࠊࢩࣜ࢝ᚤ⢏Ꮚ㛫ࡢ㛫㝽ࢆ⣽Ꮝ࡜ࡋ࡚ศᏊࡩࡿ࠸ᶵ ᵓ࡛ศ㞳ࢆ࠾ࡇ࡞࠺ࠋࢰࣝࢤࣝἲࡸ໬Ꮫ⵨╔㸦Chemical Vapor Deposition; CVD㸧ἲ࡛〇⭷ࡉ

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4

ࢀ[11],[12]_{ࠊ⣧⢋࡞ࢩࣜ࢝⭷ࡢ⣽Ꮝᚄࡣ⣙}_{0.3 nm ࡜ࡉࢀࠊ〇⭷᮲௳࡟ࡼࡾ⭷ࡢ⣽Ꮝᚄไᚚࡀྍ} ⬟࡛࠶ࡿࠋࡲࡓࠊ௚ࡢ↓ᶵᮦᩱ࡜ẚ㍑ࡋ࡚ࠊⷧ⭷≧࡟〇⭷ࡀྍ⬟࡛࠶ࡿࡇ࡜࠿ࡽࠊ㧗Ỉ⣲ 㑅ᢥ㏱㐣ᛶࢆ♧ࡍࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿ[11]_ࠋ 㸦c㸧Ⅳ⣲㸦࣮࢝࣎ࣥ㸧⭷ Ⅳ⣲⭷ࡣࠊศ㞳άᛶᒙࡀ࢔ࣔࣝࣇ࢓ࢫⅣ⣲࡟ࡼࡾᙧᡂࡉࢀࡿศ㞳⭷࡛࠶ࡾࠊ๓㥑య࡜࡞ ࡿ㧗ศᏊ⭷ࢆ୙άᛶ㞺ᅖẼୗ࡟࠾࠸࡚ 500㹼1000°C ࡛⇕ศゎ࣭Ⅳ໬ࡍࡿࡇ࡜࡟ࡼࡾ〇⭷ࡉ ࢀࠊⅣ⣲ᚤ⤖ᬗᏊࡢ㝽㛫ࡀ⣽Ꮝ࡜ࡋ࡚ᶵ⬟ࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋ୍⯡ⓗ࡟ࠊⅣ⣲⭷ ࡢ⣽Ꮝࢧ࢖ࢬࠊ྾╔≉ᛶࡣࠊࡉࡲࡊࡲ࡞⇕ศゎ᮲௳ࡸ㧗ศᏊ๓㥑య࡟ࡼࡗ࡚࠶ࡿ⛬ᗘㄪ〇 ࡍࡿࡇ࡜ࡀ࡛ࡁࡿ[13],[14]_{ࠋ≉࡟ࠊ0.3-0.5 nm ࡢ࣐࢖ࢡࣟᏍࢆ᭷ࡍࡿศᏊࡩࡿ࠸Ⅳ⣲⭷ࡣࠊ≉} ᭷ࡢศᏊࡩࡿ࠸⬟࡟ࡼࡗ࡚ࠊ࢞ࢫ࠶ࡿ࠸ࡣ⵨Ẽศ㞳⭷࡜ࡋ࡚ඃࢀࡓศ㞳ᛶ⬟ࢆ♧ࡍࡇ࡜ࡀ ▱ࡽࢀ࡚࠸ࡿ[15]_ࠋ

㸦d㸧㔠ᒓ᭷ᶵᵓ㐀య㸦Metal organic framework; MOF㸧⭷

MOF ࡣከ᰾㔠ᒓཎᏊ࡜᭷ᶵ㓄఩Ꮚࡢ㓄఩⤖ྜ࡟ࡼࡾᙧᡂࡉࢀࡿከᏍ㉁ࡢ⤖ᬗయ࡛࠶ࡾࠊ 㧗つ๎ᛶࡢ⣽Ꮝᵓ㐀࡜㧗࠸ẚ⾲㠃✚ࢆᣢࡘࡇ࡜ࠊࡉࡽ࡟ᚑ᮶ࡢከᏍᮦᩱ࡜ẚ㍑ࡋ࡚✵Ꮝ⋡ ࡀ㧗࠸࡜࠸࠺≉㛗ࢆ᭷ࡍࡿ[16],[17]_ࠋ_{MOF ࡟ࡣ㔠ᒓ✀࡜᭷ᶵ㓄఩Ꮚࡢ⤌ࡳྜࢃࡏ࡟ࡼࡾᩘከࡃ} ࡢ✀㢮ࡀᏑᅾࡋࠊ⣽Ꮝࢧ࢖ࢬࡣ0.3-2 nm ⛬ᗘ࡛࠶ࡿࠋࡲࡓࠊMOF ࡢ✀㢮࡟ࡼࡗ࡚ࡣࠊ࣐࢖ ࢡࣟᏍ࡟࠾࠸࡚≉ᐃࡢẼయศᏊ࡟ᑐࡍࡿ㧗࠸྾╔ᛶࢆ♧ࡍࡶࡢࡶᏑᅾࡍࡿࠋࡇࡢࡓࡵࠊMOF ࢆศ㞳⭷ᮦᩱ࡜ࡋ࡚⏝࠸ࡓ㔠ᒓ᭷ᶵᵓ㐀య⭷㸦MOF ⭷㸧ࡣࠊศᏊࢧ࢖ࢬࡢ㐪࠸࡟ᇶ࡙࠸࡚ Ẽయࢆศ㞳ࡍࡿศᏊࡩࡿ࠸ຠᯝ࡜ࠊ≉ᐃࡢẼయศᏊ࡟ᑐࡍࡿ㧗࠸྾╔ຠᯝ࡟ࡼࡗ࡚ࠊ㧗࠸ Ẽయ㑅ᢥ㏱㐣ᛶࢆ♧ࡍࡇ࡜ࡀᮇᚅࡉࢀࡿ[18]-[20]_ࠋ 㸦e㸧ࢮ࢜ࣛ࢖ࢺ⭷ ⤖ᬗᛶ࢔࣑ࣝࣀࢣ࢖㓟ሷ࡛࠶ࡿࢮ࢜ࣛ࢖ࢺࡣࠊࡑࡢ≉␗ⓗ࡞⤖ᬗᵓ㐀ࠊ⣽Ꮝᚄࠊ྾╔ศ 㞳⬟ࠊ࢖࢜ࣥ஺᥮⬟ࠊᅛయ㓟ᛶ࡞࡝ࡢᛶ㉁࠿ࡽࠊ྾╔ᮦࠊ࢖࢜ࣥ஺᥮ᮦࠊゐ፹࡞࡝ࡢᶵ⬟ ᛶᮦᩱ࡜ࡋ࡚ᗈࡃ฼⏝ࡉࢀ࡚࠸ࡿ[21]_{ࠋศ㞳⭷⣲ᮦ࡜ࡋ࡚ࡶࠊࢮ࢜ࣛ࢖ࢺࡢ⤖ᬗᵓ㐀࡟⏤᮶} ࡍࡿつ๎ⓗ࡞࣑ࢡࣟ⣽Ꮝᵓ㐀࡟ᇶ࡙ࡃศᏊࡩࡿ࠸స⏝ࠊ㦵᱁⤌ᡂ࡟ᇶ࡙ࡃ྾╔ᛶࡢ㐪࠸ࡀ ㏱㐣ศ㞳ᛶ⬟ࡢⓎ⌧࡟⤖ࡧࡘࡃࡇ࡜࡟ࡼࡗ࡚ࠊࡉࡲࡊࡲ࡞ศᏊΰྜ≀ࡢศ㞳ࡀᐇ⌧ࡉࢀࡿ ࡇ࡜ࡀᮇᚅࡉࢀ࡚࠸ࡿ[7]_{ࠋᮏ◊✲࡛ࡣࠊ⭷⣲ᮦ࡜ࡋ࡚ࢮ࢜ࣛ࢖ࢺ࡟╔┠ࡋࠊ௨ୗ࡟ࢮ࢜ࣛ࢖} ࢺ࠾ࡼࡧࢮ࢜ࣛ࢖ࢺ⭷࡟ࡘ࠸࡚ㄝ᫂ࡍࡿࠋ

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5 1.4. ࢮ࢜ࣛ࢖ࢺ

1.4.1. ࢮ࢜ࣛ࢖ࢺࡢᵓ㐀ⓗ≉ᚩ ࢮ࢜ࣛ࢖ࢺ㸦zeolite㸧ࡣࠊࢠࣜࢩࣕㄒ࡛ࠕἛ㦐ࡍࡿ㸦Zeo㸧▼㸦Lite㸧ࠖࢆព࿡ࡋࠊ1756 ᖺ ࡟ࢫ࢙࣮࢘ࢹࣥࡢ㖔≀Ꮫ⪅Axel F. Cronstedt ࡟ࡼࡗ࡚Ⓨぢࡉࢀࡓࠋࢮ࢜ࣛ࢖ࢺࡣࠊT ཎᏊ㸦ࢮ ࢜ࣛ࢖ࢺ㦵᱁ᵓ㐀ෆ࡛4 㓄఩ᵓ㐀ࢆ࡜ࡿཎᏊ㸧࡜࿧ࡤࢀࡿ Si ཎᏊ࠾ࡼࡧ Al ཎᏊࢆ୰ᚰඖ⣲ ࡜ࡋ࡚ࠊṇᅄ㠃యࡢ㡬Ⅼ࡟㓟⣲ࡀᏑᅾࡍࡿᵓ㐀ࢆᇶᮏ㦵᱁࡜ࡋࠊࡇࢀࡀ㡬Ⅼࡢ㓟⣲ࢆ௓ࡋ ࡓඹ᭷⤖ྜ࡟ࡼࡾ୕ḟඖⓗ࡟㐃࡞ࡗࡓᵓ㐀ࢆᣢࡘ㸦Fig. 1.3 a㸧ࠋࡇࡢṇᅄ㠃యࡀつ๎ⓗ࡟㓄 ิࡋࠊ⥙┠ᵓ㐀ࡀᙧᡂࡉࢀࡿ࡜⤖ᬗ࡜࡞ࡾࠊࡑࢀࡽࡢከࡃࡣ㦵᱁ᵓ㐀ෆ࡟つ๎ⓗ࡟㓄ิࡋ ࡓ๛┤࡞0.3-1.0 nm ⛬ᗘࡢ࣑ࢡࣟᏍࡶࡘࡇ࡜ࡀ࡛ࡁࡿࠋࢮ࢜ࣛ࢖ࢺࡣࠊࡇ࠺ࡋࡓ࣑ࢡࣟከᏍ ᛶࡢ࢔࣑ࣝࣀࢩࣜࢣ࣮ࢺ⤖ᬗࡢ⥲⛠࡛࠶ࡿࠋࢮ࢜ࣛ࢖ࢺࡢᵓ㐀ࡣࠊᅜ㝿ࢮ࢜ࣛ࢖ࢺᏛ఍

㸦International Zeolite Association; IZA㸧ࡢ Structure Commission ࡛ࡢᑂ㆟ࢆ⤒࡚ᢎㄆࡉࢀࠊ࢔

ࣝࣇ࢓࣋ࢵࢺ኱ᩥᏐ3 ಶ࠿ࡽ࡞ࡿ㦵᱁ࢱ࢖ࣉࢥ࣮ࢻ㸦Framework Type Code; FTC㸧࡛⾲ࢃࡉ

ࢀࠊ2018 ᖺ 8 ᭶⌧ᅾ 239 ✀㢮ࡶࡢᵓ㐀ࡀ▱ࡽࢀ࡚࠸ࡿ[22]_{ࠋࢮ࢜ࣛ࢖ࢺࡣ㦵᱁୰࡟}_{Al ࢆྵࡴ} ሙྜࠊSi4+_ࢆ_Al3+_{࡟ྠᆺ⨨᥮ࡋ࡚࠸ࡿࡓࡵࠊ㦵᱁ࡣ㈇㟁Ⲵࢆࡶࡕࠊ㟁Ẽⓗ୰ᛶࢆಖࡘࡓࡵ࡟} ࡣࠊ௚ࡢ࢝ࢳ࡛࢜ࣥ⿵࠺ࡇ࡜ࡀᚲせ࡜࡞ࡿ㸦Fig. 1.3 b㸧ࠋࡋࡓࡀࡗ࡚ࠊ໬Ꮫ⤌ᡂࡣ୺࡟ࠊ㦵 ᱁ࢆᵓᡂࡍࡿSiࠊAl ࡜㦵᱁ࡀࡶࡘ㈇㟁Ⲵࢆಖドࡍࡿࡓࡵࡢ࢝ࢳ࢜ࣥ㸦Na+_ࠊ_K+_ࠊ_Ca2+_㸧࠾ࡼ ࡧ⤖ᬗỈࡼࡾ࡞ࡾࠊMx/mAlxSi1-xO2࣭nH2O㸹M ࡣ౯ᩘ m ࡢ㝧࢖࢜ࣥ࡜⊃⩏࡟ᐃ⩏ࡉࢀ࡚࠸ࡿࠋ ࡇࡢࡼ࠺࡟ࠊࢮ࢜ࣛ࢖ࢺࡣ1 nm ௨ୗࡢ࣑ࢡࣟᏍ࡜㦵᱁ࡀࡶࡘ㈇㟁Ⲵ࡟ࡼࡾࠊ≉᭷ࡢ࢖࢜ࣥ ஺᥮⬟ࠊゐ፹ᶵ⬟ࠊ྾╔ศ㞳⬟ࢆⓎ⌧ࡍࡿࠋ Fig. 1.3. ࢮ࢜ࣛ࢖ࢺᵓ㐀ࡢᡂࡾ❧ࡕ㸦a㸧࡜㦵᱁ᵓ㐀㸦b㸧 ੦ম෗ત ٛ72౐ਜ਼ٜ ٛ72౐ਜ਼भ৴ਢ੥়ٜ 3ઃ੪৓प৴੥ : T = Si or Al : O ಍ሠଡୗ 1 μm

MFI-type zeolite

८ड़ছॖॺ੥အ ಍ሠྫྷ 5.3 Å 5.6 Å O M+ _M+ Si Si Al O O O O Al O O O O O O O O ෗તਗق಍ሠ৔كप଀ਗ਼෰॑ ଓ೥घॊ഻ॖड़থقM+كऋோ૔ (a) (b)

(11)

6

ࢮ࢜ࣛ࢖ࢺࡢᵓ㐀ࢆ≉ᚩ௜ࡅࡿ࣑ࢡࣟ⣽Ꮝࡣࠊ⣽Ꮝධࡾཱྀࢆᵓᡂࡍࡿ㓟⣲࢖࢜ࣥࡢᩘ࡟ ࡼࡗ࡚⾲ࡉࢀࠊᑠ⣽Ꮝࢮ࢜ࣛ࢖ࢺ㸦small pore㸹8 ဨ⎔㸧ࠊ୰⣽Ꮝࢮ࢜ࣛ࢖ࢺ㸦medium pore㸹 10 ဨ⎔㸧ࠊ኱⣽Ꮝࢮ࢜ࣛ࢖ࢺ㸦large pore㸹12 ဨ⎔㸧ࠊ㉸኱⣽Ꮝࢮ࢜ࣛ࢖ࢺ㸦ultralarge pore㸹 14 ဨ⎔௨ୖ㸧࡜ศ㢮ࡉࢀࠊ኱ࡁࡉࡣࡑࢀࡒࢀࠊ0.3-0.4 nm ⛬ᗘࠊ0.55 nmࠊ0.7 nm ⛬ᗘ࠾ࡼ ࡧ1.0 nm ⛬ᗘ࡛࠶ࡿࠋFig. 1.4 ࡟♧ࡍࡼ࠺࡟ࠊࢮ࢜ࣛ࢖ࢺ⣽Ꮝࡢ኱ࡁࡉࡣࠊ↓ᶵ࢞ࢫࡸᵝࠎ ࡞ᇶ♏໬Ꮫရ࡜࿧ࡤࢀࡿᑠศᏊࡢ኱ࡁࡉ࡟㏆࠸ࠋࢮ࢜ࣛ࢖ࢺࡣࡇࡢ⣽Ꮝࡢᵓ㐀ⓗ≉ᚩ࠿ࡽࠊ ධࡾཱྀࡢ኱ࡁࡉࡼࡾᑠࡉ࠸ศᏊࡢࡳࢆ㏱㐣ࡉࡏࠊ⣽Ꮝධࡾཱྀࡼࡾ኱ࡁ࠸ศᏊࡣ᤼㝖ࡉࢀࡿ ࡜࠸࠺ࠊࠕᙧ≧㑅ᢥᛶ㸦shape-selectivity㸧ࠖࠊ࠸ࢃࡺࡿࠕศᏊࡩࡿ࠸ࠖస⏝ࢆ♧ࡍࡇ࡜ࡀࠊ᭱ ኱ࡢ≉ᚩ࡛࠶ࡿ࡜࠸࠼ࡿࠋ ࢮ࢜ࣛ࢖ࢺࡢ྾╔⬟ࡣࠊࢮ࢜ࣛ࢖ࢺࡢぶ/␯Ỉᛶ࡟ᕥྑࡉࢀࠊࡑࡢ≉ᛶࡣ㦵᱁ࢆᵓᡂࡍࡿ Si ࡜ Al ࡢẚ࡟ࡼࡗ࡚Ỵᐃࡉࢀࡿ㸦Fig. 1.5 a㸧ࠋࢮ࢜ࣛ࢖ࢺࡢぶ/␯Ỉᛶࡣࠊ⣽Ꮝෆ࢝ࢳ࢜ࣥ

࡟㉳ᅉࡍࡿ㟼㟁ሙࡢࡓࡵ࡟ࠊSi/Al ẚࡀ㧗࠸࡯࡝ᙉ࠸ぶỈᛶࢆ♧ࡋࠊA ᆺ㸦Si/Al㸻1.0㸧ࠊX

ᆺ㸦Si/Al㸻1.0-1.5㸧ࡀࡑࡢ඾ᆺ࡛࠶ࡿࠋSi/Al ẚࡀ㧗ࡃ࡞ࡿ࡟ࡘࢀ࡚ࠊ㟼㟁ሙᙉᗘࡀపୗࡋ ࡚ࠊᴟᛶศᏊ࡟ᑐࡍࡿ┦஫స⏝ࡀᙅࡃ࡞ࡾࠊ␯Ỉⓗ࣭ぶἜⓗᛶ㉁ࡀ⌧ࢀࠊsilicalite-1㸦Si/Al 㸻∞㸧ࡀࡑࡢ඾ᆺ࡜࡞ࡿࠋࡲࡓࠊࢮ࢜ࣛ࢖ࢺࡢ㦵᱁ᵓ㐀ࡣ Si/Al ẚ࡟ࡼࡾ࠶ࡿ⛬ᗘỴࡲࡗ࡚ ࠸ࡿࡀࠊMFI ᆺࢮ࢜ࣛ࢖ࢺࡢࡼ࠺࡟ぶỈᛶ࠿ࡽ␯Ỉᛶ࡜࡞ࡿ⠊ᅖ࡛ Si/Al ẚࢆᖜᗈࡃไᚚྍ ⬟࡞ࢮ࢜ࣛ࢖ࢺࡶᏑᅾࡍࡿ㸦Fig. 1.5 b㸧ࠋ Fig. 1.4. ௦⾲ⓗ࡞ࢮ࢜ࣛ࢖ࢺࡢ㦵᱁ᵓ㐀࠾ࡼࡧ⣽Ꮝᚄ࡜ศ㞳ᑐ㇟ࡢ≀㉁࡜ࡑࡢศᏊᚄ ८ड़ছॖॺधजभ಍ሠྫྷ ী௞ৌ଴भ੟ସधजभী৕ྫྷ

0.2

0.3

0.4

0.5

0.6

0.7

[nm] H2(0.27) H₂O(0.28) CO2(0.33) p-xylene(0.51) C₂H₅OH(0.44) n-C₄H₁₀(0.43) i-C4H10(0.50) o,m-xylene(0.58) MFI (0.55) DDR (0.36¼0.44) LTA (NaA) (0.42) T-type (0.36¼0.48) CHA (SAPO-34) (0.37¼0.42) O₂(0.35) N₂(0.36) CH₄(0.38) C2H6(0.40) Benzene(0.59) C₃H₈(0.43) FER (0.43¼0.56) MOR (0.67¼0.70) FAU (0.74) *BEA (0.76)

(12)

7

Fig. 1.5. ࢮ࢜ࣛ࢖ࢺࡢぶ/␯Ỉᛶ㸦a㸧࡜ྛ✀ࢮ࢜ࣛ࢖ࢺࡢ㦵᱁ᵓ㐀࡜ Si/Al ẚࡢ㛵ಀ㸦b㸧

1.4.2. ࢮ࢜ࣛ࢖ࢺࡢྜᡂ

ࢮ࢜ࣛ࢖ࢺࢆྜᡂࡍࡿࡓࡵ࡟ᚲせ࡞ཎᩱ㸦ฟⓎ≀㉁㸧ࡣࠊ㦵᱁ࢆᵓᡂࡍࡿSi ࡸ Al ࡢ໬ྜ

≀ࠊ⤖ᬗᵓ㐀ࢆసࡿࡓࡵ࡟ᚲせ࡞ᵓ㐀つᐃ๣㸦Structure Directing Agent; SDA㸧ࠊ㖔໬๣ࠊỈ ࡛࠶ࡿࠋ≉␗࡞ᵓ㐀ࡸᙧែࢆ᭷ࡍࡿࢮ࢜ࣛ࢖ࢺ⤖ᬗࢆᚓࡿ࡟ࡣࠊᅄ⣭࢔ࣥࣔࢽ࣒࢘ሷ࡟௦ ⾲ࡉࢀࡿ᭷ᶵሷࢆῧຍࡍࡿᚲせࡀ࠶ࡿࠋࡇࡢ᭷ᶵሷࡢ 3 ḟඖⓗ࡞ᵓ㐀ࡢ㐪࠸࡟ࡼࡾࠊᚓࡽ ࢀࡿࢮ࢜ࣛ࢖ࢺࡢᵓ㐀ࢆไᚚࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋࡇࡢࡼ࠺࡞᭷ᶵሷࡣࠊࢮ࢜ࣛ࢖ࢺ⣽Ꮝࢆ ᙧᡂࡍࡿࡓࡵࡢ㗪ᆺ࡜ࡋ࡚ᙺ๭ࢆ୚࠼ࡽࢀࠊtemplate㸦㗪ᆺ㸧࡜࿧ࡤࢀࡿࡼ࠺࡟࡞ࡾࠊᚤᑠ ࡞㦵᱁ᵓ㐀ࣘࢽࢵࢺࢆ㑅ᢥⓗ࡟⏕ᡂࡉࡏࡿᙺ๭ࢆᣢࡘ࡜ࡶ⪃࠼ࡽࢀࠊSDA ࡜࿧ࡤࢀࡿࡼ࠺ ࡟࡞ࡾࠊྠᵝ࡟㑅ᢥⓗ࡞ᵓ㐀ࣘࢽࢵࢺᙧᡂࡢᙺ๭ࡀ࠶ࡿ࡜ࡉࢀ࡚࠸ࡿNa+_{ࡢࡼ࠺࡞↓ᶵ࢝ࢳ} ࢜ࣥࡶྵࡲࢀࡿࠋ㖔໬๣ࡣࠊཎᩱࢆ⁐ゎࡉࡏ෌⤖ᬗ໬ࡉࡏࡿᙺ๭ࢆᣢࡘࡶࡢ࡛࠶ࡾࠊࢮ࢜ ࣛ࢖ࢺྜᡂ࡟࠾࠸࡚ࡣNaOHࠊKOHࠊHF ࡞࡝ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡓࡔࠊࢩࣛࣀ࣮ࣝࡢ⦰ྜࡸ ࢩࣟ࢟ࢧࣥࡢ㛤⿣ࢆಁ㐍ࡉࡏࡿࡢࡣOH-_ࡸ_F-_{࡛࠶ࡿࡇ࡜ࢆ⪃៖ࡍࡿ࡜ࠊ}_{NaOH ࢆࡦ࡜ࡲ࡜ࡵ} ࡟㖔໬๣࡜࿧⛠ࡍࡿࡼࡾࠊ↓ᶵSDA ࡛࠶ࡿ Na+_{࡜㖔໬๣࡛࠶ࡿ}_OH-_{ࡢ໬ྜ≀࡜࡜ࡽ࠼ࡿ᪉}

Hydrophilic/hydrophobic of zeolite

O Na+ _Na+ Si Si Al O O O O Al O O O O O O O O O Si Si Si O O O O Si O O O O O O O O

Si/Al

ratio

Hydrophilic

Hydrophobic

LTA

FAU

MOR

MFI

1 ∞ Hydrophilic Hydrophobic 5 10 Si/Al ratio Surface properties High Low

(a)

(b)

(13)

8

ࡀṇ☜࡜ゝ࠼ࡿ࠿ࡶࡋࢀ࡞࠸ࠋࡲࡓࠊIZA ࡛ࡣࠊ௦⾲ⓗ࡞ࢮ࢜ࣛ࢖ࢺࢆྜᡂࡍࡿࡓࡵࡢཎᩱࠊ

ྜᡂ᮲௳࡞࡝ࡢヲ⣽ࢆVerified Syntheses of Zeolite Materials[23]_{࡟࡚බ㛤ࡋ࡚࠸ࡿࡀࠊࢮ࢜ࣛ}

࢖ࢺࡣ‽Ᏻᐃ┦࡛࠶ࡾࠊྜᡂ᮲௳ࡢல⣽࡞ኚ໬ࠊࡲࡓ⏝࠸ࡿヨ⸆ࡢ✀㢮ࠊ〇㐀఍♫ࡀ␗࡞ ࡿࡔࡅ࡛඲ࡃ␗࡞ࡿ㦵᱁ᵓ㐀ࡀᚓࡽࢀࡿࡇ࡜ࡀ࠶ࡿࡢ࡛ࠊ෌⌧ᛶࡼࡃ┠ⓗ࡜ࡍࡿࢮ࢜ࣛ࢖ ࢺࢆྜᡂࡍࡿ࡟ࡣࠊᵝࠎ࡞Ⅼ࡟࠾࠸࡚Ẽࢆ㓄ࡿᚲせࡀ࠶ࡿࠋ௨ୗ࡟ࢮ࢜ࣛ࢖ࢺྜᡂࡢ௦⾲ ⓗ࡞ᡭἲ࡟ࡘ࠸࡚㏙࡭ࡿࠋ 㸦a㸧Ỉ⇕ྜᡂἲ ࢮ࢜ࣛ࢖ࢺࡢ᭱ࡶ୍⯡ⓗ࡞ྜᡂ᪉ἲ࡛࠶ࡿࠋࡲࡎࠊࢩࣜ࢝※ࠊ࢔࣑ࣝࢼ※ࠊ࢔ࣝ࢝ࣜࠊ SDAࠊỈࢆΰྜࡋࡓሷᇶᛶࡢỈᛶࢤࣝࢆㄪ〇ࡋࠊࡇࡢࢮ࢜ࣛ࢖ࢺ๓㥑యỈᛶࢤࣝࢆỈ⇕ྜ ᡂ ᗘࡼࡾࡶప࠸ ᗘ࡛ࠊ᧠ᢾࡋ࡞ࡀࡽ࠶ࡿ࠸ࡣ㟼⨨ࡋ࡞ࡀࡽࠊ࢚࣮ࢪࣥࢢ㸦⇍ᡂ㸧ࢆ⾜ ࠺ࠋࡇࡢ࢚࣮ࢪࣥࢢ୰࡟๓㥑య࡟ఱࡀ㉳ࡇࡗ࡚࠸ࡿࡢ࠿ࡣ᫂☜࡟࡞ࡗ࡚࠾ࡽࡎࠊ༢⣧࡟Ỉ ⇕ྜᡂ๓ࡢ᧠ᢾ᫬㛫ࢆ㛗ࡃࡍࡿࡇ࡜࡟ࡼࡾࠊཎᩱ୰࡟ྵࡲࢀࡿ⤖ᬗᛶ≀㉁ࢆ᏶඲࡟⁐ゎࡉ ࡏࡿࡓࡵࠊ࠶ࡿ࠸ࡣ๓㥑యࡢᆒ୍ᛶࢆቑࡍࡓࡵࠊỈ⇕ྜᡂ᫬࡟᰾⏕ᡂࡢࡓࡵࡢᮦᩱࢆᙧᡂ ࡉࡏࡿࡓࡵ࠿ࡶࡋࢀ࡞࠸ࠋࡓࡔࠊࢮ࢜ࣛ࢖ࢺࡢ๓㥑యࡣࠊẕࢤࣝࡸỈᛶࢤࣝ࡞࡝࡜࿧ࡤࢀ ࡚࠸ࡿࡀࠊᐇ㝿࡟ࡣ࡯࡜ࢇ࡝ࡢሙྜࢰࣝࠊࡘࡲࡾ⢏Ꮚศᩓ⣔࡛࠶ࡿࡇ࡜ࢆ⪃࠼ࡿ࡜ࠊ࢚࣮ ࢪࣥࢢ㐣⛬ࡀ๓㥑యࡢᆒ୍໬࡟ᐤ୚ࡋ࡚࠸ࡿࡇ࡜ࡣ㛫㐪࠸࡞࠸ࠋࡑࡢᚋࠊࡇࡢ๓㥑యỈᛶ ࢤࣝࢆ࣮࢜ࢺࢡ࣮ࣞࣈ࡜࿧ࡤࢀࡿ㧗㧗ᅽᐦ㛢ᐜჾ୰࡟ᑟධࡋࠊᐜჾࢆᐦ㛢ࡋࡓࡲࡲ࡛ຍ ⇕ࡍࡿࡇ࡜࡟ࡼࡾࠊ⤖ᬗ໬᧯సࢆ⾜࠺ࠋ㧗㧗ᅽࡢ⇕ỈࡢᏑᅾୗ࡛཯ᛂࡀ㐍ࡴࡇ࡜࠿ࡽࠊ ᖖ ᖖᅽ࡛ࡣỈ࡟⁐ࡅ࡞࠸≀㉁ࡶ⁐ゎྍ⬟࡛࠶ࡿࡇ࡜ࡀከࡃࠊ㏻ᖖ࡛ࡣᚓࡽࢀ࡞࠸ࡼ࠺࡞ ≀㉁ࢆྜᡂࡍࡿࡇ࡜ࡀྍ⬟࡛࠶ࡿࠋỈ⇕ฎ⌮ᚋࠊ⏕ᡂ≀ࡣᚤ⢏Ꮚ≧ࡢᠱ⃮ᾮ࡛ᚓࡽࢀࡿࡓ ࡵࠊ྾ᘬℐ㐣ࡸ㐲ᚰศ㞳࡟ࡼࡾศ㞳ࠊᅇ཰ࡋࠊࢁᾮࡢpH ࡀ୰ᛶ⛬ᗘ࡟࡞ࡿࡲ࡛Ὑίࢆ⧞ࡾ ㏉ࡍࡢࡀ୍⯡ⓗ࡛࠶ࡿࠋ 㸦b㸧ࣇࢵ໬≀ῧຍἲ ㏻ᖖࡢỈ⇕ྜᡂἲ࡛ࡣࠊ㖔໬๣ࢆỈ㓟໬≀࢖࢜ࣥ࡜ࡋ࡚࢔ࣝ࢝ࣜ᮲௳ୗ࡛⾜ࢃࢀࡿࡀࠊ F-_{ࢆ㖔໬๣࡜ࡋ࡚⏝࠸ࡓྜᡂࡶ࠶ࡿ㸦ࣇࢵ໬≀ῧຍἲ㸧ࠋࡇࡢ᪉ἲࡣࠊỈ⇕ྜᡂἲࡢ୍✀࡛} ࠶ࡿࡀࠊ㖔໬๣࡜ࡋ࡚ࠊỈ㓟໬≀࢔ࢽ࢜ࣥࢆ⏝࠸㧗࠸pH ࡛ྜᡂࡉࢀࡿ୍⯡ⓗ࡞Ỉ⇕ྜᡂ࡜ ࡣ␗࡞ࡾࠊF-_{࢖࢜ࣥࢆᏑᅾࡉࡏ࡚୰ᛶ௜㏆࡛ྜᡂࡍࡿ᪉ἲ࡛࠶ࡿ}[24]_ࠋ_F-_{࢖࢜ࣥࡢῧຍຠᯝ࡜} ࡋ࡚ࡣࠊ㖔໬స⏝㸦ẚ㍑ⓗప࠸pH 㡿ᇦ࡟࠾࠸࡚ OH-_{࡜ྠࡌࡼ࠺࡟ࢤࣝࢆ⁐ゎࠊ⤖ᬗ໬ࡉࡏ} ࡿຠᯝ㸧ࠊᵓ㐀ไᚚຠᯝ㸦≉ᐃᵓ㐀ࡢࢮ࢜ࣛ࢖ࢺࢆ⤖ᬗ໬ࡉࡏࡿຠᯝ㸧ࠊࢸࣥࣉ࣮ࣞࢺຠᯝ 㸦᭷ᶵࢸࣥࣉ࣮ࣞࢺ࡜ྠࡌࡼ࠺࡟⤖ᬗ໬ᚋࡢᵓ㐀ࢆᏳᐃ໬ࡉࡏࡿຠᯝ㸧ࡀ࠶ࡿࠋࡲࡓࠊࣇ

(14)

9

ࢵ໬≀ῧຍἲ࡛ࡣࠊ㦵᱁ᵓ㐀ࡀྠࡌ࡛ࡶࠊḞ㝗ࡀᑡ࡞ࡃ኱ࡁ࡞⤖ᬗࡀᚓࡽࢀࡿࠋF-_※࡜ࡋ࡚

ࡣࠊࣇࢵ໬Ỉ⣲㓟ࡢ࡯࠿࡟ࠊࣇࢵ໬࢔ࣥࣔࢽ࣒࢘ࠊࣇࢵ໬ࢼࢺ࣒ࣜ࢘ࠊࣇࢵ໬࣒࢝ࣜ࢘ࠊ ୕ࣇࢵ໬࣍࢘⣲࡞࡝ࡢሷ㢮ࡀ౑⏝ࡉࢀࡿࠋ

㸦c㸧ࢻࣛ࢖ࢤࣝࢥࣥࣂ࣮ࢪࣙࣥ㸦Dry Gel Conversion; DGC㸧ἲ

Ỉ⇕ྜᡂἲࡀཎᩱࢆΰࡐ࡚ᚓࡽࢀࡿỈᛶࢤࣝ㸦hydrogel㸧ࢆࡑࡢࡲࡲ࣮࢜ࢺࢡ࣮ࣞࣈ࡟ᑟ ධࡍࡿᾮ┦ྜᡂἲ㸦Fig. 1.6 a㸧࡛࠶ࡿࡢ࡟ᑐࡋࠊDGC ἲࡣࠊỈᛶࢤࣝ࠿ࡽỈࢆ㝖ཤࡍࡿࡇ

࡜࡟ࡼࡾᚓࡽࢀࡿ஝⇱ࢤࣝ㸦dry gel㸧ࢆฟⓎ≀࡜ࡋࡓᅛ┦ྜᡂἲ㸦Fig. 1.6 b㸧࡛࠶ࡿ[25]_ࠋ_DGC

ἲࡣ኱ูࡋ࡚ࠊỈ⵨Ẽฎ⌮ἲ㸦Steam-Assisted Conversion; SAC㸧࡜Ẽ┦㍺㏦ἲ㸦Vapor Phase Transport; VPT㸧ࡢ 2 ✀㢮࡟ศࡅࡽࢀࡿࠋSAC ἲࡣࠊ஝⇱ࢤࣝࡢㄪ〇ẁ㝵࡛ SDA ࢆຍ࠼࡚࠿ ࡽỈᛶࢤࣝࢆ஝⇱ࡉࡏࠊỈࡔࡅࢆ஝⇱ࢤࣝ࡜㠀᥋ゐ᮲௳ୗ࡛࣮࢜ࢺࢡ࣮ࣞࣈ࡟ᑟධࡍࡿ᪉ ἲ࡛࠶ࡿࠋ୍᪉ࠊVPT ἲࡣࠊ᥹Ⓨࡋࡸࡍ࠸࢔࣑ࣥ➼ࢆ SDA ࡜ࡍࡿሙྜ࡟⏝࠸ࡽࢀࡿ᪉ἲ࡛ࠊ SDA ࢆຍ࠼ࡎ࡟஝⇱ࢤࣝࢆㄪ〇ࡋࠊỈ࡜ SDA ࢆ஝⇱ࢤࣝ࡜㠀᥋ゐ᮲௳ୗ࡛࣮࢜ࢺࢡ࣮ࣞࣈ ࡟௙㎸ࡳࠊSDA ࢆẼ┦࡛౪⤥ࡍࡿࠋDGC ἲࡣࠊ㸦1㸧ཎᩱࢤࣝࡢ௙㎸ࡳ⤌ᡂ࡜ྠࡌ⤌ᡂࡢࢮ ࢜ࣛ࢖ࢺ⤖ᬗࡀᚓࡽࢀࠊᗫᾮࡀ๐ῶ࡛ࡁࡿ[25]_{ࠊ㸦2㸧᪤ᏑࡢỈ⇕ྜᡂἲ࡛ࡣᚓࡽࢀ࡞࠸㠀ᖖ} ࡟ࣁ࢖ࢩࣜ࢝࡞ࢮ࢜ࣛ࢖ࢺྜᡂࡀྍ⬟࡛࠶ࡿ[26]_ࠊ㸦_{3㸧ࢮ࢜ࣛ࢖ࢺ㦵᱁ࡢ⏕ᡂࡀᅛ┦୰࡛㉳} ࡇࡿࡓࡵ⤖ᬗ⏕ᡂ㐣⛬ࡢ㏣㊧ࡀᐜ࡛᫆࠶ࡿ[27]_{ࠊ࡜࠸ࡗࡓ฼Ⅼࡀ࠶ࡿࠋ} Fig. 1.6. ୍⯡ⓗ࡞ࢮ࢜ࣛ࢖ࢺ⢊ᮎ⤖ᬗྜᡂࡢᴫ␎ᅗ 㸸㸦a㸧Ỉ⇕ྜᡂἲ,㸦b㸧ࢻࣛ࢖ࢤࣝࢥࣥࣂ࣮ࢪࣙࣥἲ

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10 1.5. ࢮ࢜ࣛ࢖ࢺ⭷

1.5.1. ࢮ࢜ࣛ࢖ࢺ⭷ࡢᵓ㐀 ࢮ࢜ࣛ࢖ࢺ⭷ࡣࢮ࢜ࣛ࢖ࢺࡢࡳ࡛⭷໬㸦⮬❧⭷㸧ࡍࡿࡇ࡜ࡶ࡛ࡁࡿࡀࠊࢮ࢜ࣛ࢖ࢺᒙࡔ ࡅ࡛ࡣᶵᲔⓗᙉᗘࡀஈࡋ࠸ࡓࡵࠊ୍⯡࡟ከᏍ㉁ࡢᨭᣢయୖ࡟〇⭷ࡉࢀࠊศ㞳⭷࡜ࡋ࡚౑⏝ ࡉࢀ࡚࠸ࡿ㸦Fig. 1.7㸧ࠋከᏍ㉁ᨭᣢయࡣࠊ࢔࣑ࣝࢼࠊ࣒ࣛ࢖ࢺࠊࢳࢱࢽ࢔ࠊࢫࢸࣥࣞࢫ➼ࡢ ↓ᶵ≀㉁࠿ࡽᵓᡂࡉࢀࠊᖹᯈࠊ⟶ࠊࣔࣀࣜࢫࠊࣇ࢓࢖ࣂ࣮➼ࡢᙧ≧ࡀ࠶ࡿࠋ⌧ᅾࡣᕤᴗ໬ ࡢࡓࡵ࡟ᚲせ࡞኱⾲㠃✚໬ࡀྍ⬟࡞⟶≧ࢱ࢖ࣉࡢᨭᣢయୖ࡬ࡢ〇⭷ᡭ㡰ࡢ◊✲ࡀ୰ᚰ࡜࡞ ࡗ࡚࠸ࡿࠋ Fig. 1.7. ࢮ࢜ࣛ࢖ࢺ⭷ࡢᵓ㐀 1.5.2. ࢮ࢜ࣛ࢖ࢺ⭷ࡢྜᡂ ࢮ࢜ࣛ࢖ࢺ⭷ࡢྜᡂ࡟ࡣࠊࢩࣜ࢝※ࠊ࢔࣑ࣝࢼ※ࠊᵓ㐀つᐃ๣ࠊ࢔ࣝ࢝ࣜ※ࠊỈ࡞࡝ࢆ ΰྜࡋࡓỈᛶࢤࣝࢆ౑⏝ࡋࡓỈ⇕ྜᡂἲࡀ㏻ᖖ⏝࠸ࡽࢀࠊ኱ࡁࡃศࡅ࡚┤᥋⤖ᬗ໬㸦In situ

crystallization㸧ἲ[28]_{࡜஧ḟᡂ㛗㸦Secondary growth㸧ἲ}[29]-[31]_{ࡀ࠶ࡿ㸦Fig. 1.8 a, b㸧ࠋ┤᥋⤖ᬗ}

໬ἲࡣࠊỈᛶࢤࣝ୰࡟ᨭᣢయࢆᑟධࡋࠊᨭᣢయୖ࡟┤᥋ࢮ࢜ࣛ࢖ࢺࢆ᰾Ⓨ⏕ࠊᡂ㛗ࡉࡏ࡚ ࢮ࢜ࣛ࢖ࢺⷧ⭷ࢆྜᡂࡍࡿ᪉ἲ࡛࠶ࡾࠊ᭱ࡶࢩࣥࣉ࡛ࣝ࠶ࡿࡀࠊ෌⌧ᛶ࡟ஈࡋ࠸ࠋࡇࢀ࡟ ᑐࡋࠊ஧ḟᡂ㛗ἲࡣࠊ┠ⓗ࡜ࡍࡿࢮ࢜ࣛ࢖ࢺ⤖ᬗࢆ࠶ࡽ࠿ࡌࡵከᏍ㉁ᨭᣢయୖ࡟ሬᕸࡋࠊ ࡇࡢࢮ࢜ࣛ࢖ࢺ⤖ᬗࢆ✀࡜ࡋ࡚Ỉᛶࢤࣝ୰࡛ඃඛⓗ࡟ᡂ㛗ࡉࡏࠊⷧ⭷ࢆᙧᡂࡉࡏࡿ᪉ἲ࡛ ࠶ࡿࠋࡑࡢࡓࡵࠊᨭᣢయୖࡢ✀⤖ᬗᒙࡢ≉ᛶ㸦✀⤖ᬗࡢ⢏Ꮚᚄ࠾ࡼࡧᙧ≧ࠊ✀⤖ᬗᒙࡢᆒ ୍ᛶࠊ㐃⥆ᛶࠊཌࡳ㸧ࡀ᭱⤊ⓗ࡞ࢮ࢜ࣛ࢖ࢺ⭷ࡢ㉁ࢆỴᐃࡍࡿ㔜せ࡞ᅉᏊ࡜࡞ࡿ[32]_ࠋ᰾Ⓨ ⏕࡜⤖ᬗᡂ㛗ࢫࢸࢵࣉࢆศ㞳ࡋࠊ⭷ࡢ࣐࢖ࢡࣟᵓ㐀ࢆไᚚ࡛ࡁࠊྜᡂ᮲௳ࡢᖜࡀᗈࡃࠊ෌ ⌧ᛶࡀ㧗࠸࡜࠸ࡗࡓ฼Ⅼ࠿ࡽࠊ⌧ᅾࢮ࢜ࣛ࢖ࢺ⭷ྜᡂࡢ࡯࡜ࢇ࡝ࡀࠊ஧ḟᡂ㛗ἲ࡟ࡼࡿࡶ ࡢ࡛࠶ࡿࠋࡇࡢ௚࡟ࠊỈ⇕ྜᡂἲ࡜ྠᵝ࡟ࢮ࢜ࣛ࢖ࢺࡢ๓㥑యỈᛶࢤࣝࢆㄪ〇ࡋࠊࡇࡢࢤ ࣝࢆᨭᣢయ⾲㠃࡟ⷧ⭷≧࡟ࢥ࣮ࢸ࢕ࣥࢢࡋࠊ஝⇱ᚋ࡟Ẽ┦୰࡛⤖ᬗ໬ࡉࡏࡿDGC ἲࡶ࠶ࡿ 㸦Fig. 1.8 c㸧[33]_ࠋ

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11

Fig. 1.8. ୍⯡ⓗ࡞ࢮ࢜ࣛ࢖ࢺ⭷ྜᡂࡢᴫ␎ᅗ㸸Ỉ⇕ྜᡂἲ㸦㸦a㸧┤᥋⤖ᬗ໬ἲ,㸦b㸧஧ḟ ᡂ㛗ἲ㸧,ࢻࣛ࢖ࢤࣝࢥࣥࣂ࣮ࢪࣙࣥἲ㸦c㸧 1.5.3. ᨭᣢయ≉ᛶࡢᙳ㡪 ᨭᣢయୖ࡟ㄪ〇ࡉࢀࡿࢮ࢜ࣛ࢖ࢺ⭷ࡢྜᡂ࡟࠾࠸࡚ࠊከᏍ㉁ᨭᣢయࡢ≉ᛶࡣ⭷ᛶ⬟࡟࠾ ࡅࡿศ㞳ᛶࠊ㏱㐣ᛶࡢ୧᪉࡟኱ࡁ࡞ᙳ㡪ࢆ୚࠼ࡿࠋᨭᣢయ࡟ᚲせ࡞᮲௳ࡣࠊỈ⇕࠾ࡼࡧ࢔ ࣝ࢝ࣜ᮲௳࡛ࡢ㧗࠸Ᏻᐃᛶࠊ⭷ᒙ⣲ᮦ࡜ࡢぶ࿴ᛶࠊᆒ㉁࡞⣽Ꮝࢆ᭷ࡍࡿᖹ⁥࡞ᨭᣢయ⾲㠃ࠊ 㧗࠸㏱㐣ᛶ࡛࠶ࡿࠋ୍⯡࡟ࠊࢮ࢜ࣛ࢖ࢺ⭷ࡣ〇⭷ᚋ࡟⣽Ꮝ୰ࡢSDA ࢆ㝖ཤࡍࡿࡓࡵ࡟↝ᡂ ࢆ⾜࠺ᚲせࡀ࠶ࡿࠋࢮ࢜ࣛ࢖ࢺࡢከࡃࡣ㈇ࡢ⇕⭾ᙇಀᩘࢆࡶࡕࠊ኱㒊ศࡢࢭ࣑ࣛࢵࢡከᏍ ㉁ᨭᣢయࡣṇࡢ⇕⭾ᙇಀᩘࢆࡶࡘࡓࡵ[34]-[36]_{ࠊ↝ᡂ㐣⛬࡛ࡢࢮ࢜ࣛ࢖ࢺ࡜ከᏍ㉁ᨭᣢయࡢ⇕} ⭾ᙇಀᩘࡢ኱ࡁ࡞㐪࠸ࡣࠊࢮ࢜ࣛ࢖ࢺ⭷ᒙ࡟Ḟ㝗ࡀᙧᡂࡍࡿ୺࡞せᅉ࡜࡞ࡿ[7],[35]_ࠋࡲࡓࠊ ㏆ᖺࠊࢮ࢜ࣛ࢖ࢺ⭷ࡢ୰࡛ࡶ㦵᱁ࡀ࣮࢜ࣝࢩ࡛ࣜ࢝ᵓᡂࡉࢀࡿࣆࣗ࢔ࢩࣜ࢝ࢮ࢜ࣛ࢖ࢺ⭷ ࡣࠊ㦵᱁ෆ࡟Al ࢆྵࡲ࡞࠸ࡇ࡜࠿ࡽࠊ␯Ỉᛶࢆ♧ࡋࠊ⪏⇕ᛶ࣭⪏⸆ရᛶ࡟ඃࢀࠊ⣽Ꮝෆ࡟ ࢝ࢳ࢜ࣥࢆಖ᭷ࡋ࡞࠸ࡓࡵࠊ࢔࣑ࣝࣀࢩࣜࢣ࣮ࢺࢮ࢜ࣛ࢖ࢺ⭷࡜ẚ㍑ࡋ࡚ࠊ⣽Ꮝᐜ✚ࡀ኱ ࡁࡃࠊศᏊᣑᩓᛶ࡟ඃࢀࡿࡇ࡜࠿ࡽὀ┠ࢆ㞟ࡵ࡚࠸ࡿ[37]_{ࠋࡋ࠿ࡋࠊ⌧ᅾࢮ࢜ࣛ࢖ࢺ⭷ྜᡂ} ࡟ᑐࡋ࡚᭱ࡶࡼࡃ⏝࠸ࡽࢀࡿ࢔࣑ࣝࢼᨭᣢయࡣࠊ〇⭷᫬࡟ᨭᣢయ࠿ࡽAl ࡀ⁐ฟࡋࠊࢮ࢜ࣛ ࢖ࢺ㦵᱁୰࡟Al ࡀྲྀࡾ㎸ࡲࢀࡿࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠾ࡾ[38]_ࠊ_{Al ࡢΰධ࡟ࡼࡿ⭷≉ᛶࡢኚ໬ࡣࠊ}

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12

ࣆࣗ࢔ࢩࣜ࢝ࢮ࢜ࣛ࢖ࢺ⭷ࢆྜᡂࡍࡿ࠺࠼࡛ࡢㄢ㢟ࡢ୍ࡘ࡜࡞ࡗ࡚࠸ࡿࠋࡲࡓࠊࢮ࢜ࣛ࢖ ࢺ⭷ࡢ㏱㐣ᛶࡣࠊࢮ࢜ࣛ࢖ࢺᒙࡢཌࡉࡔࡅ࡛ࡣ࡞ࡃᨭᣢయ⮬㌟ࡢ㏱㐣ᛶ࡟ࡶ㛵ಀࡀ࠶ࡾࠊ ᨭᣢయࡢ㧗࠸✵㝽⋡࡜ⷧ࠸ቨཌࠊ኱ࡁ࡞⣽Ꮝᚄࡣࢮ࢜ࣛ࢖ࢺ⭷ࡢ㏱㐣ᛶࢆྥୖࡉࡏࡿ[39]_ࠋ ࡋ࠿ࡋࠊⷧࡃ࡚Ḟ㝗ࣇ࣮ࣜ࡞ࢮ࢜ࣛ࢖ࢺ⭷ࢆྜᡂࡍࡿࡓࡵ࡟ࡣࠊᑠࡉ࡞⣽Ꮝ࡛࡞ࡵࡽ࠿࡞ ᨭᣢయ⾲㠃ࡀᚲせ࡜࡞ࡿࠋࡇࡢၥ㢟ࢆゎỴࡍࡿࡓࡵ࡟ࠊ࡞ࡵࡽ࠿࡛ᑠࡉ࡞⣽Ꮝࢆ᭷ࡍࡿ⾲㠃ᒙ࡜኱ࡁ࡞⣽Ꮝࢆ᭷ࡍࡿୗ఩ᒙ࡛ᵓᡂࡉࢀࡿ㠀ᑐ⛠ᨭᣢయࡀ㛤Ⓨࡉࢀࡓࡀࠊ㠀ᑐ⛠ᨭᣢ యࡢ࣓ࣜࢵࢺࡣࠊ㧗࠸〇సࢥࢫࢺ࡟ࡼࡗ࡚ᦆ࡞ࢃࢀ࡚ࡋࡲ࠺ࠋࢮ࢜ࣛ࢖ࢺ⭷ࡢࢺ࣮ࢱࣝࢥ ࢫࢺࡢ⣙70%ࡀᨭᣢయ࡟ࡼࡿࡶࡢࡔ࡜ࡉࢀ࡚࠾ࡾ[39]_{ࠊࢮ࢜ࣛ࢖ࢺ⭷ࡢ኱つᶍ࡞ၟᴗ໬࡟ࡣࠊ} Ᏻ౯࡛㏱㐣᢬ᢠࡢᑠࡉ࠸ᨭᣢయࡢ౑⏝ࡀᚲせ࡛࠶ࡿࠋ 1.5.4. ࢮ࢜ࣛ࢖ࢺ⭷ࡢศ㞳ᶵᵓ ࢮ࢜ࣛ࢖ࢺ⭷ࡢศ㞳ᶵᵓࡣ኱ࡁࡃศࡅ࡚ࠊࢮ࢜ࣛ࢖ࢺࡢ⣽Ꮝࢆ฼⏝ࡋࡓࠕศᏊࡩࡿ࠸ࠖ ࡟ࡼࡿศ㞳࡜ࢮ࢜ࣛ࢖ࢺ࡜ศ㞳ᑐ㇟ศᏊ࡜ࡢぶ࿴ຊࡢᕪࢆ฼⏝ࡋࡓࠕ྾╔ࠖ࡟ࡼࡿศ㞳ࡢ ஧ࡘ࡟ศ㢮ࡉࢀࡿࠋࠕศᏊࡩࡿ࠸ࠖ࡟ࡼࡿศ㞳࡜ࡣࠊFig. 1.9 a ࡟♧ࡍࡼ࠺࡟ࢮ࢜ࣛ࢖ࢺࡢ⣽ Ꮝᚄࡀ⏘ᴗⓗ࡟㔜せ࡞ศᏊࡢࢧ࢖ࢬ࡜㏆࠸ࡓࡵࠊࢮ࢜ࣛ࢖ࢺࡢࡶࡘᅛ᭷ࡢศᏊࣞ࣋ࣝࡢ⣽ Ꮝࢆ͆ࡩࡿ࠸͇࡜ࡋ࡚฼⏝ࡋࠊ⣽Ꮝᚄࡼࡾࡶᑠࡉ࠸ศᏊࡢࡳࢆ㏱㐣ࡉࡏࠊ⣽Ꮝᚄࡼࡾࡶ኱ ࡁ࠸ศᏊࡣ㏱㐣ࡉࡏ࡞࠸ࡇ࡜࡛ศ㞳ࢆ⾜࠺᪉ἲ࡛࠶ࡿࠋࡲࡓࠊࠕ྾╔ࠖ࡟ࡼࡿศ㞳ࡣࠊΰྜ ศᏊࡢ኱ࡁࡉࡀࢮ࢜ࣛ࢖ࢺࡢ⣽Ꮝࡼࡾᑠࡉ࠸ሙྜ࡛ࡶࠊࢮ࢜ࣛ࢖ࢺ࡜ศᏊࡢぶ࿴ຊࡢᕪࢆ ฼⏝ࡍࡿࡇ࡜࡛ࠊ≉ᐃࡢศᏊࡢࡳࢆඃඛⓗ࡟྾╔ࡉࡏศ㞳ࢆ⾜࠺ࡇ࡜ࡀྍ⬟࡛࠶ࡿࠋࡇࡢ ࢮ࢜ࣛ࢖ࢺࡢ྾╔≉ᛶࡣࠊ㦵᱁୰ࡢSi ࡜ Al ࡢẚ࡛ኚ໬ࡉࡏࡿࡇ࡜ࡀ࡛ࡁࠊSi/Al ẚࡀప࠸ ࡜ぶỈᛶࢆ♧ࡋࠊSi/Al ẚࡀ㧗ࡃ࡞ࡿ࡟ࡘࢀ࡚␯Ỉⓗ࡜࡞ࡿࠋࡇࡢᛶ㉁ࢆ฼⏝ࡍࡿࡇ࡜࡛ࠊ ᭷ᶵ≀/Ỉΰྜᾮ࠿ࡽࠊぶỈᛶࡢࢮ࢜ࣛ࢖ࢺ⭷ࡣỈࢆ㑅ᢥⓗ࡟㏱㐣ࡋࠊ␯Ỉᛶࡢࢮ࢜ࣛ࢖ࢺ ⭷ࡣࠊ᭷ᶵ≀ࢆ㑅ᢥⓗ࡟㏱㐣ࡉࡏࡿࡇ࡜ࡀ࡛ࡁࡿ㸦Fig. 1.9 b㸧ࠋ Fig. 1.9. ࢮ࢜ࣛ࢖ࢺ⭷ࡢศ㞳ᶵᵓ㸸㸦a㸧ศᏊࡩࡿ࠸࡟ࡼࡿศ㞳, 㸦b㸧྾╔࡟ࡼࡿศ㞳

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1.5.5. MFI ᆺࢮ࢜ࣛ࢖ࢺ⭷

ࢮ࢜ࣛ࢖ࢺ⭷࡟࠾࠸࡚ࠊ᭱ࡶ◊✲ࡉࢀ࡚࠸ࡿࢮ࢜ࣛ࢖ࢺᵓ㐀ࡣMFI ᆺࢮ࢜ࣛ࢖ࢺ࡛࠶ࡾࠊ

ࢮ࢜ࣛ࢖ࢺ⭷࡟㛵ࡍࡿㄽᩥࡢ୰࡛ࠊࡍ࡛࡟ၟᴗ໬ࡉࢀ࡚࠸ࡿLTA[41]_ࠊ_FAU[42]_ࠊ_CHA[43]_ࠊ_DDR[44]

࡞࡝ࡢ⭷ࡼࡾࡶከࡃࡢᩥ⊩ࡀᏑᅾࡋ࡚࠾ࡾࠊࡑࡢὀ┠ᗘࡀ㧗࠸ࡇ࡜ࡀࢃ࠿ࡿ㸦Fig. 1.10 a㸧ࠋ MFI ᆺࢮ࢜ࣛ࢖ࢺࡣࠊb ㍈᪉ྥ࡟ 10 ဨ⎔㸦0.56×0.53 nm㸧࡛┤⥺≧ࡢ⣽Ꮝࢆࡶࡕࠊa ㍈᪉ྥ ࡟ࡶ10 ဨ⎔㸦0.55×0.51 nm㸧࡛ࢪࢢࢨࢢ࡞⣽Ꮝࢆࡶࡕࠊࡇࢀࡽࡀ஫࠸࡟஺ᕪࡋ୕ḟඖ⣽Ꮝ ࢆᙧᡂࡋ࡚࠸ࡿ㸦Fig. 1.10 b㸧ࠋࡲࡓࠊ㦵᱁ᵓ㐀ෆ࡟ Al ࢆྵࡴ MFI ᆺࢮ࢜ࣛ࢖ࢺࡣ ZSM-5ࠊ Al ࢆྵࡲࡎ⣧ࢩ࡛ࣜ࢝ᵓᡂࡉࢀࡿሙྜࡣ silicalite-1 ࡜࿧ࡤࢀ࡚࠸ࡿࠋ MFI ᆺࢮ࢜ࣛ࢖ࢺࡣࠊ⏘ᴗⓗ࡟㔜せ࡞ከࡃࡢⅣ໬Ỉ⣲࡟㏆࠸⣽Ꮝᚄ㸦⣙ 5.5 Å㸧ࢆ᭷ࡍࡿ ࡇ࡜࠿ࡽࠊศᯞ≧Ⅳ໬Ỉ⣲ࡸⰾ㤶᪘␗ᛶయࡢศ㞳ࡀྍ⬟࡛࠶ࡾࠊ㦵᱁୰ࡢSi/Al ẚࢆᖜᗈࡃ ㄪᩚࡍࡿࡇ࡜࡛ぶ/␯Ỉᛶࢆไᚚ࡛ࡁࡿࡇ࡜࠿ࡽࠊ⭷࡜㏱㐣ศᏊ࡜ࡢぶ࿴ᛶࡢᕪࢆ฼⏝ࡋࡓ ศ㞳ࡀྍ⬟࡛࠶ࡿࠋࡲࡓࠊࡉࡲࡊࡲ࡞ཎᩱ࡟ࡼࡾ௚ࡢࢮ࢜ࣛ࢖ࢺ࡜ẚ㍑ࡋ࡚ẚ㍑ⓗᐜ᫆࡟ ྜᡂࡀྍ⬟࡛࠶ࡿ࡞࡝ࡢ⌮⏤࡟ࡼࡾࠊMFI ᆺࢮ࢜ࣛ࢖ࢺ⭷࡟㛵ࡍࡿ◊✲ࡀ┒ࢇ࡟⾜ࢃࢀ࡚ ࠸ࡿࠋ Fig. 1.10. ␗࡞ࡿ㦵᱁ᵓ㐀ࡢࢮ࢜ࣛ࢖ࢺ⭷ࡢㄽᩥᩘ㸦1960㹼2018 ᖺ 4 ᭶, ࠕXXX membranesࠖ ࢆScopus ᳨࡛⣴, ౛࠼ࡤ MFI=MFI+ZSM-5+silicalite-1, CHA=chabazite+CHA+SAPO-34+SSZ-13㸧㸦a㸧ࠊMFI ᆺࢮ࢜ࣛ࢖ࢺࡢ⤖ᬗᙧែ࡜⣽Ꮝᵓ㐀㸦b㸧

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1.5.6. silicalite-1 ⭷ 1.5.6.1. silicalite-1 ⭷ࡢ≉ᚩ 㦵᱁ᵓ㐀୰࡟Al ࢆྵࡲࡎࠊࣆࣗ࢔ࢩ࡛ࣜ࢝ᵓᡂࡉࢀࡿ MFI ᆺࢮ࢜ࣛ࢖ࢺࡣ silicalite-1 ࡜ ࿧ࡤࢀࠊ㧗࠸⇕ⓗ࣭໬ᏛⓗᏳᐃᛶࢆ᭷ࡋࠊ㧗࠸␯Ỉᛶࢆ♧ࡍࠋ㧗ศᏊࡸ↓ᶵ⣲ᮦࡢ୰࡛ࡶࠊ ␯Ỉⓗ࡞⣲ᮦࡣᑡ࡞ࡃࠊsilicalite-1 ࡣ㠀ᖖ࡟㨩ຊⓗ࡞⣲ᮦ࡜ࡋ࡚ὀ┠ࡉࢀ࡚࠸ࡿࠋ㏻ᖖ⢊ᮎ ࡛ᚓࡽࢀࡿsilicalite-1 ⤖ᬗࢆ⭷໬ࡍࡿࡇ࡜࡛ᚓࡽࢀࡿ silicalite-1 ⭷ࡣࠊࡑࡢศᏊࣞ࣋ࣝࡢ⣽ Ꮝᚄࢆࡩࡿ࠸࡜ࡋ࡚฼⏝ࡋࠊ࢟ࢩࣞࣥ␗ᛶయࠊ࢖࢜ࣥỈ⁐ᾮࠊ஧㓟໬Ⅳ⣲ศ㞳⭷࡜ࡋ࡚ࡢ ◊✲ࡀ⾜ࢃࢀ࡚ࡁࡓ[45]-[48]_{ࠋࡲࡓࠊࡑࡢ㧗࠸␯Ỉᛶࢆ฼⏝ࡋ࡚ࠊ࢚ࢱࣀ࣮ࣝࠊ1-ࣈࢱࣀ-ࣝࠊ} 㓑㓟ࠊ࢔ࢭࢺࣥỈ⁐ᾮࡢࡼ࠺࡞᭷ᶵ≀/Ỉΰྜᾮ࠿ࡽ᭷ᶵ≀ࢆ㑅ᢥⓗ࡟ᅇ཰ࡍࡿࡓࡵࡢศ㞳 ⭷࡜ࡋ࡚ࡢᛂ⏝ࡶᮇᚅࡉࢀ࡚࠸ࡿ[38],[49]-[61]_ࠋ 1.5.6.2. silicalite-1 ⭷ࢆ⏝࠸ࡓᾐ㏱Ẽ໬ἲ࡟ࡼࡿ᭷ᶵ≀/Ỉΰྜᾮࡢศ㞳 ࣂ࢖࢚࢜ࢱࣀ࣮ࣝࡣࠊࣂ࢖࣐࢜ࢫࡢⓎ㓝࡟ࡼࡗ࡚〇㐀ࡉࢀࡿࢡ࣮࡛ࣜࣥ෌⏕ྍ⬟࡞ᕤᴗ ⏝ཎᩱ࡛࠶ࡾࠊ㏆ᖺ▼Ἔ௦࢚᭰ࢿࣝࢠ࣮※࡜ࡋ࡚ὀ┠ࡉࢀ࡚࠸ࡿ[61]_{ࠋⓎ㓝ᇵ㣴ᾮ୰ࡢ࢚ࢱ} ࣀ࣮ࣝ⃰ᗘࡣ㏻ᖖ10 wt.%⛬ᗘ࡛࠶ࡿࡓࡵࠊࡑࡢᚋࡢᕤᴗⓗ࡞౑⏝ࡢࡓࡵ࡟ࡣࠊ࢚ࢱࣀ࣮ࣝ ࢆ㧗⃰ᗘ࡟ࡲ࡛ศ㞳࣭⢭〇ࡋ࡞ࡅࢀࡤ࡞ࡽ࡞࠸ࠋࡋ࠿ࡋࠊࡇࢀࡽࡢᕤ⛬ࡣ኱㔞ࡢ࢚ࢿࣝࢠ ࣮ࢆᚲせ࡜ࡋࠊࣂ࢖࢚࢜ࢱࣀ࣮ࣝࡢᗈ⠊ᅖ࡛ࡢ౑⏝ࢆጉࡆࡿཎᅉࡢ୍ࡘ࡜࡞ࡗ࡚࠸ࡿ[62]_ࠋ ࡑࡢࡓࡵࠊ㏆ᖺࠊ⭷ࢆ⏝࠸ࡓᾐ㏱Ẽ໬ἲ㸦Pervaporation; PV㸧࡟ࡼࡿศ㞳ࡀࠊ⵨␃࠾ࡼࡧ྾ ╔ࡢࡼ࠺࡞ᚑ᮶ࡢศ㞳᪉ἲ࡜ẚ㍑ࡋ࡚ࠊప࢚ࢿࣝࢠ࣮ᾘ㈝ࠊ⡆౽ᛶ࣭⤒῭ᛶ࡟ඃࢀࠊప⎔ ቃ㈇Ⲵ࡞࡝ࡢ฼Ⅼࢆ᭷ࡍࡿࡇ࡜࠿ࡽࠊὀ┠ࢆ㞟ࡵ࡚࠸ࡿ[63],[64]_{ࠋᾮ┦୰࡛ࡢ} _{PV ἲ࡟ࡼࡿศ} 㞳ࡢཎ⌮ࡣᴟࡵ࡚⡆༢࡛ࠊฎ⌮ᑐ㇟ᡂศ࡜ぶ࿴ᛶࡢ࠶ࡿศ㞳⭷ࢆ౑࠸ࠊ⭷ࡢ౪⤥ഃࢆᾮయ ΰྜ≀࡜᥋ゐࡉࡏࠊ㏱㐣ഃࢆῶᅽࡍࡿࡇ࡜࡛ࠊྛᡂศࡢ㏱㐣㏿ᗘᕪ࡟ࡼࡾศ㞳ࡀ⾜ࢃࢀࡿࠋ ࡑࡢࡓࡵࠊẼᾮᖹ⾮࡟ᨭ㓄ࡉࢀࡎ࡟ศ㞳ࡀྍ⬟࡛࠶ࡾࠊ⵨␃࡛ࡣศ㞳ࡀ㞴ࡋ࠸ඹἛࡶࡋࡃ ࡣἛⅬࡢ㏆࠸ΰྜ≀ࡢศ㞳ࠊ⇕ⓗ࡟୙Ᏻᐃ࡞ᾮయ≀㉁ࡢศ㞳࡟ᑐࡋ࡚≉࡟㨩ຊⓗ࡛࠶ࡿ[64]_ࠋ ࡲࡓࠊ⭷ᛶ⬟ࡣࠊ㏱㐣ὶ᮰㸦Flux [kg m-2 _h-1_{]㸧࡜ศ㞳ಀᩘ㸦α [-]㸧࡛⾲ࡉࢀࠊศ㞳ಀᩘ α} A/B ࡣA, B ࡢ 2 ᡂศ⣔ࡢሙྜࠊ౪⤥ഃ࡜㏱㐣ഃࡢ A, B ࡢᡂศ⃰ᗘࢆࡑࢀࡒࢀ XA, XB࠾ࡼࡧYA, YB࡜ࡍࡿ࡜ࠊαA/B=(YA/ YB)/ (XA/ XB)࡛⾲ࡉࢀࡿࠋ ␯Ỉᛶ⭷ࡣ᭷ᶵ≀㑅ᢥᛶࢆ♧ࡋࠊప⃰ᗘ᭷ᶵ≀⁐ᾮࢆ㧗⃰ᗘ࡟ࡲ࡛⃰⦰ࡍࡿࡢ࡟㐺ࡋ࡚ ࠸ࡿࠋ␯Ỉᛶࢮ࢜ࣛ࢖ࢺ⭷࡜ࡋ࡚᭱ࡶ◊✲ࡀ⾜ࢃࢀ࡚࠸ࡿࡢࡣsilicalite-1 ࡛࠶ࡾࠊ1994 ᖺ࡟ Sano ࡽ[38]_ࡀ_{silicalite-1 ⭷ࢆ⏝࠸ࡓ࢚ࢱࣀ࣮ࣝ/Ỉΰྜᾮࡢ PV ศ㞳ࢆ᭱ึ࡟ሗ࿌ࡋ࡚௨᮶ࠊ} silicalite-1 ⭷ࢆ⏝࠸ࡓ᭷ᶵ≀/Ỉศ㞳ࠊ≉࡟࢚ࢱࣀ࣮ࣝ/Ỉศ㞳࡟ᑐࡍࡿ◊✲ࡀ┒ࢇ࡟⾜ࢃࢀ ࡚࠸ࡿ[49]-[61]_{ࠋsilicalite-1 ⭷ࢆ௓ࡋ࡚᭷ᶵ≀/Ỉΰྜᾮ࠿ࡽ᭷ᶵ≀ࢆ㑅ᢥⓗ࡟ศ㞳ᅇ཰ࡍࡿሙ}

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15

ྜࠊsilicalite-1 ⤖ᬗ⾲㠃࡬ࡢ᭷ᶵศᏊࡢ྾╔ࡀඃඛࡉࢀࠊ୺࡞ศ㞳㑅ᢥᛶࢆ୚࠼ࡿࠋࡋࡓࡀ ࡗ࡚ࠊsilicalite-1 ⭷ࢆ⏝࠸ࡓ PV ศ㞳࡟࠾࠸࡚ࠊ⭷ࡢ␯Ỉᛶࡀྥୖࡍࡿࡇ࡜ࡣศ㞳㑅ᢥᛶࡢ ྥୖ࡟ࡘ࡞ࡀࡿ࡜ࡉࢀ࡚࠸ࡿࠋ

1.6. ᮏ◊✲ࡢ┠ⓗ࡜ㄽᩥᵓᡂ

silicalite-1 ⭷ࢆྵࡵࡓࢮ࢜ࣛ࢖ࢺ⭷ࡢ኱㒊ศࡣࠊከᏍ㉁ࡢᨭᣢయୖ࡟ㄪ〇ࡉࢀࠊศ㞳⭷࡜ ࡋ࡚⏝࠸ࡽࢀ࡚࠸ࡿࠋࡑࡢࡓࡵࠊ㧗ᛶ⬟ࢮ࢜ࣛ࢖ࢺ⭷ࢆྜᡂࡍࡿࡓࡵ࡟ࡣࠊከᏍ㉁ᨭᣢయ ୖ࡟࠸࠿࡟͆┠ⓗ⤌ᡂࡢࢮ࢜ࣛ࢖ࢺ⤖ᬗࢆḞ㝗࡞ࡃ⦓ᐦⷧ⭷໬͇ࡍࡿࡢ࠿ࡀ࢝ࢠ࡜࡞ࡿࠋ ⌧ᅾࡲ࡛࡟ࡉࡲࡊࡲ࡞◊✲⪅ࡽ࡟ࡼࡗ࡚silicalite-1 ⭷ࡢྜᡂࡣ⾜ࢃࢀ࡚ࡁࡓࡀࠊ1.5 ❶࡛ࡶ ㏙࡭ࡓࡼ࠺࡟ࢮ࢜ࣛ࢖ࢺ⭷ྜᡂࡣࠊ✀⤖ᬗᒙࡸከᏍ㉁ᨭᣢయ≉ᛶࡢᙳ㡪ࢆ኱ࡁࡃཷࡅࡿࡓ ࡵࠊᨭᣢయୖ࡟ silicalite-1 ࢮ࢜ࣛ࢖ࢺᮏ᮶ࡢศ㞳≉ᛶࢆ༑ศ࡟Ⓨ᥹ࡍࡿ⭷ࡢྜᡂࡣ㞴ࡋࡃࠊ ࢚ࢱࣀ࣮ࣝ/Ỉศ㞳࡟ᑐࡋ࡚ศ㞳ᛶ࣭㏱㐣ᛶ࡜ࡶ࡟㧗࠸⭷ࡢྜᡂࡣ࡛ࡁ࡚࠸࡞࠸[38],[49]-[61]_ࠋ ࡲࡓࠊ⌧ᅾࡲ࡛࡟silicalite-1 ⭷ྜᡂ࡟ᑐࡋ࡚ࡉࡲࡊࡲ࡞ᥦ᱌ࡀ࡞ࡉࢀ࡚࠸ࡿࡀࠊ⡆౽࡛⤒῭ ⓗ࡛⎔ቃ㈇Ⲵࡢᑠࡉ࠸᪉ἲࡣ࡯࡜ࢇ࡝࡞ࡃࠊᕤᴗⓗ࡞ᛂ⏝࡟ᑐࡋ࡚ࡣᮍࡔከࡃࡢㄢ㢟ࡀṧ ࡉࢀ࡚࠸ࡿࠋ ࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ᭷ᶵ≀/Ỉΰྜᾮࡢศ㞳࡟ྥࡅࡓ㧗ᛶ⬟ silicalite-1 ⭷ࡢྜᡂࢆ┠ᣦࡋࠊ ᨭᣢయୖࡢ✀⤖ᬗᒙࡢ≉ᛶ࠾ࡼࡧᨭᣢయ≉ᛶࡢᙳ㡪࡟ࡘ࠸᳨࡚ウࡍࡿ࡜࡜ࡶ࡟ࠊᕤᴗⓗ࡞ ᛂ⏝ࢆ┠ᣦࡋࡓ᪂つ࡞〇⭷ἲ࠾ࡼࡧ✀⤖ᬗሬᕸ᪉ἲࡢ㛤Ⓨࢆ⾜ࡗࡓࠋᮏㄽᩥࡣࠊ7 ❶࠿ࡽ࡞ ࡿࠋ➨1 ❶ࡢᗎㄽ࡟ጞࡲࡾࠊ➨ 2 ❶࡛ࡣࠊsilicalite-1 ⭷ྜᡂ࡟࠾ࡅࡿ✀⤖ᬗࡢ Si/Al ẚࡀศ 㞳ᛶ⬟࡟୚࠼ࡿᙳ㡪࡟ࡘ࠸᳨࡚ウࡋࡓࠋ➨3 ❶࡛ࡣࠊsilicalite-1 ⭷ྜᡂ࡟࠾ࡅࡿ✀⤖ᬗሬᕸ 㔞࠾ࡼࡧࡑࡢሬᕸᙧែࡀ࢔࣑ࣝࢼᨭᣢయࡢ⁐ゎ࡟୚࠼ࡿᙳ㡪ࢆ᳨ウࡋࡓࠋ➨ 4 ❶࡛ࡣࠊᨭ ᣢయ࡜ࡋ࡚࢔࣑ࣝࢽ࣒࢘ࢆྵࡲ࡞࠸᪂つ࡞ࢩࣜ࢝ᨭᣢయࢆ฼⏝ࡋࠊࢩࣜ࢝ᨭᣢయୖ࡬ࡢ silicalite-1 ⭷ࡢྜᡂࢆ⾜ࡗࡓࠋ➨ 5 ❶࡛ࡣࠊࢩࣜ࢝ᨭᣢయࡢ⁐ゎࢆ฼⏝ࡋ࡚ࢤࣝࣇ࣮ࣜ᮲௳ ୗ࡛ࡢ⭷ྜᡂࡢྍ⬟ᛶࢆ᳨ウࡋࡓࠋ➨ 6 ❶࡛ࡣࠊᚑ᮶ࡢᨭᣢయୖ࡬ࡢ✀⤖ᬗሬᕸ᪉ἲࡢၥ 㢟ⅬࢆゎỴࡍࡿࡓࡵࠊ᪂つ࡞✀⤖ᬗሬᕸᢏ⾡film seeding ࢆ㛤Ⓨࡋࠊࡑࡢຠᯝࢆ᳨ウࡋࡓࠋ ࡑࡋ࡚ࠊ᭱ᚋࡢ➨7 ❶࡛ࡣࠊᮏ◊✲ࡢ⥲ᣓ࡜௒ᚋࡢ◊✲ㄢ㢟ࢆ♧ࡍࠋ

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mixture, Sep. Purif. Technol. 136 (2014) 144–149.

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21 ➨

➨

2 ❶ silicalite-1 ⭷ྜᡂ࡟࠾ࡅࡿ✀⤖ᬗࡢ Si/Al ẚࡢᙳ㡪

2.1. ⥴ゝ

silicalite-1 ⭷ࡣࠊ㧗࠸␯Ỉᛶࢆ♧ࡋࠊ࢚ࢱࣀ࣮ࣝ/Ỉΰྜᾮࡢ PV ἲ࡟ࡼࡿศ㞳࡟࠾࠸࡚ࠊ ప⃰ᗘ࢚ࢱࣀ࣮ࣝࢆ㧗⃰ᗘ࡟ࡲ࡛⃰⦰ࡀྍ⬟࡞␯Ỉᛶศ㞳⭷࡜ࡋ࡚ᗈࡃ◊✲ࡉࢀ࡚࠸ࡿ [1]-[14]_ࠋ_{silicalite-1 ⭷ࡣࠊ୍⯡࡟ከᏍ㉁ࡢᨭᣢయୖ࡟࠶ࡽ࠿ࡌࡵ silicalite-1 ✀⤖ᬗࢆሬᕸࡋࠊ} ࡑࡢ✀⤖ᬗࢆsilicalite-1 ྜᡂࡢࡓࡵࡢ๓㥑యࢤࣝ࡟ࡼࡾ஧ḟᡂ㛗ࡉࡏࡿࡇ࡜࡟ࡼࡾ〇⭷ࡍࡿࠋ ࡇࡢ஧ḟᡂ㛗ἲࢆ⏝࠸ࡓࢮ࢜ࣛ࢖ࢺ⭷ࡢྜᡂ࡟࠾࠸࡚ࠊᨭᣢయୖࡢ✀⤖ᬗᒙࡢ≉ᛶࡣࠊ⭷ ࡢศ㞳≉ᛶࢆỴᐃࡍࡿ㔜せ࡞せ⣲࡛࠶ࡾࠊ✀⤖ᬗࡢᙧ≧ࠊሬᕸ㔞ࠊᆒ୍ᛶ࡞࡝ࡀ஧ḟᡂ㛗 ᚋࡢ⭷ࡢᙧែ࠾ࡼࡧᛶ⬟࡟୚࠼ࡿᙳ㡪࡟ࡘ࠸࡚ࡣከࡃࡢሗ࿌ࡀ࠶ࡿ[11]-[13], [21]-[25]_{ࠋ࡜ࡇࢁ࡛ࠊ} MFI ᆺࢮ࢜ࣛ࢖ࢺࡣ㦵᱁୰ࡢ Si/Al ẚࡢㄪᩚࡀྍ⬟࡛࠶ࡾࠊࡑࡢ≀⌮໬Ꮫⓗ≉ᛶࢆኚ໬ࡉࡏ ࡿࡇ࡜ࡀ࡛ࡁࡿ࡜࠸ࡗࡓ≉ᚩࢆ᭷ࡋ࡚࠸ࡿࠋࡋ࠿ࡋࠊ⌧ᅾࡲ࡛࡟ࠊPV ἲ࡟ࡼࡿ࢚ࢱࣀ࣮ࣝ /Ỉศ㞳ࡢࡓࡵࡢ silicalite-1 ⭷ࡢㄪ〇࡟ᑐࡋ࡚ࠊᨭᣢయୖ࡟ሬᕸࡉࡏࡿ✀⤖ᬗࡢᴟᛶ㸦Si/Al ẚ㸧ࡀ⭷ᛶ⬟࡟୚࠼ࡿᙳ㡪ࡣሗ࿌ࡉࢀ࡚࠸࡞࠸ࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊsilicalite-1 ⭷ࡢྜᡂ࡟ ࠾࠸࡚ࠊᨭᣢయୖ࡟Si/Al ẚࡢ␗࡞ࡿ MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗᒙࢆᙧᡂࡉࡏࠊ஧ḟᡂ㛗ἲ࡟ ࡼࡾsilicalite-1 ⭷ࢆㄪ〇ࡋࡓࠋࡘࡲࡾࠊᮏ◊✲ࡢ silicalite-1 ⭷ࡣ✀⤖ᬗᒙ⏤᮶ࡢࢮ࢜ࣛ࢖ࢺ ᒙ࡜ࠊ஧ḟᡂ㛗ࢤࣝ⏤᮶ࡢsilicalite-1 ⾲㠃ᒙ࠿ࡽᡂࡿ஧ᒙᵓ㐀ࢆ᭷ࡋ࡚࠾ࡾࠊMFI ᆺࢮ࢜ࣛ ࢖ࢺ✀⤖ᬗᒙࡢ≉ᛶ㸦Si/Al ẚ࠾ࡼࡧሬᕸ㔞㸧ࡀࠊ࢚ࢱࣀ࣮ࣝ/Ỉΰྜᾮࡢศ㞳࡟୚࠼ࡿᙳ㡪 ࡟ࡘ࠸᳨࡚ウࡋࡓࠋࡉࡽ࡟ࠊࢥࣁࢡ㓟ࢆຍ࠼ࡓࣂ࢖࢚࢜ࢱࣀ࣮ࣝࡢ␲ఝⓎ㓝⁐ᾮ㸦࢚ࢱࣀ ࣮ࣝ/Ỉ/ࢥࣁࢡ㓟ΰྜᾮ㸧࡬ࡢ㐺⏝ࡶ⾜ࡗࡓࠋ

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22 2.2. ᐇ㦂᪉ἲ

2.2.1. ␗࡞ࡿ Si/Al ẚࢆ᭷ࡍࡿ MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗࡢྜᡂ

␗࡞ࡿSi/Al ẚࢆ᭷ࡍࡿ MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗࡣࠊࢩࣜ࢝※࡜ࡋ࡚ colloidal silica

㸦Cataloid SI-30㸸SiO2 30.17%ࠊNa2O 0.40%ࠊH2O 69.43%, ᪥᥹ゐ፹໬ᡂᕤᴗᰴᘧ఍♫〇㸧ࠊ

࢔࣑ࣝ※࡜ࡋ࡚◪㓟࢔࣑ࣝࢽ࣒࢘9 Ỉ࿴≀㸦Al(NO3)3࣭9H2O, ᐩኈࣇ࢖࣒ࣝ࿴ග⣧⸆ᰴᘧ఍

♫㸸99.9%㸧ࠊᵓ㐀つᐃ๣࡜ࡋ࡚ࢸࢺࣛ-n -ࣉࣟࣆࣝ࢔ࣥࣔࢽ࣒࢘ࣈ࣑ࣟࢻ㸦TPABr㸸98%௨

ୖ, ᮾி໬ᡂᕤᴗᰴᘧ఍♫〇㸧ࠊỈ㓟໬ࢼࢺ࣒ࣜ࢘㸦NaOH㸸 99%, MERCK 〇㸧ࠊ࢖࢜ࣥ஺

᥮Ỉࢆ⏝࠸࡚ࠊ1SiO2 : 0-0.029Al2O3 : 0.1-0.3TPABr : 0.1-0.2NaOH : 40H2O ࡢࣔࣝ⤌ᡂ࡟ࡼࡾ

ㄪ〇ࡋࡓ㸦Table 2.1㸧ࠋࡲࡎࠊ1L ࢸࣇࣟࣥ〇ࣅ࣮࣮࢝࡟ TPABr ࢆධࢀࠊ᧠ᢾ᮲௳ୗ࡛Ỉࢆຍ

࠼⁐ゎࡉࡏࡓࡢࡕࠊAl(NO3)3࣭9H2O ࢆຍ࠼ 10 ศ㛫᧠ᢾࡋࡓࠋࡑࡢᚋࠊcolloidal silica ࢆຍ

࠼ࠊ࠶ࡽ࠿ࡌࡵỈ࡛⁐ゎࡉࡏ࡚࠾࠸ࡓNaOH Ỉ⁐ᾮࢆࡺࡗࡃࡾ࡜⁲ୗࡋࠊᐊ ࡟࠾࠸࡚ 24 ᫬㛫᧠ᢾ᮲௳ୗ࡛⇍ᡂࡍࡿࡇ࡜࡛Ỉᛶࢤࣝΰྜ≀ࢆㄪ〇ࡋࡓࠋᚓࡽࢀࡓỈᛶࢤࣝΰྜ≀ࢆࠊ 1L ࣏ࣜࣉࣟࣆࣞࣥ〇୕ゅࣇࣛࢫࢥ࡟ᑟධࡋࠊ࠶ࡽ࠿ࡌࡵ 100°C ࡟ ࡵ࡚࠾࠸ࡓ࢜࢖ࣝࣂࢫ ࡟ᑟධࡋࠊ᧠ᢾࡉࡏ࡞ࡀࡽࠊ㛤ᨺ⣔࡛ࡢᖖᅽୗ࡟࠾࠸࡚100°C ࡛ 6-21 ᪥㛫ࠊỈ⇕ฎ⌮ࢆࡋ ࡓ[8]_{ࠋࡑࡢᚋࠊ෭Ỉ࡟ࡉࡽࡋᛴ෭ࡉࡏࠊᚓࡽࢀࡓ⢊ᮎࢆ㐲ᚰศ㞳࡟ࡼࡾᅇ཰ࡋࡓᚋࠊከ㔞ࡢ} Ỉ࡛Ὑίࡋࠊ60°C ୍࡛ᬌ஝⇱ࡉࡏࡿࡇ࡜࡛ MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗ࡜ࡋࡓࠋྜᡂᡭ㡰ࡢ ᴫ␎࠾ࡼࡧ⿦⨨ᅗࢆFig. 2.1 ࡟♧ࡍࠋ

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2.2.2. ✀⤖ᬗሬᕸᨭᣢయࡢㄪ〇 ከᏍ㉁⟶≧࢔࣑ࣝࢼᨭᣢయ㸦㛗ࡉ㸸80 mm, እᚄ㸸12 mm, ෆᚄ㸸9 mm, ⣽Ꮝᚄ㸸1.4 μm, ✵ 㝽⋡㸸38%, ᰴᘧ఍♫ࢽࢵ࢝ࢺ࣮〇㸧ࡣࠊ౑⏝ࡍࡿ๓࡟ᩘ᪥㛫࢔ࢭࢺࣥ࡟ᾐₕࡉࡏࡿࡇ࡜࡛ Ὑίࡋࠊ500°C ࡛ 5 ᫬㛫↝ᡂࡋࡓࠋࡲࡓࠊMFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗࡣࢮ࢜ࣛ࢖ࢺ࡬ࡢỈࡢ ྾╔ࢆᢚ࠼ࡿࡓࡵ࡟ࠊ60°C ࡢ࣮࢜ࣈ࡛ࣥ஝⇱ࡉࡏ࡚࠾࠸ࡓࠋ

ᨭᣢయୖ࡬ࡢ✀⤖ᬗࡢሬᕸࡣࠊὋື㟁╔ἲ㸦electrophoretic deposition; EPD㸧ࢆ⏝࠸࡚ࠊFig.

2.2 ࡟♧ࡋࡓᡭ㡰࡜⿦⨨ࢆ⏝࠸࡚⾜ࡗࡓࠋࣅ࣮࣮࢝࡟⁐፹㸦࢔ࢭࢺࣥ㸸99.5%, ᐩኈࣇ࢖࣒ࣝ ࿴ග⣧⸆ᰴᘧ఍♫㸧ࢆ100 ml ධࢀࠊࡑࡇ࡟ MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗ 0.5 g ࢆຍ࠼ࠊ30 ศ㛫 ௨ୖ㉸㡢Ἴฎ⌮ࡍࡿࡇ࡜࡛ࢮ࢜ࣛ࢖ࢺᠱ⃮ᾮࢆᚓࡓࠋࡑࡢᚋࠊࣇࢵ⣲ᶞ⬡〇࣓ࢫࢩࣜࣥࢲ ࣮࡟ከᏍ㉁ᨭᣢయ㸦ࢸࣇࣟࣥ〇἞ල࡟ྲྀࡾ௜ࡅ㸧࠾ࡼࡧᠱ⃮ᾮࢆᑟධࡋࠊ༳ຍ㟁ᅽ100 V ࡛ 1-10 ศ㛫㟁ὶࢆὶࡍࡇ࡜࡛ᨭᣢయእ⾲㠃࡟ MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗࢆሬᕸࡋࡓࠋሬᕸᚋࡢ ᨭᣢయࡣᐊ ࡛30 ศ஝⇱ᚋࠊᨭᣢయ࡜✀⤖ᬗ㛫ࡢ⤖ྜຊࢆ㧗ࡵࡿࡓࡵ࡟ 300°C ࡛ 6 ᫬㛫↝ ᡂࡋࠊ✀⤖ᬗሬᕸᨭᣢయ࡜ࡋࡓࠋ࡞࠾ࠊᨭᣢయୖ࡬ࡢ✀⤖ᬗሬᕸ㔞ࡀ⭷ࡢศ㞳ᛶ⬟࡟ཬࡰ ࡍᙳ㡪ࢆ᳨ウࡍࡿࡓࡵࠊὋື㟁╔ࡢ᫬㛫ࢆኚ໬ࡉࡏࠊ✀⤖ᬗሬᕸ㔞ࢆኚ໬ࡉࡏࡓࠋᨭᣢయ ୖ࡬ࡢ✀⤖ᬗሬᕸ㔞ࡣࠊEPD ๓ᚋࡢᨭᣢయࡢ㔜㔞࠿ࡽ⟬ฟࡋࠊᨭᣢయ༢఩⾲㠃✚ᙜࡓࡾ࡟ ኚ᥮ࡋࠊ௨ୗWseed࡜⾲グࡍࡿࠋ Fig. 2.2. ᨭᣢయୖ࡬ࡢ✀⤖ᬗሬᕸᡭ㡰㸦a㸧ࠊᐇ㦂⿦⨨ࡢᴫ␎ᅗ㸦b㸧

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24

2.2.3. silicalite-1 ⭷ࡢㄪ〇

silicalite-1 ⭷ࡣࠊࢩࣜ࢝※࡜ࡋ࡚ colloidal silica㸦Cataloid SI-30㸸SiO2 30.17%ࠊNa2O 0.40%ࠊ

H2O 69.43%, ᪥᥹ゐ፹໬ᡂᕤᴗᰴᘧ఍♫〇㸧ࠊᵓ㐀つᐃ๣࡜ࡋ࡚ࢸࢺࣛ-n -ࣉࣟࣆࣝ࢔ࣥࣔࢽ

࣒࢘ࣈ࣑ࣟࢻ㸦TPABr㸸99.9%௨ୖ, ᮾி໬ᡂᕤᴗᰴᘧ఍♫〇㸧ࠊỈ㓟໬ࢼࢺ࣒ࣜ࢘㸦NaOH㸸

99%, MERCK 〇㸧ࠊ࢖࢜ࣥ஺᥮Ỉࢆ⏝࠸࡚ࠊ1SiO2㸸0.005TPABr㸸0.05NaOH㸸100H2O ࡢࣔࣝ

⤌ᡂ࡟ࡼࡾㄪ〇ࡋࡓࠋࡲࡎࠊ1L ࢸࣇࣟࣥ〇ࣅ࣮࣮࢝࡟ TPABr ࢆධࢀࠊ᧠ᢾ᮲௳ୗ࡛Ỉࢆຍ

࠼⁐ゎࡉࡏࡓࡢࡕࠊcolloidal silica ࢆຍ࠼ࠊ࠶ࡽ࠿ࡌࡵỈ࡛⁐ゎࡉࡏ࡚࠾࠸ࡓ NaOH Ỉ⁐ᾮ

ࢆࡺࡗࡃࡾ࡜⁲ୗࡋࠊᐊ ࡟࠾࠸࡚ 1 ᫬㛫᧠ᢾ᮲௳ୗ࡛⇍ᡂࡍࡿࡇ࡜࡛Ỉᛶࢤࣝΰྜ≀ࢆ ㄪ〇ࡋࡓࠋᚓࡽࢀࡓỈᛶࢤࣝࢆ✀⤖ᬗሬᕸᨭᣢయ࡜࡜ࡶ࡟ࢸࣇࣟࣥ〇ෆ⟄ࢆ᭷ࡍࡿ 300 ml ࣮࢜ࢺࢡ࣮ࣞࣈ࡬ᑟධࡋࠊ㟼⨨᮲௳ୗࠊ⮬ᕫᅽୗ࡟࠾࠸࡚160°C ࡛ 24 ᫬㛫Ỉ⇕ฎ⌮ࡍࡿࡇ ࡜࡛〇⭷ࡋࡓࠋࡑࡢᚋࠊ෭Ỉ࡟ࡉࡽࡋᛴ෭ࡉࡏࠊᚓࡽࢀࡓ⭷ࢆ Ỉ࡛Ὑίࡋࠊ60°C ୍࡛ᬌ ஝⇱ࡋࡓࠋࡉࡽ࡟ࠊࢮ࢜ࣛ࢖ࢺ㦵᱁୰ࡢᵓ㐀つᐃ๣ࢆ㝖ཤࡍࡿࡓࡵ࡟ࠊ375°C ࡛ 60 ᫬㛫↝ ᡂࢆ⾜࠸silicalite-1 ⭷ࢧࣥࣉࣝ࡜ࡋࡓࠋྜᡂᡭ㡰ࡢᴫ␎࠾ࡼࡧ⿦⨨ᅗࢆ Fig. 2.3 ࡟♧ࡍࠋ

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25

2.2.4. ࢟ࣕࣛࢡࢱࣜࢮ࣮ࢩࣙࣥ

ᚓࡽࢀࡓ⢊ᮎ࠾ࡼࡧ⭷ࡢྠᐃࡣࠊ⢊ᮎ X ⥺ᅇᢡ⿦⨨㸦X-ray diffraction; XRD), D8

Advance, Bruker, Germany㸧ࢆ⏝࠸࡚ࠊ⟶㟁ᅽ 40 kVࠊ⟶㟁⌫ 40 mA ࡢ᮲௳࡛⾜ࡗࡓࠋࡲ

ࡓࠊ⢊ᮎࡢ㦵᱁⤌ᡂ㸦Si/Al ẚ㸧ࡣࠊ⺯ග X ⥺ศᯒ⿦⨨㸦X-ray fluorescence; XRF, S8 Tiger,

Bruker, Germany㸧࡟ࡼࡾ ᐃࡋࡓࠋ❅⣲྾╔➼ ⥺ࡢ ᐃࡣࠊ❅⣲⮬ື࢞ࢫ྾╔⿦⨨

㸦BELSORP-mini, Microtrac Bel, Japan㸧ࢆ⏝࠸ࡓࠋヨᩱ⣙ 0.1g ࢆ 400°C ࡛ 10 ᫬㛫┿✵᤼

Ẽฎ⌮ࡋࡓᚋࠊ-196°C ࡟࡚ ᐃࡋࡓࠋBET ἲ࠾ࡼࡧ t-plot ἲ࡟ࡼࡾࢮ࢜ࣛ࢖ࢺࡢẚ⾲㠃 ✚࠾ࡼࡧ࣐࢖ࢡࣟ⣽Ꮝᐜ✚ࢆ⟬ฟࡋࡓࠋ⤖ᬗᙧែࡣࠊ㧗ศゎ⬟㟁ゎᨺฟᆺ㉮ᰝᆺ㟁Ꮚ㢧

ᚤ㙾㸦scanning electron microscopy; SEM, S-4800, Hitachi, Japan㸧ࢆ⏝࠸ࠊ༳ຍ㟁ᅽࡣ 1.0 kV

࡛ほᐹࡋࡓࠋ⭷᩿㠃ࡢඖ⣲ศᯒࡣ࢚ࢿࣝࢠ࣮ศᩓᆺ X ⥺ศᯒ㸦energy-dispersive X-ray

analysis; EDX, EX-250, Horiba, Japan)ࢆ⏝࠸ࠊ༳ຍ㟁ᅽࡣ 15 kV ࡛⾜ࡗࡓࠋ 2.2.5. ᾐ㏱Ẽ໬㸦PV㸧ヨ㦂

ࡲࡎࠊsilicalite-1 ⭷ࢆ┤ᚄ⣙ 12 mm ࡢࢫࢸࣥࣞࢫ⟶࡟ࣇࢵ⣲ᶞ⬡⣔ࡢ⪏⇕ࢩ࣮ࣝ㸦Tyco

Electronics/Raychem 〇, RS ရ␒ 344-0647㸧࠾ࡼࡧ polyolefin ⣔㸦Tyco Electronics/Raychem

〇, RS ရ␒ 288-5241㸧࡟ࡼࡾ᥋╔ࡍࡿࡇ࡜࡛⭷ࣔࢪ࣮ࣗࣝࢆస〇ࡋࡓ㸦Fig. 2.4 a㸧ࠋ

⭷ᛶ⬟ࡣ౪⤥ᾮ ᗘ50°C ࡟࠾ࡅࡿ 10 wt.%ࡢ࢚ࢱࣀ࣮ࣝ/Ỉΰྜ⁐ᾮ࠾ࡼࡧ 0.3 wt.%

ࡢࢥࣁࢡ㓟ࢆῧຍࡋࡓ࢚ࢱࣀ࣮ࣝ/Ỉ/ࢥࣁࢡ㓟ΰྜᾮ࡛ࡢศ㞳࡟ࡼࡾホ౯ࡋࡓࠋ㏱㐣⵨Ẽ ࡣᾮయ❅⣲࡛෭ࡸࡉࢀࡓࢧࣥࣉࣜࣥࢢࢺࣛࢵࣉෆ࡛ᾮయ࡟ᡠࡋ࡚ᅇ཰ࡋࠊ౪⤥ᾮ࠾ࡼࡧ㏱㐣ᾮࡢ⤌ᡂࡣᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮㸦Prominence, Shimadzu, Japan㸧ࢆ⏝࠸᳨࡚ฟࡋࡓࠋ

௨ୗࠊ࢚ࢱࣀ࣮ࣝࢆEtOH ࡜⾲グࡍࡿࠋ㏱㐣ὶ᮰ J [kg m-2 _h-1_{]࠾ࡼࡧศ㞳ಀᩘ α ࡣ௨ୗࡢ}

ᘧࢆ⏝࠸࡚⟬ฟࡋࡓࠋ

Flux (J)

J = m / (A㺃t),

m: permeate [kg], A: membrane area [m2_{], t: permeate time [h]}

Separation factor (α)

αethanol/water = (Yethanol / Ywater)permeate / (Xethanol / Xwater)feed

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26

Fig. 2.4. ⭷ࣔࢪ࣮ࣗࣝ㸦a㸧࠾ࡼࡧ PV ヨ㦂⿦⨨ࡢᴫ␎ᅗ㸦b㸧

(a)

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27 2.3. ⤖ᯝ࡜⪃ᐹ

2.3.1. MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗࡢྜᡂ

␗࡞ࡿSi/Al ẚࢆ᭷ࡍࡿ MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗࡣࠊTable 2.1 ࡟♧ࡍ⤌ᡂ࠾ࡼࡧྜᡂ᪥ᩘ

࡟ࡼࡾㄪ〇ࡋࠊᚓࡽࢀࡓ⤖ᬗࡢ≀ᛶ್ࢆࡲ࡜ࡵ࡚♧ࡍࠋỈᛶࢤࣝࡢ௙㎸ࡳSi/Al ẚࢆ∞ࠊ100ࠊ

50ࠊ36ࠊ17 ࡛ㄪ〇ࡋࡓ⤖ᬗ⢊ᮎࡢྜᡂᚋࡢ Si/Al ẚࡣࡑࢀࡒࢀ∞ࠊ104ࠊ47ࠊ28ࠊ16 ࡛࠶ࡗ

ࡓࠋࡲࡓࠊᚓࡽࢀࡓ⤖ᬗ⢊ᮎࡢXRD ࣃࢱ࣮ࣥ࠾ࡼࡧ SEM ീࢆ Fig. 2.5ࠊFig. 2.6 ࡟ࡑࢀࡒࢀ

♧ࡍࠋXRD ࣃࢱ࣮ࣥ࠿ࡽࠊᚓࡽࢀࡓ⢊ᮎ඲࡚࡛ MFI ᆺࢮ࢜ࣛ࢖ࢺ࡟ᇶ࡙ࡃࣆ࣮ࢡࡢࡳࡀほ ᐹࡉࢀࠊ௚ࡢ⤖ᬗ┦ࡢᙧᡂࡣ☜ㄆࡉࢀ࡞࠿ࡗࡓࠋࡲࡓࠊ␗࡞ࡿSi/Al ẚ࡛ྜᡂࡉࢀࡓ✀⤖ᬗ ࡢ⤖ᬗᛶࡣࠊ㦵᱁୰ࡢAl 㔞ࡀቑຍࡍࡿ࡟ࡘࢀ࡚పୗࡋࡓࠋSEM ീほᐹࡼࡾࠊᚓࡽࢀࡓ⤖ᬗ ࡣ⌫≧࡛ࠊ⤖ᬗᚄࡣ1-3 μm ⛬ᗘ࡛࠶ࡗࡓࠋ❅⣲྾╔ ᐃ࠿ࡽࠊSi/Al ẚ࡟౫ࡽࡎ඲࡚ࡢࢧࣥ ࣉ࡛ࣝࠊI ᆺࡢ➼ ⥺ࢆ♧ࡋࠊBET ẚ⾲㠃✚࠾ࡼࡧ⣽Ꮝᐜ㔞ࡶ MFI ᆺࢮ࢜ࣛ࢖ࢺ࡟ᇶ࡙ࡃ ࡶࡢ࡜୍⮴ࡋࡓࠋ௨ୖࡢ⤖ᯝࡼࡾࠊSi/Al ẚࡢ␗࡞ࡿ MFI ᆺࢮ࢜ࣛ࢖ࢺ⤖ᬗࡢྜᡂ࡟ᡂຌࡋ ࡓࡇ࡜ࡀࢃ࠿ࡾࠊ௨ୗ࡟⥆ࡃsilicalite-1 ⭷ㄪ〇࡟ᑐࡍࡿ✀⤖ᬗ࡜ࡋ࡚౑⏝ࡋࡓࠋ Table 2.1 MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗࡢྜᡂ᮲௳࠾ࡼࡧᚓࡽࢀࡓ⢊ᮎࡢ≀ᛶ್ Sample name Si/Al ratio of gel

Molar composition of gel a) _Syn. time [d] Si/Al ratio of product b) Av. particle diameter [μm] BET specific surface area [m2_g-1_] Pore volume [cm3_g-1_] Al2O3/SiO2 TPABr/SiO2 S1 ∞ 0 0.1 6 - 1.0 487 0.20 S2 100 0.005 0.1 10 104 2.5 402 0.18 S3 50 0.010 0.1 11 47 2.7 449 0.17 S4 36 0.014 0.3 18 28 1.0 441 0.17 S5 17 0.029 0.3 21 16 0.9 419 0.12

a) NaOH/SiO2 = 0.2, H2O/SiO2 = 40, Synthesis temperature = 100°C.

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28

Fig. 2.5. MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗࡢ XRD ࣃࢱ࣮ࣥ㸸(a) S1, (b) S2, (c) S3, (d) S4, (e) S5

Fig. 2.6. MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗࡢ SEM ീ㸸(a) S1, (b) S2, (c) S3, (d) S4, (e) S5

5 10 15 20 25 30 35 40 45 50 In te nsity [a. u .] 2θ [degree] (a) (b) (c) (d) (e)

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29

2.3.2. silicalite-1 ⭷ࡢㄪ〇

␗࡞ࡿSi/Al ẚࢆ᭷ࡍࡿ MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗࢆ⏝࠸࡚ࠊ✀⤖ᬗࡢ Si/Al ẚ࠾ࡼࡧሬᕸ

㔞ࡀsilicalite-1 ⭷ࡢᙧែ࠾ࡼࡧศ㞳ᛶ⬟࡟୚࠼ࡿᙳ㡪ࢆ᳨ウࡋࡓࠋFig. 2.7ࠊ2.8 ࡟✀⤖ᬗሬ

ᕸ㔞ࡣ୍ᐃ࡜ࡋࠊ␗࡞ࡿ Si/Al ẚࢆ᭷ࡍࡿ MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗࢆ⏝࠸࡚ㄪ〇ࡋࡓ

silicalite-1 ⭷ࡢ XRD ࣃࢱ࣮ࣥ࠾ࡼࡧ SEM ീࢆࡑࢀࡒࢀ♧ࡍࠋXRD ࣃࢱ࣮ࣥࡼࡾ㸦Fig. 2.7㸧ࠊ

✀⤖ᬗࡢSi/Al ẚ࡟ࡼࡽࡎ඲࡚ࡢ⭷࡛ MFI ᆺࢮ࢜ࣛ࢖ࢺࡢࣆ࣮ࢡࢆ♧ࡋࠊ࢔࣑ࣝࢼᨭᣢయ௨

እࡢ௚ࡢ⤖ᬗ┦ࡢࣆ࣮ࢡࡣぢࡽࢀ࡞࠿ࡗࡓࠋࡲࡓࠊSEM ほᐹࡼࡾ㸦Fig. 2.8㸧ࠊ✀⤖ᬗࡢ Si/Al

ẚ࡟ࡼࡽࡎࠊ⭷⾲㠃ࡣ✀⤖ᬗࡀᡂ㛗ࡍࡿࡇ࡜࡟ࡼࡾᙧᡂࡋࡓMFI ᆺࢮ࢜ࣛ࢖ࢺ⭷≉᭷ࡢᰕ

≧⤖ᬗ࡛そࢃࢀࡓከ⤖ᬗ⭷࡛࠶ࡾࠊ⤖ᬗ㛫࡟ࡣከࡃࡢ㝽㛫ࡀࡳࡽࢀࡓࠋࡲࡓࠊ⭷⾲㠃ࢆᵓ ᡂࡍࡿ⤖ᬗࡢ኱ࡁࡉࡣࠊᨭᣢయୖ࡟ሬᕸࡋࡓ✀⤖ᬗࡢ኱ࡁࡉ࡟౫Ꮡࡋࡓഴྥࢆ♧ࡋࡓࠋ᩿

㠃ほᐹࡼࡾࠊᨭᣢయୖ࡟ᙧᡂࡋࡓࢮ࢜ࣛ࢖ࢺ⭷ᒙࡢཌࡉࡣࠊ✀⤖ᬗࡢSi/Al ẚ࡟౫ࡽࡎ 7 μm

⛬ᗘ࡛࠶ࡗࡓ㸦Fig. 2.9㸧ࠋࡲࡓࠊFig. 2.9 ࡟࢔࣑ࣝࢼᨭᣢయୖ࡟␗࡞ࡿ Si/Al ẚ㸦S-1 ࠾ࡼࡧ

S-4㸧ࡢ✀⤖ᬗࢆ⏝࠸࡚ㄪ〇ࡋࡓ silicalite-1 ⭷ࡢ EDX ࡟ࡼࡿ⭷᩿㠃ࡢ⤌ᡂศᯒࡢ⤖ᯝࢆ♧ࡍࠋ Al ࢆྵࡲ࡞࠸ MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗ㸦S-1, Si-MFI㸧ࢆ⏝࠸ࡓ࡜ࡁࠊᨭᣢయୖࡢࢮ࢜ࣛ࢖

ࢺ⭷ᒙࡣSi ࡢࡳ࡛ᵓᡂࡉࢀ࡚࠸ࡓ㸦Fig. 2.9 a㸧ࠋ୍᪉ࠊAl ྵ᭷ MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗ㸦S2

㸫S5㸧ࢆ⏝࠸ࡓሙྜࠊᨭᣢయୖࡢࢮ࢜ࣛ࢖ࢺ⭷ᒙࡣ 2 ࡘࡢ㡿ᇦ࡟ศ࠿ࢀ࡚࠸ࡿࡇ࡜ࡀ☜ㄆ

࡛ࡁࠊᨭᣢయୖࡢSi ࡜ Al ࡟ࡼࡾᵓᡂࡉࢀࡓ㡿ᇦ࡜ࠊ⭷ᒙ᭱⾲㠃ࡢ Si ࡢࡳ࡛ᵓᡂࡉࢀࡓ㡿

ᇦ࠿ࡽᵓᡂࡉࢀ࡚࠸ࡓ㸦Fig. 2.9 b㸧ࠋࡇࡢ⤖ᯝࡣࠊᨭᣢయୖ࡟✀⤖ᬗᒙ⏤᮶ࡢࢮ࢜ࣛ࢖ࢺᒙࠊ

ࡉࡽ࡟ࡑࡢୖ࡟Ỉᛶࢤࣝ࡟ࡼࡾᙧᡂࡋࡓsilicalite-1 ᒙ࠿ࡽ࡞ࡿ 2 ᒙᵓ㐀ࡢ silicalite-1 ⭷ࡢㄪ

(35)

30

Fig. 2.7. ␗࡞ࡿ Si/Al ẚࢆ᭷ࡍࡿ MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗ㸦(a) S1, (b) S2, (c) S3, (d) S4, (e) S5㸧

ࢆ⏝࠸࡚ㄪ〇ࡋࡓsilicalite-1 ⭷ࡢ XRD ࣃࢱ࣮ࣥ

Fig. 2.8. ␗࡞ࡿ Si/Al ẚࢆ᭷ࡍࡿ MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗ㸦(a) S1, (b) S2, (c) S3, (d) S4, (e) S5㸧

ࢆ⏝࠸࡚ㄪ〇ࡋࡓsilicalite-1 ⭷ࡢ SEM ീ 5 10 15 20 25 30 35 40 45 50 In te n sity [a.u.] 2θ [degree] (a) (b) (c) (d) (e) : α-Al2O3support

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31

Fig. 2.9. ✀⤖ᬗ࡜ࡋ࡚ S1㸦a㸧࠾ࡼࡧ S4㸦b㸧ࢆ⏝࠸࡚ㄪ〇ࡋࡓ silicalite-1 ⭷ࡢ EDX ࡟ࡼࡿ᩿㠃ࡢ⤌ᡂศᯒ

2.3.3. PV ᛶ⬟

2.3.3.1. ࢚ࢱࣀ࣮ࣝ/Ỉΰྜᾮࡢศ㞳

␗࡞ࡿSi/Al ẚࢆ᭷ࡍࡿ MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗ࡟ࡼࡾㄪ〇ࡋࡓ silicalite-1 ⭷ࢆ⏝࠸࡚ࠊ

10 wt.% ࢚ࢱࣀ࣮ࣝΰྜᾮ㸦50˚C㸧࡟ᑐࡍࡿ⭷ᛶ⬟ࢆホ౯ࡋࡓ㸦Fig. 2.10㸧ࠋ✀⤖ᬗ࡜ࡋ࡚ Si-MFI㸦S1㸧ࢆ⏝࠸ࡓሙྜࠊẚ㍑ⓗ㧗࠸ศ㞳ಀᩘࢆ♧ࡋࠊ✀⤖ᬗሬᕸ㔞ࡢቑຍ࡜࡜ࡶ࡟ศ

㞳ಀᩘࡣྥୖࡋࡓࡀࠊ✀⤖ᬗሬᕸ㔞ࢆ6 g m-2_{௨ୖ࡟ቑຍࡉࡏࡿ࡜ศ㞳ಀᩘࡣపୗࡋࡓ㸦}_Fig.

2.10 a㸧ࠋࡇࢀࡣ silicalite-1 ⭷ࡢྜᡂ࡟࠾࠸࡚ࠊ㐣๫࡞㔞ࡢ silicalite-1 ✀⤖ᬗᒙࡢሁ✚ࡣ⭷ᒙ

ࡢᡂ㛗ࢆጉࡆࡿ࡜࠸࠺᪤ሗࡢ⤖ᯝ[11],[22]_{࡜୍⮴ࡋࡓࠋ✀⤖ᬗሬᕸ㔞ࢆኚ໬ࡉࡏࡿࡇ࡜࡟ࡼࡾ}

ㄪ〇ࡋࡓsilicalite-1 ⭷ࡢ XRD ࣃࢱ࣮ࣥ㸦Fig. 2.11㸧࠿ࡽࡶ✀⤖ᬗ㔞ࡀከ࠸ሙྜࠊMFI ᆺࢮ࢜

ࣛ࢖ࢺ࡟ᇶ࡙ࡃࣆ࣮ࢡᙉᗘࡣపୗࡋ࡚࠾ࡾ㸦Fig. 2.11 a㸧ࠊ⭷ྜᡂ࡟ᑐࡋ࡚㐺ษ࡞㔞ࡀ࠶ࡿ

ࡇ࡜ࡀࢃ࠿ࡿࠋ୍᪉࡛ࠊAl ྵ᭷ MFI ᆺࢮ࢜ࣛ࢖ࢺ✀⤖ᬗࢆ⏝࠸ࡓሙྜ㸦S2-S5㸧ࠊ✀⤖ᬗሬ

ᕸ㔞࡜࡜ࡶ࡟⭷ᛶ⬟ࡣྥୖࡋࡓ㸦Fig. 2.10 b-d㸧ࠋࡇࢀࡣࠊ✀⤖ᬗሬᕸ㔞ࢆቑຍࡉࡏ࡚ࡶ⭷

ᒙࡀୖᡭࡃㄪ〇ࡉࢀࡓ⤖ᯝ࡛࠶ࡾ㸦Fig. 2.11 b, c㸧ࠊAl ྵ᭷✀⤖ᬗࡣỈ⇕ฎ⌮᫬࡟ Si-MFI

ࡢ✀⤖ᬗ࡟ẚ࡭࡚⁐ゎࡋࡸࡍ࠸ࡓࡵ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿ[23]_ࠋࡇࡢ_{Al ྵ᭷ࡢ✀⤖ᬗࢆ⏝࠸ࡓ} 㝿ࡢ✀⤖ᬗሬᕸ㔞ࡢቑຍ࡟ࡼࡾ⭷ᛶ⬟ࡀྥୖࡍࡿ࡜࠸࠺⤖ᯝࡣࠊMasuda ࡽࡢሗ࿌࡜ࡶ୍⮴ ࡋࡓ[24],[25]_{ࠋ⯆࿡῝࠸ࡇ࡜࡟ࠊ}_{Al ྵ᭷✀⤖ᬗࢆ⏝࠸ࡓሙྜࠊ࢚ࢱࣀ࣮ࣝ/Ỉศ㞳࡟ᑐࡍࡿศ㞳} ಀᩘࡣ✀⤖ᬗ୰࡟ྵࡲࢀࡿAl ྵ᭷㔞࡟౫Ꮡࡋኚ໬ࡍࡿഴྥࢆ♧ࡋࡓࠋ✀⤖ᬗ࡜ࡋ࡚ S2 ࠾ ࡼࡧ S3 ࢆ⏝࠸ࡓሙྜࠊ✀⤖ᬗሬᕸ㔞ࡢቑຍ࡜࡜ࡶ࡟ศ㞳ಀᩘ࡜㏱㐣ὶ᮰ࡣྥୖࡋࡓ㸦Fig. 2.10 b, c㸧ࠋࡋ࠿ࡋࠊS4 ࠾ࡼࡧ S5 ࢆ⏝࠸ࡓሙྜࠊ✀⤖ᬗሬᕸ㔞ࡢቑຍ࡜࡜ࡶ࡟㏱㐣ὶ᮰ࡣ ྥୖࡋࡓࡀࠊศ㞳ಀᩘࡣ࡯࡜ࢇ࡝୍ᐃ࡛⣙30 ࡜ప࠸ࡲࡲ࡛࠶ࡗࡓ㸦Fig. 2.10 d, e㸧ࠋࡇࡢ㐪 ࠸ࡣࡇࢀࡽࡢ⭷ࡢྛᡂศ㏱㐣ὶ᮰ࢆẚ㍑ࡍࡿࡇ࡜࡛᫂ࡽ࠿࡜࡞ࡿ㸦Fig. 2.12㸧ࠋ✀⤖ᬗ࡜ࡋ