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Title 低品位炭の自然発火機構の解明および自然発火抑制法の 検討
Title Author(s) Citation Issue Date 低品位炭の自然発火機構の解明および自然発火抑制法の 検討( Dissertation_全文 ) 藤墳, 大裕 Kyoto University (京都大学) 2014-03-24 URL https://doi.org/10.14989/doctor.k18309 Right 許諾条件により本文は2015-03-23に公開 Type Thesis or Dissertation Textversion ETD Kyoto University పရⅣ䛾⮬↛Ⓨⅆᶵᵓ䛾ゎ᫂䛚䜘䜃 ⮬↛Ⓨⅆᢚไἲ䛾᳨ウ 2014 ᖺ ⸨ቡ㻌 ⿱ 㻌㻌㻌㻌 ┠ḟ ⥴ㄽ 䠊䠊䠊䠊䠊䠊 1 0. 1. పရⅣ䛾ᵓ㐀䝰䝕䝹 䠊䠊䠊䠊䠊䠊 2 0. 2. ▼Ⅳ䛾ప 㓟ᶵᵓ䛻㛵䛩䜛⥲ㄽ 䠊䠊䠊䠊䠊䠊 5 0. 2. 1. ప 㓟ᛂ䛾⏕ᡂ≀䛚䜘䜃ᛂᶵᵓ 䠊䠊䠊䠊䠊䠊 6 0. 2. 2. ప 㓟ᛂᛶ䛻ᐤ䛩䜛せᅉ 䠊䠊䠊䠊䠊䠊 10 䠊䠊䠊䠊䠊䠊 11 0. 3. 1. ప 㓟ᛂᛶ䛾ホ౯ἲ 䠊䠊䠊䠊䠊䠊 12 0. 3. 2. ㏿ᗘゎᯒᡭἲ 䠊䠊䠊䠊䠊䠊 14 䠊䠊䠊䠊䠊䠊 17 䠊䠊䠊䠊䠊䠊 25 1. 1. ⥴ゝ 䠊䠊䠊䠊䠊䠊 25 1. 2. ᐇ㦂 䠊䠊䠊䠊䠊䠊 25 1. 2. 1. 㔜㔞ኚ䛚䜘䜃䜺䝇⏕ᡂ㏿ᗘ 䠊䠊䠊䠊䠊䠊 26 1. 2. 2. Ⓨ⇕㏿ᗘ 䠊䠊䠊䠊䠊䠊 27 1. 2. 3. ▼Ⅳ୰䛾ᐁ⬟ᇶ㔞ኚ 䠊䠊䠊䠊䠊䠊 27 䠊䠊䠊䠊䠊䠊 28 1. 3. 1. 㔜㔞ኚ䠈䜺䝇⏕ᡂ㏿ᗘ䛚䜘䜃Ⓨ⇕㏿ᗘ 䠊䠊䠊䠊䠊䠊 28 1. 3. 2. ᐁ⬟ᇶ㔞䛾ኚ 䠊䠊䠊䠊䠊䠊 32 1. 3. 3. ప 㓟ᶵᵓ䛾᳨ウ 䠊䠊䠊䠊䠊䠊 41 1. 3. 4. ప 㓟ᶵᵓ䛸⮬↛Ⓨⅆᛶ䛸䛾ᑐᛂ 䠊䠊䠊䠊䠊䠊 44 䠊䠊䠊䠊䠊䠊 48 0. 3. ▼Ⅳ䛾ప 㓟ᛂᛶ䛻㛵䛩䜛⥲ㄽ 0. 4. ᮏ◊✲䛾┠ⓗ䛸ෆᐜ ➨ 1 ❶ ▼Ⅳ䛾ప 㓟ᶵᵓ䛾ゎ᫂ 1. 3. ⤖ᯝ䛸⪃ᐹ 1. 4. ⤖ゝ i ➨ 2 ❶ ๓ฎ⌮䛜ప 㓟ᣲື䛻ཬ䜌䛩ᙳ㡪 䠊䠊䠊䠊䠊䠊 50 2. 1. ⥴ゝ 䠊䠊䠊䠊䠊䠊 50 2. 2. ᐇ㦂 䠊䠊䠊䠊䠊䠊 50 2. 2. 1. ヨᩱ䛾ㄪ〇 䠊䠊䠊䠊䠊䠊 50 2. 2. 2. ⏕ᡂ≀䛾ᛶ≧ศᯒ 䠊䠊䠊䠊䠊䠊 52 2. 2. 3. 㓟ᣲື䛾 ᐃ 䠊䠊䠊䠊䠊䠊 55 䠊䠊䠊䠊䠊䠊 55 2. 3. 1. ヨᩱ䛾ᛶ≧ 䠊䠊䠊䠊䠊䠊 55 2. 3. 2. ฎ⌮Ⅳ䛾ప 㓟ᣲື 䠊䠊䠊䠊䠊䠊 57 2. 3. 3. ๓ฎ⌮䛜ప 㓟ᶵᵓ䛻䛘䜛ᙳ㡪 䠊䠊䠊䠊䠊䠊 60 2. 3. 4. ⮬↛Ⓨⅆᛶ䛸䛾ᑐᛂ 䠊䠊䠊䠊䠊䠊 61 䠊䠊䠊䠊䠊䠊 64 2. 3. ⤖ᯝ䛸⪃ᐹ 2. 4. ⤖ゝ ➨ 3 ❶ ⁐ฎ⌮ἲ䛾⬺Ỉ䞉ᨵ㉁䜢క䛖⮬↛Ⓨⅆᢚไἲ䛸䛧䛶䛾⏝ྍ⬟ᛶ 䠊䠊䠊䠊䠊䠊 66 3. 1. ⥴ゝ 䠊䠊䠊䠊䠊䠊 66 3. 2. ᐇ㦂 䠊䠊䠊䠊䠊䠊 67 3. 2. 1. ヨᩱ䛾ㄪ〇 䠊䠊䠊䠊䠊䠊 67 3. 2. 2. ⏕ᡂ≀䛾ᛶ≧ศᯒ 䠊䠊䠊䠊䠊䠊 69 3. 2. 3. 65 °C 䛻䛚䛡䜛㓟⣲྾╔ᣲື 䠊䠊䠊䠊䠊䠊 70 䠊䠊䠊䠊䠊䠊 71 3. 3. 1. ⏕ᡂ≀䛾⋡ 䠊䠊䠊䠊䠊䠊 71 3. 3. 2. ฎ⌮ヨᩱ䛾ඖ⣲⤌ᡂ䠈Ⓨ⇕㔞 䠊䠊䠊䠊䠊䠊 72 3. 3. 3. ᐁ⬟ᇶ㔞䛾ኚ 䠊䠊䠊䠊䠊䠊 78 3. 3. 4. 㓟⣲྾╔ᣲື(LY Ⅳ䠈PD Ⅳ) 䠊䠊䠊䠊䠊䠊 80 3. 3. ⤖ᯝ䛸⪃ᐹ ii 䠊䠊䠊䠊䠊䠊 83 䠊䠊䠊䠊䠊䠊 85 4. 1. ⥴ゝ 䠊䠊䠊䠊䠊䠊 85 4. 2. ᐇ㦂䛚䜘䜃ゎᯒ 䠊䠊䠊䠊䠊䠊 85 4. 2. 1. 㔜㔞ኚ䛚䜘䜃䜺䝇⏕ᡂ㏿ᗘ 䠊䠊䠊䠊䠊䠊 85 4. 2. 2. Ⓨ⇕㏿ᗘ 䠊䠊䠊䠊䠊䠊 86 4. 2. 3. ᛂ㏿ᗘゎᯒ 䠊䠊䠊䠊䠊䠊 86 4. 2. 4. ᩿⇕ ᗘୖ᪼ᩘ್䝅䝭䝳䝺䞊䝅䝵䞁 䠊䠊䠊䠊䠊䠊 87 䠊䠊䠊䠊䠊䠊 89 4. 3. 1. ᪼ ㏿ᗘ䛾ᙳ㡪 䠊䠊䠊䠊䠊䠊 89 4. 3. 2. ᛂ㏿ᗘゎᯒ 䠊䠊䠊䠊䠊䠊 93 4. 3. 3. ᩿⇕ ᗘୖ᪼ᩘ್䝅䝭䝳䝺䞊䝅䝵䞁 䠊䠊䠊䠊䠊䠊 100 䠊䠊䠊䠊䠊䠊 105 ⥲ㄽ 䠊䠊䠊䠊䠊䠊 107 ㅰ㎡ 䠊䠊䠊䠊䠊䠊 111 ᮏ◊✲䛻㛵䛩䜛ⴭ⪅䛾Ⓨ⾲ㄽᩥ 䠊䠊䠊䠊䠊䠊 113 3. 4. ⤖ゝ ➨ 4 ❶ ▼Ⅳప 㓟䛾㏿ᗘゎᯒ 4. 3. ⤖ᯝ䛸⪃ᐹ 4. 4. ⤖ゝ iii 㻌㻌㻌㻌 ደᛯ ⥴ㄽ 㻌 2010 ᖺ䛻䛚䛡䜛ୡ⏺䛾୍ḟ䜶䝛䝹䜼䞊ᾘ㈝㔞䛾䛖䛱 80 %䜢▼㈨※䛜䠈27 %䜢▼Ⅳ 䛜༨䜑䛶䛔䜛[1]䠊ྛ▼㈨※䛾ྍ᥇ᖺᩘ䛿 2012 ᖺᮎ䛻䛚䛔䛶▼Ἔ䛜 53 ᖺ䠈ኳ↛䜺䝇䛜 56 ᖺ䛷䛒䜛䛾䛻ᑐ䛧䠈▼Ⅳ䛿 109 ᖺ䛷䛒䜚[2, 3]䠈▼Ⅳ䛿䛾▼㈨※䛾 2 ಸ⛬ᗘ䛾ྍ᥇ ᖺᩘ䜢᭷䛧䠈㇏ᐩ䛺㈨※䛷䛒䜛䠊㏆ᖺ䠈䜰䝆䜰䛺䛹䜢୰ᚰ䛻▼Ⅳ䛾ᾘ㈝㔞䛜ቑຍ䛧䛶䛚䜚䠈 ᚋ䜒୍ḟ䜶䝛䝹䜼䞊ᾘ㈝㔞䛻༨䜑䜛▼Ⅳ䛾ྜ䛜ቑຍ䛩䜛䛸ண 䛥䜜䛶䛔䜛䠊▼Ⅳ䛾 ྍ᥇ᇙⶶ㔞䛿 8609 ൨䝖䞁䛒䜛䛸䛔䜟䜜䛶䛔䜛䛜䠈䛭䛾୰䛻䛿ள℡㟷Ⅳ䜔〓Ⅳ䛸䛔䛳䛯ప ရⅣ䜒ྵ䜎䜜䛶䛚䜚䠈పရⅣ䛾ྍ᥇ᇙⶶ㔞䛿 4562 ൨䝖䞁䛸▼Ⅳయ䛾ྍ᥇ᇙⶶ㔞 䛾 53 %䜢༨䜑䛶䛔䜛䠊䛭䛾䛯䜑䠈㟂せ䛾㐕㏕䛻క䛔䠈ᚋ䛿㉁䛾Ⰻ䛔㧗ရⅣ䛾䜏䛺 䜙䛪䠈పရⅣ䛾⏝䛜ᚲせྍḞ䛷䛒䜛䠊䛧䛛䛧䛺䛜䜙䠈పရⅣ䛿Ỉศ䞉㓟⣲ศ䜢ከ 䛟ྵ䜐䛯䜑Ⓨ⇕㔞䛜ᑠ䛥䛟ၟရ౯್䛜ᑠ䛥䛔䛣䛸䛸䠈⇱≧ែ䛷䛿㧗䛔⮬↛Ⓨⅆᛶ䜢᭷ 䛩䜛䛯䜑䠈㛗ᮇ㛫䛾㈓ⶶ䜔㛗㛫䛾㍺㏦䛜ᴟ䜑䛶ᅔ㞴䛷䛒䜛䛯䜑䠈పရⅣ䛾つᶍ ⏝䛿Ⅳ㖔䛻㞄᥋䛩䜛Ⓨ㟁ᡤ䛷䛾⏝䛻㝈䜙䜜䛶䛔䜛䠊≉䛻䠈⮬↛Ⓨⅆ䛾῝้䛥䛿䠈ప ရⅣ䜢⏘ฟ䛩䜛Ⅳ㖔䛻䛚䛔䛶䛧䜀䛧䜀⮬↛Ⓨⅆ䛻䜘䜛⿕ᐖ䛜㉳䛝䛶䛔䜛䛣䛸䜔䠈㏆ᖺ 䝻䝅䜰䜔䜲䞁䝗䝛䝅䜰䛷㧗 䛻䜘䜚⇱䛧䛯ἾⅣᒙ䛾⮬↛Ⓨⅆ䛻㉳ᅉ䛩䜛つᶍⅆ⅏䛛 䜙䜒䛖䛛䛜䛘䜛䠊௨ୖ䛾䛣䛸䛛䜙䠈పရⅣ䜢Ᏻ䛻⏝䛷䛝䜛䜘䛖䠈䜎䛯᪥ᮏ䛾䜘䛖䛺▼Ⅳ 䜢㍺ධ䛻㢗䛳䛶䛔䜛ᅜ䚻䛷䜒᭷ຠ⏝䛷䛝䜛䜘䛖䛻䛩䜛䛻䛿䠈ᅗ 0. 1 䛻♧䛩䜘䛖䛻䜎䛪⬺ Ỉฎ⌮䛚䜘䜃⮬↛Ⓨⅆᢚไฎ⌮䛻䜘䜚㍺㏦䛚䜘䜃㈓ⶶ䜢ྍ⬟䛻䛩䜛䛣䛸(Level 1)䠈䛥䜙 䛻䜶䝛䝹䜼䞊※䛸䛧䛶⏝䛩䜛䛯䜑䛻䛿䠈䛭䜜䜙䛾ฎ⌮䛻ຍ䛘䠈ᨵ㉁ฎ⌮䛻䜘䜚పရ Ⅳ䛾Ⓨ⇕㔞䜢ྥୖ䛥䛫䜛䛣䛸(Level 2)䛜ồ䜑䜙䜜䜛䠊ຍ䛘䛶䠈⬺Ỉฎ⌮䠈⮬↛Ⓨⅆᢚไฎ ⌮䠈ᨵ㉁ฎ⌮䛿䜶䝛䝹䜼䞊ຠ⋡䛜㧗䛟䠈ᕤᴗⓗ䛻⏝䛷䛝䜛ฎ⌮䛜ᮃ䜎䛧䛔(Level 3)䠊䛧 䛛䛧䠈⮬↛Ⓨⅆᢚไἲ䛿ᮍ䛰☜❧䛥䜜䛶䛚䜙䛪䠈పရⅣ䜢᭷ຠ⏝䛩䜛䛖䛘䛷䛝䛺 ጉ䛢䛸䛺䛳䛶䛔䜛䠊䜘䜚᭷ຠ䛺⮬↛Ⓨⅆᢚไἲ䜢㛤Ⓨ䛩䜛䛯䜑䛻䛿䠈⮬↛Ⓨⅆ䛜㉳䛣䜛ᶵ ᵓ䜢᫂䜙䛛䛻䛧䛯䛖䛘䛷䠈䛭䜜䜢ᢚไ䛷䛝䜛᪉ἲ䜢ぢฟ䛩䛣䛸䛜ᚲせ䛷䛒䜛䠊୍᪉䠈ᐇ㦂 1 ⬺Ỉ ⮬↛Ⓨⅆᢚไ ᨵ㉁ 䜶䝛䝹䜼䞊ຠ⋡ + ప䝁䝇䝖 Level 1 ㍺㏦䞉㈓ⶶ Level 2 Ⓨ⇕㔞ྥୖ Level 3 ప䜶䝛䝹䜼䞊䝻䝇 0. 1. ˯Լˮ໗↝ஊјМဇ↝↰↚൭↰↸↻↺ϼྸ 㠃䛛䜙䛿㐺ษ䛺⮬↛Ⓨⅆᛶホ౯ἲ䛾㛤Ⓨ䛜ᚲせ䛷䛒䜛䠊 㻌 ᮏ◊✲䛷䛿䠈పရⅣ䛾ప 㓟ᶵᵓ䜢ヲ⣽䛻᳨ウ䛩䜛䛣䛸䛷⮬↛Ⓨⅆᶵᵓ䛾ゎ᫂ 䜢ヨ䜏䛯䠊䜎䛯䠈䛭䛾⮬↛Ⓨⅆᶵᵓ䛻ᇶ䛵䛝䠈⮬↛Ⓨⅆᢚไἲ䛸䛧䛶䛾ྍ⬟ᛶ䛜♧䛥䜜 䛯⁐ฎ⌮䛻䛴䛔䛶⮬↛Ⓨⅆᢚไ䛸ᨵ㉁䜢ྠ䛻ᐇ⌧䛷䛝䜛䛛䛻䛴䛔䛶᳨ウ䛧䛯䠊䛥䜙 䛻䠈ప 㓟䛾ᛂ㏿ᗘゎᯒ䜢⾜䛔䠈ప 䛷䛾 ᗘୖ᪼䛾ᩘ್䝅䝭䝳䝺䞊䝅䝵䞁䜢ヨ䜏 䛯䠊䛣䛾⥴ㄽ䛷䛿䠈▼Ⅳ䛾⮬↛Ⓨⅆᶵᵓ䛚䜘䜃ᩘ್䝅䝭䝳䝺䞊䝅䝵䞁䛻㛵䛩䜛᪤ 䛾◊ ✲䛻䛴䛔䛶⤂䛧䠈䛭䛾ၥ㢟Ⅼ䛻䛴䛔䛶♧䛧䛯䛾䛱䠈ᮏ◊✲䛾┠ⓗ䛸ෆᐜ䜢♧䛩䠊 0. 1. పရⅣ䛾ᵓ㐀䝰䝕䝹 㻌 పရⅣ䛾⮬↛Ⓨⅆᶵᵓ䜢᳨ウ䛩䜛䛖䛘䛷䠈పရⅣ䛾Ꮫⓗᵓ㐀䜢ᢕᥱ䛧䛶䛚䛟䛣 䛸䛿㔜せ䛷䛒䜛䠊ᅗ 0. 2 ~ 0. 4 䛻✀䚻䛾పရⅣ䛾ᵓ㐀䝰䝕䝹䜢♧䛩䠊ᅗ 0. 2 䛿 Hüttinger 䜙[4]䛻䜘䜛䝗䜲䝒⏘〓Ⅳ䛾䝰䝕䝹䛷䛒䜚䠈1 ~ 3 ⎔䛜⬡⫫᪘Ⅳ⣲䜔䜶䞊䝔䝹⤖ྜ 䛷䛴䛺䛜䛳䛶䛔䜛䠊䜎䛯䠈⬡⫫᪘Ⅳ⣲䛾㛗䛔┤㙐䛜䛒䜚䠈䜹䝹䝪䜻䝅䝹ᇶ䛻㔠ᒓ䜹䝏䜸䞁 䛜䜲䜸䞁⤖ྜ䛧䛶䛔䜛䛸䛔䛳䛯≉ᚩ䜢᭷䛩䜛䠊ᅗ 0. 3 䛿 Kumagai 䜙[5]䛜ᥦၐ䛧䛯䜸䞊䝇䝖 䝷䝸䜰⏘〓Ⅳ䛷䛒䜛 Yallourn Ⅳ䛾༢ᵓ㐀䛷䛒䜚䠈䛣䜜䛜䜶䞊䝔䝹⤖ྜ䛷㔜ྜ䛩䜛䛸䛧䛶 2 ደᛯ 0. 2. Hüttinger ↸[4]ⅻ੩కↆᙓ໗↝ನᡯ 0. 3. Kumagai ↸[5]ⅻ੩కↆᙓ໗↝ನᡯ 䛔䜛䛾䛜䛣䛾䝰䝕䝹䛾≉ᚩ䛷䛒䜛䠊ᅗ 0. 4 䛿 Salmon 䜙[6]䛻䜘䜛 Morwell Ⅳ㖔䛾ᮌ㉁Ⅳ䛾 䝰䝕䝹䛷䛒䜚䠈䛾 2 䛴䜘䜚䜒䜘䜚㉁䛾ప䛔▼Ⅳ䛾䝰䝕䝹䛸䛺䛳䛶䛔䜛䠊1 ဨ⎔䛜⬡⫫᪘Ⅳ ⣲䛷䛴䛺䛜䜚䠈䝸䜾䝙䞁䛻㢮ఝ䛾ᵓ㐀䛸䛺䛳䛶䛔䜛䠊䛣䜜䜙䛾䝰䝕䝹䛾ඹ㏻Ⅼ䛸䛧䛶䠈ከ䛟 䛾ྵ㓟⣲ᐁ⬟ᇶ䠈䛸䜚䜟䛡䜹䝹䝪䜻䝅䝹ᇶ䛚䜘䜃䝣䜵䝜䞊䝹ᛶỈ㓟ᇶ䜢᭷䛧䛶䛔䜛䛣䛸䛜 ᣲ䛢䜙䜜䜛䠊୍᪉䠈ᅗ 0. 5 䛿 Shinn 䜙[7]䛜ᥦၐ䛧䛯℡㟷Ⅳ䛷䛒䜛 Illinois No. 6 Ⅳ䛾ᵓ㐀䛷 䛒䜚䠈పရⅣ䛾ᵓ㐀䛸ẚ㍑䛩䜛䛸䠈䜹䝹䝪䜻䝅䝹ᇶ䛜䜋䛸䜣䛹Ꮡᅾ䛫䛪䠈ⰾ㤶⎔䛜Ⓨ㐩 䛧䠈⬡⫫᪘Ⅳ⣲䛾ྜ䜒ప䛔䛸䛔䛳䛯㐪䛔䛜䜏䜙䜜䜛䠊䛺䛚䠈▼Ⅳ䛿ᅗ 0. 5 䛾ᵓ㐀䛻䛒䜛 䜘䛖䛻䠈ᕧศᏊ䛾୰䛻◚⥺䛷ᅖ䜎䜜䛯䜘䛖䛺ẚ㍑ⓗపศᏊ㔞䛾ศᏊ䛜ෆໟ䛥䜜䜛䝩䝇䝖 -䝀䝇䝖ᵓ㐀䜢ྲྀ䜛䛸䛔䜟䜜䛶䛔䜛䛜పရⅣ䛾ᵓ㐀䝰䝕䝹䛷䛭䛾䜘䛖䛺䝰䝕䝹䛿ᑡ䛧䛿 䛒䜛䠊 3 0. 4. Salmon ↸[6]ⅻ੩కↆஙឋ໗↝ನᡯ 0. 5. Shinn ↸[7]ⅻ੩కↆົ᩷໗↝ನᡯ 4 ደᛯ ᘙ 0. 1. ˯ภᣠ҄ೞನⅹ↷↢ᡮࡇᚐௌ↚ဇⅳ↸↻↺ඥ ยݣܭᝋ ยܭඥ ᚐௌ‚ⅎ‒МဇӧᏡ≏⃬‒Мဇↄ↻↉‛ Ӓࣖೞನ ᡮࡇᚐௌ [҄٭32~35] TG ʊ ⅎ power law, Elovich’s eq ဃ⇒⇟[11~15] GC ⅎ ⅎ power law, Elovich’s eq ᣠእԈბ[31] TG, GC ʊ ⅎ power law, Elovich’s eq ႆ༏ᡮࡇ[36~44] DSC Basket method Wire basket method Chen’s method ʊ ⅎ power law, Elovich’s eq (DSC) Transit heat balance ˳ನᡯ[16~22] FT-IR XPS ESR/ESP 13C-NMR ⅎ ʊ ᡮࡇᚐௌඥ 0. 2. ▼Ⅳ䛾ప 㓟ᶵᵓ䛻㛵䛩䜛⥲ㄽ 㻌 పရⅣ䛾⮬↛Ⓨⅆ䛿㔞䛾పရⅣ䛜㔝✚䜏䛻䛥䜜䛯䜚䠈Ⅳᒙ䛜✵Ẽ䛻㟢ฟ䛧䛶 䛔䜛㝿䛻㉳䛣䜛⌧㇟䛸䛧䛶▱䜙䜜䛶䛚䜚䠈✵Ẽ୰䛾㓟⣲䛸▼Ⅳ䛜ᛂ䛩䜛䛣䛸䛷⏕䛨䛯⇕ 䛜▼Ⅳ୰䛻✚䛩䜛䛣䛸䛷㉳䛣䜛䛸䛔䜟䜜䛶䛔䜛䠊ᛂ⇕䛻䜘䜚▼Ⅳ䛾 ᗘ䛜ୖ᪼䛩䜛䛸䠈 㓟䛾ᛂ㏿ᗘ䛜䛝䛟䛺䜚䠈༑ศ䛻 ᗘ䛜ୖ䛜䜚ᛂ䛜㏿䛟䛺䜛䛸䠈▼Ⅳ䛜⮬↛Ⓨⅆ䛩 䜛䠊▼Ⅳ䛾⮬↛Ⓨⅆ䛿ྂ䛟䛛䜙䛾ၥ㢟䛷䛒䜚䠈᪥ᮏ䛻䛚䛔䛶䜒 4 ᖺ䛻ᐑᕝ䜙[8]䛜▼Ⅳ 䛾⮬⇞ᛶ䛾ᑠ䜢䠈᩿⇕᮲௳䛷䛾㓟䛻䛚䛡䜛 ᗘୖ᪼䜘䜚ホ౯䛧䛯⤖ᯝ䜢ሗ࿌䛧䛶䛔 䜛䠊⾲ 0. 1 䛻ప 㓟ᶵᵓ䛾ᢕᥱ䛚䜘䜃䛭䛾㏿ᗘゎᯒ䛻⏝䛔䜙䜜䛶䛔䜛ᡭἲ䜢䜎䛸䜑䛯䠊 ᮏ⠇䛷䛿䠈ప 㓟ᶵᵓ䛸䛭䛾せᅉ䛻䛴䛔䛶㏙䜉䜛䠊 5 0. 2. 1. ▼Ⅳ䛾ప 㓟䛻䜘䜛⏕ᡂ≀䛚䜘䜃䛭䛾ᛂᶵᵓ 㻌 ప 㓟䛷䛿䠈䜺䝇䛾⏕ᡂ䛸▼Ⅳ䛾ᵓ㐀ኚ䛜㉳䛣䜛䛸䛔䜟䜜䛶䛚䜚䠈䜺䝇⏕ᡂ≀䛿䜺 䝇䜽䝻䝬䝖䜾䝷䝣䛻䜘䜛ᐃ㔞䛜䠈▼Ⅳ䛾ᵓ㐀ኚ䛻䛿㉥እศග(FT-IR)䠈X ⥺㟁Ꮚศග (XPS)䠈᰾☢Ẽඹ㬆(13C-NMR)䛚䜘䜃㟁Ꮚ䝇䝢䞁ඹ㬆(ESR)䛸䛔䛳䛯 ᐃἲ䛜⏝䛔䜙䜜䛶 䛔䜛䠊䜎䛯䠈䜺䝇⏕ᡂ≀䛸▼Ⅳ䛾ᵓ㐀ኚ䛛䜙▼Ⅳ䛾ప 㓟ᶵᵓ䛾᳨ウ䛜䛺䛥䜜䛶䛔 䜛䠊 㻌 ᐇ㝿䛾Ⅳ㖔䛷᥇ྲྀ䛧䛯䜺䝇䛻䛿ⅣỈ⣲(CxHy)䜔 CO2䠈CO䠈H2O 䛚䜘䜃ᚤ㔞䛾 H2 䛜 ྵ䜎䜜䛶䛔䜛[9]䛜䠈䝷䝪䝇䜿䞊䝹䛷䛾ᐇ㦂䛷䛿 CO2䠈CO 䛚䜘䜃 H2O 䛾䜏䛜ほᐹ䛥䜜䜛䠊 ୍⯡䛻䛿䠈CO2 䛾⏕ᡂ㏿ᗘ䛿 ᗘ䛜㧗䛔䜋䛖䛜䛝䛟䠈䜎䛯ྠ䛨 ᗘ䛷䛿䠈ᛂ㛫䛜 㛗䛟䛺䜛䜋䛹ᑠ䛥䛟䛺䜛䛸䛔䛳䛯ഴྥ䛜ሗ࿌䛥䜜䛶䛔䜛[10]䠊CO2 䛸 CO 䛷䛿 CO2 䛾䜋䛖䛜ከ 䛟⏕ᡂ䛩䜛䛸䛔䜟䜜䛶䛚䜚䠈ள℡㟷Ⅳ䛾㓟䛻䛚䛔䛶䠈CO 䛜䜋䛸䜣䛹ほᐹ䛥䜜䛺䛔䛸䛔 䛳䛯ሗ࿌[11 ~ 13]䜒䛒䜛䠊୍᪉䠈H2O 䛾⏕ᡂ䛿 ᐃ䛜ᅔ㞴䛷䛒䜛䛯䜑䛻䠈ሗ࿌䛿䛒䜎䜚ከ䛟䛿 䛺䛔䠊Wang 䜙[14]䛿䠈᩿⇕ᛂჾ䜢⏝䛔䠈60 ~ 90 °C 䛷℡㟷Ⅳ䜢 4 ~ 27 㛫㓟䛥䛫䠈⏕ ᡂ䛧䛯䜺䝇䜢྾‵䜢ሸ䛧䛯䝖䝷䝑䝥䜢㏻䛧䛯䛾䛱䠈䜺䝇䜽䝻䝬䝖䜾䝷䝣䛷ศᯒ䛩䜛䛣䛸䛷 CO2 䛸 CO 䛾ᐃ㔞䜢䠈䝖䝷䝑䝥䛾㔜㔞ኚ䜢 ᐃ䛩䜛䛣䛸䛷 H2O 䛾ᐃ㔞䜢䛭䜜䛮䜜⾜䛔䠈 ྛ䜺䝇䛾⏕ᡂ㏿ᗘ䜢ẚ㍑䛧䛯䠊䛭䛾⤖ᯝ䠈H2O 䛜᭱䜒ከ䛟⏕ᡂ䛧䠈䛭䛾⏕ᡂ㏿ᗘ䛿 CO 䛾 ⏕ᡂ㏿ᗘ䛾 20 ಸ䠈CO2 䛾⏕ᡂ㏿ᗘ䛾 7 ಸ䛷䛒䜛䛣䛸䜢ሗ࿌䛧䛶䛔䜛䠊Swann 䜙[15]䜒℡㟷 Ⅳ䛾ప 㓟䛾䜺䝇⏕ᡂ≀䜢 ᐃ䛧䠈H2O 䛜᭱䜒ከ䛟⏕ᡂ䛩䜛䛸ሗ࿌䛧䛶䛔䜛䠊୍᪉䠈 Kelemen 䜙䛿[13]ள℡㟷Ⅳ䜢 125 °C 䛷㓟䛥䛫䛯䛸䛣䜝 CO2 䛾⏕ᡂ㏿ᗘ䛾䜋䛖䛜 H2O 䛾 ⏕ᡂ㏿ᗘ䜘䜚䜒䛝䛟䛺䛳䛯䛸ሗ࿌䛧䛶䛔䜛䠊䛥䜙䛻䠈H2O 䛾⏕ᡂ㏿ᗘ䛾 ᗘ౫Ꮡᛶ䛿䠈ప 䛾䜋䛖䛜䛝䛟䛺䜛䛸䛔䛳䛯ሗ࿌[15]䜒䛒䜚䠈H2O 䛾⏕ᡂᣲື䛻䛴䛔䛶᫂䜙䛛䛻䛺䛳䛶䛔 䛺䛔䠊䜎䛯䠈▼Ⅳ䛾䛖䛱䛹䛾㒊ศ䛜ᛂ䛧䛶䛔䜛䛛䛸䛔䛳䛯䜺䝇䛾⏕ᡂᶵᵓ䛿䜺䝇⏕ᡂ≀ 䛾 ᐃ䛾䜏䛷䛿᫂䜙䛛䛻䛺䜙䛺䛔䠊 6 ደᛯ 0. 6. Calemma ↸[17]↝੩కↆ˯ภᣠ҄↝ನᡯ҄٭ 0. 7. Yürüm ↸[18]↝੩కↆ˯ภᣠ҄↝ನᡯ҄٭ 㻌 ᅛయ⏕ᡂ≀䛾ᵓ㐀ኚ䛷䛿䠈FT-IR 䜔 XPS 䛻䜘䜛ᐁ⬟ᇶ㔞䛾ኚ䜔 ESR 䛻䜘䜛ᵓ㐀 ゎᯒ䛜⏝䛔䜙䜜䜛䠊䛸䜚䜟䛡 FT-IR 䛿ከ䛟䛾◊✲䜾䝹䞊䝥[16-21]䛷⏝䛔䜙䜜䠈䛭䛾ሙ ᐃ䜔 ㏵୰䛷ྲྀ䜚ฟ䛧䛶䛾 ᐃ䛻䜘䜛ྵ㓟⣲ᐁ⬟ᇶ㔞䛾ኚ䛜ሗ࿌䛥䜜䛶䛔䜛䠊Liotta 䜙[16]䛿 ℡㟷Ⅳ䜢ᐊ 䛷㓟䛥䛫䜛䛣䛸䛷䜶䞊䝔䝹ᇶ䛜ቑຍ䛧䛯䛣䛸䛛䜙䠈䝷䝆䜹䝹ᛂ䛻䜘䜚㐣 㓟≀䛜⏕ᡂ䛧䠈2 䛴䛾㐣㓟≀䛛䜙䜶䞊䝔䝹䛜⏕ᡂ䛩䜛ᶵᵓ䜢ᥦ䛧䛯䠊Calemma 䜙 7 [17] 䛿⡿ᅜ⏘ள℡㟷Ⅳ䛻ᑐ䛧䠈200, 250, 275 °C 䛷㓟䛥䛫䛯䛸䛣䜝䠈⬡⫫᪘Ⅳ⣲䛾ῶᑡ䛸 䜹䝹䝪䜻䝅䝹ᇶ䠈䜶䝇䝔䝹ᇶ䛜ቑຍ䛧䛯䛣䛸䜢ぢฟ䛧䠈ᅗ 0. 6 䛻♧䛩䜘䛖䛺ⰾ㤶⎔䛸⤖ྜ 䛩䜛⬡⫫᪘Ⅳ⣲䛜㓟䛥䜜䜛ᶵᵓ䜢ᥦ䛧䛶䛔䜛䠊 Yürüm[18]䜒〓Ⅳ䜢 50 ~ 150 °C 䛷 1500 ศ㛫㓟䛥䛫䛯ヨᩱ䛾 FT-IR 䝇䝨䜽䝖䝹䜢 ᐃ䛧䠈Calemma 䜙䛸ఝ䛯䜘䛖䛺ኚ䜢☜ ㄆ䛧䠈ᅗ 0. 7 䛻♧䛩䜘䛖䛺㓟ᶵᵓ䜢ᥦ䛧䛶䛔䜛䠊䛣䜜䜙䛾ᶵᵓ䛻ඹ㏻䛩䜛Ⅼ䛸䛧䛶䠈ⰾ 㤶⎔䛸⤖ྜ䛧䛶䛔䜛⬡⫫᪘Ⅳ⣲䛾ᛂ䛻䛴䛔䛶䛾ᶵᵓ䛷䛒䜚䠈䜹䝹䝪䜻䝅䝹ᇶ䜔䜿䝖䞁 ᇶ䜢⤒䛶䠈㓟↓Ỉ≀䛜⏕ᡂ䛩䜛Ⅼ䛜ᣲ䛢䜙䜜䜛䠊୍᪉䛷䠈Calemma 䜙䛿䝔䝖䝷䝸䞁䜢㦵᱁ 䛸䛧䠈⬡⫫᪘Ⅳ⣲ഃ䛜㓟䛥䜜䛶䠈㓟↓Ỉ≀䛜⏕ᡂ䛩䜛䛸䛧䛶䛔䜛䛜䠈Yürüm 䜙䛿䠈䝖䝹 䜶䞁䜔䝆䝣䜵䝙䝹䝯䝍䞁䛺䛹䜢㦵᱁䛸䛧䠈2 䛴䛾䜹䝹䝪䜻䝅䝹ᇶ䛜⬺Ỉ⦰ྜ䛩䜛䛣䛸䛷㓟 ↓Ỉ≀䛜⏕ᡂ䛩䜛䛸䛧䛶䛚䜚䠈▼Ⅳ䛾䝰䝕䝹ᵓ㐀䜔㓟↓Ỉ≀䛾⏕ᡂᶵᵓ䛻㐪䛔䛜䜏䜙 䜜䜛䠊䜎䛯䠈Yürüm 䜙䛾ᥦ䛧䛯㓟ᶵᵓ䛷䛿䜰䝹䝕䝠䝗䛾⏕ᡂ䜒⪃៖䛥䜜䛶䛔䜛䠊 Gether[19]䜙䛿℡㟷Ⅳ䛾㓟䛻䜘䜛ᅛయᵓ㐀䛾ኚ䜢䛭䛾ሙ ᐃ䛧䛯⤖ᯝ䠈䜹䝹䝪䜻䝅䝹 ᇶ䛾ῶᑡ䛻╔┠䛧䠈⬡⫫᪘Ⅳ⣲䛾㓟䛸䛸䜒䛻䠈䜹䝹䝪䜻䝅䝹ᇶ䛾⇕ศゎ䜒㉳䛣䜛ྍ⬟ ᛶ䜢ሗ࿌䛧䛯䠊Worasuwannarak 䜙[20]䜒℡㟷Ⅳ䜢 250 ~ 300 °C 䛷㓟䛥䛫䛯㝿䛾ᵓ㐀ኚ 䜢䛭䛾ሙほᐹ䛧䠈䜹䝹䝪䜻䝅䝹ᇶ䛾ῶᑡ䜢ሗ࿌䛧䛶䛔䜛䠊䜎䛯䠈Wang 䜙[21]䛿↓↮Ⅳ䛛䜙 〓Ⅳ䛻ᑐ䛧䛶 60 ~ 220 °C 䛷㓟䛧䛯㝿䛾䠈䛔䛪䜜䛾ヨᩱ䜒㓟 ᗘ䛜ୖ᪼䛩䜛䛸⬡⫫ ᪘Ⅳ⣲䛜ῶᑡ䛧䠈䜹䝹䝪䜻䝅䝹ᇶ䛜ቑຍ䛧䛯䛾䛱䛻ῶᑡ䛩䜛䛸䛔䛳䛯ഴྥ䜢ሗ࿌䛧䛶䛔 䜛䠊௨ୖ䛾䜘䛖䛻䠈FT-IR 䛻䜘䜛 ᐃ䛷䛿⬡⫫᪘Ⅳ⣲䛾ῶᑡ䛸ྵ㓟⣲ᐁ⬟ᇶ䛾⏕ᡂ䛜ሗ ࿌䛥䜜䛶䛔䜛䠊䛧䛛䛧䠈FT-IR 䛻䜘䜛 ᐃ䛷䛿䠈ᐃ㔞ⓗ䛺ホ౯䛜㞴䛧䛔䛸䛔䛳䛯ၥ㢟Ⅼ䛜 䛒䜛䠊䜎䛯䠈Kelemen 䜙[13]䛿㓟㐣⛬䛷䛾䜹䝹䝪䜻䝅䝹ᇶ䛾ᐃ㔞䛻 XPS 䜢⏝䛔䠈Dack 䜙 [22] 䛿㓟㐣⛬䛻䛚䛡䜛Ⅳ⣲ୖ䛾䝣䝸䞊䝷䝆䜹䝹⃰ᗘ䛾 ᐃ䛻 ESR 䜢⏝䛔䛶䛔䜛䠊 㻌 䜎䛯䠈▼Ⅳ䛾ప 㓟䛻䛚䛡䜛᭱ึ䛾ᅛయ⏕ᡂ≀䛿㐣㓟≀䛷䛒䜛䛸ゝ䜟䜜䛶䛔䜛䠊 㐣㓟≀䛾⏕ᡂ䛿┤᥋☜ㄆ䛩䜛䛣䛸䛜ᅔ㞴䛷䛒䜛䛜䠈Jones 䜙[23]䛿㓟䛥䛫䛯▼Ⅳ䜢䝏 䜸䝅䜰䞁㓟㕲(FeSCN)䛷ᐃ䛧䠈㐣㓟≀䛾Ꮡᅾ䜢☜ㄆ䛧䛶䛔䜛䠊 8 ደᛯ 㻌 䛣䜜䜙䛾⤖ᯝ䜢䜎䛸䜑䛶䠈Wang 䜙[24]䛿▼Ⅳ䛾ప 㓟䛻䛿 2 ✀㢮䛾ᛂ⤒㊰䛜䛒䜛䛸 䛧䛶䛔䜛䠊1 䛴䛿䠈▼Ⅳ䛜㓟䛥䜜 CO2 䜔 H2O 䛸䛔䛳䛯䜺䝇䛜㎿㏿䛻⏕ᡂ䛩䜛⤒㊰䛷䛒䜚䠈 䜒䛖 1 䛴䛿䠈▼Ⅳୖ䛻㓟⣲䛜Ꮫ྾╔䛧䠈▼Ⅳ䛾ᵓ㐀䛜ኚ䛧䛶䛔䛟⤒㊰䛷䛒䜛䠊ప 㓟 䛾▼Ⅳ䛾ᵓ㐀ኚ䛾⤒㊰䛿ᅗ 0. 8 䛷䛒䜛䛸ሗ࿌䛧䛶䛔䜛䠊䛿䛨䜑䠈⬡⫫᪘Ⅳ⣲ୖ䛾 䝷䝆䜹䝹䛜㓟⣲䜎䛯䛿䝠䝗䝻䜻䝅䝹䝷䝆䜹䝹䛸ᛂ䛧䠈㐣㓟≀䜒䛧䛟䛿Ỉ㓟ᇶ䜢⏕ᡂ䛧䠈 䜰䝹䝕䝠䝗ᇶ䠈䜹䝹䝪䜻䝅䝹ᇶ䜢⤒䛶㓟↓Ỉ≀䜢⏕ᡂ䛩䜛ᶵᵓ䛸䜶䝇䝔䝹ᇶ䜢⏕ᡂ䛩䜛 ᶵᵓ䛸䛺䛳䛶䛔䜛䠊䛧䛛䛧䠈◊✲⪅䛻䜘䛳䛶 ᐃ᮲௳䛜␗䛺䜛䛯䜑䠈䛭䜜䛮䜜䛾㓟ᶵᵓ 䛷⏕ᡂ䛩䜛ྵ㓟⣲ᐁ⬟ᇶ䛜␗䛺䛳䛶䛚䜚䠈୍ᴫ䛻ẚ㍑䛷䛝䛺䛔䠈䜎䛯䠈䜺䝇⏕ᡂ≀䜢 ᐃ䛧䛯◊✲⪅䜙䛸䛾ᐇ㦂᮲௳䛸䜒ྜ䜟䛪䠈▼Ⅳ䛾ᵓ㐀ኚ䛸䜺䝇⏕ᡂᣲື䛾ᑐᛂ䛜ྲྀ䜜 䛺䛔䛸䛔䛳䛯ၥ㢟Ⅼ䛜ᣲ䛢䜙䜜䜛䠊ຍ䛘䛶䠈ప 㓟ᶵᵓ䛸⮬↛Ⓨⅆ䛸䛾ᐃ㔞ⓗ䛺㛵ಀ 䛜᫂䜙䛛䛻䛺䛳䛶䛚䜙䛪䠈䛹䛾ᛂ䛜⮬↛Ⓨⅆ䜈䛾ᐤ䛾䛝䛔ᛂ䛛䛿᫂䜙䛛䛻䛥䜜 䛶䛔䛺䛔䠊 0. 8. Wang ↸[24]ⅻ↭↗↰˯ภᣠ҄ೞನ 9 ᘙ 0. 2. ჽ໗↝ᐯႆ້↚݃ɨↈ↺↗ᎋⅷ↸↻↕ⅳ↺ᙲ׆ ▼Ⅳ䛾ᛶ≧ 䛻䜘䜛䜒䛾 ⎔ቃ䛻䜘䜛䜒䛾 せᅉ ⮬↛Ⓨⅆᛶ䜈䛾ᙳ㡪 Ⅳ⣲ྵ᭷⋡ ྵ㓟⣲ᐁ⬟ᇶ䚸⬡⫫᪘Ⅳ⣲㔞 H/CཎᏊẚ ⬡⫫᪘Ⅳ⣲㔞 Ⓨศ ᛂ≀ ◲㯤ྵ᭷⋡ ᭷ᶵ◲㯤䛻䜘䜛ゐ፹ຠᯝ ⅊ศ ゐ፹ຠᯝ(᭷ᶵሷ䠈FeS2) ྵỈ⋡ ゐ፹ຠᯝ ⢏ᚄ ᣑᩓᢠ䛾ᑠ ⾲㠃✚ 㓟⣲䛸䛾᥋ゐ㠃✚ 㓟Ṕ άᛶ䝃䜲䝖䛾ᩘ ᗘ ᛂ㏿ᗘᐃᩘ 㓟⣲ศᅽ ᛂ≀⃰ᗘ 0. 2. 2. ▼Ⅳ䛾ప 㓟ᛶ䛻ᐤ䛩䜛せᅉ 㻌 ▼Ⅳ䛾ప 㓟䛻ᐤ䛩䜛せᅉ䛸䛧䛶䛿䠈⾲ 0. 2 䛻♧䛩䜘䛖䛻▼Ⅳ䛾㉁(㓟⣲ྵ᭷⋡䠈 H/C ཎᏊẚ䠈Ⓨศ㔞)䠈◲㯤ศ䠈⅊ศ㔞䠈ྵỈ⋡䠈⢏ᚄ䠈⣽Ꮝ⾲㠃✚䛸䛔䛳䛯▼Ⅳ䛾ᛶ ≧䛻䜘䜛䜒䛾䛸䠈 ᗘ䠈㓟⣲ศᅽ䠈✵Ẽ୰䛾‵ᗘ䛸䛔䛳䛯⎔ቃ䛻䜘䜛䜒䛾䛜ᣲ䛢䜙䜜䛶䛔 䜛䠊▼Ⅳ䛾ప 㓟䛿䠈Ẽᅛᛂ䛷䛒䜚䠈▼Ⅳ䛾እ⾲㠃䛚䜘䜃⣽Ꮝ⾲㠃䛷ᛂ䛜㉳䛣䜛 䛸䛔䜟䜜䛶䛚䜚䠈▼Ⅳ䛾⣽Ꮝ⾲㠃✚䜔⢏Ꮚᚄ䛜㓟㏿ᗘ䛻ᙳ㡪䜢ཬ䜌䛩䛣䛸䛿᫂䜙䛛䛷 䛒䜛䠊䜎䛯䠈㓟⣲ศᅽ䜔 ᗘ䛾ୖ᪼䛻䜘䜛㓟㏿ᗘ䛾ಁ㐍䜒⣡ᚓ䛷䛝䜛䜒䛾䛷䛒䜛䠊▼Ⅳ 䛾㉁䛾ᙳ㡪䛿୍⯡ⓗ䛻ゝ䜟䜜䛶䛔䜛ഴྥ䛷䛒䜚䠈㉁䛜ప䛔䛸ప 㓟ᛶ䛜㧗䛟䠈㉁䛜㧗 䛔䛸ప 㓟ᛶ䛿ప䛟䛺䜛䠊䛣䜜䛿₍↛䛸䛧䛯ഴྥ䛷䛒䜚䠈ලయⓗ䛻ఱ䛜ᙳ㡪䛧䛶䛔䜛䛛 䛿䛔䜎䛰䛻ゎ᫂䛥䜜䛶䛔䛺䛔䠊⅊ศ䛾ゐ፹ຠᯝ䛻䛴䛔䛶䛿⣽䛛䛟᳨ウ䛥䜜䛶䛚䜚䠈Zhang 䜙[25, 26]䛿䜸䞊䝇䝖䝷䝸䜰⏘〓Ⅳ䛸✀䚻䛾㔠ᒓሷ䜢ΰྜ䛧䠈䛭䛾ప 㓟ᛶ䜢ホ౯䛧䛶䛔䜛䠊 䛭䛾⤖ᯝ䠈FeS2 䜢ΰ䛬䜛䛣䛸䛷ⴭ䛧䛔㓟㏿ᗘ䛾ಁ㐍䛜ぢ䜙䜜䛯䛸ሗ࿌䛧䛶䛔䜛䠊䜎䛯䠈 10 ደᛯ 㓑㓟䛾䜘䛖䛺᭷ᶵ㓟䜢䜰䝙䜸䞁䛸䛧䛶⏝䛔䜛䛸㓟㏿ᗘ䛜ಁ㐍䛥䜜䠈ሷ≀䜲䜸䞁䛾䜘䛖 䛺↓ᶵ䜲䜸䞁䜢䜰䝙䜸䞁䛸䛧䛶⏝䛔䜛䛸ప 㓟ᛶ䛜ᢚไ䛥䜜䜛䛸䛔䛳䛯ഴྥ䜔▼Ⅳ䛾䜺 䝇ᛂ䛾ゐ፹䛸䛧䛶▱䜙䜜䜛䜹䝸䜴䝮䜔䝘䝖䝸䜴䝮䜢䜹䝏䜸䞁䛻⏝䛔䛶䜒ప 㓟ᛶ䛜 ಁ㐍䛥䜜䜛䛸䛔䛳䛯䛣䛸䜢ぢฟ䛧䛶䛔䜛䠊 㻌 䜎䛯䠈▼Ⅳ୰䛺䛔䛧✵Ẽ୰䛾Ỉ䛿ゐ፹స⏝䜢♧䛧䛯䜚䠈▼Ⅳ䛸ᛂ䛩䜛䛸ゝ䜟䜜䛶䛔䜛䠊 Moxon 䜙[27]䛿ỈᏑᅾୗ䛷䛾▼Ⅳ䛾㓟䛷䛿▼Ⅳ䛻྾╔䛧䛯Ỉ䛜▼Ⅳ䇷Ỉ䇷㓟⣲⤖ྜ 䜢ᙧᡂ䛩䜛䛣䛸䛷▼Ⅳୖ䜈䛾㓟⣲䛾྾╔䜢ಁ㐍䛩䜛䛸ሗ࿌䛧䛶䛔䜛䠊 Clemens 䜙[28]䛿ྵ Ỉ⋡䛜 50 %௨ୗ䛾పရⅣ䛾㓟㏿ᗘ䜢 ᐃ䛧䠈ྵỈ⋡ 6 wt%⛬ᗘ䛷㓟㏿ᗘ䛜᭱ 䛻䛺䜛䛸ሗ࿌䛧䛶䛔䜛䠊䛣䛾ྵỈ⋡䛻䛚䛔䛶䠈Ỉ䛿୍ᒙ䛾䜏䛷▼Ⅳ䛸ᙉ䛟྾╔䛧䛶䛚䜚䠈 䛻Ỉ䛜䛺䛔≧ែ䜘䜚䜒䝷䝆䜹䝹䛜Ᏻᐃ䛧䛶Ꮡᅾ䛷䛝䜛䛯䜑䛻㓟䛜ಁ㐍䛥䜜䠈䛭䜜 ௨ୖ䛻Ỉ䛜䛒䜛䛸Ỉ䛾ᒙ䛜㓟⣲䛾ᣑᩓ䜢㜼ᐖ䛧䠈㓟䛜ᢚไ䛥䜜䜛䛯䜑䛷䛒䜛䛸⪃ᐹ䛧 䛶䛔䜛䠊୍᪉䠈Petit[29,30]䛿䠈℡㟷Ⅳ䜢 150 °C 䛷㓟䛥䛫䠈㏵୰䛷 H2O 䜢㞺ᅖẼ䜺䝇䛻ῧ ຍ䛧䠈㓟ᣲື䛾ኚ䜢ほᐹ䛧䛯䠊䛭䛾⤖ᯝ䠈Ỉ䛾ῧຍ䛻䜘䜚䠈ᛂ㏿ᗘ䛜ቑຍ䛧䠈CO2 䛜ከ䛟⏕ᡂ䛩䜛䜘䛖䛻䛺䛳䛯䛸ሗ࿌䛧䛶䛔䜛䠊䛣䜜䛻䛴䛔䛶㓟䛥䜜䛯▼Ⅳ䛾ྵ㓟⣲ᐁ⬟ ᇶ䛸Ỉ䛜ᛂ䛧䠈CO2 䜢⏕ᡂ䛩䜛ྍ⬟ᛶ䜢㏙䜉䛶䛔䜛䠊䛣䛾䜘䛖䛻䠈▼Ⅳ䛾ప 㓟䛻ᑐ 䛩䜛Ỉ䛾ᙳ㡪䛿ಁ㐍ຠᯝ䜔ᢚไຠᯝ䛰䛡䛷䛺䛟䠈ᛂ≀䛸䛧䛶䛾ྍ⬟ᛶ䜒ሗ࿌䛥䜜䛶䛚 䜚䠈ప 㓟ᛶ䛻ᑐ䛩䜛ᙳ㡪䜒᫂☜䛻䛿᫂䜙䛛䛻䛿䛺䛳䛶䛔䛺䛔䠊䜎䛯䠈୍䛴୍䛴䛾せ ᅉ䛿ヲ䛧䛟᳨ウ䛥䜜䛶䛔䜛䛜䠈䛭䜜䜙䛾せᅉ䛾ᐤ䛾ᑠ䛿᫂䜙䛛䛻䛥䜜䛶䛔䛺䛔䠊 0. 3. ▼Ⅳ䛾ప 㓟ᛶ䛾ホ౯䛻㛵䛩䜛⥲ㄽ 㻌 ▼Ⅳ䛾ప 㓟䛾ホ౯䛻䛿ᵝ䚻䛺ᡭἲ䛜⏝䛔䜙䜜䛶䛔䜛䠊䜎䛯䠈ప 㓟㏿ᗘ䛾ゎᯒ 䜒✀䚻䛾ᡭἲ䛜㐺⏝䛥䜜䛶䛔䜛䠊䛣䛣䛷䛿䠈ప 㓟ᛶ䛾ホ౯ἲ䜢㏙䜉䛯䛖䛘䛷䠈㏿ᗘゎ ᯒ䛾ᡭἲ䛻䛴䛔䛶⤂䛩䜛䠊 11 0. 3. 1. ప 㓟ᛶ䛾ホ౯ἲ 㻌 ▼Ⅳ䛾ప 㓟ᛶ䛻䛿䠈CO2 䛾⏕ᡂ㏿ᗘ䜔㓟⣲ᾘ㈝㔞䠈㔜㔞ኚ㏿ᗘ䠈䛚䜘䜃Ⓨ⇕ ㏿ᗘ䛻ᇶ䛵䛔䛯ホ౯䛜䛻⏝䛔䜙䜜䛶䛔䜛䠊 㻌 CO2 ⏕ᡂ㏿ᗘ䜔㓟⣲ᾘ㈝㔞䛿▼Ⅳ䜢ሸ䛧䛯ᛂჾ䜢䛒䜛 ᗘ䛻ಖ䛱䜺䝇䜢ὶ㏻䛥䛫䠈 ⏕ᡂ䜺䝇䛒䜛䛔䛿ᮍᛂ䜺䝇䛾⃰ᗘ䜢䜺䝇䜽䝻䝬䝖䜾䝷䝣䜘䜚ᐃ㔞䛧䠈䛭䛾⃰ᗘ䛾⤒ኚ 䛛䜙䜺䝇⏕ᡂ㏿ᗘ䜔㓟⣲ᾘ㈝㏿ᗘ䛜ᑟฟ䛥䜜䜛䠊 㻌 㔜㔞ኚ䛻䛿䠈ᛂ๓ᚋ䛷䛾㔜㔞ቑຍ䜢 䜛䛣䛸䛷㓟⣲྾╔㔞䜢ồ䜑䜛䜒䛾[31]䛸䠈⇕ 㔜㔞ศᯒ(TGA)䛻䜘䜚䠈ヨᩱ䛾㓟㐣⛬䛻䛚䛡䜛㔜㔞ኚ(TG)䛚䜘䜃㔜㔞ኚ㏿ᗘ (DTG)䜢 ᐃ䛩䜛䜒䛾䛜䛒䜛䠊ᛂ๓ᚋ䛾㔜㔞ኚ䜢 ᐃ䛩䜛ሙྜ䛻䛿䠈ከ㔞䛾▼Ⅳ䜢 ⏝䛔䜛䛣䛸䛜䛷䛝䜛䛜䠈▷䛔㛫㛫㝸䛷䛾㔜㔞ኚ䜢 ᐃ䛩䜛䛾䛿㞴䛧䛔䛸䛥䜜䜛䠊୍᪉䠈 TGA 䜢⏝䛔䜛䛸䠈ᑡ㔞䛾▼Ⅳ䛧䛛⏝䛷䛝䛺䛔䛜䠈⤒ኚ䛾 ᐃ䛿ᐜ᫆䛷䛒䜛䠊TGA 䛿 Smith 䜙[32]䠈Benfell 䜙[33]䠈Mahidin 䜙[34]䠈Moon 䜙[35]䛾◊✲䛷⏝䛔䜙䜜䠈㔜㔞ῶᑡ䛜ጞ 䜎䛳䛯 ᗘ䠈㔜㔞ῶᑡ㏿ᗘ䛜᭱䛸䛺䜛 ᗘ䜔ヨᩱ㔜㔞䛜༙ῶ䛧䛯䛸䛝䛾 ᗘ䛜⏝䛔䜙 䜜䛶䛔䜛䠊Smith 䜙䛿Ⅳ⣲ྵ᭷⋡䛸㔜㔞䛜༙ῶ䛩䜛 ᗘ䛸䛾㛫䛻ᙉ䛔ṇ䛾┦㛵䛜䛒䜛䛣䛸 䜢ሗ࿌䛧䠈Benfell 䜙䛿 7 ✀㢮䛾ள℡㟷Ⅳ䜢⏝䛔䛶䠈᭱㔜㔞ῶᑡ㏿ᗘ䛸Ⓨศ䛾┦㛵䜢 ᳨ウ䛧䠈Ⓨศ䛜 20 wt%䛾䛸䛝䛻᭱䜒㏿ᗘ䛜ᑠ䛥䛟䛺䜛䛣䛸䜢ሗ࿌䛧䛶䛔䜛䠊㔜㔞ኚ䛿 ᅛయ䜈䛾㓟⣲྾╔䛻䜘䜛㔜㔞ቑຍ䛸䜺䝇⏕ᡂ䛻䜘䜛㔜㔞ῶᑡ䛜䛒䜚䠈䛭䜜䜙䛾༊ู䛜䛴 䛛䛺䛔䛸䛔䛳䛯ၥ㢟䛜䛒䛢䜙䜜䜛䠊䜎䛯䠈100 °C ௨ୗ䛷䛿྾╔Ỉ䛾Ⓨ䛻䜘䜛㔜㔞ኚ 䜒䛒䜚䠈㓟䛾ᛂ㏿ᗘゎᯒ䛿 100 °C ௨ୖ䛷⾜䛖䛛䠈⇱Ⅳ䜢⏝䛔䜛ᚲせ䛜䛒䜛䠊 㻌 Ⓨ⇕ᣲື䛾 ᐃ䛻䛿䠈⇕㔞ィ(DTA䠈DSC)䜢⏝䛔䛯Ⓨ⇕㏿ᗘ䛾 ᐃ䜔䠈᩿⇕ᛂჾ䜢 ⏝䛔䛯 ᗘୖ᪼䛾 ᐃ䛜ᣲ䛢䜙䜜䜛䠊⇕㔞ィ䜢⏝䛔䛯 ᐃ䛷䛿䠈➼ 㐣⛬[36, 37]䜔᪼ 㐣⛬[38, 39] 䛻䛚䛡䜛Ⓨ⇕㏿ᗘ䜢 ᐃ䛩䜛䠊ᚓ䜙䜜䛯Ⓨ⇕㔞䛾ᑠ䛛䜙ప 㓟ᛶ䛾ホ౯ 䜔㏿ᗘゎᯒ䛜䛥䜜䜛䠊Kaji 䜙[36]䛿䠈ள℡㟷Ⅳ䛛䜙↓↮Ⅳ䜎䛷䛾▼Ⅳ䛻ᑐ䛧䛶䠈25 °C 䛚䜘 䜃 65 °C 䛷䛾㓟⣲྾╔䛻䜘䜛Ⓨ⇕䜢 DSC 䛷 ᐃ䛧䠈ள℡㟷Ⅳ䛾Ⓨ⇕㏿ᗘ䛜℡㟷Ⅳ䜔↓ 12 ደᛯ ↮Ⅳ䜘䜚䜒䛝䛟䠈℡㟷Ⅳ௨ୖ䛷䛿Ⓨ⇕㏿ᗘ䛜ཎᩱ䛻䜘䜙䛺䛔䛣䛸䜢ぢฟ䛧䠈䜎䛯䠈Ⓨ⇕㏿ ᗘ䛾㏿ᗘゎᯒ䜢⾜䛳䛶䛔䜛䠊Clemens 䜙[37]䛿〓Ⅳ䛛䜙℡㟷Ⅳ䜎䛷䛾⇱Ⅳ䛾Ⓨ⇕㏿ᗘ䜢 DTA 䛷 ᐃ䛧䠈పရⅣ䛾Ⓨ⇕㏿ᗘ䛜䛝䛔䛣䛸䜢ሗ࿌䛧䛶䛔䜛䠊Zhao 䜙[38]䛿䠈᪼ 㐣 ⛬䛷䛾Ⓨ⇕㏿ᗘ䜢 ᐃ䛧䠈TGA 䛾ゎᯒ䛷⏝䛔䜙䜜䜛䜘䛖䛺䠈Ⓨ⇕㏿ᗘ䛜᭱䛸䛺䜛 ᗘ䠈 Ⓨ⇕㔞䛜ṇ䛸䛺䜛 ᗘ䜢⏝䛔䛶䠈ప 㓟ᛶ䜢ホ౯䛧䛶䛔䜛䠊䛥䜙䛻䠈᪼ ㏿ᗘ䜢ኚ䛘䛯 ᐃ䜢⾜䛔䠈Ⓨ⇕㏿ᗘ䛻ཬ䜌䛩ᙳ㡪䜢᳨ウ䛧䛶䛔䜛䠊 㻌 ᩿⇕ᛂჾ䜢⏝䛔䛯ప 㓟ᛶ䛾ホ౯ἲ䛿 Bowes 䜙[40]䛻䜘䛳䛶ᥦ䛥䜜䛯 Basket method 䜔䠈Wire basket method[41, 42]䠈Chen’s method[43]䛸䜀䜜䜛ᡭἲ䛜䛒䜛䠊䛣䜜䜙䛾ᡭ ἲ䛷䛿ᅗ 0. 9[43]䛻♧䛩䜘䛖䛻≉ᐃ䛾ᙧ䛾䝞䝇䜿䝑䝖䛻㎸䜣䛰▼Ⅳ䛻」ᩘᮏ䛾⇕㟁ᑐ䜢 ᤄධ䛧䠈䜸䞊䝤䞁䛾୰䛻ධ䜜䠈✵Ẽ䜢ὶ䛧䛺䛜䜙タᐃ䛧䛯 ᗘ䜎䛷᪼ 䛧䠈ᅗ 0. 10 䛾䜘䛖 䛻䝞䝇䜿䝑䝖୰ᚰ䛾 ᗘ(T1)䛚䜘䜃䠈䝞䝇䜿䝑䝖୰ᚰ䛛䜙ྠ䛨㊥㞳䛰䛡㞳䜜䛯 2 Ⅼ䛾 ᗘ (T2, T3)䛾 3 Ⅼ䜢 䜛䛣䛸䛷▼Ⅳ䛾ศᕸ䛸⤒ኚ䜢 ᐃ䛧䠈▼Ⅳ䛜Ⓨⅆ䛧ᛴ⃭䛺 ᗘୖ ᪼䛜⏕䛨䛺䛔䛛䜢ุᐃ䛩䜛䜒䛾䛷䛒䜛䠊䜸䞊䝤䞁䛾タᐃ ᗘ䜢ኚ䛘䛶ྠᵝ䛾ᐇ㦂䜢⧞䜚 ㏉䛧䠈▼Ⅳ䛜Ⓨⅆ䛧䛺䛔 ᗘ䛾ୖ㝈䛾䜸䞊䝤䞁 ᗘ(Critical ambient temperature, Tcrit)䜢 ồ䜑䠈䛣䜜䜢⏝䛔䛶▼Ⅳ䛾㓟ᛶ䜢ホ౯䛩䜛䠊Bowes 䜙䛿䠈άᛶⅣ䛾㓟ᛶ䜢䠈Zhang 䜙 0. 9. Basket method ↝ᘺፗಒဦ[43] 13 0. 10. Basket method ↝ยܭኽௐ̊[42] [25, 26] 䛿〓Ⅳ䛻㔠ᒓሷ䜢ΰྜ䛧䠈㔠ᒓሷ䛾ゐ፹ຠᯝ䜢䠈Fei 䜙[44]䛿✀䚻䛾᮲௳䛷ᶵᲔⓗ ⇕ᅽᦢ(Mechanical thermal expression)ฎ⌮䜢䛧䛶〓Ⅳ୰䛾ྵỈ⋡䜢ኚ䛥䛫䠈ྵỈ⋡ 䛾ᙳ㡪䜢䛭䜜䛮䜜 ᐃ䛧䛶䛔䜛䠊䜎䛯䠈䛣䛾ᡭἲ䛿ḟ⠇䛻㏙䜉䜛 transit heat balance 䜢⏝ 䛔䛯㏿ᗘゎᯒ䛻䜒⏝䛥䜜䜛䠊 0. 3. 2. ㏿ᗘゎᯒᡭἲ 㻌 ప 㓟㏿ᗘ䛾ゎᯒ䛸䛧䛶䛿㓟⣲྾╔㔞䜔䜺䝇⏕ᡂ㏿ᗘ䛾ᐃᘧ䛜⾜䜟䜜䛶䛚䜚䠈▼ Ⅳ䛾 ᗘୖ᪼䜢ィ⟬䛩䜛䛯䜑䛻Ⓨ⇕㏿ᗘ䛾ᐃᘧ䜒⾜䜟䜜䛶䛔䜛䠊 㻌 㓟⣲྾╔㏿ᗘ䛿▼Ⅳ䛾ᮍᛂ⋡䛻ᑐ䛧䛶 0 ḟ䛺䛔䛧 1 ḟ䛷䛒䜛䛸௬ᐃ䛧䛯ᘧ(0. 1 ᘧ䛚 䜘䜃 0. 2 ᘧ)䜔 Elovich ᘧ(0. 3 ᘧ)䛻䜘䛳䛶⾲⌧䛥䜜䜛䜒䛾䛜ከ䛔䠊Elovich ᘧ䛿䠈ᅛయ⾲ 㠃䛻䛚䛡䜛䜺䝇䛾྾╔㏿ᗘ䛾⾲⌧䛻⏝䛔䜙䜜䜛⤒㦂ᘧ䛷䛒䜛䠊 rO2 k ' g (CO2 ) rO2 k ' g (CO2 )(1 X ) rO2 dqO2 dt k (0. 1) k (1 X ) a exp(DqO2 ) (0. 2) (0. 3) 14 ደᛯ ᘙ 0. 3. ˯ภᣠ҄↝ย∞⇔∑⇳⇎ࣱ҄↗̊ܭ ยܭภࡇ؏ ࣱ҄⇎⇳∑⇔∞ [kJ/mol] ⁍°C] ᚾ૰ Ӓࣖᡮࡇࡸ Mahidin et al.[50] TGA ᙓ໗≏ોឋ໗ írO2 = k0eíE/RTCO2 Smith et al.[32] ᙓ໗⊡ົ᩷໗ írcoal = k0eíE/RT(1-X) 125 ~ 350 Nordon et al.[45] GC(O2ຜࡇ) ᙓ໗≏༏Ўᚐ໗ Elovichࡸ 45 ~ 83 63.9 ~ 69.0 Wang et al.[51] GC(CO2≏CO) ົ᩷໗ írO2 = k0eíE/RT 60 ~ 90 62.3 ~ 70.1 Kaji et al.[36] (1) GC(O2ຜࡇ) (2) DSC ʣົ᩷໗⊡໗ Elovichࡸ 40 ~ 160 (1) 51.1 ~ 54.0 (2) 48.5 ~ 50.3 Sujanti et al.[52] Wire basket method ᙓ໗ írcoal = k0eíE/RT 118 ~ 165 94.7 ~ 111.3 Zhang et al.[42] Wire basket method ᙓ໗≏ طޓฆӳ໗ írcoal = k0eíE/RT 120 ~ 170 102.8 ~ 125.1 ᄂᆮ⇖∑∞⇽ ยܭඥ TGA 45 ~ 83 8.9 ~ 40.9 53 ~ 290 㻌 (0. 1)ᘧ䠈(0. 2)ᘧ䛻䛚䛔䛶䠈k’䛿┿䛾ᛂ㏿ᗘᐃᩘ䛷 g(CO2)䛿㓟⣲⃰ᗘ౫Ꮡᛶ䜢⾲䛩 㛵ᩘ䛷䛒䜛䠊㓟⣲ศᅽ୍ᐃ᮲௳ୗ䛷ᐇ㦂䛧䛯䜒䛾䛷䛿䠈䜏䛛䛡䛾ᛂ㏿ᗘᐃᩘ k 䛻䜘䜛 ⾲⌧䛸䛺䜛䠊(0. 3)ᘧ䛻䛚䛔䛶 a 䛿㓟⣲྾╔䛾ึᮇ㏿ᗘ䠈D 䛿ᐃᩘ䠈qO2 䛿㓟⣲྾╔㔞䛷 䛒䜛䠊䛣䛾ᘧ䛿ከ䛟䛾ᐇ㦂[31, 45, 46]䛻ᑐ䛧䛶㐺⏝䛥䜜䛶䛔䜛䠊Allardice[31]䛻䜘䜛䛸D 䛿 ᗘ 䛻䛿౫Ꮡ䛧䛺䛔䛜㓟⣲ศᅽ䛾ቑຍ䛻ᑐ䛧䛶ῶᑡ䛧䠈a 䛿 ᗘ䛻౫Ꮡ䛩䜛䛜㓟⣲ศᅽ䛻 䛿䛚䛚䜐䛽౫Ꮡ䛧䛺䛔䛸䛔䛳䛯≉ᚩ䜢ሗ࿌䛧䛶䛔䜛䠊Ismail[46]䜙䛿✀䚻䛾㉁䛾▼Ⅳ䛛䜙 ㄪ〇䛧䛯⇕ศゎⅣ䛾㓟㏿ᗘ䜢ゎᯒ䛧䛯䛜䠈a 䜔D 䛸▼Ⅳ䛾㉁䛸䛾㛫䛻┦㛵䛿ㄆ䜑䜙䜜 䛺䛛䛳䛯䠊䜎䛯䠈Elovich ᘧ䛿䠈ᛂᚊ㏿䛾䛸䛝䛰䛡䛷䛺䛟ᣑᩓᚊ㏿䛻䛚䛡䜛㏿ᗘ䜒ྠ䛨ᘧ ᙧ䜢⏝䛔䛶⾲⌧䛷䛝䜛䛸䛔䛳䛯ሗ࿌䜒䛒䜛[47]䠊 㻌 㓟⣲⃰ᗘ౫Ꮡᛶ䛿㓟⣲⃰ᗘ䛾 n 䛻ẚ䛩䜛䛸䛔䛳䛯௬ᐃ䛜䛻⏝䛔䜙䜜䠈Wang 䜙 [48] 䛻䜘䜛䛸䠈䛚䛚䜐䛽㓟⣲⃰ᗘ䛾 0 ~ 1 䛻ẚ䛩䜛䠊 㻌 䛣䛾䜋䛛䛻䜒䠈㓟䛜䛒䜛⛬ᗘ㐍⾜䛩䜛䛸䠈䜘䜚ᑠ䛥䛺⣽Ꮝ䛷ᛂ䛜㉳䛣䜛䜘䛖䛻䛺䜚䠈 ᛂᚊ㏿䛛䜙ᣑᩓᚊ㏿䛻ኚ䜟䜛䛸䛧䛶ᣑᩓᚊ㏿᮲௳ୗ䛷㏿ᗘゎᯒ䜢⾜䛳䛯ሗ࿌䜒䛒䜛[48]䠊 䜎䛯䠈▼Ⅳ䛾㓟ᶵᵓ䛜 2 ㏻䜚䛒䜛䛸䛔䛖⪃䛘䛻ᇶ䛵䛝䠈Krishnaswamy 䜙[11, 12]䜔 Karsner 15 䜙[48]䛿௨ୗ䛾䜘䛖䛺㏿ᗘᘧ䜢ᥦ䛧䛶䛔䜛䠊 k1 f a CO2 M rO2 wf a wt (0. 4) ྑ㎶ 1 㡯┠䛿䜺䝇䛜⏕ᡂ䛩䜛ᛂ㏿ᗘ䜢䠈2 㡯┠䛿㓟⣲྾╔䛾ᛂ㏿ᗘ䜢⾲䛧䛶䛚䜚䠈 k1 䛿䜺䝇⏕ᡂᛂ䛾༢య✚ᙜ䛯䜚䛾ᛂ㏿ᗘᐃᩘ䠈fa 䛿▼Ⅳ⾲㠃䛻䛒䜛άᛶ䝃䜲䝖䛾 䛖䛱䜺䝇⏕ᡂᛂ䛜㉳䛣䜛䝃䜲䝖䛾ྜ䠈CO2 䛿Ẽ┦㓟⣲⃰ᗘ䠈M 䛿༢య✚䛒䛯䜚䛻྾ ╔䛷䛝䜛㓟⣲䛾⥲䝰䝹ᩘ䛷䛒䜛䠊 㻌 Ⓨ⇕㏿ᗘ䛿㓟⣲ᾘ㈝㏿ᗘ䛸ᛂ䜶䞁䝍䝹䝢䞊䛾✚䛷⾲䛩䛣䛸䛜䛷䛝䜛䛯䜑䠈㓟⣲ᾘ㈝ ㏿ᗘ䛸ྠᵝ䛾ゎᯒ䛜⾜䜟䜜䜛䠊䛣䛾䛸䛝䠈(0. 1)ᘧ ~ (0. 3)ᘧ䛾ᛂ㏿ᗘᐃᩘ䛚䜘䜃㓟⣲ ྾╔ึᮇ㏿ᗘ䛻䛒䛯䜛್䛿䠈䛭䜜䜙䛸ᛂ䜶䞁䝍䝹䝢䞊䛸䛾✚䛾ᙧ䛻䛺䛳䛶ồ䜑䜙䜜䜛䠊 Ismail 䜙䛿 TGA 䛻䜘䜛㓟㏿ᗘ䛸 DSC 䛻䜘䜛Ⓨ⇕㏿ᗘ䜢䛭䜜䛮䜜 Elovich ᘧ䛷ᐃᘧ 䛧䠈㓟⣲྾╔ึᮇ㏿ᗘ䛸Ⓨ⇕ึᮇ㏿ᗘ䛸䛾㛫䛻䛿䛚䛚䜐䛽┦㛵䛜䛒䜛䛜䠈ᐃᩘ㡯䛷䛒䜛 D 䛻䛿┦㛵䛜䜏䜙䜜䛺䛛䛳䛯䛸ሗ࿌䛧䛶䛔䜛䠊䜎䛯䠈Zhao 䜙[38]䛿␗䛺䜛㔜㔞䛷䛾Ⓨ⇕㏿ ᗘ䛾ẚ䛛䜙㓟㏿ᗘ䛿㓟⣲⃰ᗘ䛾 1.67 䛻ẚ䛩䜛䛸ሗ࿌䛧䛶䛔䜛䠊 㻌 䜎䛯䠈basket method 䜢⏝䛔䛯ሙྜ䛻䛿䠈Transit heat balance 䛸䜀䜜䜛⇕ᨭᘧ䜢⏝䛔 䛶Ⓨ⇕㏿ᗘ䛜ィ⟬䛥䜜䜛䠊 UC p wT wt § E · k 2T QUk 0 exp¨ ¸ © RT ¹ (0. 5) 䛒䜛⛬ᗘ✚ᒙ䛥䜜䛯▼Ⅳ䜢᪼ 䛧䛺䛜䜙㓟䛥䛫䜛䛸䠈ᅗ 0. 10 䛻♧䛧䛯䜘䛖䛻䠈䛿䛨䜑䛿 እ㒊䛛䜙䛾ఏ⇕䛻䜘䜚▼Ⅳ䛾እഃ䛜㧗 䛻䛺䜛(T2䠈T3 > T1)䛜䠈ᛂ䛜ෆ㒊䛷㉳䛣䜛䛻䛴 䜜䛶䠈▼Ⅳෆ㒊䛾䜋䛖䛜㧗 䛻䛺䜛(T1 > T2䠈T3)䠊䛣䛾㛫䛻▼Ⅳෆ㒊䛾 ᗘศᕸ䛜䛺䛟䛺 䜛Ⅼ䛜Ꮡᅾ䛩䜛䠊䛣䛾 ᗘ䛿 crossing point temperature (Tp)䛸䜀䜜䠈ఏ⇕䛜䛺䛟䛺䜛䛾 䛷(0. 5)ᘧ䛿ḟ䛾䜘䛖䛻᭩䛝䛘䜛䛣䛸䛜䛷䛝䜛䠊 Cp wT wt T Tp § E Qk 0 exp¨ ¨ RT p © · ¸ ¸ ¹ (0. 6) 16 ደᛯ Tp 䛿䜸䞊䝤䞁䛾タᐃ ᗘ䛻䜘䛳䛶ኚ䛩䜛䛾䛷䠈✀䚻䛾䜸䞊䝤䞁䛾タᐃ ᗘ䛻ᑐ䛧䛶 ᚓ䜙䜜䛯 Tp 䛸䛭䛾䛸䛝䛾▼Ⅳ䛾 ᗘኚ㏿ᗘ䛛䜙Ⓨ⇕㏿ᗘ䛾㏿ᗘᐃᩘ䜢ィ⟬䛷䛝䜛䜘䛖 䛻䛺䜛䠊 㻌 ྛ㏿ᗘ䝟䝷䝯䞊䝍䞊䛾 ᗘ౫Ꮡᛶ䛿 Arrhenius ᆺ䜢௬ᐃ䛧䛶䛚䜚䠈䜋䛸䜣䛹䛾ゎᯒ䛷ά ᛶ䜶䝛䝹䜼䞊䛜ồ䜑䜙䜜䛶䛔䜛䠊✀䚻䛾᪉ἲ䛻䜘䜚ᚓ䜙䜜䛯άᛶ䜶䝛䝹䜼䞊䜢⾲ 0. 3 䛻䜎䛸䜑䜛䠊▼Ⅳ䛾✀㢮䛚䜘䜃⏝䛔䛯ᘧ䛾ᙧ䛻䜘䛳䛶್䛜␗䛺䜛䛜䠈άᛶ䜶䝛䝹䜼䞊 䛿䛚䛚䜐䛽 100 kJ/mol ௨ୗ䛷䛒䛳䛯䠊䜎䛯䠈Basket method 䛻䜘䜛άᛶ䜶䝛䝹䜼䞊䛿 䛾ᡭἲ䜘䜚䜔䜔䛝䛟䛺䜛ഴྥ䛜䛖䛛䛜䛘䜛䠊 㻌 ๓⠇䛷㏙䜉䛯䜘䛖䛻䠈▼Ⅳ䛾ప 㓟䛿」ྜᛂ䛷䛒䜚䠈㉳䛣䜛ᛂ䜒㏲ḟⓗ䛻ኚ䜟䜛 䛸⪃䛘䜙䜜䜛䠊䛧䛛䛧䛺䛜䜙䠈䜋䛸䜣䛹䛾㏿ᗘゎᯒ䛜䠈༢୍ᛂ䜢௬ᐃ䛧䛶䛚䜚䠈ᛂᶵᵓ 䛻ᇶ䛵䛔䛯㏿ᗘゎᯒ䛸䛺䛳䛶䛔䛺䛔䠊άᛶ䜶䝛䝹䜼䞊䛺䛹䛾㏿ᗘ䝟䝷䝯䞊䝍䞊䜒ᛂ 䛾㐍⾜䛻䜘䛳䛶ኚ䛩䜛䛸⪃䛘䜙䜜䜛䛜䠈ᛂ⋡䛻䜘䜛㏿ᗘ䝟䝷䝯䞊䝍䞊䛾ኚ䛻㛵䛩䜛 ◊✲䛿䜋䛸䜣䛹䛥䜜䛶䛚䜙䛪䠈Yip 䜙[53]䛜ᛂ䛾㐍⾜䛻క䛔άᛶ䜶䝛䝹䜼䞊䛚䜘䜃㢖 ᗘᅉᏊ䛜ቑຍ䛩䜛䛸ሗ࿌䛧䛶䛔䜛⛬ᗘ䛷䛒䜛䠊 0. 4. ᮏ◊✲䛾┠ⓗ䛸ෆᐜ 㻌 䛣䜜䜎䛷㏙䜉䛶䛝䛯䜘䛖䛻䠈పရⅣ䛾᭷ຠ⏝䛻䛚䛔䛶⮬↛Ⓨⅆᛶ䛾ᢚไ䛿ᚲせ ྍḞ䛷䛒䜛䠊▼Ⅳ䛾ప 㓟ᶵᵓ䛻㛵䛩䜛◊✲䛻䛚䛡䜛ㄢ㢟䛸䛧䛶䠈ప 㓟ᶵᵓ䛾 ㇺ䛜᫂䜙䛛䛻䛺䛳䛶䛔䛺䛔Ⅼ䠈ప 㓟ᶵᵓ䛸⮬↛Ⓨⅆ䛸䛾㛵ಀ䛜᫂☜䛷䛿䛺䛔Ⅼ䛜 ᣲ䛢䜙䜜䜛䠊䛭䜜䜙䛾ゎỴἲ䛸䛧䛶䠈✀䚻䛾 ᐃ䛻䜘䜛ໟᣓⓗ䛺ప 㓟ᶵᵓ䛾ゎ᫂䠈 ప 㓟ᣲື䛾ᐃ㔞ⓗ䛺ᢕᥱ䛻䜘䜛⮬↛Ⓨⅆᶵᵓ䛾ゎ᫂䛜⪃䛘䜙䜜䜛䠊䜎䛯䠈⮬↛Ⓨⅆ ᢚไἲ䜢㛤Ⓨ䛩䜛䛻䛿⮬↛Ⓨⅆ䛾せᅉ䜢᫂䜙䛛䛻䛩䜛䛣䛸䛜㔜せ䛷䛒䜛䛜䠈ᣦ䛥䜜䛶 䛔䜛✀䚻䛾せᅉ䛾ᑠ㛵ಀ䛿᫂䜙䛛䛸䛺䛳䛶䛔䛺䛔Ⅼ䠈⮬↛Ⓨⅆ䛾ண 䛻䛿▼Ⅳ㓟 䛾ᛂ㏿ᗘゎᯒ䛜ྍḞ䛷䛒䜛䛜䜋䛸䜣䛹䛜༢୍ᛂ䜢௬ᐃ䛧䛶䛚䜚䠈ప 㓟ᶵᵓ䛻 17 ᇶ䛵䛔䛯ᛂ㏿ᗘゎᯒ䛿䛥䜜䛶䛔䛺䛔Ⅼ䜒ゎỴ䛥䜜䜛䜉䛝ၥ㢟䛷䛒䜛䠊⮬↛Ⓨⅆᛶ䛻ᐤ 䛩䜛せᅉ䛾ᑠ㛵ಀ䜢ᢕᥱ䛩䜛䛯䜑䛻䛿⮬↛Ⓨⅆ䛷䛻㉳䛣䜛ᛂ䜢᫂䜙䛛䛻䛩䜛䛣 䛸䛷䠈ప 㓟ᶵᵓ䛻ᇶ䛵䛔䛯ᛂ㏿ᗘゎᯒ䛸䛧䛶䛿䠈ᛂ䛾㐍⾜䛻క䛖㏿ᗘ䝟䝷䝯䞊 䝍䞊䛾ኚ䜢⾲⌧䛷䛝䜛䜘䛖䛺ᛂ㏿ᗘゎᯒ䜢⾜䛖䛣䛸䛷ゎỴ䛷䛝䜛䛸⪃䛘䜙䜜䜛䠊 㻌 ᮏㄽᩥ䛷䛿䠈▼Ⅳ䛾ప 㓟ᣲື䜢ヲ⣽䛻ほᐹ䛩䜛䛣䛸䛷ప 㓟ᶵᵓ䛾ゎ᫂䜢ヨ 䜏䛯䠊ᚓ䜙䜜䛯ప 㓟ᶵᵓ䛸⮬↛Ⓨⅆ䛸䛾㛵ಀ䜢ᐃ㔞ⓗ䛻᫂䜙䛛䛻䛧䛯䛖䛘䛷䠈⮬↛ Ⓨⅆᢚไἲ䛻䛴䛔䛶᳨ウ䜢⾜䛳䛯䠊䜎䛯䠈ప 㓟䛾ᛂ㏿ᗘゎᯒ䜢⾜䛔䠈ᛂ䛾㐍 ⾜䛻క䛖㏿ᗘ䝟䝷䝯䞊䝍䞊䛾ኚ䜢ồ䜑䠈ప 㓟ᣲື䛾ᩘ್䝅䝭䝳䝺䞊䝅䝵䞁䜢⾜䛳 䛯䠊 㻌 ➨ 1 ❶䛷䛿䠈పရⅣ 2 ✀㢮䛸㧗ရⅣ 1 ✀㢮䛾 3 ✀㢮䛾▼Ⅳ䛻䛴䛔䛶䠈ᅛయ䛾ᵓ㐀 ኚ䠈⏕ᡂ䜺䝇䠈㔜㔞ኚ䠈Ⓨ⇕㏿ᗘ䜢 ᐃ䛩䜛䛣䛸䛷ప 㓟ᣲື䜢ヲ⣽䛻ほᐹ䛧䛯䠊 䜎䛯䠈ప 㓟ᶵᵓ䛸ᛂึᮇ䛻䛚䛡䜛ඖ⣲ᨭ䠈Ⓨ⇕㔞䜢䜒䛸䛻ప 㓟ᶵᵓ䛸⮬↛ Ⓨⅆᛶ䛾㛵㐃ᛶ䛻䛴䛔䛶᳨ウ䛧䛯䠊 㻌 ➨ 2 ❶䛷䛿䠈〓Ⅳ䛻ᑐ䛧䛶䠈⇕ศゎฎ⌮䛚䜘䜃୕ᾆ䜙䛻䜘䛳䛶㛤Ⓨ䛥䜜䛯⁐ฎ⌮[54, 55] 䜢䛧䠈ฎ⌮Ⅳ䛾⏕ᡂ䜺䝇䠈㔜㔞ኚ䠈Ⓨ⇕㏿ᗘ䜢 ᐃ䛧䠈ప 㓟ᣲື䜢ほᐹ䛧䛯䠊 䜎䛯䠈䛭䜜䛮䜜䛾ฎ⌮Ⅳ䛸ཎⅣ䛸䛾ప 㓟ᣲື䛾㐪䛔䜢ฎ⌮୰䛾ᵓ㐀ኚ䛛䜙ㄝ᫂ 䜢ヨ䜏䠈ప 㓟ᛶ䛻ᐤ䛩䜛せᅉ䛻䛴䛔䛶᳨ウ䛧䛯䠊 㻌 ➨ 3 ❶䛷䛿䠈๓❶䛷▼Ⅳ䛾ప 㓟ᛶ䛾ᢚไ䛻᭷ຠ䛷䛒䜛ྍ⬟ᛶ䛜♧䛥䜜䛯⁐ฎ ⌮䛻╔┠䛧䠈✀䚻䛾పရⅣ⣲㈨※䛻ᑐ䛧䛶⁐ฎ⌮ἲ䛾㐺⏝ྍ⬟ᛶ䜢᳨ウ䛩䜛䛸䛸䜒 䛻䠈ᚓ䜙䜜䛯ฎ⌮ヨᩱ䛾ᛶ≧䜢ㄪ䜉䠈⁐ฎ⌮䛜⮬↛Ⓨⅆᢚไฎ⌮䛸䛧䛶䛰䛡䛷䛺䛟⬺ Ỉ䞉ᨵ㉁䜒ྠ䛻ᐇ⌧䛷䛝䜛䠈ᅗ 0. 1 ୰䛾 Level 2 䛻┦ᙜ䛩䜛ฎ⌮䛷䛒䜛䛛䜢᳨ウ䛧䛯䠊 㻌 ➨ 4 ❶䛷䛿䠈3 ✀㢮䛾▼Ⅳ䛻䛴䛔䛶ప 㓟䛾ᛂ㏿ᗘゎᯒ䜢⾜䛳䛯䠊ప 㓟䛿」 ྜᛂ䛷䛒䜛䛛䜙䠈୪ิ୍ḟᛂ䝰䝕䝹(Distributed Activation Energy Model, DAEM)[56, 57] 䛾㐺⏝䜢ヨ䜏䛯䠊䜎䛪䠈DAEM ἲ䛾㐺⏝ྍ⬟ᛶ䜢᳨ウ䛧䠈▼Ⅳ㓟䛜 56 ಶ䛾ᛂ䛷 ⾲⌧䛷䛝䜛䜒䛾䛸䛧䛶ྛᛂ䛾ᛂ㏿ᗘ䝟䝷䝯䞊䝍䞊䜢ᑟฟ䛧䠈ᛂ䛾㐍⾜䛻క䛖㏿ᗘ䝟 18 ደᛯ 䝷䝯䞊䝍䞊䛾ኚ䠈ཎⅣ䛾㐪䛔䛻䜘䜛㏿ᗘ䝟䝷䝯䞊䝍䞊䛾㐪䛔䜢᳨ウ䛧䛯䠊䜎䛯䠈ᚓ䜙䜜 䛯䝟䝷䝯䞊䝍䞊䜢⏝䛔䠈᩿⇕᮲௳䜢௬ᐃ䛧䠈▼ⅣⓎⅆ䛾ᩘ್䝅䝭䝳䝺䞊䝅䝵䞁䜢⾜䛳䛯䠊 ཧ⪃ᩥ⊩ [1] ㈨※䜶䝛䝹䜼䞊ᗇ 䛂2013 ᖺ 䜶䝛䝹䜼䞊ⓑ᭩䛃 [2] BP Statistic. “Statistical Review of World Energy June 2013.” [3] World Energy Council. “Survey of Energy Resources 2010.” [4] Hüttinger, J. 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[57] Miura, K., Maki, T., A new and simple method for estimating f(E) and k0(E) in the distributed activation model, Energy & Fuels, 1998, 12, 864869. 24 ᇹ1ᇘ ➨ 1 ❶ ▼Ⅳ䛾ప 㓟ᶵᵓ䛾ゎ᫂ 1. 1. ⥴ゝ 㻌 ▼Ⅳ䛾⮬↛Ⓨⅆᶵᵓ䜢ᢕᥱ䛩䜛䛖䛘䛷䠈▼Ⅳ䛾ప 㓟ᣲື䜢ヲ⣽䛻᫂䜙䛛䛻䛩䜛䛣 䛸䛜㔜せ䛸䛺䜛䠊䛩䛺䜟䛱䠈ప 㓟䛾㔜㔞ኚ䜔ᅛయ⏕ᡂ≀䛾ᵓ㐀ኚ䠈⏕ᡂ䜺䝇 䜢ྠ୍᮲௳䛷 ᐃ䛩䜛䛣䛸䛻䜘䜛ໟᣓⓗ䛺ᛂᶵᵓ䛾ゎ᫂䛜ᚲせ䛷䛒䜛䠊䛧䛛䛧䠈ᐊ ⛬ᗘ䛷䛿ᛂ㏿ᗘ䛜㠀ᖖ䛻ᑠ䛥䛟䠈䛭䜜䜙䛾ኚ䜢⢭ᗘ䜘䛟 ᐃ䛩䜛䛣䛸䛿ᅔ㞴䛷䛒䜛䠊 䛭䛣䛷䠈▼Ⅳ䜢ᐊ ⛬ᗘ䛷ಖᣢ䛫䛪᪼ 䛩䜛䛣䛸䛷䠈ᛂ㏿ᗘ䜢㧗䛟䛩䜜䜀䠈䛭䜜䛮䜜 䛾ኚ䜢༑ศ⢭ᗘ䜘䛟ほᐹ䛷䛝䜛䜘䛖䛻䛺䜛䛸⪃䛘䜙䜜䜛䠊䜎䛯䠈䛭䛾ሙ ᐃ䛩䜛䛣䛸䛻䜘䜚䠈 ᛂ䛾㐍⾜䛻క䛖䠈ኚ䜢ほᐹ䛷䛝䜛䛸⪃䛘䜙䜜䜛䠊 㻌 䜎䛯䠈⮬↛Ⓨⅆ㐣⛬䛷䛿䠈ᛂ䛻䜘䛳䛶⏕䛨䛯⇕䛜▼Ⅳ䛾 ᗘ䜢ୖ᪼䛥䛫䠈ᛂ䜢䛥䜙 䛻ຍ㏿䛧䛶䛔䛟䛯䜑䠈⮬↛Ⓨⅆᛶ䛾㆟ㄽ䛷䛿ప 䛷䛾㓟ᛶ䛰䛡䛷䛺䛟Ⓨ⇕㏿ᗘ䜒㔜せ 䛸䛺䜛䠊 㻌 ᮏ❶䛷䛿䠈3 ✀㢮䛾▼Ⅳ䛾㔜㔞ኚ䠈䜺䝇⏕ᡂ㏿ᗘ䠈Ⓨ⇕㏿ᗘ䛚䜘䜃ᅛయ⏕ᡂ≀୰䛾 ᐁ⬟ᇶ㔞䛾ኚ䜢୍ᐃ㏿ᗘ䛷᪼ 䛧䛺䛜䜙䛭䛾ሙ ᐃ䛩䜛䛣䛸䛷ప 㓟ᣲື䛾ᢕᥱ 䜢ヨ䜏䛯䠊䜎䛯䠈ᛂึᮇ䛷䛾㓟⣲ᾘ㈝㔞䛚䜘䜃Ⓨ⇕㔞䛛䜙䠈ప 㓟ᶵᵓ䛸⮬↛Ⓨⅆ ᛶ䛸䛾㛵ಀ䜢᳨ウ䛧䠈⮬↛Ⓨⅆ䛻ᐤ䜢ཬ䜌䛩ᛂ䜢⪃ᐹ䛧䠈⮬↛Ⓨⅆᢚไἲ䛸䛧䛶ồ 䜑䜙䜜䜛ฎ⌮䛻䛴䛔䛶᳨ウ䛧䛯䠊 1. 2. ᐇ㦂 㻌 ヨᩱ䛸䛧䛶䠈ᕞ⏘〓Ⅳ䛷䛒䜛 Loy Yang Ⅳ(LY Ⅳ)䠈⡿ᅜ⏘ள℡㟷Ⅳ䛷䛒䜛 Powder River Basin Ⅳ(PRB Ⅳ)䠈⡿ᅜ⏘℡㟷Ⅳ䛷䛒䜛 Alabama Ⅳ(AL Ⅳ)䜢⏝䛔䛯䠊䛔䛪䜜䛾▼ Ⅳ䜒䝯䝜䜴〇ங㖊䜢⏝䛔䛶 0.2 mm ௨ୗ䛻⢊○䛧䛯䜒䛾䜢⏝䛧䛯䠊ヨᩱ䛾ᛶ≧䜢⾲ 1. 1 25 ჽ໗↝˯ภᣠ҄ೞನ↝ᚐଢ 䛻♧䛩䠊ᮏ◊✲䛷䛿▼Ⅳ䛿㓟ᐇ㦂䛾๓䛻䛻⬺Ỉ䛧䠈⤯᮲௳䛷㓟ᐇ㦂䜢⾜䛳 䛯䠊 ᘙ 1. 1. ̅ဇẲẺჽ໗ỉࣱཞ Sample Elemental composition [wt% d. a. f.] C H N O (diff) Atomic ratio [-] H/C O/C Loy Yang (LY) 68.2 4.6 0.6 26.5 0.80 0.29 48.1 50.2 1.7 54.1 Powder River Basin (PRB) 73.2 5.0 1.0 20.7 0.81 0.21 38.9 58.0 3.1 17.7 Alabama (AL) 81.4 5.7 1.6 11.3 0.83 0.10 40.4 55.9 3.8 1.6 Proximate analysis [wt% d. b.] Ash VM FC Moisture [wt% a. r.] (d. a. f. = dry ash free (↓⅊↓Ỉᇶ‽), d. b. = dry basis (⇱ᇶ‽), a. r. = as received (฿╔ᇶ‽)) 1. 2. 1. 㔜㔞ኚ䛚䜘䜃䜺䝇⏕ᡂ㏿ᗘ 㻌 ▼Ⅳ䛾㔜㔞ኚ䛚䜘䜃䜺䝇⏕ᡂ㏿ᗘ䛿ᅗ 1. 1 䛻♧䛩䜘䛖䛺䝬䜲䜽䝻䜺䝇䜽䝻䝬䝖䜾䝷䝣 (Varian, CP-4900)䜢┤⤖䛧䛯⇕ኳ⛗(Shimadzu, TGA-50)䜢⏝䛔䛶ྠ䛻 ᐃ䛧䛯䠊䛣䜜 䜙䜢ྠ䛻 ᐃ䛩䜛䛣䛸䛷䠈≀㉁ᨭ䛚䜘䜃ඖ⣲ᨭ䜢䛸䜛䛣䛸䛜䛷䛝䜛䠊ヨᩱ䜈䛾ᛂ ⇕䛾⇕䜢㑊䛡䜛䛯䜑䠈ヨᩱ㔞䛿⣙ 2 mg-d a. f.䛸䛧䛯䠊ヨᩱ䜢⇕ኳ⛗䛻ධ䜜䠈䝦䝸䜴䝮㞺 Thermobalance (TGA-50, Shimadzu) Micro GC (CP-4900,VARIAN) He Sample 10 mg TC Electric furnace He or 22 % O2/ He 50 cm3/min Platinum pan Reactor i.d.19 mm Mass flow controller 1. 1. TG ấợỎ GC ỉᘺፗಒဦ 26 ᇹ1ᇘ ᅖẼୗ䠈110 °C 䛷 30 ศಖᣢ䛩䜛䛣䛸䛷ヨᩱ୰䛾Ỉศ䜢㝖ཤ䛧䛯䠊䛭䛾ᚋ䠈40 °C 䜎䛷෭ ༷䛧䠈 ᗘ䛜Ᏻᐃ䛧䛯䛸䛣䜝䛷㞺ᅖẼ䜺䝇䜢䝦䝸䜴䝮䛛䜙ᶍᨃ✵Ẽ(22 % O2/He)㞺ᅖẼ䛻 ษ䜚᭰䛘䠈5 K/min 䛷᪼ 䛧䠈1 ⛊㛫㝸䛷▼Ⅳ䛾㔜㔞䜢 ᐃ䛧䛯䠊⇕ኳ⛗䛻౪⤥䛩䜛䜺䝇 䛾ὶ㔞䛿 50 cm3/min 䛸䛧䛯䠊 㻌 ⏕ᡂ䛧䛯䜺䝇䛿䝬䜲䜽䝻䜺䝇䜽䝻䝬䝖䜾䝷䝣䛷 110 ⛊䛚䛝䛻 ᐃ䛧䛯䠊䜹䝷䝮䛿 MS-5A 䛚 䜘䜃 PPQ 䜢⏝䛔䠈H2䠈CH4䠈CO䠈CO2 䛚䜘䜃 H2O 䛾 5 ✀㢮䛾䜺䝇䜢ᐃ㔞䛧䛯䠊H2O 䛿䝅 䝳䜴㓟䜹䝹䝅䜴䝮୍Ỉ≀䛾⇕ศゎᐇ㦂䛻䜘䜚ᚓ䜙䜜䛯 H2O 䛾 CO2 䛻ᑐ䛩䜛┦ᑐឤᗘ䜢 ⏝䛔䛶ᐃ㔞䛧䛯䠊 1. 2. 2. Ⓨ⇕㏿ᗘ 㻌 Ⓨ ⇕ ㏿ ᗘ 䛿 ♧ ᕪ ㉮ ᰝ ⇕ 㔞 ィ (Differential scanning calorimeter, DSC; Shimadzu, DSC-60)䜢⏝䛔䛶 ᐃ䛧䛯䠊ヨᩱ䛿⇕ኳ⛗䜢⏝䛔䝦䝸䜴䝮㞺ᅖẼୗ䠈110 °C 䛷 30 ศಖᣢ 䛩䜛䛣䛸䛷䛒䜙䛛䛨䜑Ỉศ䜢㝖ཤ䛧䛯䠊⇱ヨᩱ⣙ 4 mg-d. a. f.䜢䜰䝹䝭䝙䜴䝮〇䛾䝉䝹䛻 ධ䜜䠈⏬㗩䛷 10 ᩘಶ✰䜢㛤䛡䛯䜰䝹䝭䝙䜴䝮〇䛾䜅䛯䜢䛾䛫䠈䜽䝸䞁䝟䞊䛷䜽䝸䞁䝥䛧䛯 䜒䛾䜢 ᐃ䛻⏝䛔䛯䠊䛣䛣䛷䠈䜅䛯䛻✰䜢㛤䛡䛶䛔䜛䛾䛿㞺ᅖẼ䜺䝇䛜ヨᩱ䛸᥋ゐ䛷䛝䜛 䜘䛖䛻䛩䜛䛯䜑䛷䛒䜛䠊䝸䝣䜯䝺䞁䝇䛻䛿✵䛾䝉䝹䜢⏝䛔䠈ᶍᨃ✵Ẽ䜢 50 cm3/min 䛷ὶ䛧䛺 䛜䜙 40 °C 䛛䜙 450 °C 䜎䛷 5 K/min 䛷᪼ 䛧䠈1 ⛊㛫㝸䛷 ᗘᕪ䜢 ᐃ䛧⇕ὶ᮰䛻⟬ 䛧䛯䠊䛒䜙䛛䛨䜑 ᐃ䛧䛯䜲䞁䝆䜴䝮䛾⼥ゎᣲື䛛䜙䠈 ᗘ䜢ᰯṇ䛧䠈⇕ὶ᮰䜢Ⓨ⇕㏿ᗘ 䛻⟬䛧䛯䠊 1. 2. 3. ▼Ⅳ୰䛾ᐁ⬟ᇶ㔞ኚ 㻌 ▼Ⅳ୰䛾ᐁ⬟ᇶ㔞䛿㉥እศගィ(FT-IR; Jeol, JIR-WINSPEC50)䜢⏝䛔䛶 ᐃ䛧䛯䠊䛣 䛾㉥እศගィ䛻䛿㢧ᚤ㙾䛸䝩䝑䝖䝇䝔䞊䝆䛜ᤣ䛘䛡䜙䜜䛶䛚䜚䠈᪼ 㐣⛬䛷䛾ᐁ⬟ᇶ 27 ჽ໗↝˯ภᣠ҄ೞನ↝ᚐଢ 㔞ኚ䜢䛭䛾ሙ ᐃ䛩䜛䛣䛸䛜ྍ⬟䛷䛒䜛䠊ヨᩱ⣙ 0.5 mg 䜢䝩䝑䝖䝇䝔䞊䝆ୖ䛾䝃䞁䝥䝹 䝩䝹䝎䞊䛻㧗䛥䛜ᆒ୍䛻䛺䜛䜘䛖䛻䛾䛫䠈༑ศ䛺ᙉᗘ䛜ฟ䜛䜘䛖䛻䝩䝑䝖䝇䝔䞊䝆䛾⨨䛸 ほᐹ⠊ᅖ䛾⤠䜚䜢ㄪᩚ䛧䠈ᶍᨃ✵Ẽὶ㏻㞺ᅖẼ䛾䜒䛸 5 K/min 䛷 500 °C 䜎䛷᪼ 䛧䛯䠊 ᣑᩓᑕ䝇䝨䜽䝖䝹䛿 20 °C 䛚䛝䛻䠈 ᗘ 1 Ⅼ䛒䛯䜚 64 ᅇ䠈4 cmí1 䛾ศゎ⬟䛷 ᐃ䛧䛯䠊 ᚓ䜙䜜䛯䝇䝨䜽䝖䝹䛿 Kubelka-Munk 㛵ᩘ䜢⏝䛔䛶 K-M ኚ䜢⾜䛳䛯䠊௨㝆䠈K-M ኚ 䜢䛧䛯ᚋ䛾䝢䞊䜽䜢 FT-IR 䝇䝨䜽䝖䝹䛸䜆䠊 1. 3. ⤖ᯝ䛸⪃ᐹ 1. 3. 1. 㔜㔞ኚ䠈䜺䝇⏕ᡂ㏿ᗘ䛚䜘䜃Ⓨ⇕㏿ᗘ 㻌 LY Ⅳ䠈PRB Ⅳ䛚䜘䜃 AL Ⅳ䛾㓟㐣⛬䛻䛚䛡䜛㔜㔞ኚ䠈䜺䝇⏕ᡂ㏿ᗘ䛚䜘䜃Ⓨ⇕ ㏿ᗘ䜢ᅗ 1. 2 ~ 1. 4 䛻䛭䜜䛮䜜♧䛩䠊䛣䜜䜙䛾ᅗ䜘䜚䠈3 ✀㢮䛾▼Ⅳ䛾㓟㐣⛬䛻䛚䛡䜛 ඹ㏻Ⅼ䛸䛧䛶䠈᭱ึ䛾䜺䝇⏕ᡂ≀䛜 H2O 䛷䛒䜛䛣䛸䠈Ⓨ⇕㏿ᗘ䛿 350 °C ௨ୗ䛸 350 °C ௨ ୖ䛷䛭䜜䛮䜜䝢䞊䜽䜢᭷䛧䛶䛚䜚䠈䜺䝇䛾⏕ᡂ㏿ᗘ䛜䛝䛔䜋䛹Ⓨ⇕㏿ᗘ䜒䛝䛟䛺䜛䛣 䛸䠈350 °C ௨ୖ䛷䛿ከ㔞䛾 CO2䠈H2O䠈䛚䜘䜃 CO 䛜⏕ᡂ䛩䜛䛣䛸䛜䛒䛢䜙䜜䜛䠊 㻌 ୍᪉䠈350 °C ௨ୗ䛷䛿ཎⅣ䛻䜘䛳䛶␗䛺䜛㓟ᣲື䛜ほᐹ䛥䜜䛯䠊LY Ⅳ䛷䛿 100 °C ㏆䛛䜙㔜㔞ῶᑡ䛜䜏䜙䜜䛯䠊H2O 䛿 120 °C ㏆䛛䜙䠈CO2 䛿 200 °C ㏆䛛䜙䠈CO 䛿 220 °C ㏆䛛䜙䛭䜜䛮䜜 ᐃ䛥䜜䛯䠊䜎䛯䠈Ⓨ⇕㏿ᗘ䛿 150 °C ㏆䛷ṇ䛾್䜢䛸䜛䜘䛖 䛻䛺䛳䛯䠊PRB Ⅳ䛿 LY Ⅳ䛸ఝ䛯䜘䛖䛺ᣲື䜢♧䛧䛯䛜䠈㔜㔞ኚ㏿ᗘ䛚䜘䜃䜺䝇⏕ᡂ㏿ ᗘ䛜 LY Ⅳ䜘䜚䜒ᑠ䛥䛛䛳䛯䠊䛣䜜䛿䠈LY Ⅳ䛾䜋䛖䛜㓟⣲䛸䛾ᛂᛶ䛜㧗䛔䛣䛸䜢♧၀䛧䛶 䛔䜛䠊୍᪉䠈AL Ⅳ䛿䛾 2 ✀㢮䛾▼Ⅳ䛸␗䛺䜚䠈100 °C 䛛䜙 300 °C 䛻䛚䛔䛶㔜㔞ቑຍ 䛜䜏䜙䜜䛯䠊䜎䛯䠈H2O 䛿 160 °C ㏆䠈CO2 䛚䜘䜃 CO 䛿 300 °C ㏆䜘䜚䛭䜜䛮䜜ほ 䛥䜜䠈䛾▼Ⅳ䜘䜚䜒䜺䝇⏕ᡂ㏿ᗘ䛜ᑠ䛥䛟䛺䛳䛯䠊 28 1.2 300 Loy Yang 1 Heat generation rate [mJ/(K•mg-sample)] Relative weight [g/g-coal daf] Gas formation rate [mmol/(g-coal daf•K)] ᇹ1ᇘ Heat generation 250 Weight change 䢢䢢䢢䢢䢢 0.8 200 0.6 150 CO2 0.4 100 0.2 50 H2O 0 0 100 CO 200 300 400 Temperature [°C] 500 0 600 1.2 300 Weight change 1 PRB Heat generation [mJ/(K•mg-sample)] Relative weight [g/g-coal daf] Gas formation rate [mmol/(g-coal daf•K)] 1. 2. LY ໗ỉ˯ภᣠ҄ਫѣ 250 0.8 200 0.6 150 Heat generation 0.4 H2O 0.2 0 CO2 CO 0 100 200 300 400 Temperature [°C] 500 1. 3. PRB ໗ỉ˯ภᣠ҄ਫѣ 29 100 50 0 600 1.2 300 Alabama Weight change 1 250 CO2 0.8 Heat generation 0.6 200 150 0.4 100 0.2 0 Heat generation [mJ/(K•mg-sample)] Relative weight [g/g-coal daf] Gas formation rate [mmol/(g-coal daf•K)] ჽ໗↝˯ภᣠ҄ೞನ↝ᚐଢ 0 100 H2O CO 200 300 400 Temperature [°C] 500 50 0 600 1. 4. AL ໗ỉ˯ภᣠ҄ਫѣ 㻌 ḟ䛻䠈㓟๓䛾ඖ⣲⤌ᡂ䛸㔜㔞ኚ㏿ᗘ䛚䜘䜃䜺䝇⏕ᡂ㏿ᗘ䛸䜢⏝䛔ඖ⣲ᨭ䜢䛸䜛 䛣䛸䛷䠈ྛ ᗘ䛻䛚䛡䜛ᅛయ⏕ᡂ≀䛾ඖ⣲⤌ᡂ䜢ィ⟬䛧䠈㓟㛤ጞ䛾▼Ⅳ㔜㔞䜢ᇶ‽ 䛸䛧䛯ྛ ᗘ䛻䛚䛡䜛㓟⣲ྵ᭷⋡ nO 䜢ḟᘧ䛾䜘䛖䛻ィ⟬䛧䛯䠊 nO = 䛒䜛 ᗘ䛷䛾ᅛయ୰䛾㓟⣲㔜㔞[g-O] 㓟๓䛾▼Ⅳ㔜㔞 [g-sample] (1. 1) 䛴䜎䜚䠈㔜㔞ኚ䛻㛵ಀ䛺䛟䠈ᅛయ୰䛾㓟⣲㔜㔞䛜ῶ䜛䛸䠈nO 䛿ᑠ䛥䛟䛺䜚䠈㓟㛤ጞ 䛾ᅛయ୰䛾㓟⣲㔜㔞䛜䛒䜛 ᗘ䛷䛾ᅛయ䛾㓟⣲㔜㔞䛸➼䛧䛡䜜䜀 nO 䛿ྠ䛨್䛸䛺䜛䠊 300 °C ௨ୗ䛻䛚䛡䜛ྛヨᩱ䛾ᅛయ⏕ᡂ≀୰䛾 nO 䛾 ᗘኚ䜢ᅗ 1. 5 ~ 1. 7 䛻♧䛩䠊䜎 䛯䠈H2O ⏕ᡂ㏿ᗘ䛚䜘䜃㔜㔞ኚ䜒ྠᅗ୰䛻♧䛧䛯䠊 㻌 LY Ⅳ䛚䜘䜃 PRB Ⅳ䛷䛿㔜㔞ῶᑡ䛚䜘䜃 H2O ⏕ᡂ䛜䜏䜙䜜䛯 ᗘᇦ䛷䜒 nO 䛜䜋䜌୍ ᐃ䛸䛺䛳䛯䠊䜒䛧䠈⇕ศゎ䛻䜘䛳䛶 H2O 䛜⏕ᡂ䛧䛯䛸௬ᐃ䛩䜛䛸䠈H2O 䛾⏕ᡂ䛻క䛔䠈㓟⣲ ྵ᭷⋡䛿పୗ䛩䜛䠊䛴䜎䜚䠈LY Ⅳ䛚䜘䜃 PRB Ⅳ䛷䛿䠈ᛂึᮇ䛻䛚䛔䛶 H2O 䛸䛧䛶ᅛ య䛛䜙㝖ཤ䛥䜜䛯㓟⣲䛾㔞䛸ྠ䛨㔞䛾㓟⣲䛜྾╔䛧䛯䠈䜒䛧䛟䛿䠈Ẽ┦䛾㓟⣲䛸▼Ⅳ୰䛾 30 ᇹ1ᇘ Ỉ⣲䛜ᛂ䛧䛶 H2O 䛜⏕ᡂ䛧䛯䛸⪃䛘䜙䜜䜛䠊୍⯡ⓗ䛻䠈▼Ⅳ䛾ప 㓟䛾᭱ึ䛾ẁ㝵 Relative weight [kg/kg-sample daf] 1.1 0.3 Loy Yang Oxygen mass fraction 1.05 Relative weight 1 0.95 0.9 0 0.2 0.1 0 H2O production 50 100 150 200 Temperature [°C] 250 -0.1 300 H2O production rate [mmol/(g-sample daf•K)] Oxygen mass fraction, nO [g/g-sample daf] 䛿㓟⣲྾╔䛷䛒䜛䛸䛔䜟䜜䛶䛔䜛[1]䛣䛸䛛䜙䠈๓⪅䛾ᛂ䛜⏕䛨䛯䛸⪃䛘䜙䜜䜛䠊 1. 5. LY ໗ỉӒࣖИỆấẬỦ҄٭ύH2O ဃấợỎ˳ Relative weight [kg/kg-sample daf] 1.1 0.3 PRB 1.05 Oxygen mass fraction Relative weight 1 0.95 0.9 0 H2O production 0.2 0.1 0 H2O production rate [mmol/(g-sample daf•K)] Oxygen mass fraction, nO [g/g-sample daf] ᣠእԃஊྙ -0.1 100 150 200 250 300 Temperature [°C] 1. 6. PRB ໗ỉӒࣖИỆấẬỦ҄٭ύH2O ဃấợỎ˳ 50 ᣠእԃஊྙ 31 Relative weight [kg/kg-sample daf] 1.1 0.3 Alabama 1.05 Relative weight 0.2 Oxygen mass fraction 1 0.1 0.95 0.9 0 0 H2O production 50 100 150 200 Temperature [°C] 250 -0.1 300 H2O production rate [mmol/(g-sample daf•K)] Oxygen mass fraction, nO [g/g-sample daf] ჽ໗↝˯ภᣠ҄ೞನ↝ᚐଢ 1. 7. AL ໗ỉӒࣖИỆấẬỦ҄٭ύH2O ဃấợỎ˳ ᣠእԃஊྙ 㻌 ୍᪉䠈AL Ⅳ䛷䛿㔜㔞ቑຍ䛻క䛔䠈nO 䛜ቑຍ䛧䛶䛔䜛䛣䛸䛛䜙䠈ప 㓟䛾ึᮇᛂ䛿 㓟⣲྾╔䛜㉳䛣䛳䛯䛸⪃䛘䜙䜜䜛䠊䜎䛯䠈H2O 䛜⏕ᡂ䛩䜛 ᗘᇦ䛷䜒㔜㔞䛚䜘䜃 nO 䛜ቑ ຍ䛧䛯䛣䛸䛛䜙䠈AL Ⅳ䛷䛿 H2O 䛸䛧䛶ྲྀ䜚㝖䛛䜜䛯㓟⣲㔞௨ୖ䛾㓟⣲䛜྾╔䛧䛶䛔䜛䛣䛸 䛜䜟䛛䜛䠊 1. 3. 2. ᐁ⬟ᇶ㔞䛾ኚ 㻌 㓟㐣⛬䛻䛚䛡䜛 FT-IR 䝇䝨䜽䝖䝹䛾 ᗘኚ䜢ᅗ 1. 8 ~ 1. 10 䛻♧䛩䠊䛔䛪䜜䛾▼Ⅳ 䜒 ᗘ䛜ୖ䛜䜛䛻䛴䜜䛶ᕥഃ䛾ᅗ䛻♧䛩䜘䛖䛻 2840 ~ 2920 cmí1 䛻䛒䜛⬡⫫᪘Ⅳ⣲䛚䜘 䜃 2600 ~ 3600 cmí1 䛻䛒䜛Ỉ㓟ᇶ䛾䝢䞊䜽䛜ᚎ䚻䛻ᑠ䛥䛟䛺䛳䛯䠊୍᪉䠈ྑഃ䛾ᅗ䛷䛿 1700 cmí1 ㏆䛾䜹䝹䝪䜻䝅䝹ᇶ䠈1760 cmí1 ㏆䛾䜶䝇䝔䝹ᇶ䛚䜘䜃 1850 cmí1 ㏆䛾 㓟↓Ỉ≀䛻ᑐᛂ䛩䜛䝢䞊䜽䛾ቑῶ䛜㢧ⴭ䛻ぢ䜙䜜䛯䠊䜎䛪䠈220 °C ௨ୗ䛻䛚䛔䛶䜹䝹䝪 32 ᇹ1ᇘ 䜻䝅䝹ᇶ䛾䝢䞊䜽䛜ቑຍ䛧䠈ḟ䛻䠈220 °C ~ 260 °C 䛻䛚䛔䛶䜶䝇䝔䝹ᇶ䛾䝢䞊䜽䛜ቑຍ 䛧䛯䠊䛭䛾ᚋ䠈260 °C ~ 300 °C 䛻䛚䛔䛶㓟↓Ỉ≀䛾䝢䞊䜽䛜ቑຍ䛧䛯䠊᭱⤊ⓗ䛻䛿䛩䜉 䛶䛾䝢䞊䜽䛜ῶᑡ䛧䠈360 °C ௨㝆䛷䛿䛩䜉䛶䛾䝢䞊䜽䛜ぢ䜙䜜䛺䛟䛺䛳䛯䠊 㻌 䜘䜚ヲ⣽䛺ᐁ⬟ᇶ㔞䛾ኚ䜢䜏䜛䛯䜑䠈䛣䜜䜙䛾䝇䝨䜽䝖䝹䜢䜹䞊䝤䝣䜱䝑䝔䜱䞁䜾䛻䜘䜚䠈 2000 ~ 4000 cmí1 䛿⾲ 1. 2 䛻♧䛩 10 ಶ䛾䝢䞊䜽䛻䠈1500 ~ 2000 cmí1 䛿⾲ 1. 3 䛻♧䛩 10 ಶ䛾䝢䞊䜽䛻䛭䜜䛮䜜ศ䛧䛯[2, 3]䠊䛭䜜䛮䜜䛾䝢䞊䜽㠃✚䜢ィ⟬䛩䜛䛣䛸䛷䠈ᐁ⬟ᇶ 㔞䛾 ᗘኚ䜢ồ䜑䛯䠊䛭䜜䛮䜜䛾ᐁ⬟ᇶ㔞䛾 ᗘኚ䜢ᅗ 1. 11 ~ 1. 13 䛻♧䛩䠊䛔 䛪䜜䛾▼Ⅳ䜒ᛂ䛾㐍⾜䛻క䛔䠈⬡⫫᪘䛚䜘䜃ⰾ㤶᪘䛾 C-H ⤖ྜ䛜ᚎ䚻䛻ῶᑡ䛧䛯䠊 FT-IR 䛻䛚䛔䛶䛿䠈⤖ྜ䛤䛸䛷䝢䞊䜽䛾ᙉᗘ䛜␗䛺䜛䛯䜑䠈⤖ྜ㛫䛾䝢䞊䜽㠃✚䛾ẚ䛸ᐇ 㝿䛾⤖ྜ䛾㔞䛾ẚ䛸䛿ᚲ䛪䛧䜒୍⮴䛧䛺䛔䠊䛧䛛䛧䠈▼Ⅳ୰䛻䛿ከ䛟䛾ⰾ㤶᪘Ⅳ⣲䛜Ꮡ ᅾ䛩䜛䛜䛭䛾ከ䛟䛜 C-C ⤖ྜ䛷䛒䜚䠈ⰾ㤶᪘䛾 C-H ⤖ྜ䛿⬡⫫᪘䛾 C-H ⤖ྜ䜘䜚ᑡ䛺䛔䠊 䛥䜙䛻䠈1610 cm䌦1 ㏆䛾ⰾ㤶⎔䛾 C-C ⤖ྜ䛻ᑐᛂ䛩䜛䝢䞊䜽䛿䛒䜎䜚ῶ䛳䛶䛔䛺䛔䛣䛸 䛛䜙䠈ప 㓟䛻䛚䛔䛶䛿ⰾ㤶᪘䛾 C-H 䜘䜚䜒ከ䛟䛾⬡⫫᪘䛾 C-H 䛜ᛂ䛧䛯䛸⪃䛘䜙 䜜䠈ⰾ㤶⎔䛜㛤䛩䜛䜘䛖䛺ᛂ䛿䜋䛸䜣䛹㉳䛣䛳䛶䛔䛺䛔䛸⪃䛘䜙䜜䜛䠊䜎䛯䠈ྵ㓟⣲ᐁ ⬟ᇶ䛷䛿䠈䜎䛪䜹䝹䝪䜻䝅䝹ᇶ䛜ቑຍ䛧䠈ḟ䛻䜹䝹䝪䜻䝅䝹ᇶ䛾ῶᑡ䛸䛸䜒䛻䜶䝇䝔䝹ᇶ 䛾ቑຍ䛜䜏䜙䜜䛯䠊䛭䛾ᚋ䠈䜶䝇䝔䝹ᇶ䛜ῶᑡ䛧䠈㓟↓Ỉ≀䛜ቑຍ䛧䠈᭱⤊ⓗ䛻䛿䛩䜉 䛶䛾ᐁ⬟ᇶ㔞䛜ῶᑡ䛧䛯䠊䛭䜜䛮䜜䛾ኚ䛜㉳䛣䜛 ᗘ䛿䠈▼Ⅳ䛻䜘䜚ⱝᖸ䛾㐪䛔䛜䜏 䜙䜜䠈䜹䝹䝪䜻䝅䝹ᇶ䛿䠈LY Ⅳ䛷䛿 200 °C ㏆䛷䠈PRB Ⅳ䛚䜘䜃 AL Ⅳ䛷䛿 240 °C ㏆䛷᭱䛸䛺䛳䛯䠊䜶䝇䝔䝹ᇶ䛷䛿䛔䛪䜜䛾▼Ⅳ䜒 260 °C ㏆䛷䠈㓟↓Ỉ≀䛿 LY Ⅳ䛚 䜘䜃 PRB Ⅳ䛷䛿 300 °C ㏆䛷䠈AL Ⅳ䛷䛿 340 °C ㏆䛷䛭䜜䛮䜜᭱䛸䛺䛳䛯䠊 33 K-M function [a. u.] 34 0 4000 2 4 6 8 10 12 3800 3600 120 °C 140 °C 160 °C 180 °C 200 °C 220 °C 240 °C 16 14 Loy Yang 18 20 3400 260 °C 280 °C 300 °C 320 °C 340 °C 360 °C 380 °C 3000 -1 2800 2600 2400 2200 2000 K-M function [a. u.] 0 2000 1950 1900 120 °C 140 °C 160 °C 180 °C 200 °C 220 °C 240 °C Loy Yang 1850 260 °C 280 °C 300 °C 320 °C 340 °C 360 °C 380 °C 1750 -1 1700 Wavenumber [cm ] 1800 1. 8. LY ໗ỉᣠ҄ᢅᆉỆấẬỦ FT-IR ἋἬἁἚἽỉ҄٭ Wavenumber [cm ] 3200 10 20 30 40 50 60 70 1650 1600 1550 1500 ჽ໗↝˯ภᣠ҄ೞನ↝ᚐଢ K-M function [a. u.] 35 3000 2800 2600 2400 2200 -1 1900 120 °C 140 °C 160 °C 180 °C 200 °C 220 °C 240 °C 1950 PRB 1850 1800 1750 -1 1700 Wavenumber [cm ] 260 °C 280 °C 300 °C 320 °C 340 °C 360 °C 1. 9. PRB ໗ỉᣠ҄ᢅᆉỆấẬỦ FT-IR ἋἬἁἚἽỉ҄٭ Wavenumber [cm ] 2000 0 2000 3200 20 30 40 50 0 4000 3400 260 °C 280 °C 300 °C 320 °C 340 °C 360 °C 60 70 10 3600 120 °C 140 °C 160 °C 180 °C 200 °C 220 °C 240 °C 3800 PRB K-M function [a. u.] 2 4 6 8 10 12 14 16 1650 1600 1550 1500 ᇹ1ᇘ K-M function [a. u.] 36 0 4000 2 4 6 8 10 12 14 16 18 20 3800 3600 120 °C 140 °C 160 °C 180 °C 200 °C 220 °C 240 °C Alabama 3400 3000 -1 2800 2600 2400 2200 2000 K-M function [a. u.] 0 2000 5 10 15 20 1950 1900 120 °C 140 °C 160 °C 180 °C 200 °C 220 °C 240 °C Alabama 1850 1750 -1 1700 Wavenumber [cm ] 1800 260 °C 280 °C 300 °C 320 °C 340 °C 360 °C 380 °C 1. 10. AL ໗ỉᣠ҄ᢅᆉỆấẬỦ FT-IR ἋἬἁἚἽỉ҄٭ Wavenumber [cm ] 3200 260 °C 280 °C 300 °C 320 °C 340 °C 360 °C 380 °C 25 30 1650 1600 1550 1500 ჽ໗↝˯ภᣠ҄ೞನ↝ᚐଢ ᇹ1ᇘ ᘙ 1. 2. 2000 ~ 4000 cmí1 ỉἦὊἁɟᚁ Wavenumber [cmí1] Peak identification 2650 COOH dimers 2840 aliphatic C–H stretching band 2920 aliphatic C–H stretching band 2940 OH–N (acid/base structures) 3050 aromatic C–H stretching band 3150 tightly bound cyclic OH tetramers 3280 OH–ether O 3400 self-associated OH n–mers (n > 3) 3516 OH– ᘙ 1. 3. 1500 ~ 2000 cmí1 ỉἦὊἁɟᚁ Wavenumber [cmí1] Peak identification 1560 carboxylate anion COOí symmetric mode 1580 carboxylate anion COOí asymmetric mode 1610 aromatic C=C bond 1650 highly conjugated carbonyl 1700 carboxyl groups 1740 aldehydes 1760 esters 1800 anhydride asymmetric mode 1840 anhydride symmetric mode 37 ჽ໗↝˯ภᣠ҄ೞನ↝ᚐଢ Intensity [a. u.] Loy Yang Aliphatic C-H Aromatic C-H 100 150 200 250 300 Temperature [°C] 350 400 Loy Yang Intensity [a. u.] carboxyls esters anhydrides OH 100 150 200 250 300 Temperature [°C] 350 400 1. 11. LY ໗ỉᣠ҄ᢅᆉỆấẬỦӲܫᏡؕỉ҄٭ 38 ᇹ1ᇘ Intensity [a. u.] PRB Aliphatic C-H Aromatic C-H 100 150 200 250 300 Temperature [°C] 350 400 PRB Intensity [a. u.] carboxyls anhydrides esters OH 100 150 200 250 300 Temperature [°C] 350 400 1. 12. PRB ໗ỉᣠ҄ᢅᆉỆấẬỦӲܫᏡؕỉ҄٭ 39 ჽ໗↝˯ภᣠ҄ೞನ↝ᚐଢ Intensity [a. u.] Alabama Aliphatic C-H Aromatic C-H 100 150 200 250 300 Temperature [°C] 350 400 Intensity [a. u.] Alabama carboxyls anhydrides esters OH 100 150 200 250 300 Temperature [°C] 350 1. 13. AL ໗ỉᣠ҄ᢅᆉỆấẬỦӲܫᏡؕỉ҄٭ 40 400 ᇹ1ᇘ 1. 3. 3. ప 㓟ᶵᵓ䛾᳨ウ 㻌 ௨ୖ䛾⤖ᯝ䛛䜙䠈ప 㓟䛾ึᮇ䛷䛿పရⅣ䛸㧗ရⅣ䛷␗䛺䜛㔜㔞ኚᣲື䛜 䜏䜙䜜䛯䛜䠈䜺䝇⏕ᡂᣲື䛚䜘䜃ᐁ⬟ᇶ㔞䛾ኚ䛿㏿ᗘ䛾ᑠ䛾㐪䛔䛿䛒䜛䛜ᴫ䛽ྠ 䛨ᣲື䜢♧䛧䛯䛣䛸䛜ศ䛛䜛䠊FT-IR 䝇䝨䜽䝖䝹䜘䜚 360 °C ௨ୖ䛷䛿䛩䜉䛶䛾ᐁ⬟ᇶ䛜ぢ 䜙䜜䛺䛛䛳䛯䛣䛸䛛䜙䠈TG䠈GC 䛚䜘䜃 DSC 䛷ほᐹ䛥䜜䛯 350 °C ௨ୗ䛷䛾㓟ᣲື䛿 䛻ᐁ⬟ᇶ㒊ศ䛾㓟ᣲື䛷䛒䜚䠈350 °C ௨ୖ䛷䜏䜙䜜䛯㓟ᣲື䛿ᐁ⬟ᇶ䛾㓟䛜ྵ 䜎䜜䛪䠈▼Ⅳ㦵᱁䛷䛾㓟ᣲື䜢♧䛧䛶䛔䜛䛸⪃䛘䜙䜜䜛䠊350 °C ௨ୖ䛷䛿ᐁ⬟ᇶ䛜䜋 䛸䜣䛹ྵ䜎䜜䛺䛔䛣䛸䛛䜙䠈䛭䛾 ᗘ䛻䛚䛡䜛ᅛయ⏕ᡂ≀䛿ཎⅣ䛻䜘䜙䛪ఝ䛯䜘䛖䛺ᵓ㐀 䜢ᣢ䛳䛶䛚䜚䠈350 °C ௨㝆䛾㓟ᣲື䛿▼Ⅳ䛻䜘䜙䛪㠀ᖖ䛻ఝ䛶䛔䛯䛸⪃䛘䜙䜜䜛䠊 㻌 ୍᪉䠈350 °C ௨ୗ䛷䛿▼Ⅳ䛻䜘䛳䛶㔜㔞ኚᣲື䛜␗䛺䜚䠈AL Ⅳ䛿ᛂึᮇ䛷⬡⫫ ᪘Ⅳ⣲ୖ䜈㓟⣲䛜Ꮫ྾╔䛩䜛䛣䛸䛷㔜㔞ቑຍ䛜⏕䛨䛯䛸⪃䛘䜙䜜䜛䠊䛧䛛䛧䠈㔜㔞ቑ ຍ䛿 100 °C ㏆䛛䜙ほᐹ䛥䜜䛯䛾䛻ᑐ䛧䠈䜹䝹䝪䜻䝅䝹ᇶ䛾⏕ᡂ䛿 140 °C ㏆䛛䜙ほ ᐹ䛥䜜䛯䠊䛣䛾䛣䛸䛿䠈⬡⫫᪘Ⅳ⣲䛛䜙䜹䝹䝪䜻䝅䝹ᇶ䜈䛾㓟䛾㐣⛬䛷୰㛫⏕ᡂ≀䛜 Ꮡᅾ䛩䜛䛣䛸䜢♧၀䛧䛶䛔䜛䠊୍⯡䛻䠈⬡⫫᪘Ⅳ⣲䛾㓟㐣⛬䛷䛿䜎䛪㐣㓟≀䛜⏕ᡂ 䛧䛶䛔䜛䛸䛔䜟䜜䛶䛚䜚䠈AL Ⅳ䛾㓟䛻䛚䛔䛶䜒ྠᵝ䛻㐣㓟≀䛜⏕ᡂ䛧䛯䛸⪃䛘䜙䜜 䜛䠊୍᪉䠈LY Ⅳ䜔 PRB Ⅳ䛷䛿㔜㔞ῶᑡ䛸䛸䜒䛻 H2O 䛾⏕ᡂ䛜ほᐹ䛥䜜䠈ᅛయ⏕ᡂ≀୰ 䛾㓟⣲ྵ᭷⋡䛻ኚ䛜䛺䛛䛳䛯䠊䛣䜜䜙䛾పရⅣ䛿ྵ㓟⣲ᐁ⬟ᇶ䜢ከ䛟䜒䛴䛯䜑䠈㓟 ⣲䛾྾╔䛜㉳䛣䜚䛻䛟䛟䠈䜎䛯྾╔䛧䛯㓟⣲䛸➼㔞䛾 H2O 䛜⏕ᡂ䛧䛯䛸⪃䛘䜙䜜䜛䠊 㻌 ௨ୖ䛾⤖ᯝ䛛䜙䚸▼Ⅳ䛾㓟㐣⛬䛻䛿ᅗ 1. 14 䛻♧䛩䜘䛖䛻䛝䛟ศ䛡䛶 3 䛴䛾ẁ㝵䛜 䛒䜛䛸⪃䛘䜙䜜䜛䠊1 ẁ㝵┠䛿▼Ⅳ䛾⬡⫫᪘Ⅳ⣲ୖ䜈䛾㓟⣲䛾྾╔䠈2 ẁ㝵┠䛿䜺䝇䛾 ⏕ᡂ䜢క䛖ྵ㓟⣲ᐁ⬟ᇶ䛾㓟䠈3 ẁ㝵┠䛿▼Ⅳ㦵᱁䠈䛴䜎䜚▼Ⅳయ䛾㓟䛷䛒䜚ከ 㔞䛾 CO2䠈H2O 䛚䜘䜃 CO 䛜⏕ᡂ䛩䜛䠊ᅗ 1. 14 䛻䛿 LY Ⅳ䛾㓟䛻䛚䛔䛶䛭䜜䛮䜜䛾 ྵ㓟⣲ᐁ⬟ᇶ㔞䛜ቑຍ䛧䛯 ᗘᇦ䜢♧䛧䛯䠊PRB Ⅳ䛾㓟䛷䛿䠈LY Ⅳ䛾㓟䛸ྠᵝ䛻 140 °C ~ 240 °C 䛻䛚䛔䛶䜹䝹䝪䜻䝅䝹ᇶ䛜䠈180 °C ~ 240 °C 䛻䛚䛔䛶䜶䝇䝔䝹ᇶ䛜䠈䛭 41 ჽ໗↝˯ภᣠ҄ೞನ↝ᚐଢ 䛧䛶 240 °C ~ 300 °C 䛻䛚䛔䛶㓟↓Ỉ≀䛜ቑຍ䛧䛯䠊LY Ⅳ䛚䜘䜃 PRB Ⅳ䛷䛿 1 ẁ㝵┠䛸 2 ẁ㝵┠䛜ྠ䛻㉳䛣䛳䛯䛯䜑䠈ᛂึᮇ䛷㔜㔞ῶᑡ䛸 H2O ⏕ᡂ䛜ほᐹ䛥䜜䛯䠊୍᪉䠈 ℡㟷Ⅳ䛷䛒䜛 AL Ⅳ䛾㓟䛷䛿 100 °C ~ 140 °C 䛷㓟⣲྾╔䛻䜘䜛㔜㔞ቑຍ䛜⏕䛨䛯䠊 ྵ㓟⣲ᐁ⬟ᇶ㔞䛜ቑຍ䛩䜛 ᗘᇦ䛿〓Ⅳ䛾㓟䛻䛚䛡䜛 ᗘᇦ䜘䜚䜒㧗 ഃ䛻䝅䝣䝖䛧䠈 140 °C ~ 240 °C 䛷䜹䝹䝪䜻䝅䝹ᇶ䛜䠈180 °C ~ 260 °C 䛷䜶䝇䝔䝹ᇶ䛜䠈260 °C ~ 340 °C 䛷㓟↓Ỉ≀䛜䛭䜜䛮䜜ቑຍ䛧䛯䠊ᮏ◊✲䛻䜘䜚᫂䜙䛛䛻䛧䛯ྵ㓟⣲ᐁ⬟ᇶ䛾⏕ᡂᶵᵓ 䛿䛣䜜䜎䛷䛻ᥦ䛥䜜䛶䛝䛯ప 㓟ᶵᵓ[4~6]䛾䛺䛛䛷䜒 Yürüm 䜙[4]䛜ᥦ䛧䛯ᛂᶵ ᵓ䛸㢮ఝ䛧䛶䛔䜛䠊䛺䛚䠈䛣䛣䛻♧䛧䛯 ᗘ䛿 5 K/min 䛷᪼ 䛧䛯ሙྜ䛾 ᗘ䛷䛒䜚䠈᪼ ㏿ᗘ䛜ᑠ䛥䛟䛺䜛䛸䛭䜜䜙䛾ᛂ䛜㉳䛣䜛 ᗘ䛜ప䛟䛺䜛䠊 aliphatic C-H3 peroxide O OH C H H CO2 CO2 H2O H2O carboxyl (1) ᣠእԈბ H2O O C O O O C O C CO2 200 ~260°C 260 ~300°C 360°C ~ O C OH 140 ~ 200°C CO2 H2O ester anhydride (2) ԃᣠእܫᏡؕỉဃ CO (3) ჽ໗ᭌỉᣠ҄ 1. 14. ஜᄂᆮỂଢỤẦỆẲẺ LY ໗ỉ˯ภᣠ҄ೞನ 㻌 ௨ୖ䛾⤖ᯝ䜘䜚䠈Hüttinger 䜙[7]䛾〓Ⅳ䛾ᵓ㐀䛻ᑐ䛧䛶ప 㓟䛻䜘䜛▼Ⅳ䛾ᵓ㐀䛿ᅗ 1. 15 䛾䜘䛖䛻ኚ䛩䜛䛸᥎ᐹ䛥䜜䜛䠊200 °C ௨ୗ䛷䛿⬡⫫᪘Ⅳ⣲䛜䛻㓟䛥䜜䠈㐣㓟 ≀䛚䜘䜃䜹䝹䝪䜻䝅䝹ᇶ䛾⏕ᡂ䛻క䛔 H2O 䛾⏕ᡂ䛜㉳䛣䜛䠊䜎䛯䠈350 °C ௨ୗ䛷䛿ከ 䛟䛾⬡⫫᪘Ⅳ⣲䜔䜋䜌䛩䜉䛶䛾ᐁ⬟ᇶ䛜㓟䛥䜜䠈ከ䛟䛾䜶䞊䝔䝹⤖ྜ䛻䜘䜛㓟⣲ᯫᶫ 䛜㉳䛝䠈CO2 䜔 H2O 䛜⏕ᡂ䛩䜛䛸⪃䛘䜙䜜䜛䠊 42 ᇹ1ᇘ HO OH O O KO C OH C HO OH OH O HO O O O H Ca O C O R O CH2 O R OH O H3C O O CH3 O OH O HO O O O OCH3 C OH C O ONa H C O O Mg O KO O C OH C O H2C Ca O C O O O HO CH C CH3 OH O H7C3 O H2O O H2O KO O C15H31 C3H6 O O O COOH C O H2O OH O R H2O Al O O O O H2O H2O O O O N C2H5 C R OOH Ca O OH O O C O O OH H2O HO O Fe O O OCH3 O O OH O C R O Ca O O C O CH2 C O O OH CH3 O C O OOH ONa O C C HO N O O HO CH3 O HO CH C CH3 C S OH O OH O O C HO O O H H 7C3 O Mg O O H R N OH2O O C O O O C O O CH2 O C OH Ca OH OH O O HO O H2O OH C HO OH OOH HO O H2O O H3C O H2O H2O OH ONa C O O OH O O CH3 O ~ 200 °C HO N O O O O C2H5 N Fe O O R O O CH3 C HO HO C OH O O C O C O O O S C15H31 C3H7 O KO O OH H C H 5 2 Ca O C O CH2 OO HH C Al OH O R N O O C OH OH O O O O H3C OH ONa C O OH O O 25 °C (ᐊ ) H3C O O OH KO O H Ca O O C O C O O O O O O O O O R CH2 O O O N O R N O O H3C O O O HO O O OH O O OH S O O C O O O CH3 O C O O O C O C O O O O O C O KO O O O HO C OH N O H3C O O C H O O Mg O 1. 15.˯ภᣠ҄↚ⅹↀ↺ᙓ໗↝ನᡯ↝҄٭ࡸ 43 O HO H7C3 O O O OH C HO O O O ~ 350 °C ჽ໗↝˯ภᣠ҄ೞನ↝ᚐଢ 1. 3. 4. ప 㓟ᶵᵓ䛸⮬↛Ⓨⅆᛶ䛸䛾ᑐᛂ 㻌 䛣䜜䜎䛷䛾㆟ㄽ䛻䜘䜚▼Ⅳ䛾ప 㓟ᶵᵓ䜢᫂䜙䛛䛻䛧䛯䛜䠈⮬↛Ⓨⅆ䛻䛚䛔䛶䛿䛣 䛾ᶵᵓ䛾䛹䛾ᛂ䛜ᙳ㡪䜢ཬ䜌䛩䛾䛛䠈䜎䛯䛹䛾ẁ㝵䜎䛷䛾ᛂ䛜㉳䛝䛯䜙⮬↛Ⓨⅆ䛜 ㉳䛣䜚ᚓ䜛䛾䛛䛸䛔䛳䛯Ⅼ䜢᫂䜙䛛䛻䛩䜛ᚲせ䛜䛒䜛䠊䛭䛾䛯䜑䛻䛿䠈ప 䛻䛚䛡䜛㓟⣲ 䛸䛾ᛂᛶ䛚䜘䜃Ⓨ⇕䛻క䛖 ᗘୖ᪼䛜㠀ᖖ䛻㔜せ䛸䛺䜛䠊䛣䛣䛷䠈▼Ⅳ䛸㓟⣲䛾ᛂ䛻 䛚䛔䛶䛿䠈䜎䛪▼Ⅳୖ䜈䛾㓟⣲䛾྾╔䛜㉳䛣䜛䛸⪃䛘䜙䜜䜛䠊䛭䛾⏕ᡂ≀䛜༑ศ䛻Ᏻᐃ 䛺ሙྜ䛻䛿䛥䜙䛺䜛ᛂ䛜㉳䛣䜙䛪䠈୍᪉䠈䛭䛾⏕ᡂ≀䛜Ᏻᐃ䛺ሙྜ䛻䛿䛭䛾⏕ᡂ≀ 䛜䛥䜙䛻ᛂ䛧䜺䝇䛾⏕ᡂ䛜⏕䛨䜛䛸⪃䛘䜙䜜䜛䠊ᮏㄽᩥ䛷䛿䠈๓⪅䛾䜘䛖䛻⏕ᡂ≀䛜Ᏻ ᐃ䛷྾╔䛧䛯㓟⣲䛜䛭䛾䜎䜎ᅛయ୰䛻䛸䛹䜎䜛䜘䛖䛺ᛂ䜢䛂㓟⣲྾╔䛃䛸䜃䠈䛥䜙䛻 ᛂ䛜㐍⾜䛧䠈྾╔䛧䛯㓟⣲䛜▐䛻䜺䝇⏕ᡂ≀䛸䛧䛶䠈ᅛయ䛛䜙⬺╔䛩䜛ᛂ䜢䛂䜺䝇⏕ ᡂᛂ䛃䛸䜆䛣䛸䛸䛩䜛䠊䜎䛯䠈䛂㓟ᛶ䛃䠈䛚䜘䜃䛂㓟⣲䛸䛾ᛂᛶ䛃䛿᩿䜚䛜䛺䛔㝈䜚䛣 䜜䜙 2 䛴䛾ᛂ䜢ྵ䜐䜒䛾䛸䛩䜛䠊 㻌 䛒䜛 ᗘ䛻⮳䜛䜎䛷䛻⏕䛨䛯Ⓨ⇕㔞䛸㓟⣲ᾘ㈝㔞䜢Ⅳ⣲ཎᏊ 100 mol ᇶ‽䛷ồ䜑䛯䠊 ᅗ 1. 16 ~ 1. 18 䛻 250 °C ௨ୗ䛷䛾㓟⣲ᾘ㈝㔞䛸Ⓨ⇕㔞䛾㛵ಀ䜢♧䛩䠊ྠ䛨 ᗘ䛷ẚ㍑ 䛧䛯ሙྜ䠈㓟⣲ᾘ㈝㔞䛜䛝䛔䜒䛾䜋䛹㓟⣲䛸䛾ᛂᛶ䛜㧗䛟䠈Ⓨ⇕㔞䛜䛝䛔䜋䛹 ᗘୖ᪼䛜䛝䛟䛺䜛䠊䜎䛯䠈Ⓨ⇕㔞䛾✚⟬್䛾ഴ䛝䛿Ẽ┦䛾㓟⣲ཎᏊ 1 mol 䛒䛯䜚䛾䜏䛛 䛡䛾ᛂ䜶䞁䝍䝹䝢䞊䜢⾲䛧䠈▼Ⅳ䛾⇕ᐜ㔞䛜 ᗘ䛸ᛂ䛾㐍⾜䛻䜘䜙䛪 1.2 kJ/(kg·K) 䛷୍ᐃ䛷䛒䜛䛸௬ᐃ䛩䜛䛣䛸䛷䠈䛒䜛 ᗘ䜎䛷䛾Ⓨ⇕䛾⥲㔞䛛䜙▼Ⅳ 1 kg 䛒䛯䜚䛾᩿⇕ ᗘୖ᪼䜢ィ⟬䛩䜛䛣䛸䛜䛷䛝䜛䠊䛣䛾᩿⇕ ᗘୖ᪼䛿ప 㓟䛾ึᮇ䛾ᛂ䛻䜘䜛Ⓨ⇕ 䛻㉳ᅉ䛧䛯 ᗘୖ᪼䛷䛒䜛䛯䜑䠈⮬↛Ⓨⅆᛶ䛾ᑠ䛸῝䛟㛵ಀ䛧䛶䛔䜛䛸⪃䛘䜙䜜䜛䠊䜎 䛯䠈ྠᵝ䛾ᐇ㦂䜢⾜䛘䜀䠈 ᐃ⪅䛻䜘䜙䛪ᚲ䛪ྠ䛨್䛜ᚓ䜙䜜䜛ᣦᶆ䛷䛒䜛䠊200 °C 䛻 䛚䛡䜛㓟⣲ᾘ㈝㔞䠈㓟⣲ཎᏊ 1 mol 䛒䛯䜚䛾䜏䛛䛡䛾ᛂ䜶䞁䝍䝹䝢䞊䛚䜘䜃 200 °C 䜎 䛷䛾Ⓨ⇕䛻䜘䜛᩿⇕ ᗘୖ᪼䜢⾲ 1. 4 䛻♧䛩䠊 㻌 㓟⣲ᾘ㈝㔞䛿 LY Ⅳ䛷 4.6 mol-O/100 mol-C 䛷䛒䜚䠈PRB Ⅳ䛾⣙ 2 ಸ䠈AL Ⅳ䛾 2.7 ಸ䛸 44 ᇹ1ᇘ 䛺䜚䠈᭱䜒㉁䛾ప䛔 LY Ⅳ䛜᭱䜒㓟⣲䛸䛾ᛂᛶ䛜㧗䛟䛺䛳䛯䠊䛣䜜䜙䛾್䜘䜚䠈200 °C 䜎 䛷䛻▼Ⅳ୰䛾Ỉ⣲䛾䛖䛱 LY Ⅳ䛷䛿 8 %䛜䠈PRB Ⅳ䛷䛿 5 %䛜䛭䜜䛮䜜 H2O 䛻㓟䛥 䜜䛯䛣䛸䛻䛺䜛䠊 㻌 㓟⣲ཎᏊ 1 mol 䛒䛯䜚䛾䜏䛛䛡䛾ᛂ䜶䞁䝍䝹䝢䞊䛿í145 ~ í185 kJ/mol-O 䛷䛒䜚䠈㧗 ရⅣ䜋䛹⤯ᑐ್䛜䛝䛟䛺䛳䛯䠊⬡⫫᪘Ⅳ⣲䛾㒊ศ㓟䛷䛒䜛䝖䝹䜶䞁䛛䜙䛾Ᏻᜥ㤶 㓟⏕ᡂᛂ䛿䠈ᛂ䜶䞁䝍䝹䝢䞊䛜 í165 kJ/mol-O 䛷䛒䜚䠈ᮏ◊✲䛷ồ䜑䛯ప 㓟ึ 200 °C 4 20 Loy Yang Oxygen adsorption 3 CO2 2 15 10 H2O 1 5 Heat generation 0 0 5 10 15 O2 consumption [mol-O/100 mol-C] Gas production [mol/100 mol-C] Accumulation of heat generation [MJ/100 mol-C] ᮇ䛾ᛂ䜶䞁䝍䝹䝢䞊䛿䛣䜜䛸㠀ᖖ䛻㏆䛔್䛸䛺䛳䛯䠊 0 20 1. 16. LY ໗ỉᣠእෞᝲύዮႆ༏ấợỎỾἋဃ 45 200 °C 4 20 PRB 3 Heat generation 2 Oxygen adsorption 15 10 CO2 1 5 H2O 0 0 5 10 15 O2 consumption [mol-O/100 mol-C] Gas production [mol/100 mol-C] Accumulation of heat generation [MJ/100 mol-C] ჽ໗↝˯ภᣠ҄ೞನ↝ᚐଢ 0 20 200 °C 4 20 Alabama 3 15 2 10 Heat generation Oxygen adsorption 1 5 CO2 Gas production [mol/100 mol-C] Accumulation of heat generation [MJ/100 mol-C] 1. 17. PRB ໗ỉᣠእෞᝲύዮႆ༏ấợỎỾἋဃ H2O 0 0 5 10 15 O2 consumption [mol-O/100 mol-C] 0 20 1. 18. AL ໗ỉᣠእෞᝲύዮႆ༏ấợỎỾἋဃ 46 ᇹ1ᇘ ᘙ 1. 4. Ӳᚾ૰ỉ 200 °C ộỂỉᣠእෞᝲύӒࣖỺὅἑἽἦὊấợỎૺ༏ภࡇɥଞ Oxygen consumption Apparent enthalpy Adiabatic temperature increase, ¨Tad of reaction, ¨rHapp [kJ/mol-O] [°C] [mol-O/100 mol-C] Accumulation of heat generation [MJ/100 mol-C] LY 4.6 0.7 í 145 317 PRB 2.2 0.4 í 165 181 AL 1.7 0.3 í 185 182 Sample 㻌 䛣䛣䛷䠈ྛ䜺䝇䛾⏕ᡂ㔞䛾✚⟬್䜒ᅗ 1. 16 ~ 1. 18 䛻♧䛧䛯䠊H2O 1 mol 䜒䛧䛟䛿 CO2 1 mol ⏕ᡂ䛩䜛䛾䛻Ẽ┦䛾㓟⣲ཎᏊ 1 mol 䛜ᾘ㈝䛥䜜䜛䛸௬ᐃ䛩䜛䛸䠈㯮䛾◚⥺䛸⥳䛾◚ ⥺䛾㛫䛜ᅛయ⏕ᡂ≀䛸䛺䛳䛯㓟⣲䛾㔞䛻┦ᙜ䛩䜛䠊䛣䛾௬ᐃ䜢⏝䛔䜛䛸䠈200 °C 䛻䛚䛡 䜛 H2O 䛾㑅ᢥ⋡䛿䠈LY Ⅳ䛸 PRB Ⅳ䛷 1 䛸䛺䜚䠈AL Ⅳ䛷䛿 0.75 䛸䛺䛳䛯䠊AL Ⅳ䛾䛾 ⏕ᡂ≀䛿ᅛయ⏕ᡂ≀䛷䛒䛳䛯䠊䛣䛾䛣䛸䛛䜙䠈LY Ⅳ䛚䜘䜃 PRB Ⅳ䛾ᛂ䜶䞁䝍䝹䝢䞊䛿 H2O 䛜⏕ᡂ䛩䜛ᛂ䛻䛴䛔䛶䛾䜒䛾䛷䛒䜛䛜䠈AL Ⅳ䛷䛿 H2O 䛜⏕ᡂ䛩䜛ᛂ䜶䞁䝍䝹 䝢䞊䛸㓟⣲྾╔䛾ᛂ䜶䞁䝍䝹䝢䞊䜢ྜ䜟䛫䛯䜒䛾䛸䛺䜛䠊AL Ⅳ䛾ᛂ䜶䞁䝍䝹䝢䞊䛾 ⤯ᑐ್䛜䛾▼Ⅳ䛾䜒䛾䜘䜚䜒䛝䛟䛺䛳䛯䛣䛸䛛䜙䠈㓟⣲྾╔䛻䜘䜛Ⓨ⇕䛿 H2O 䛾⏕ᡂ 䜢క䛖ᛂ䛾Ⓨ⇕䜘䜚䜒䛝䛔ྍ⬟ᛶ䛜♧䛥䜜䛯䠊 㻌 ⮬↛Ⓨⅆᛶ䛾ホ౯ᣦᶆ䛸䛧䛶⪃䛘䜙䜜䜛᩿⇕ ᗘୖ᪼䜢ẚ㍑䛩䜛䛸䠈LY Ⅳ䛜᭱䜒䛝 䛟䠈8 %䛾Ỉ⣲䛜ᛂ䛧䛯䛰䛡䛻䜒䛛䛛䜟䜙䛪䠈317 °C 䜒䛾 ᗘୖ᪼䛻┦ᙜ䛩䜛⇕䛜⏕ᡂ 䛧䛯䠊䜎䛯䠈PRB Ⅳ䛚䜘䜃 AL Ⅳ䛷䛿䛔䛪䜜䜒 180 °C ⛬ᗘ䛷䛒䛳䛯䠊✀䚻䛾≀㉁䛾Ⓨⅆ Ⅼ[8]䛿䝫䝸䝇䝏䝺䞁䛷 282 °C䠈ᮌⅣ䛷 250 ~ 300 °C䠈ἾⅣ䛷 225 ~ 280 °C䠈↓↮Ⅳ䛷 440 ~ 500 °C 䛸ゝ䜟䜜䛶䛔䜛䠊䜎䛯䠈୍᪦ ᗘ䛜㧗䛟䛺䜛䛸䠈㓟䛜ಁ㐍䛥䜜䠈 ᗘ䛜䛥䜙䛻ୖ ᪼䛧䠈Ⓨⅆ䛜㉳䛣䜛䠊ᮏ◊✲䛷ồ䜑䛯 ᗘୖ᪼䛿䠈᩿⇕䜢௬ᐃ䛧䛶䛔䜛䛯䜑䠈ᐇ㝿䛾 ᗘୖ᪼䜘䜚್䛜ᑠ䛥䛟䛺䜛䛜䠈200 °C ௨ୗ䛷䛾ᛂ䛾䜏䛷䜒⮬↛Ⓨⅆ䜢ᘬ䛝㉳䛣䛩ྍ⬟ ᛶ䛜♧䛥䜜䛯䠊๓⠇䛾ᛂᶵᵓ䛸ྜ䜟䛫䜛䛸䠈⮬↛Ⓨⅆᛶ䛻䛝䛟ᐤ䛩䜛ᛂ䛿䠈⬡ ⫫᪘Ⅳ⣲䜈䛾㓟⣲྾╔䛚䜘䜃䜹䝹䝪䜻䝅䝹ᇶ䛜⏕ᡂ䛩䜛䜘䛖䛺ᛂ䛷䛒䜛䛣䛸䛜♧၀䛥 䜜䛯䠊䛧䛯䛜䛳䛶䠈䛣䛾䜘䛖䛺ᛂ䝃䜲䝖䜢ྲྀ䜚㝖䛟䛣䛸䛷⮬↛Ⓨⅆᛶ䛜ᢚไ䛥䜜䜛ྍ⬟ᛶ 47 ჽ໗↝˯ภᣠ҄ೞನ↝ᚐଢ 䛜䛒䜛䠊 1. 4. ⤖ゝ 㻌 2 ✀㢮䛾పရⅣ䛸 1 ✀㢮䛾㧗ရⅣ䜢⏝䛔䛶䠈▼Ⅳ䛾㓟㐣⛬䛻䛚䛡䜛㔜㔞ኚ䠈 䜺䝇⏕ᡂ㏿ᗘ䠈Ⓨ⇕㏿ᗘ䛚䜘䜃ᅛయ୰䛾ᐁ⬟ᇶ㔞䛾ኚ䜢 5 K/min 䛷᪼ 䛧䛺䛜䜙䛭䛾 ሙ ᐃ䛩䜛䛣䛸䛷▼Ⅳ䛾㓟ᣲື䛾ゎ᫂䜢ヨ䜏䛯䠊350 °C ௨ୗ䛷䛿 H2O 䛜ከ䛟⏕ᡂ䛧䛯 䛜䠈350 °C ௨ୖ䛷䛿ከ㔞䛾 CO2 䛜⏕ᡂ䛧䠈䜺䝇⏕ᡂ㏿ᗘ䛾ቑῶ䛻క䛔䠈Ⓨ⇕㏿ᗘ䜒ቑῶ 䛧䛯䠊㓟䛾᭱ึ䛾ẁ㝵䛻䛚䛔䛶䠈㧗ရⅣ䛷䛿⬡⫫᪘Ⅳ⣲ୖ䜈䛾㓟⣲྾╔䛻䜘䜛㔜 㔞ቑຍ䛜䜏䜙䜜䛯䛜పရⅣ䛷䛿▼Ⅳ୰䛾㓟⣲ྵ᭷⋡䛜ኚ䜟䜙䛺䛔䜎䜎 H2O ⏕ᡂ䜢క 䛖㔜㔞ῶᑡ䛜䜏䜙䜜䛯䠊ᅛయ⏕ᡂ≀䛾ᐁ⬟ᇶ㔞ኚ䛾ほᐹ䛻䜘䜚䠈350 °C ௨ୗ䛷䛿⬡⫫ ᪘Ⅳ⣲䛜ῶᑡ䛩䜛䛻క䛔䠈䜹䝹䝪䜻䝅䝹ᇶ䠈䜶䝇䝔䝹ᇶ䠈㓟↓Ỉ≀䛾㡰䛻ྵ㓟⣲ᐁ⬟ ᇶ䛜⏕ᡂ䛩䜛ᛂ䛜㐍⾜䛩䜛䛣䛸䜢᫂䜙䛛䛻䛧䛯䠊䛣䜜䜙䛛䜙䠈▼Ⅳ䛾㓟ᶵᵓ䛿䛝䛟 ศ䛡䛶⬡⫫᪘Ⅳ⣲䜈䛾㓟⣲྾╔䠈ྵ㓟⣲ᐁ⬟ᇶ䛾⏕ᡂ䠈▼Ⅳ㦵᱁䛾㓟䛾 3 ẁ㝵䛛䜙 䛺䜛䛣䛸䜢᫂䜙䛛䛻䛧䛯䠊 㻌 200 °C 䜎䛷䛾㓟⣲ᾘ㈝㔞䛸㓟⣲ཎᏊ 1 mol 䛒䛯䜚䛾ᛂ䜶䞁䝍䝹䝢䞊䜢ẚ㍑䛩䜛䛸䠈▼ Ⅳ䛾㉁䛜ప䛔㡰䛻㓟⣲ᾘ㈝㔞䛜䛝䛟䛺䜚䠈ᛂ䜶䞁䝍䝹䝢䞊䛾⤯ᑐ್䛜ᑠ䛥䛟䛺䛳䛯䠊 LY Ⅳ䛷䛿Ⅳ⣲ 100 mol 䛻ᑐ䛧䛶㓟⣲ཎᏊ 4.6 mol 䛜ᛂ䛧䛯䛰䛡䛷䜒 380 °C 䛾 ᗘୖ ᪼䛻┦ᙜ䛩䜛⇕䛜⏕ᡂ䛧䠈㧗䛔⮬↛Ⓨⅆᛶ䜢᭷䛩䜛ྍ⬟ᛶ䛜♧၀䛥䜜䛯䠊䛥䜙䛻䠈3 ✀ 㢮䛾▼Ⅳ䛾⮬↛Ⓨⅆᛶ䛿 200 °C ௨ୗ䛻䛚䛡䜛ᛂ䛻䜘䜛᩿⇕ ᗘୖ᪼䛻䜘䜚ホ౯䛷䛝 䜛䛣䛸䛜♧၀䛥䜜䛯䠊ᮏ◊✲䛷᫂䜙䛛䛻䛧䛯ప 㓟ᶵᵓ䜘䜚 200 °C ௨ୗ䛷䛿㓟⣲྾╔ 䛺䜙䜃䛻䜹䝹䝪䜻䝅䝹ᇶ䛜⏕ᡂ䛩䜛ᛂ䛜㉳䛣䜛䛯䜑䠈䛣䜜䜙䛾ᛂ䛜⮬↛Ⓨⅆᛶ䛻 䛝䛟ᐤ䛩䜛ྍ⬟ᛶ䛜♧၀䛥䜜䛯䠊⬡⫫᪘Ⅳ⣲䜔ྵ㓟⣲ᐁ⬟ᇶ䛸䛔䛳䛯㓟⣲䛸䛾ᛂᛶ 䛜㧗䛔㒊ศ䜢ྲྀ䜚㝖䛟䛣䛸䛷⮬↛Ⓨⅆᛶ䛜ᢚไ䛷䛝䜛ྍ⬟ᛶ䛜䛒䜛䛸⪃䛘䜙䜜䜛䠊 48 ᇹ1ᇘ ཧ⪃ᩥ⊩ [1] Jones, R. 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[8] ᅜ❧ኳᩥྎ⦅, ⌮⛉ᖺ⾲, ၿ䠈2014, 491. 49 Эϼྸⅻ˯ภᣠ҄ਫѣ↚ӏ↫ↈࢨ᪪ ➨ 2 ❶ ๓ฎ⌮䛜ప 㓟ᣲື䛻ཬ䜌䛩ᙳ㡪 2. 1. ⥴ゝ 㻌 ➨ 1 ❶䜘䜚䠈▼Ⅳ䛾㓟ᶵᵓ䛿䜎䛪⬡⫫᪘Ⅳ⣲ୖ䛻㓟⣲䛜྾╔䛩䜛䛣䛸䛷㐣㓟≀䜢 ⏕ᡂ䛧䠈ḟ䛻ᐁ⬟ᇶ㒊ศ䛜㓟䛥䜜䛶䜹䝹䝪䜻䝅䝹ᇶ䠈䜶䝇䝔䝹ᇶ䠈㓟↓Ỉ≀䛜⏕ᡂ䛧䠈 ᭱⤊ⓗ䛻䛿▼Ⅳయ䛾㓟䛜㐍⾜䛩䜛䛣䛸䛜᫂䜙䛛䛻䛺䛳䛯䠊䛺䛛䛷䜒ప 㓟ᶵᵓ䛾 ➨ 1 ẁ㝵䛷䛒䜛⬡⫫᪘Ⅳ⣲䛾㓟䛚䜘䜃➨ 2 ẁ㝵䛾ึᮇ䛻㉳䛣䜛䜹䝹䝪䜻䝅䝹ᇶ䛜⏕ ᡂ䛩䜛ᛂ䛰䛡䛷⮬↛Ⓨⅆ䛜㉳䛣䜛䛾䛻༑ศ䛺 ᗘୖ᪼䛜㉳䛣䜚䛖䜛䛣䛸䛜᫂䜙䛛䛻䛺䛳 䛯䠊䛴䜎䜚䠈⮬↛Ⓨⅆ䛷䛿⬡⫫᪘Ⅳ⣲ୖ䜈䛾㓟⣲྾╔䛚䜘䜃䜹䝹䝪䜻䝅䝹ᇶ䛾⏕ᡂ䛜 䛻㉳䛝䛶䛔䜛䛸⪃䛘䜙䜜䜛䠊䛣䛾䛣䛸䛛䜙䠈⬡⫫᪘Ⅳ⣲䜔ྵ㓟⣲ᐁ⬟ᇶ䛸䛔䛳䛯㓟⣲䛸 䛾ᛂᛶ䛜㧗䛔㒊ศ䜢ྲྀ䜚㝖䛟䛣䛸䛷⮬↛Ⓨⅆᛶ䛜ᢚไ䛷䛝䜛ྍ⬟ᛶ䛜♧၀䛥䜜䛯䠊䛭 䛣䛷䠈▼Ⅳ୰䛾⬡⫫᪘Ⅳ⣲䛚䜘䜃ྵ㓟⣲ᐁ⬟ᇶ䜢ྲྀ䜚㝖䛟ฎ⌮䛸䛧䛶⇕ศゎฎ⌮䛚䜘䜃 ୕ᾆ䜙䛜ᥦ䛧䛯⁐ฎ⌮[1, 2]䛻╔┠䛧䛯䠊⁐ฎ⌮䛿䠈▼Ⅳ䜢↓ᴟᛶ⁐፹୰䛷 350 °C ⛬ᗘ䛷ฎ⌮䛩䜛䛣䛸䛷ྵ㓟⣲ᐁ⬟ᇶ䜢ศゎ䞉㝖ཤ䛩䜛䜒䛾䛷䛒䜛䠊▼Ⅳ䛾྾╔Ỉ䛚䜘䜃 ศゎ䛷⏕䛨䛯Ỉ䛿ᐊ 䛻෭༷䛧䛯㝿䛻ᾮ┦䛾䜎䜎㝖ཤ䛥䜜䜛䛯䜑ᑡ䛺䛔ᢞධ䜶䝛䝹䜼 䞊䛷ᨵ㉁䜢⾜䛖䛣䛸䛜䛷䛝䜛䛸䛔䜟䜜䛶䛔䜛䠊ᮏ❶䛷䛿䠈Loy Yang Ⅳ䜢⏝䛔䛶䛣䜜䜙䛾๓ ฎ⌮䜢⾜䛳䛯䠊ཎⅣ䛸ฎ⌮Ⅳ䛾ప 㓟ᣲື䜢ほᐹ䛩䜛䛣䛸䛷䠈䛣䜜䜙䛾ฎ⌮䛜ప 㓟 ᣲື䛻䛘䜛ᙳ㡪䜢᳨ウ䛧䠈⮬↛Ⓨⅆᢚไἲ䛸䛧䛶䛾⏝ྍ⬟ᛶ䜢᳨ウ䛧䛯䠊 2. 2. ᐇ㦂 2. 2. 1. ヨᩱ䛾ㄪ〇 㻌 ヨᩱ䛿ᕞ〓Ⅳ䛾 Loy Yang Ⅳ(LY Ⅳ)䜢⏝䛔䛯䠊➨ 1 ❶䛸ྠᵝ䛻 0.2 mm ௨ୗ䛻⢊○ 50 ᇹ2ᇘ 䛧䛯䜒䛾䜢⏝䛧䛯䠊 (1) ⇕ศゎⅣ(Char)䛾ㄪ〇 㻌 ⇕ศゎⅣ䛿䠈⇕ኳ⛗(Shimadzu, TGA-50)䜢⏝䛔䛶ㄪ〇䛧䛯䠊LY Ⅳ⣙ 4.5 mg-a. r.䜢⇕ኳ ⛗୰䛷䝦䝸䜴䝮ὶ㏻㞺ᅖẼ䛾䜒䛸䠈20 K/min 䛷 400 °C 䜎䛷᪼ 䛧 30 ศ㛫ಖᣢ䛩䜛䛣䛸䛷 ㄪ〇䛧䛯䠊ㄪ〇䛧䛯ヨᩱ䛿䛩䛠䛻㓟ᐇ㦂䛻⏝䛧䛯䠊 (2) ⁐ฎ⌮Ⅳ(STC)䛾ㄪ〇 㻌 ⏝䛧䛯⨨䛾ᴫ␎ᅗ䜢ᅗ 2. 1 䛻♧䛩䠊Loy Yang Ⅳ⣙ 15 g-a. r.䛸⁐䛸䛧䛶↓ᴟᛶ⁐ ፹䛷䛒䜛 1-䝯䝏䝹䝘䝣䝍䝺䞁 200 cm3 䜢 SUS316 〇䛾ᅽຊᐜჾ(ᐜ㔞 350 cm3䠈ෆᚄ 55 mm䠈እᚄ 130 mm䠈⬗䛾㛗䛥 150 mm)䛻㎸䜏䠈ᅽຊᐜჾ୰䛾✵Ẽ䜢❅⣲䛷䝟䞊䝆䛧 䛯䛾䛱᧠ᢾ⩼䛷 300 rpm 䛷᧠ᢾ䛧䛺䛜䜙䠈⣙ 4 K/min 䛷 350 °C 䜎䛷᪼ 䛧䠈1 㛫ಖᣢ 䛧䛯䠊䛭䛾ᚋ䠈ᐊ 䜎䛷෭༷䛧䠈Ẽయᡂศ䛿䜺䝇䝞䝑䜾䛷ᅇ䛧䠈⁐䜢ྵ䜐ᾮయᡂศ䛚 䜘䜃ᅛయᡂศ䛿ᐜ㔞 300 cm3 䛾ᗏ䝣䝷䝇䝁䛻ᅇ䛧䛯䠊ᆺ䝣䝷䝇䝁ෆ䛾ヨᩱ䛿䝻䞊䝍 Autoclave 350 mL TC Pressure gauge Impeller Raw coal Furnace Valve Stainless Steel Filter 0.5 Pm 2. 1. ๋дϼྸᘺፗಒဦ 51 Эϼྸⅻ˯ภᣠ҄ਫѣ↚ӏ↫ↈࢨ᪪ 䝸䞊䜶䝞䝫䝺䞊䝍䞊(BÜCHI, 䝻䞊䝍䝸䞊䜶䝞䝫䝺䞊䝍䞊 R210)䛷 140 °C䠈2 kPa ௨ୗ䛷 ⁐䜢ศ㞳䞉㝖ཤ䛧䠈ᅛయᡂศ䜢ᚓ䛯䠊ᚓ䜙䜜䛯ᅛయᡂศ䜢⁐ฎ⌮Ⅳ(Solvent Treated Coal; STC)䛸䛧䛯䠊 2. 2. 2. ⏕ᡂ≀䛾ᛶ≧ศᯒ (1) 䜺䝇ศᯒ 㻌 ฎ⌮䛻క䛔⏕ᡂ䛧䛯䜺䝇䛿䜺䝇䜽䝻䝬䝖䜾䝷䝣(Shimadzu, GC-2014)䜢⏝䛔䛶䠈H2䠈CH4䠈 CO 䛚䜘䜃 CO2 䜢ᐃ㔞ศᯒ䛧䛯䠊䜹䝷䝮䛻䛿 Shincarbon 䜢⏝䛔䛯䠊 (2) ᕤᴗศᯒ 㻌 ᕤᴗศᯒ䛿⇕ኳ⛗(Shimadzu, TGA-50)䜢⏝䛔䠈❅⣲㞺ᅖẼୗ䛷 110 °C 䛷 30 ศ㛫ಖᣢ 䛧䠈900 °C 䜎䛷᪼ 䛧 30 ศ㛫ಖᣢ䛧䛯䠊᪼ ㏿ᗘ䛿䛩䜉䛶 10 K/min 䛷 900 °C 䛷䛾ಖᣢ ୰䛷㔜㔞䛜Ᏻᐃ䛧䛯䛸䛝䛻㞺ᅖẼ䜺䝇䜢❅⣲䛛䜙ᅽ⦰✵Ẽ䛻ษ䜚᭰䛘⇞↝䛥䛫䛯䠊 110 °C 䜎䛷䛾㔜㔞ῶᑡ䛛䜙Ỉศ㔞䜢䠈900 °C 䜎䛷䛾㔜㔞ῶᑡ䛛䜙Ⓨศ(VM; Volatile Matter)䜢䠈900 °C ⇞↝䛾㔜㔞ῶᑡ䛛䜙ᅛᐃⅣ⣲㔞(FC; Fixed Carbon)䜢䠈ᮍ⇞ศ㔜㔞 䛛䜙⅊ศ㔞(Ash)䜢䛭䜜䛮䜜ồ䜑䛯䠊䜎䛯䠈STC 䛷䛿 250 °C 䜎䛷䛾㔜㔞ῶᑡ䜘䜚ṧᏑ⁐ 㔞䜢ồ䜑䛯䠊 (3) ඖ⣲⤌ᡂ䛚䜘䜃Ⓨ⇕㔞 㻌 Ⅳ⣲䠈Ỉ⣲䠈❅⣲ྵ᭷㔞䜢 CHN corder (Yanako, MT-6)䛷 ᐃ䛧䠈㓟⣲ྵ᭷㔞䜢ᕪศ䜘 䜚ồ䜑䛯䠊ཎⅣ䛿䠈୍ᬌᐊ 䛷㟼⨨䛧䛶ᖹ⾮ྵỈ⋡䛻䛧䠈㔜㔞䜢Ᏻᐃ䛥䛫䛯䜒䛾䜢⏝䛔 52 ᇹ2ᇘ 䛯䠊ヨᩱ୰䛾Ỉศ䜔⁐䜒Ỉ⣲㔞䛚䜘䜃Ⅳ⣲㔞䛻ྵ䜎䜜䜛䛾䛷䠈 ᐃ䛻⏝䛧䛯ヨᩱ 䛾ྵỈ㔞䛚䜘䜃ṧᏑ⁐㔞䜢⏝䛔䛶⿵ṇ䛧䛯䠊 㻌 ྛヨᩱ䛾Ⓨ⇕㔞䛿(2. 1)䠈(2. 2)ᘧ䛻♧䛩 Mott-Spooner ᘧ[3]䜢⏝䛔䛶↓Ỉ↓⅊ᇶ‽䛷䛾 㧗Ⓨ⇕㔞(higher heating value; HHV, Q)䛾್䜢᥎⟬䛧䛯䠊 (1) (O) 15 %䛾䛸䛝 Q [kJ/kg] = 336.2(C) + 1419.3(H) + 94.2(S) í 145.3(O) (2. 1) (2) (O) 15 %䛾䛸䛝 Q [kJ/kg] = 336.2(C) + 1419.3(H) + 94.2(S) í [153.2í 0.720(O)](O) (2. 2) 䛣䛣䛷䠈(C)䠈(H)䠈(S)䠈(O)䛿䛭䜜䛮䜜Ⅳ⣲䠈Ỉ⣲䠈◲㯤䠈㓟⣲䛾↓Ỉ↓⅊ᇶ‽䛾㔜㔞ศ ⋡䜢ⓒศ⋡(%)䛷⾲䛧䛯䜒䛾䛷䛒䜛䠊䛩䜉䛶䛾ヨᩱ䛻䛴䛔䛶◲㯤䛿ྵ䜎䜜䛺䛔䜒䛾䛸䛧 䛯䠊 (4) Ⅳ⣲ᙧែศᕸ 㻌 䛭䜜䛮䜜䛾ヨᩱ䛾Ⅳ⣲ᙧែศᕸ䜢Ⅳ⣲᰾☢Ẽඹ㬆ศᕸ⨨(13C solid-state CP/MAS NMR, Chemagnetics, CMX-500)䛿䠈ඹ㬆࿘Ἴᩘ 500 MHz䠈䝇䝢䝙䞁䜾䝇䝢䞊䝗 17 kHz 䛷 5000 ᅇ ᐃ䛧䠈✚⟬䛧䛯䜒䛾䜢䝇䝨䜽䝖䝹䛸䛧䛶⏝䛔䛯䠊 (5) ⣽Ꮝ⾲㠃✚ 㻌 ヨᩱ䛾⣽Ꮝ⾲㠃✚(Sp)䛿䠈⮬ື䜺䝇྾╔⨨(BEL JAPAN, Belsorp 28)䜢⏝䛔䛶 25 °C䠈0 ~ 100 kPa 䛻䛚䛡䜛 CO2 ྾╔㔞䜢 ᐃ䛧䠈Medek ἲ[4]䜢⏝䛔䛶⣽Ꮝ⾲㠃✚䛻 ⟬䛧䛯䠊 53 54 4.9 78.5 74.8 LY STC LY Char 3.3 4.6 0.6 0.9 0.6 21.3 15.7 26.5 Elemental composition [wt% d. a. f.] C H N O (diff) Loy Yang (LY) 68.2 Sample 0.52 0.74 0.80 0.21 0.15 0.29 Atomic ratio [-] H/C O/C 21.3 42.0 48.1 68.1 55.8 50.2 2.3 2.3 1.7 0.74 0.81 ʊ 234.4 66.0 174.1 26.9 31.1 25.9 Proximate analysis [wt% d. b.] HHV Yield Sp VM FC Ash [kg/kg d. a. f.] [m2/g-sample] [MJ/kg] ᘙ 2. 1. ᛦᙌẲẺᚾ૰ỉࣱཞ Эϼྸⅻ˯ภᣠ҄ਫѣ↚ӏ↫ↈࢨ᪪ ᇹ2ᇘ 2. 2. 3. 㓟ᣲື䛾 ᐃ 㻌 1. 2. 1 㡯䛚䜘䜃 1. 2. 2 㡯䛸ྠᵝ䛻㔜㔞ኚ䠈䜺䝇⏕ᡂ㏿ᗘ䛚䜘䜃Ⓨ⇕㏿ᗘ䜢 5 K/min 䛷᪼ 䛧䛺䛜䜙 ᐃ䛧䛯䠊䛯䛰䛧䠈STC 䛿䛒䜙䛛䛨䜑䝦䝸䜴䝮㞺ᅖẼୗ䠈10 K/min 䛷 250 °C 䜎䛷᪼ 䛧䠈ṧᏑ䛩䜛⁐䜢䛻㝖ཤ䛧䛯䜒䛾䜢⏝䛔䛯䠊 2. 3. ⤖ᯝ䛸⪃ᐹ 2. 3. 1. ヨᩱ䛾ᛶ≧ 㻌 ྛヨᩱ䛾ඖ⣲⤌ᡂ䠈ᕤᴗศᯒ್䠈⋡䠈Ⓨ⇕㔞䛚䜘䜃⣽Ꮝ⾲㠃✚䜢⾲ 2. 1 䛻♧䛩䠊䛔 䛪䜜䛾ฎ⌮Ⅳ䜒㓟⣲ྵ᭷⋡䛚䜘䜃Ⓨศ䛜ῶᑡ䛧䠈Ⅳ⣲ྵ᭷⋡䛜ቑຍ䛧䛯䠊䜎䛯䠈⁐ ฎ⌮Ⅳ(STC)䛾䜋䛖䛜⇕ศゎฎ⌮Ⅳ(Char)䜘䜚䜒⋡䛚䜘䜃Ⓨ⇕㔞䛜䛝䛟䠈⣽Ꮝ⾲㠃✚ 䛜ᑠ䛥䛟䛺䛳䛯䠊≉䛻䠈STC 䛾ཎⅣᇶ‽䛾Ⓨ⇕㔞䛿ཎⅣ䛸䜋䜌ྠ⛬ᗘ䛷䛒䜚䠈ຠ⋡䜘䛟ᨵ Yield [kmol/100 kg-raw coal daf] 6 Tar Tar 5 H2O 4 3 H 2O STC Char 2 H2O CO2 STC Char 1 0 Tar STC Char Raw Solvent Pyro. coal treatment C Raw Solvent Pyro. coal treatment Raw Solvent Pyro. coal treatment H 2. 2. ӲϼྸỂỉΨእӓૅ 55 O Эϼྸⅻ˯ภᣠ҄ਫѣ↚ӏ↫ↈࢨ᪪ ㉁䛜⾜䜟䜜䛯䛣䛸䜢♧䛧䛶䛔䜛䠊䜺䝇⏕ᡂ≀䜢ྵ䜑䛯ඖ⣲⋡䜢ᅗ 2. 2 䛻♧䛩䠊䛣䛣䛷 H2O ⋡䛿㓟⣲䛾ᨭ䜘䜚䠈Tar ⋡䛿ᕪศ䜘䜚䛭䜜䛮䜜ィ⟬䛧䛯䠊䛣䛾ᅗ䜘䜚䠈⁐ฎ⌮ 䛷䛿䠈85 %௨ୖ䛾Ⅳ⣲䛚䜘䜃Ỉ⣲䛜 STC 䛻䛺䛳䛶䛚䜚䠈⇕ศゎἲ䛾䜘䛖䛻 Tar ⏕ᡂ䛻䜘 䜛Ⅳ⣲䛚䜘䜃Ỉ⣲䛾䝻䝇䛜ᑡ䛺䛔䛯䜑䠈Ⓨ⇕㔞䛚䜘䜃⋡䛜䛝䛟䛺䛳䛯䛸⪃䛘䜙䜜䜛䠊 㻌 䜎䛯䠈ྛヨᩱ䛾 13C-NMR 䝇䝨䜽䝖䝹䜢ᅗ 2. 3 䛻♧䛩䠊䛔䛪䜜䛾䝇䝨䜽䝖䝹䜒つ᱁䛧䛯 䜒䛾䛷䛒䜛䠊STC䠈Char 䛸䜒䛻⬡⫫᪘Ⅳ⣲䛻┦ᙜ䛩䜛䝢䞊䜽(䜿䝭䜹䝹䝅䝣䝖 0 ~ 60 ppm)䛜 ῶᑡ䛧䠈ⰾ㤶᪘Ⅳ⣲䛻┦ᙜ䛩䜛䝢䞊䜽(䜿䝭䜹䝹䝅䝣䝖 90 ~ 175 ppm)䛜ቑຍ䛧䛯䠊⬡⫫᪘ Ⅳ⣲䛻┦ᙜ䛩䜛䝢䞊䜽䛿 STC 䛸 Char 䛷䜋䛸䜣䛹ኚ䜟䜙䛺䛛䛳䛯䛜䠈ⰾ㤶᪘Ⅳ⣲䛾䝢䞊䜽 䛿 STC 䛾䜋䛖䛜䛝䛟䛺䛳䛯䠊Ⅳ⣲ᩘ䛾䛖䛱ⰾ㤶᪘Ⅳ⣲䛾ྜ䜢♧䛩ⰾ㤶᪘Ⅳ⣲ᣦᩘ (fa)䛿ཎⅣ䛷䛿 0.62 䛷䛒䛳䛯䛾䛻ᑐ䛧䠈Char 䛷䛿 0.76䠈STC 䛷䛿 0.80 䛸䛝䛟䛺䛳䛯䠊䜎 䛯䠈䜹䝹䝪䜻䝅䝹ᇶ䛾䝢䞊䜽(䜿䝭䜹䝹䝅䝣䝖 175 ~ 200 ppm)䛜䜋䛸䜣䛹䛺䛟䛺䛳䛯䠊Ⅳ⣲ ᨭ䜘䜚 STC 䛿ཎⅣ୰䛾䜋䛸䜣䛹䛾Ⅳ⣲䛜ṧ䛳䛶䛔䜛䛾䛻ᑐ䛧䠈Char 䛷䛿୍㒊䛜 Tar 䛸 -CH3 O-CH3 -CH2 Bridgehead Ar-H Ar-C Ar-O COOH 䛺䛳䛶䛔䜛䛣䛸䜒ྜ䜟䛫䜛䛸䠈ฎ⌮୰䛷 STC 䛿⬡⫫᪘Ⅳ⣲䛜ⰾ㤶᪘Ⅳ⣲䜈㌿䛧䠈Char Intensity [a.u.] LY STC 200 LY LY Char 150 100 50 Chemical Shift [ppm] 2. 3. Ӳᚾ૰ỉ໗እ࢟७Ўࠋ 56 0 -40 ᇹ2ᇘ 䛷䛿⬡⫫᪘Ⅳ⣲䛜୍㒊ⰾ㤶᪘Ⅳ⣲䜈㌿䛧䛯䛸䛸䜒䛻 Tar 䛺䛹䛾పศᏊ㔞ᡂศ䛸䛺䛳䛯 䛸⪃䛘䜙䜜䜛䠊䜎䛯䠈䛔䛪䜜䛾ฎ⌮䛻䛚䛔䛶䜒䜹䝹䝪䜻䝅䝹ᇶ䛿䜋䜌䛻ศゎ㝖ཤ䛥 䜜䛯䛣䛸䛜䜟䛛䜛䠊 2. 3. 2. ฎ⌮Ⅳ䛾ప 㓟ᣲື 㻌 STC 䛸 Char 䛾㓟㐣⛬䛻䛚䛡䜛㔜㔞ኚ䠈䜺䝇⏕ᡂ㏿ᗘ䛚䜘䜃Ⓨ⇕㏿ᗘ䜢ᅗ 2. 4 䛚 䜘䜃ᅗ 2. 5 䛻♧䛩䠊䛔䛪䜜䛾ฎ⌮Ⅳ䜒䛩䛷䛻 350 °C 䜎䛷ຍ⇕ฎ⌮䛥䜜䛶䛔䜛䛻䜒䛛䛛䜟 䜙䛪 80 °C ㏆䛛䜙㓟䛜㐍⾜䛧䛯䠊䛣䜜䛿 350 °C ⛬ᗘ䛾⇕ฎ⌮䛷䛿㓟⣲䛸䛾ᛂ䛧䜔 䛩䛔㒊ศ䜢䛻䛿ྲྀ䜚㝖䛟䛣䛸䛜䛷䛝䛺䛔䛣䛸䜢♧䛧䛶䛔䜛䠊ᛂึᮇ䛷㔜㔞ቑຍ䛜ぢ 䜙䜜䠈Char 䛾䜋䛖䛜 STC 䜘䜚䜒ቑຍ㔞䛜䛝䛟䠈Char 䛾䜋䛖䛜䜘䜚ከ䛟䛾㓟⣲䛜྾╔䛧䛯䛣 䛸䜢♧၀䛧䛶䛔䜛䠊䜎䛯䠈㔜㔞ῶᑡ䛜ጞ䜎䜛 ᗘ䛿 Char 䛾䜋䛖䛜 10 °C 䜋䛹ప䛛䛳䛯䠊䜺 䝇⏕ᡂᣲື䛿䠈STC 䛸 Char 䛿㠀ᖖ䛻ఝ䛶䛚䜚䠈᭱ึ䛾⏕ᡂ≀䛿 H2O 䛷䛒䜚 300 °C ㏆ 䛷ᑠ䛥䛺䝢䞊䜽䛜䜏䜙䜜䛯䠊䜎䛯䠈350 °C ௨ୖ䛷䛿ከ㔞䛾 CO2 䛜⏕ᡂ䛧䠈H2O 䛾⏕ᡂ㏿ ᗘ䛸 CO 䛾⏕ᡂ㏿ᗘ䛿䛚䛚䜘䛭ྠ䛨䛷䛒䛳䛯䠊䜺䝇⏕ᡂᣲື䛾㐪䛔䛿䠈350 °C ௨ୗ䛻䛚 䛡䜛 H2O ⏕ᡂ㏿ᗘ䛷䜏䜙䜜䠈H2O 䛾⏕ᡂ㛤ጞ ᗘ䛜 STC 䛷䛿 200 °C ㏆䠈Char 䛷䛿 170 °C ㏆䛷䛒䜚䠈STC 䛾䜋䛖䛜䜘䜚ከ䛟䛾 H2O 䛜⏕ᡂ䛧䛯䠊䛣䛾䛣䛸䛿䠈STC 䛾䜋䛖䛜 Char 䜘䜚䜒Ỉ⣲ྵ᭷㔞䛜䛝䛔䛣䛸䛸ྜ⮴䛩䜛䠊Ⓨ⇕㏿ᗘ䛿䜺䝇⏕ᡂ㏿ᗘ䛸ఝ䛯䜘䛖䛺ᣲ ື䜢♧䛧䠈Char 䛾䜋䛖䛜䜘䜚ప 䛷 H2O 䛜⏕ᡂ䛧䛯䜘䛖䛻 Char 䛾Ⓨ⇕㏿ᗘ䛿 STC 䜘䜚ప 䛷ṇ䛾್䜢ྲྀ䜛䜘䛖䛻䛺䛳䛯䠊䜎䛯䠈300 °C 䛻䛚䛡䜛 H2O 䛾⏕ᡂ㏿ᗘ䛿 STC 䛾䜋䛖䛜 䛝䛔䛯䜑䛻䠈300 °C 䛻䛚䛡䜛Ⓨ⇕㏿ᗘ䛾䝢䞊䜽䜒 STC 䛾䜋䛖䛜䛝䛺್䜢ྲྀ䛳䛯䠊Char 䛿ప 䛷䜘䜚ከ䛟䛾㓟⣲䛜྾╔䛩䜛䛯䜑ప 㓟ᛶ䛜㧗䛔䛰䛡䛷䛺䛟䠈䜘䜚ప䛔 ᗘ䛷 Ⓨ⇕㏿ᗘ䛜ṇ䛾್䜢ྲྀ䜛䛾䛷䠈Ⓨ⇕㔞䜒䛝䛟⮬↛Ⓨⅆᛶ䜒㧗䛔䛸⪃䛘䜙䜜䜛 㻌 䜎䛯䠈ᅗ 1. 2 䛻♧䛧䛯 LY ཎⅣ䛾㓟ᣲື䛸ẚ㍑䛩䜛䛸䠈350 °C ௨ୖ䛷䛾㓟ᣲື䛿ཎ Ⅳ䛸ฎ⌮Ⅳ䛷䜋䛸䜣䛹㐪䛔䛜ぢ䜙䜜䛪䠈350 °C ௨ୗ䛷䛾㓟ᣲື䛻䛝䛺㐪䛔䛜䜏䜙䜜 57 Эϼྸⅻ˯ภᣠ҄ਫѣ↚ӏ↫ↈࢨ᪪ 䛯䠊ᛂึᮇ䛷䛿ཎⅣ䛿㔜㔞䛜ῶᑡ䛩䜛䛜ฎ⌮Ⅳ䛷䛿㔜㔞䛜ቑຍ䛧䛶䛚䜚䠈䜎䛯䠈ཎⅣ 䛿 H2O ⏕ᡂ㏿ᗘ䛚䜘䜃 CO2 ⏕ᡂ㏿ᗘ䛜ฎ⌮Ⅳ䜘䜚䛝䛟䛺䛳䛯䠊䛣䜜䜙䜘䜚䠈๓ฎ⌮䛻䜘 1.2 400 Heat generation rate [mJ/(mg-sample•K)] Relative weight [kg/kg sample-daf] Gas formation rate [mmol/(g-sample daf•K)] 䛳䛶䠈ึᮇ䛾䜺䝇⏕ᡂᛂ䜢ᢚไ䛧䠈㓟⣲྾╔䛜䜏䜙䜜䜛䜘䛖䛻䛺䛳䛯䛸⪃䛘䜙䜜䜛䠊 LY STC 1 Weight change 300 Heat generation 0.8 0.6 200 0.4 CO2 100 0.2 0 H2O 0 100 CO 200 300 400 Temperature [°C] 500 0 600 1.2 400 LY Char 1 Weight change Heat generation 0.8 0.6 300 200 CO2 0.4 CO 100 0.2 H2O 0 Heat generation rate [mJ/(mg-sample•K)] Relative weight [kg/kg-sample daf] Gas formation rate [mmol/(g-sample daf•K)] 2. 4. LY STC ỉ˯ภᣠ҄ਫѣ 0 100 200 300 400 Temperature [°C] 500 2. 5. LY Char ỉ˯ภᣠ҄ਫѣ 58 0 600 1.1 0.3 LY STC 1.05 1 0.95 0.9 0 H2O production rate [mmol/(g-sample daf•K)] Oxygen mass fraction, nO [g/g-sample daf] Relative weight [kg/kg-sample daf] ᇹ2ᇘ Oxygen mass fraction, nO 0.1 Relative weight 0 H2O production 50 0.2 100 150 200 250 Temperature [°C] -0.1 300 2. 6. LY STC ỉӒࣖИỆấẬỦ҄٭ύH2O ဃᡮࡇấợỎ 1.1 0.3 LY Char 1.05 Oxygen mass fraction, nO 1 0.95 0.9 0 H2O production rate [mmol/(g-sample daf•K)] Oxygen mass fraction, nO [g/g-sample daf] Relative weight [kg/kg-sample daf] ˳ᣠእԃஊྙ Relative weight H2O production 50 100 150 200 250 Temperature [°C] 0.2 0.1 0 -0.1 300 2. 7. LY Char ỉӒࣖИỆấẬỦ҄٭ύH2O ဃᡮࡇấợỎ ˳ᣠእԃஊྙ 59 Эϼྸⅻ˯ภᣠ҄ਫѣ↚ӏ↫ↈࢨ᪪ 㻌 䜎䛯䠈(1. 1)ᘧ䛻䜘䜚 300 °C ௨ୗ䛾㓟㐣⛬䛻䛚䛡䜛ᅛయ⏕ᡂ≀୰䛾㓟⣲ྵ᭷⋡(nO)䠈 㔜㔞ኚ䛚䜘䜃 H2O ⏕ᡂ㏿ᗘ䜢ᅗ 2. 6 䛚䜘䜃ᅗ 2. 7 䛻♧䛩䠊ᅛయ⏕ᡂ≀䛾㔜㔞ቑຍ 䛻㓟⣲ྵ᭷⋡䛜ቑຍ䛧䛯䛣䛸䛛䜙䠈㓟⣲྾╔䛜䛻㐍⾜䛧䛯䛣䛸䛜䜟䛛䜛䠊䜎䛯䠈H2O 䛾 ⏕ᡂ㏿ᗘ䛜ቑຍ䛩䜛䛻క䛔䠈260 ~ 270 °C ௨ୖ䛷䛿䠈㔜㔞ῶᑡ䛜ぢ䜙䜜䛯䛜䠈㓟⣲ྵ᭷ ⋡䛿༢ㄪ䛻ቑຍ䛧䛶䛚䜚䠈H2O 䛾⏕ᡂ䛻ᾘ㈝䛥䜜䛯㔞䜘䜚䜒ከ䛟䛾㓟⣲䛜྾╔䛧䛯䛣䛸䛜 䜟䛛䜛䠊300 °C 䛻䛚䛔䛶 STC 䛷䛿㓟⣲ྵ᭷⋡䛜 0.17 g/g-sample 䛛䜙 0.23 g/g-sample 䛻 ቑຍ䛧䠈Char 䛷䛿㓟⣲ྵ᭷⋡䛜 0.21 g/g-sample 䛛䜙 0.30 g/g-sample 䛻ቑຍ䛧䛶䛚䜚䠈㓟 ๓䛾㔜㔞ᇶ‽䛷 STC 䛷䛿 5 wt%䠈Char 䛷䛿 9 wt%䛾㓟⣲䛜྾╔䛧䛯䛣䛸䜢♧䛧䛶䛔䜛䠊 䛴䜎䜚 Char 䛿 300 °C 䛻䛚䛔䛶 STC 䛾⣙ 2 ಸ䛾㔞䛾㓟⣲䛜྾╔䛧䛶䛚䜚䠈ప 䛻䛚䛡䜛 㓟⣲䛸䛾ᛂᛶ䛜㧗䛟䠈䛻ᅛయ୰䛻㓟⣲䛜䛸䛹䜎䜛㓟⣲྾╔䛜㉳䛣䜛䛣䛸䛜♧၀䛥䜜 䜛䠊 2. 3. 3. ๓ฎ⌮䛜ప 㓟ᶵᵓ䛻䛘䜛ᙳ㡪 㻌 ཎⅣ䛸ฎ⌮Ⅳ䛸䛾ᵓ㐀䛾㐪䛔䛿䠈ྵ㓟⣲ᐁ⬟ᇶ䛚䜘䜃⬡⫫᪘Ⅳ⣲䛾ῶᑡ䛸ⰾ㤶᪘Ⅳ ⣲䛾ቑຍ䛜ᣲ䛢䜙䜜䜛䠊๓❶䛾ప 㓟ᶵᵓ䛸↷䜙䛧ྜ䜟䛫䜛䛸䠈ཎⅣ䛸ฎ⌮Ⅳ䛸䛾ప 㓟ᣲື䛾㐪䛔䛿䠈⬡⫫᪘Ⅳ⣲䛾㔞䛚䜘䜃ྵ㓟⣲ᐁ⬟ᇶ䛾㔞䛾㐪䛔䛻㉳ᅉ䛩䜛䛸⪃䛘 䜙䜜䜛䠊䛔䛪䜜䛾ฎ⌮Ⅳ䜒⬡⫫᪘Ⅳ⣲䛾㔞䛿ῶᑡ䛧䛯䛜ྵ㓟⣲ᐁ⬟ᇶ䛾ከ䛟䛜ศゎ㝖 ཤ䛥䜜䛶䛚䜚䠈㓟䛾᭱ึᮇ䛿⬡⫫᪘Ⅳ⣲䜈䛾㓟⣲྾╔䛷䛒䜛䛸⪃䛘䜙䜜䜛䠊 㻌 ୍᪉䠈ཎⅣ䜒⬡⫫᪘Ⅳ⣲䜢᭷䛧䛶䛚䜚䠈䛭䜜䜙䜒ฎ⌮Ⅳ䛾⬡⫫᪘Ⅳ⣲䛾㓟䛸ྠ䛨 ᗘ ᇦ䛷㓟䛜㐍⾜䛩䜛䛸⪃䛘䜙䜜䜛䠊䜎䛯䠈LY Ⅳ䛷䛿䜘䜚ప 䛛䜙 H2O 䛜⏕ᡂ䛧䛯䛜䠈⬡⫫ ᪘Ⅳ⣲䛾㓟䛾䜏䛜㉳䛣䛳䛶䛔䜛䛸⪃䛘䜙䜜䜛ฎ⌮Ⅳ䛾᭱ึᮇ䛷䛿 H2O 䛜⏕ᡂ䛧䛺䛛䛳 䛯䛣䛸䛛䜙䠈LY Ⅳ䛾㓟䛾᭱ึᮇ䛻䛿⬡⫫᪘Ⅳ⣲䛾㓟௨እ䛻 H2O 䛜⏕ᡂ䛩䜛ᛂ䜒 㐍⾜䛧䛯䛸⪃䛘䜙䜜䜛䠊LY Ⅳ䛾᭱ึᮇ䛷䛾㔜㔞ῶᑡ䛸 H2O ⏕ᡂ䛿ฎ⌮Ⅳ䛷䛿ぢ䜙䜜䛺 䛛䛳䛯ᣲື䛷䛒䜛䛣䛸䛛䜙䠈ฎ⌮䛻䜘䛳䛶ྲྀ䜚㝖䛛䜜䛯㒊ศ䛾㓟ᣲື䛷䛒䜛䛸⪃䛘䜙䜜 60 ᇹ2ᇘ 䜛䠊䛴䜎䜚䠈ཎⅣ䛾᭱ึᮇ䛷䛾㓟䛻䛿ྵ㓟⣲ᐁ⬟ᇶ䛾㓟䛻䜘䜛 H2O ⏕ᡂ䜒⬡⫫᪘Ⅳ ⣲䛾㓟䛸ྠ䛻㉳䛣䛳䛶䛔䜛䛸᥎ᐹ䛥䜜䜛䠊 㻌 䜎䛯䠈Char 䛿 STC 䜘䜚䜒⬡⫫᪘Ⅳ⣲䛜ከ䛟Ꮡᅾ䛧䛶䛔䜛䛰䛡䛷䛺䛟䠈⾲ 2. 1 䛻♧䛧䛯䜘䛖 䛻⣽Ꮝ⾲㠃✚䛜䛝䛟䠈ᅛయ⾲㠃䛻䜘䜚ከ䛟䛾⬡⫫᪘Ⅳ⣲䛜Ꮡᅾ䛧䛶䛔䜛䛸⪃䛘䜙䜜䜛䠊 䛩䛺䜟䛱䠈Char 䛿 STC 䜘䜚䜒ከ䛟䛾ᛂ䝃䜲䝖䜢᭷䛧䛶䛔䜛䛸⪃䛘䜙䜜䜛䠊䛭䛾䛯䜑䠈Char 䛿㓟⣲䛸䛾ᛂᛶ䛜 STC 䜘䜚䜒䛝䛟䛺䛳䛯䛸⪃䛘䜙䜜䜛䠊 2. 3. 4. ⮬↛Ⓨⅆᛶ䛸䛾ᑐᛂ 㻌 ᅗ 2. 8 䛚䜘䜃ᅗ 2. 9 䛻 250 °C 䜎䛷䛾Ⅳ⣲ 100 mol 䛒䛯䜚䛾Ⓨ⇕㔞䛾✚⟬್䛚䜘䜃䜺䝇 ⏕ᡂ㔞䜢㓟⣲ᾘ㈝㔞䛻ᑐ䛧䛶䝥䝻䝑䝖䛧䛯䠊䛭䜜䜙䛾ᅗ䜘䜚 1. 3. 4 ⠇䛸ྠᵝ䛻ồ䜑䛯 200 °C 䛻䛚䛡䜛㓟⣲ᾘ㈝㔞䠈㓟⣲ཎᏊ1 mol 䛒䛯䜚䛾䜏䛛䛡䛾ᛂ䜶䞁䝍䝹䝢䞊䠈▼Ⅳ1 kg 䛒䛯䜚䛾᩿⇕ ᗘୖ᪼䜢⾲ 2. 2 䛻♧䛩䠊ฎ⌮Ⅳ䛾㓟⣲ᾘ㈝㔞䛿 STC 䛷 2.1 mol-O/100 mol-C䠈Char 䛷 5.6 mol-O/100 mol-C 䛸䛺䛳䛯䠊200 °C ௨ୗ䜎䛷䛻 LY ཎⅣ䛸ᛂ䛧䛯㓟 ⣲䛾㔞䛿 4.6 mol-O/100 mol-C 䛷䛒䜛䛣䛸䛛䜙䠈STC 䛿ཎⅣ䜘䜚䜒ప 䛻䛚䛡䜛㓟⣲䛸䛾 ᛂᛶ䛜ప䛟䛺䛳䛯䛜䠈Char 䛷䛿ཎⅣ䜘䜚䜒ప 䛷䛾㓟⣲䛸䛾ᛂᛶ䛜㧗䛟䛺䛳䛯䠊 㻌 200 °C 䛷䛾䜏䛛䛡䛾ᛂ䜶䞁䝍䝹䝢䞊䛿 STC 䛷í210 kJ/mol-O䠈Char 䛷䛿í258 kJ/mol-O 䛷䛒䜚䠈LY ཎⅣ䛾í145 kJ/mol-O 䜘䜚䜒䛔䛪䜜䜒⤯ᑐ್䛜䛝䛟䛺䛳䛯䠊䛣䛾䛣䛸 䛛䜙䠈H2O 䛜⏕ᡂ䛩䜛ᛂ䛻䜘䜛Ⓨ⇕䜘䜚䜒▼Ⅳୖ䛻㓟⣲䛜྾╔䛩䜛ᛂ䛾Ⓨ⇕䛾䜋䛖 䛜䛝䛔䛣䛸䛜♧၀䛥䜜䜛䠊⏕ᡂ≀䛻╔┠䛩䜛䛸䠈䛔䛪䜜䛾ヨᩱ䜒 200 °C ௨ୗ䛷䛾⏕ᡂ ≀䛿ᅛయ⏕ᡂ≀䛸 H2O 䛾䜏䛷䛒䛳䛯䠊H2O 䛾㑅ᢥ⋡䛿 LY Ⅳ䛷 1 䛷䛒䛳䛯䛾䛻ᑐ䛧䛶䠈 STC 䛷 0.29䠈Char 䛷 0.20 䛷䛒䛳䛯䠊ฎ⌮Ⅳ䛾䜏䛛䛡䛾ᛂ䜶䞁䝍䝹䝢䞊䛿 H2O ⏕ᡂ ᛂ䛾䜒䛾䛸㓟⣲྾╔䛾䜒䛾䛸䛾䛻䛺䛳䛶䛚䜚䠈䛭䛾ྜ䛿㑅ᢥ⋡䛻୍⮴䛩䜛䠊䛭䛣䛷䠈 H2O ⏕ᡂᛂ䛾䜶䞁䝍䝹䝢䞊䛜ཎⅣ䛾䜒䛾䛸ྠ䛨䛷䛒䜛䛸௬ᐃ䛩䜛䛸䠈㓟⣲྾╔䛾䜶䞁䝍 䝹䝢䞊䛿 STC 䛷䛿í237 kJ/mol-O䠈Char 䛷䛿í286 kJ/mol-O 䛷䛒䛳䛯䠊䛣䜜䜙䛾್䛿 Kaji 61 200 °C 4 20 LY STC 3 15 Heat generation 2 10 Oxygen adsorption 1 CO2 5 H 2O 0 0 Gas production [mol/100 mol-C] Accumulation of heat generation [MJ/100 mol-C] Эϼྸⅻ˯ภᣠ҄ਫѣ↚ӏ↫ↈࢨ᪪ 0 5 10 15 20 O2 consumption [mol-O/100 mol-C] 200 °C 4 20 LY Char Heat generation 3 15 2 10 Oxygen adsorption 1 CO2 5 H2 O 0 0 Gas production [mol/100 mol-C] Accumulation of heat generation [MJ/100 mol-C] 2. 8. LY STC ỉᣠእෞᝲύዮႆ༏ấợỎỾἋဃ 0 5 10 15 20 O2 consumption [mol-O/100 mol-C] 2. 9. LY Char ỉᣠእෞᝲύዮႆ༏ấợỎỾἋဃ 䜙 [5] 䛜ሗ࿌䛧䛶䛔䜛㓟⣲྾╔䛾ᛂ䜶䞁䝍䝹䝢䞊䛷䛒䜛í157 ~ í188 kJ/mol-O 䜔 Bradbury 䜙[6]䛜ሗ࿌䛧䛶䛔䜛㓟⣲྾╔䛾ᛂ䜶䞁䝍䝹䝢䞊䛷䛒䜛 í146 ~ í230 kJ/mol-O 䜘䜚䜒⤯ᑐ್䛜䛝䛔䠊䜎䛯䠈䜾䝷䝣䜯䜲䝖䛾㓟(C + O2 ĺ CO2)䛾ᛂ䜶䞁䝍䝹䝢䞊 62 ᇹ2ᇘ ᘙ 2. 2. Ӳᚾ૰ỉ 200 °C ộỂỉᣠእෞᝲύӒࣖỺὅἑἽἦὊấợỎૺ༏ภࡇɥଞ [mol-O/100 mol-C] Accumulation of heat generation [MJ/100 mol-C] LY 4.6 0.7 í 145 317 LY STC 2.1 0.4 í 210 120 LY Char 5.6 1.1 í 258 480 Oxygen consumption Sample Apparent enthalpy Adiabatic temperature of reaction, ¨rHapp increase, ¨Tad [kJ/mol-O] [°C] 䛷䛒䜛í197 kJ/mol-O 䜔䠈䝯䝍䞁䛾⇞↝ᛂ(CH4 + 2O2 ĺ CO2 + 2H2O)䛾ᛂ䜶䞁 䝍䝹䝢䞊䛷䛒䜛í223 kJ/mol-O 䜘䜚䜒⤯ᑐ್䛜䛝䛔್䜢ྲྀ䛳䛶䛔䜛䠊ᛂ≀䛜ྠ䛨ሙྜ䠈 ᛂ䜶䞁䝍䝹䝢䞊䛾⤯ᑐ್䛜䛝䛟䛺䜛䜋䛹䠈⏕ᡂ≀䛿䜘䜚Ᏻᐃ䛺ᵓ㐀䜢స䜛䛸⪃䛘䜙䜜 䜛䠊䛭䛾䛯䜑䠈䛭䛾㒊ศ䛾䛥䜙䛺䜛㓟䛿⏕䛨䛻䛟䛟䛺䜛䛸⪃䛘䜙䜜䜛䠊 Char 䛾㓟⣲྾╔ 䛾ᛂ䜶䞁䝍䝹䝢䞊䛾⤯ᑐ್䛿㠀ᖖ䛻䛝䛺್䜢ྲྀ䛳䛶䛔䜛䛯䜑䠈Char 䛻྾╔䛧䛯㓟⣲ 䛿Ᏻᐃ䛺ᵓ㐀䜢ྲྀ䜚䠈䛥䜙䛺䜛㓟䠈䛯䛸䛘䜀 H2O 䛜⏕ᡂ䛩䜛䜘䛖䛺ᛂ䛿⏕䛨䛻䛟䛟䛺䜛 䛸⪃䛘䜙䜜䜛䠊 㻌 䛣䛣䛷䠈ྠ䛨䜘䛖䛺ᛂ䛜㉳䛣䜛ሙྜ䛻䛿䛭䜜䜙䛾άᛶ䜶䝛䝹䜼䞊䛜䛒䜎䜚ኚ䜟䜙䛺䛔 䛾䛷䠈ᛂ㏿ᗘ䛾ẚ䛿 ᗘ䛻䜘䛳䛶ኚ䛫䛪䠈᪼ ㏿ᗘ䜔᩿⇕ ᗘୖ᪼䛾ィ⟬䛻⏝䛔 䜛ᛂ䛾 ᗘ⠊ᅖ䛿᩿⇕ ᗘୖ᪼䛾ᑠ䛻䛿䛒䜎䜚ᙳ㡪䜢ཬ䜌䛥䛺䛔䛸⪃䛘䜙䜜䜛䠊䛧 䛛䛧䠈ཎⅣ䛸ฎ⌮Ⅳ䛸䛷䛿䠈ప 㓟䛾ึᮇ䛷㉳䛣䜛ᛂ䛜␗䛺䜛䛯䜑䠈䛭䜜䜙䛾ᛂ䛾 άᛶ䜶䝛䝹䜼䞊䛜␗䛺䜚䠈ᛂ㏿ᗘ䛾ẚ䛜 ᗘ䛻䜘䛳䛶ኚ䛩䜛䛯䜑䠈᪼ ㏿ᗘ䜢ኚ 䛥䛫䛯㝿䛻䠈᩿⇕ ᗘୖ᪼䛾ᑠ㛵ಀ䛜ኚ䜟䜛䛚䛭䜜䛜䛒䜛䠊䛭䛾䛯䜑䠈ཎⅣ䛸ฎ⌮ Ⅳ䛸䛾⮬↛Ⓨⅆᛶ䛾ᑠ䛿䠈᩿⇕ ᗘୖ᪼䛜┠Ᏻ䛸䛺䜚䛖䜛䛜䠈䜘䜚ཝᐦ䛻ẚ㍑䛩䜛䛻䛿 ప 䛷䛾Ⓨ⇕㏿ᗘ䠈䛩䛺䜟䛱㓟䛾ึᮇ䛻㉳䛝䛶䛔䜛ᛂ䛾ప 䛻䛚䛡䜛ᛂ㏿ᗘ䛜 㔜せ䛻䛺䜛䛸⪃䛘䜙䜜䜛䠊 㻌 200 °C ௨ୗ䛷䛾ヨᩱ䛾᩿⇕ ᗘୖ᪼䛿䠈STC 䛿 120 °C 䛸䠈Char 䛾 480 °C 䜔ཎⅣ䛾 317 °C 䜘䜚䜒ⴭ䛧䛟ᑠ䛥䛺್䜢䛸䛳䛯䠊䛣䛾䛣䛸䛛䜙 STC 䛿ཎⅣ䜔 Char 䜘䜚䜒⮬↛Ⓨⅆᛶ䛜 ప䛔䛸ᛮ䜟䜜䜛䠊䛣䜜䛿 STC 䛾⣽Ꮝ⾲㠃✚䛜ᑠ䛥䛟㓟⣲䛾䜰䜽䝉䝇䛜ᢚไ䛥䜜䛯䛯䜑䛻䠈 ཎⅣ䜔 Char 䜘䜚䜒㓟⣲྾╔㔞䛜ᑠ䛥䛟䛺䛳䛯䛯䜑䛷䛒䜛䛸⪃䛘䜙䜜䜛䠊䛣䛾䛣䛸䛛䜙䠈⮬↛ 63 Эϼྸⅻ˯ภᣠ҄ਫѣ↚ӏ↫ↈࢨ᪪ Ⓨⅆᢚไ䛻䛿⬡⫫᪘Ⅳ⣲䜔ྵ㓟⣲ᐁ⬟ᇶ䛸䛔䛳䛯㓟⣲䛸ᛂ䛧䜔䛩䛔㒊ศ䜢ྲྀ䜚㝖䛟 䛰䛡䛷䛺䛟䠈㓟⣲䛾䜰䜽䝉䝇䛭䛾䜒䛾䜢ᢚ䛘䜛䛣䛸䛜᭷ຠ䛷䛒䜛䛣䛸䛜♧䛥䜜䛯䠊䛥䜙䛻䠈୕ ᾆ䜙䛻䜘䛳䛶ᥦ䛥䜜䛯⁐ฎ⌮ἲ䛿⮬↛Ⓨⅆᢚไἲ䛸䛧䛶᭷ຠ䛷䛒䜛ྍ⬟ᛶ䛜♧၀䛥 䜜䛯䠊 2. 4. ⤖ゝ 㻌 㓟⣲䛸䛾ᛂᛶ䛜㧗䛔⬡⫫᪘Ⅳ⣲䛚䜘䜃ྵ㓟⣲ᐁ⬟ᇶ䜢ྲྀ䜚㝖䛟䛣䛸䛻䜘䜛⮬↛Ⓨⅆ ᢚไ䜢┠ᣦ䛧䠈⁐ฎ⌮䛚䜘䜃⇕ศゎฎ⌮䛻䜘䜛๓ฎ⌮䛜ప 㓟ᣲື䛻䛚䜘䜌䛩ᙳ 㡪䜢᳨ウ䛧䛯䠊䛔䛪䜜䛾ฎ⌮Ⅳ䜒⬡⫫᪘Ⅳ⣲䛚䜘䜃ྵ㓟⣲ᐁ⬟ᇶ䛜ῶᑡ䛧䠈⁐ฎ⌮ Ⅳ䛷䛿⣽Ꮝ⾲㠃✚䛜ῶᑡ䛧䠈⇕ศゎฎ⌮Ⅳ䛷䛿⣽Ꮝ⾲㠃✚䛜ቑຍ䛧䛯䠊 㻌 䛔䛪䜜䛾ฎ⌮Ⅳ䜒ఝ䛯䜘䛖䛺ప 㓟ᣲື䜢♧䛧䠈ึᮇẁ㝵䛷䛿⬡⫫᪘Ⅳ⣲䜈䛾㓟⣲ ྾╔䛻䜘䜛㔜㔞ቑຍ䛜䜏䜙䜜䛯䠊STC 䛸ẚ㍑䛧䛶䠈Char 䛿㔜㔞ቑຍ㔞䛜䛝䛟䠈䜎䛯䜘䜚 ప 䛷 H2O 䛜⏕ᡂ䛧䛯䛣䛸䛛䜙 STC 䜘䜚䜒ప 䛻䛚䛡䜛㓟⣲䛸䛾ᛂᛶ䛜㧗䛔䛣䛸䛜♧၀ 䛥䜜䛯䠊䜎䛯 Char 䛾䜋䛖䛜䜘䜚ప 䛛䜙Ⓨ⇕㏿ᗘ䛜ṇ䛾್䛻䛺䛳䛯䠊ཎⅣ䛾ప 㓟ᣲ ື䛸ẚ㍑䛩䜛䛸䠈ཎⅣ䛾䜋䛖䛜䜘䜚ప 䛛䜙 H2O 䛜⏕ᡂ䛧䛶䛚䜚䠈ཎⅣ䛾ప 㓟䛾᭱ึ ᮇ䛻䛿ྵ㓟⣲ᐁ⬟ᇶ䛾㓟䛻䜘䜛 H2O 䛾⏕ᡂ䛸⬡⫫᪘Ⅳ⣲ୖ䜈䛾㓟⣲䛾྾╔䛜䛒䜛ྍ ⬟ᛶ䛜♧၀䛥䜜䛯䠊 㻌 ཎⅣ䛚䜘䜃ฎ⌮Ⅳ䛾⮬↛Ⓨⅆᛶ䜢ẚ㍑䛩䜛䛸䠈STC 䛿ཎⅣ䜘䜚䜒⮬↛Ⓨⅆᛶ䛜ⴭ䛧䛟 ప䛟䛺䛳䛯䠊䛣䜜䛿䠈⬡⫫᪘Ⅳ⣲䛾㔞䛸⣽Ꮝ⾲㠃✚䛾ᙳ㡪䛷䛒䜛䛸⪃䛘䜙䜜䜛䠊STC 䛿⬡ ⫫᪘㓟⣲䛜䜘䜚ᑡ䛺䛟䠈⣽Ꮝ⾲㠃✚䛜᭱䜒ᑠ䛥䛔䛯䜑䛻㓟⣲䛾䜰䜽䝉䝇䛜ᢚไ䛥䜜ప 㓟ᛶ䛜ᑠ䛥䛟䛺䛳䛯䛾䛷䠈ᛂ䜶䞁䝍䝹䝢䞊䛾⤯ᑐ್䛜ཎⅣ䜘䜚䛝䛔䛻䜒䛛䛛䜟䜙䛪䠈 ⮬↛Ⓨⅆᛶ䛜ཎⅣ䜘䜚ᑠ䛥䛟䛺䛳䛯䛸⪃䛘䜙䜜䜛䠊௨ୖ䜘䜚䠈⮬↛Ⓨⅆᛶ䛾ᢚไ䛻䛿㓟⣲ 䛸䛾ᛂᛶ䛾㧗䛔㒊ศ䜢ྲྀ䜚㝖䛟䛰䛡䛷䛺䛟䠈㓟⣲䛾䜰䜽䝉䝇䜢ᢚไ䛩䜛䛣䛸䛜㔜せ䛷䛒䜚䠈 ⁐ฎ⌮䛿䛭䜜䜙䜢ᐇ⌧䛧䠈⮬↛Ⓨⅆᢚไฎ⌮䛸䛧䛶᭷ຠ䛷䛒䜛ྍ⬟ᛶ䛜♧䛥䜜䛯䠊 64 ᇹ2ᇘ ཧ⪃ᩥ⊩ [1] Miura, K., Hasegawa, Y., Ashida, R., Upgrading of brown coal using solvent extraction at high temperature, American Chemical Society Division of Fuel Chemistry, 2009, 54 2, 870871. 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W., Shafizadeh, F., Role of oxygen chemisorption in low-temperature ignition of cellulose, Combustion and Flame, 1980, 37, 8589. 65 ๋дϼྸඥ↝Ꮾ൦∝ોឋ⇁ˤⅵᐯႆ້৮Сඥ↗ↆ↕↝МဇӧᏡࣱ ➨ 3 ❶㻌 ⁐ฎ⌮ἲ䛾⬺Ỉ䞉ᨵ㉁䜢క䛖⮬↛Ⓨⅆᢚไἲ䛸䛧䛶䛾 ⏝ྍ⬟ᛶ 3. 1. ⥴ゝ 㻌 పရⅣ䛾᭷ຠ⏝䛾䛯䜑䛻䛿䠈ᅗ 0. 1 䛻♧䛧䛯䜘䛖䛻⮬↛Ⓨⅆᛶ䛾ᢚไ䛰䛡䛷䛺䛟 ⬺Ỉ䛜ᚲせྍḞ䛷䛒䜛(Level 1)䠊䜎䛯䠈䜶䝛䝹䜼䞊※䛸䛧䛶䛾⏝䜢⪃䛘䛯ሙྜ䠈ᨵ㉁ ฎ⌮䛻䜘䜛Ⓨ⇕㔞䛾ྥୖ䛜ồ䜑䜙䜜䜛(Level 2)䠊䛥䜙䛻ᕤᴗⓗ䛻⏝䛩䜛䛯䜑䛻䛿⮬↛ Ⓨⅆᢚไฎ⌮䠈⬺Ỉฎ⌮䠈䛚䜘䜃ᨵ㉁ฎ⌮䛿䜶䝛䝹䜼䞊䝻䝇䛜ᑡ䛺䛔ฎ⌮䛷䛒䜛䛣䛸䛜 ᮃ䜎䜜䜛䠊๓❶䜘䜚 Loy Yang Ⅳ䜢୕ᾆ䜙䛾ᥦ䛧䛯⁐ฎ⌮ἲ[1, 2]䜢⏝䛔䜛䛣䛸䛷ᚓ䜙䜜 䛯⁐ฎ⌮Ⅳ䛿⮬↛Ⓨⅆᛶ䛜ᢚไ䛥䜜䛶䛚䜚䠈⮬↛Ⓨⅆᢚไἲ䛸䛧䛶⁐ฎ⌮䛜᭷ຠ 䛷䛒䜛ྍ⬟ᛶ䛜♧၀䛥䜜䛯䠊䜎䛯䠈ᚓ䜙䜜䛯ฎ⌮Ⅳ䛿ຠ⋡ⓗ䛻⬺Ỉ䞉ᨵ㉁䛥䜜䠈పရ Ⅳ䛾᭷ຠ⏝ἲ䛸䛧䛶ᮇᚅ䛥䜜䜛䠊䛣䛾⁐ฎ⌮䛜ᐇ⏝ⓗ䛻⏝䛥䜜䜛䛻䛿䠈⬺Ỉ䞉ᨵ㉁ 䛚䜘䜃⮬↛Ⓨⅆᛶ䛾ᢚไ䛜ྠ䛻ᐇ⌧䛷䛝䜛䛣䛸䛸䠈ᖜᗈ䛔ཎᩱ䛻ᑐ䛧䛶㐺⏝ྍ⬟䛷䛒 䜛䛣䛸䛾 2 Ⅼ䛜㔜せ䛷䛒䜛䠊 㻌 䛭䛣䛷䠈ᮏ❶䛷䛿⁐ฎ⌮ἲ䛜 Level 2 䛻┦ᙜ䛩䜛䜘䛖䛺పရⅣ䛾᭷ຠ⏝ἲ䛷䛒䜛 䛛䜢䝞䜲䜸䝬䝇䛛䜙℡㟷Ⅳ䜎䛷䛾Ⅳ⣲㈨※䛻ᑐ䛧䛶ฎ⌮䜢䛩䛣䛸䛷᳨ウ䛧䛯䠊䜎䛯䠈⇕ ศゎฎ⌮䛸䛾ẚ㍑䛛䜙⁐䜢⏝䛔䜛䛣䛸䛻䜘䜛ᛂ䛾㐪䛔䜢᳨ウ䛧䛯䠊䛥䜙䛻䠈⁐ฎ⌮ ᘙ 3. 1. ဇẟẺᚾ૰ỉࣱཞ Sample (Abbrev.) Elemental composition [wt% d. a. f.] C H N O (diff) White Haven (WH) 81.5 5.4 1.9 11.2 28.8 64.9 6.3 3.8 33.4 Tanito Harum (TH) 73.1 5.2 1.5 20.2 39.4 51.3 9.3 11.9 29.6 Adaro (AD) 70.0 5.2 1.7 23.2 44.8 52.5 2.7 16.6 27.7 Pendopo (PD) 68.5 5.0 1.0 25.5 53.8 37.5 8.7 58.8 26.7 Loy Yang (LY) 68.2 4.6 0.6 26.5 48.1 50.2 1.7 57.8 25.9 Belarus Peat (BP) 58.9 4.9 3.3 32.9 53.3 35.1 11.7 30.2 22.5 Rice Straw (RS) 46.5 5.6 0.4 47.5 68.9 18.1 13.0 5.7 18.0 66 Proximate analysis [wt% d. b.] Moisture HHV VM FC Ash [wt% a. r.] [MJ/kg] ᇹ3ᇘ ヨᩱ䜢 3 䛴䛾䝣䝷䜽䝅䝵䞁䛻ศ㞳䛧䠈⁐ฎ⌮ヨᩱ䛾ᛶ≧䜢ヲ⣽䛻᳨ウ䛧䛯䠊⏝䛔䛯ヨᩱ 䛾䛖䛱䠈2 ✀㢮䛾〓Ⅳ䛻䛴䛔䛶䛿⁐ฎ⌮Ⅳ䛾㓟⣲྾╔ᣲື䜢 ᐃ䛧䛯䠊 3. 2. ᐇ㦂 3. 2. 1. ヨᩱ䛾ㄪ〇 (1) ⏝䛧䛯ヨᩱ 㻌 ⏝䛧䛯ヨᩱ䛿䠈℡㟷Ⅳ䛷䛒䜛䜸䞊䝇䝖䝷䝸䜰⏘䛾 White Heaven Ⅳ(WH)䠈ள℡㟷Ⅳ䛷 䛒䜛䜲䞁䝗䝛䝅䜰⏘䛾 Tanito Harum Ⅳ(TH)䛚䜘䜃 Adaro Ⅳ(AD)䛾 2 ✀㢮䠈〓Ⅳ䛷䛒䜛䜲 䞁䝗䝛䝅䜰⏘䛾 Pendopo Ⅳ(PD)䛚䜘䜃䜸䞊䝇䝖䝷䝸䜰⏘䛾 Loy Yang Ⅳ(LY)䛾 2 ✀㢮䠈Ἶ Ⅳ䛷䛒䜛䝧䝷䝹䞊䝅⏘䛾 Belarus Peat (BP)䠈䛚䜘䜃䝞䜲䜸䝬䝇䛷䛒䜛᪥ᮏ⏘䛾✄䜟䜙(RS) 䛾 9 ✀㢮䛷䛒䜛䠊ྛヨᩱ䛾ᛶ≧䜢⾲ 3. 1 䛻♧䛩䠊Ⅳ⣲ྵ᭷⋡䛿 81.5 ~ 46.5 wt%䠈㓟⣲ྵ ᭷⋡䛿 11.2 ~ 47.5 wt%䛸ᖜᗈ䛔್䜢䛸䛳䛶䛔䜛䠊䜎䛯䠈〓Ⅳ䛿㠀ᖖ䛻㧗䛔ྵỈ⋡䜢᭷䛧 䛶䛔䜛䠊 (2) ⁐ฎ⌮ 㻌 ⁐ฎ⌮䛻⏝䛔䛯⨨ᴫ␎䜢ᅗ 3. 1 䛻♧䛩䠊2. 2. 1 㡯(2)䛸ྠᵝ䛻䠈ヨᩱ⣙ 15 g-a. r.䜢 1-䝯䝏䝹䝘䝣䝍䝺䞁 200 cm3 ୰䛷 350 °C 䛻䛚䛔䛶 1 㛫ฎ⌮䛩䜛䛣䛸䛷⁐ฎ⌮ヨᩱ (Solvent Treated Product; STP)䜢ㄪ〇䛧䛯䠊䜎䛯䠈STP 䛾ᛶ≧䜢ヲ⣽䛻᳨ウ䛩䜛䛯䜑䠈 350 °C 䛷 1 㛫ಖᣢ䛧䛯䛾䛱䛻䠈ᅽຊᐜჾୗ㒊䛾䝞䝹䝤䜢㛤䛝䠈┠㛤䛝 0.5 mm 䛾䝣䜱 䝹䝍䞊䛻䜘䜚ฎ⌮ ᗘ䛷⁐䛻⁐䛡䛶䛔䜛ᡂศ䛸⁐䛻⁐䛺ᡂศ䛻ℐ㐣ศ㞳䛧䛯䠊⁐ 䛻⁐䛡䛶䛔䜛ᡂศ䛿ᐊ 䛻෭༷ᚋ䠈྾ᘬℐ㐣䜢⏝䛔䛶ᐊ 䛻䛚䛔䛶⁐䛻⁐䛡䛶䛔 67 ๋дϼྸඥ↝Ꮾ൦∝ોឋ⇁ˤⅵᐯႆ້৮Сඥ↗ↆ↕↝МဇӧᏡࣱ 䜛ᡂศ䛸ᯒฟ䛩䜛ᡂศ䛻ศ㞳䛧䠈ᐊ 䛷䜒⁐䛻⁐䛡䛶䛔䜛ᡂศ䛿䝻䞊䝍䝸䞊䜶䝞䝫䝺 䞊䝍䞊䛷 140 °C䠈2 kPa ௨ୗ䛷⁐䛸ศ㞳䛧䛯䠊ฎ⌮ ᗘ䛷⁐䛻⁐䛺ᡂศ䜢 Residue䠈 ฎ⌮ ᗘ䛷䛿⁐ྍ⁐䛰䛜ᐊ 䛷ᯒฟ䛩䜛ᡂศ䜢 Deposit䠈䛚䜘䜃ᐊ 䛷䜒⁐ྍ⁐䛺 ᡂศ䜢 Soluble 䛸䜆䠊STP 䛿 Residue䠈Deposit䠈Soluble 䛾ΰྜ≀䛸⪃䛘䜛䛣䛸䛜䛷䛝䜛䠊 Autoclave 350 mL TC Pressure gauge Impeller Residue Furnace Valve N2 Stainless Steel Filter 0.5 Pm Gas Soluble Deposit Reservoir 350 mL 3. 1. ๋дϼྸ↚ဇⅳᘺፗಒဦ (3) ⇕ศゎฎ⌮ 㻌 ⁐䜢⏝䛔䛯ຠᯝ䜢☜ㄆ䛩䜛䛯䜑䛻ẚ㍑ᑐ㇟䛸䛧䛶ྠ䛨ヨᩱ䛾䝞䝑䝏⇕ศゎฎ⌮䜢⾜ 䛳䛯䠊⇕ศゎฎ⌮䛻䛿ᅗ 3. 2 䛻♧䛩䜘䛖䛻 SUS 〇䛾 1/2 䜲䞁䝏⟶(㛗䛥 10 cm)䛷స〇䛧 䛯ᛂჾ䜢⏝䛔䛯䠊ᛂჾ䛻ヨᩱ⣙ 2 g-a. r.䜢ሸ䛧䠈ᛂჾෆ❅⣲䛷䝟䞊䝆䛧䛯䛾䛱 䛻䠈ὶື◁ᾎ䛻ධ䜜䠈350 °C 䜎䛷᪼ 䛧䠈1 㛫ฎ⌮䛧䛯䠊ฎ⌮ᚋ䛾ᛂჾ䛿Ỉ䜢䛯䜑 䛯䝞䜿䝒䛻ධ䜜䛶ᛴ෭䛧䠈⏕ᡂ䜺䝇䛿䜺䝇䝞䝑䜾䛻ᅇ䛩䜛䛸䛸䜒䛻䠈ᅛయ⏕ᡂ≀䛷䛒䜛 68 ᇹ3ᇘ 3. 2. ༏Ўᚐϼྸ↚ဇⅳᘺፗಒဦ ⇕ศゎⅣ(Batch Char)䜢ᅇ䛧䛯䠊 3. 2. 2. ⏕ᡂ≀䛾ᛶ≧ศᯒ 㻌 ๓❶ 2. 2. 2 㡯䛸ྠᵝ䛻⏕ᡂ≀䛾䜺䝇⏕ᡂ≀䠈ᕤᴗศᯒ್䠈ඖ⣲⤌ᡂ䠈Ⅳ⣲ᙧែศᕸ䛚 䜘䜃⣽Ꮝ⾲㠃✚䜢 ᐃ䛧䛯䠊䜎䛯䠈ඖ⣲⤌ᡂ䛛䜙(2. 1)䛚䜘䜃(2. 2)ᘧ䛻䜘䜚Ⓨ⇕㔞䜢᥎⟬ 䛧䛯䠊 㻌 䛥䜙䛻䠈ᅛయ⏕ᡂ≀䛾 FT-IR 䝇䝨䜽䝖䝹䜢 KBr 㘄ἲ䛷 ᐃ䛧䛯䠊⢊ᮎ≧ KBr ヨᩱ (120-63380䠈䜻䝅䝎Ꮫ)⣙ 500 mg 䛻ヨᩱ⣙2.5 mg-d. a. f.䜢ΰ䛬䛶䠈ங㖊䛷ヨᩱ䜢⣽䛛 䛟䠈ᆒ୍䛻䛺䜛䜘䛖䛻ΰྜ䛧䠈┿✵⇱ᶵ䛷┿✵୰䠈80 °C 䛷 30 ศ㛫⇱䛧䛯䠊⇱ᚋ䛾 ヨᩱ䜢 200 mg 㔞䜚䛸䜚䠈Ἔᅽᘧ KBr 㘄ᡂᆺჾ(200-32010䠈ᓥὠ GLC)䛻䜘䜚䠈20 MPa 䛷 10 ศ㛫ಖᣢ䛧䛯䛾䛱 64 MPa 䛷 30 ศ㛫ಖᣢ䛧䠈䝨䝺䝑䝖䜢స〇䛧䛯䠊 1000 ~ 4000 cm 䌦㻝 䛾㏱㐣䝇䝨䜽䝖䝹䜢 64 ᅇ ᐃ䛧䠈䛭䛾ᖹᆒ䜢ヨᩱ䛾䝇䝨䜽䝖䝹䛸䛧䛯䠊ᚓ䜙䜜䛯䝇䝨䜽䝖 䝹䛿 Beer 䛾ᘧ䛻䜘䜚䠈྾䝇䝨䜽䝖䝹䛻ኚ䛧䛯䠊 69 ๋дϼྸඥ↝Ꮾ൦∝ોឋ⇁ˤⅵᐯႆ້৮Сඥ↗ↆ↕↝МဇӧᏡࣱ 3. 2. 3. 65 °C 䛻䛚䛡䜛㓟⣲྾╔ᣲື 㻌 2 ✀㢮䛾〓Ⅳ䠈LY Ⅳ䛚䜘䜃 PRB Ⅳ䛾ཎⅣ䠈⁐ฎ⌮ヨᩱ䛚䜘䜃⇕ኳ⛗୰䝦䝸䜴䝮㞺 ᅖẼୗ䛷 350 °C 䛷 1 㛫⇕ฎ⌮䛧䛯⇕ศゎⅣ(Char)䛻䛴䛔䛶ప 䛻䛚䛡䜛㓟⣲䛸䛾 ᛂᛶ䜢ホ౯䛧䛯䠊Soluble 䛿ప 䛷Ⓨ䛩䜛䛯䜑䠈๓❶䛾䜘䛖䛺᪼ 㐣⛬䛷䛿䠈㓟䛸䛸䜒 䛻Ⓨ䜒㉳䛣䜚䠈㓟ᣲື䛾䜏䛾 ᐃ䛜ᅔ㞴䛸䛺䜛䠊䛭䛣䛷䠈➼ 㐣⛬䛻䛚䛡䜛㓟ᣲື 䜘䜚ప 㓟ᛶ䜢ホ౯䛧䛯䠊 ᐃ䛻䛿䠈1. 2. 1 㡯䛾ᅗ 1. 1 䛻♧䛧䛯䝬䜲䜽䝻䜺䝇䜽䝻䝬䝖䜾 䝷䝣䜢┤⤖䛧䛯⇕ኳ⛗䜢⏝䛔䛯䠊ప 㓟ᛶ䛾ホ౯䛻⏝䛔䛯 ᗘ䝥䝻䝣䜯䜲䝹䜢ᅗ 3. 3 䛻♧䛩䠊ヨᩱ⣙ 10 mg-d. a. f.䜢⇕ኳ⛗䛻ධ䜜䠈䝦䝸䜴䝮ὶ㏻㞺ᅖẼ䛾䜒䛸䠈ཎᩱ䛚䜘䜃 Char 䛿 20 K/min 䛷 110 °C 䜎䛷᪼ 䛧 30 ศ㛫ಖᣢ䛩䜛䛣䛸䛷Ỉศ䜢䠈⁐ฎ⌮䜢䛧䛯 ヨᩱ䛿 20 K/min 䛷 250 °C 䜎䛷᪼ 䛧ಖᣢ䛺䛧䛷ṧᏑ䛩䜛⁐䜢䛭䜜䛮䜜ྲྀ䜚㝖䛔䛯䠊 䛭䛾ᚋ䠈65 °C 䜎䛷෭༷䛧䠈 ᗘ䛜Ᏻᐃ䛧䛯䛾䛱䠈㞺ᅖẼ䜺䝇䜢䝦䝸䜴䝮䛛䜙ᶍᨃ✵Ẽ (22 % O2/He)䛻ษ䜚᭰䛘䠈2 㛫ಖᣢ䛧䛯䠊⏕ᡂ䜺䝇䛿 80 ⛊㛫㝸䛷 ᐃ䛧䠈MS-5A 䛸 PPQ 䛾䜹䝷䝮䜢⏝䛔䛶 H2䠈CH4䠈CO䠈CO2 䛚䜘䜃 H2O 䜢ᐃ㔞䛧䛯䠊65 °C 䛷䛾ಖᣢᮇ㛫䛻䛚䛔 䛶㔜㔞ኚ䛚䜘䜃䜺䝇⏕ᡂ㔞䛛䜙ṇ䛾㓟⣲྾╔㔞(qO)䛾⤒ኚ䜢ồ䜑䛯䠊ᮏ❶䛷 ⏝䛔䜛㓟⣲྾╔㔞 qO 䛸➨ 1 ❶䛚䜘䜃➨ 2 ❶䛷⏝䛔䛯㓟⣲ྵ᭷⋡ nO 䛾㛫䛻䛿௨ୗ䛾㛵 ಀ䛜ᡂ䜚❧䛴䠊 1.2 1 Relative weight 600 0.8 22 % O2/He He 0.6 400 200 0 0 50 Adsorption 65ιC, 2 h 0.4 Temperature 0.2 100 150 Time [min] 200 3. 3. ᣠእԈბ↝ย(̊ܭSTP) 70 0 250 Relative weight [kg/kg–d.a.f.] Temperature [ιC] 800 ᇹ3ᇘ qO = nO – nO,0 (3. 1) 䛣䛣䛷䠈nO,0 䛿㓟㛤ጞ䛾㓟⣲ྵ᭷⋡䛷䛒䜛䠊ᮏ◊✲䛷䛿䠈ᶍᨃ✵Ẽ㞺ᅖẼ䛻ษ䜚᭰ 䛘䛶䛛䜙 2 㛫ᚋ䛾㓟⣲྾╔㔞(qO, 2h)䛾್䜢ప 䛻䛚䛡䜛㓟⣲䛸䛾ᛂᛶ䛾ホ౯ᣦᶆ䛸 䛧䛯䠊 3. 3. ⤖ᯝ䛸⪃ᐹ 3. 3. 1. ⏕ᡂ≀䛾⋡ 㻌 ᅗ 3. 4 䛻ྛヨᩱ䛛䜙ᚓ䜙䜜䛯⏕ᡂ≀䛾⋡䜢♧䛩䠊H2O 䛿㓟⣲ᨭ䜘䜚䠈⇕ศゎฎ⌮ 䛷ᚓ䜙䜜䜛ᾮయ䛾⏕ᡂ≀䛷䛒䜛 Tar 䛿≀㉁ᨭ䜘䜚䛭䜜䛮䜜ồ䜑䛯䠊⁐ฎ⌮ヨᩱ (STP)䛿⃰㉥Ⰽ䛾◚⥺䛷ᅖ䜣䛰㒊ศ䛻┦ᙜ䛧䠈䛭䛾୰䛻䠈Residue䠈Deposit䠈Soluble 䛾 ྜ䜢♧䛧䛯䠊䛯䛰䛧䠈BP 䛚䜘䜃 RS 䛿⁐ฎ⌮䛷䜒 1-䝯䝏䝹䝘䝣䝍䝺䞁䛸ྠ⛬ᗘ䛾ἛⅬ䜢 䜒䛴⏕ᡂ≀(Liquid ᡂศ䛸グ䛩)䜒⏕ᡂ䛩䜛䛯䜑䠈Liquid ᡂศ䛸 H2O 䛾㔞䜢ู䚻䛻ồ䜑䜛 䛣䛸䛜ᅔ㞴䛷䛒䜛䠊䛭䛾䛯䜑䠈BP 䛚䜘䜃 RS 䛷䛿䠈Liquid ᡂศ䛸 H2O 䛾㔞䜢ྜ⟬䛧䛶ồ䜑 STP 1 H2O Yield [kg/kg-raw coal] Soluble 0.8 Tar H2O H2 O + + Tar Liquid CO2 Deposit 0.6 Batch Char 0.4 Residue 0.2 0 Solvent Pyro. Solvent Pyro. Solvent Pyro. Solvent Pyro. Solvent Pyro. Solvent Pyro. Solvent Pyro. treatment WH treatment TH treatment AD treatment treatment treatment treatment PD LY BP RS 3. 4. Ӳᚾ૰↝๋дϼྸⅹ↷↢༏Ўᚐϼྸ↝ӓྙ 71 ๋дϼྸඥ↝Ꮾ൦∝ોឋ⇁ˤⅵᐯႆ້৮Сඥ↗ↆ↕↝МဇӧᏡࣱ 䛯䠊WH Ⅳ䛷䛿䜋䛸䜣䛹ኚ䛜ぢ䜙䜜䛪䠈ᮏ◊✲䛷⏝䛔䛯⁐ฎ⌮䛚䜘䜃⇕ศゎฎ⌮䛾 ᮲௳䛿䝞䜲䜸䝬䝇䠈〓Ⅳ䛚䜘䜃ள℡㟷Ⅳ䛻ᑐ䛧䛶᭷ຠ䛷䛒䜛䛣䛸䛜♧၀䛥䜜䛯䠊ཎᩱ䛾 Ⅳ⣲ྵ᭷⋡䛜䛝䛔䜋䛹 STP 䛚䜘䜃⇕ศゎヨᩱ(Batch Char)䛾⋡䛜䛝䛟䛺䜛ഴྥ䛜 ぢ䜙䜜䠈䜺䝇䛾⋡䛜ᑠ䛥䛟䛺䛳䛯䠊 㻌 ⁐ฎ⌮䛻╔┠䛩䜛䛸䠈ᅛయ⏕ᡂ≀䛷䛒䜛 STP 䛸䛭䛾䝣䝷䜽䝅䝵䞁䛷䛒䜛 Residue䠈 Deposit 䛚䜘䜃 Soluble 䛿䛔䛪䜜䜒䛻⬺Ỉ䛥䜜䛶䛔䛯䠊ฎ⌮୰䛾䛺䜺䝇⏕ᡂ≀䛿 CO2 䛷䛒䜚䠈䜘䜚㉁䛾ప䛔ཎᩱ䜋䛹ከ䛟䛾 CO2 䛜⏕ᡂ䛧䛯䠊Residue䠈Deposit 䛚䜘䜃 Soluble 䛻䛴䛔䛶ẚ㍑䛩䜛䛸䠈BP 䜢㝖䛟䛸Ⅳ⣲ྵ᭷⋡䛜ᑠ䛥䛔䜋䛹⁐ྍ⁐ᡂศ䛷䛒䜛 Deposit 䛚䜘䜃 Soluble 䛾ྜ䛜䛝䛟䛺䜛ഴྥ䛜ぢ䜙䜜䛯䠊䜎䛯䠈⇕ศゎฎ⌮䛻╔┠䛩 䜛䛸䠈ཎᩱ䛾㉁䛜ప䛔䜋䛹 Batch Char 䛾⋡䛜ᑠ䛥䛟䠈Tar ᡂศ䛾⋡䛜䛝䛟䛺䛳䛯䠊⁐ ฎ⌮䛸⇕ศゎฎ⌮䜢ẚ㍑䛩䜛䛸䠈䛩䜉䛶䛾ヨᩱ䛷䠈STP 䛾⋡䛜 Batch Char 䛾⋡䜢 ୖᅇ䜚䠈⇕ศゎฎ⌮䛷䛿 Tar 䛸䛧䛶Ⓨ䛧䛶䛧䜎䛖ᡂศ䛾୍㒊䜢⁐ฎ⌮䛷䛿ᅛయᡂศ䛸 䛧䛶ᅇ䛷䛝䜛䛣䛸䜢♧䛧䛶䛔䜛䠊 3. 3. 2. ฎ⌮ヨᩱ䛾ඖ⣲⤌ᡂ䠈Ⓨ⇕㔞 㻌 ⾲ 3. 2 䛻ᅛయ⏕ᡂ≀䛾ඖ⣲⤌ᡂ䠈ඖ⣲ẚ䠈⋡䛚䜘䜃Ⓨ⇕㔞䜢♧䛩䠊WH 䛷䛿 STP 䛸 ཎᩱ䛾ඖ⣲⤌ᡂ䛿䛒䜎䜚ኚ䜟䜙䛺䛛䛳䛯䛜䠈䛭䜜௨እ䛾ヨᩱ䛷䛿 STP 䛿䛔䛪䜜䜒Ⅳ⣲ྵ ᭷⋡䛜 74 wt%௨ୖ䛸ཎᩱ䜘䜚䛝䛟䠈㓟⣲ྵ᭷⋡䛜 18 wt%௨ୗ䛸ཎᩱ䜘䜚ᖜ䛻ᑠ䛥䛟 䛺䛳䛯䠊Mott-Spooner ᘧ[3]䛻䜘䜚⟬ฟ䛧䛯ฎ⌮ヨᩱᇶ‽䛾Ⓨ⇕㔞䛿 30 MJ/kg ⛬ᗘ䛸䛺䛳 䛶䛚䜚䠈ள℡㟷Ⅳ⛬ᗘ䛻䜎䛷ᨵ㉁䛥䜜䛯䛣䛸䛜䜟䛛䛳䛯䠊䛥䜙䛻䠈℡㟷Ⅳ䛛䜙〓Ⅳ䜎䛷䛾 ヨᩱ䛷䛿 STP 䛾ཎᩱᇶ‽䛾Ⓨ⇕㔞䛜ཎᩱ䜘䜚䜒䛝䛟䛺䛳䛶䛚䜚䠈⁐ฎ⌮䛻䜘䛳䛶䜶䝛 䝹䜼䞊䝻䝇䛾䛺䛔ຠ⋡ⓗ䛺ᨵ㉁䛜⾜䜟䜜䛯䛣䛸䛜♧䛥䜜䛯䠊୍᪉䠈BP 䛚䜘䜃 RS 䛷䛿ཎ ᩱᇶ‽䛾Ⓨ⇕㔞䛜ཎᩱ䜘䜚䜒ῶᑡ䛧䠈Liquid ᡂศ䛜ᅇ䛷䛝䛺䛛䛳䛯䛯䜑䛻䜶䝛䝹䜼䞊 䝻䝇䛜⏕䛨䛯䛸⪃䛘䜙䜜䜛䠊 72 ᇹ3ᇘ 㻌 䜎䛯䠈Residue䠈Deposit 䛚䜘䜃 Soluble 䜢ẚ㍑䛩䜛䛸䠈⁐⁐ᡂศ䛷䛒䜛 Residue 䛿Ⅳ ⣲ྵ᭷⋡䛜 68 ~ 83 wt%䠈㓟⣲ྵ᭷⋡䛜 10 ~ 30 wt%䛸ཎᩱ䛻䜘䜚䛝䛺㐪䛔䛜䜏䜙䜜䠈 ཎᩱ䛾㉁䛜ప䛟䛺䜛䛻䛴䜜䛶䠈Ⅳ⣲ྵ᭷⋡䛿ῶᑡ䛧䠈㓟⣲ྵ᭷⋡䛿ቑຍ䛧䛯䠊୍᪉䠈⁐ ᘙ 3. 2. Ӳဃཋ↝Ψእኵ≏Ψእൔ≏ӓྙⅹ↷↢᭗ˮႆ༏ Sample WH TH AD PD LY BP RS Fraction Raw coal STP Residue Deposit Soluble Batch Char Raw coal STP Residue Deposit Soluble Batch Char Raw coal STP Residue Deposit Soluble Batch Char Raw coal STP Residue Deposit Soluble Batch Char Raw coal STP Residue Deposit Soluble Batch Char Raw coal STP Residue Deposit Soluble Batch Char Raw coal STP Residue Deposit Soluble Batch Char Elemental composition [wt% d. a. f.] C H N O(diff) 81.5 84.3 83.4 84.0 87.0 81.9 73.1 79.1 77.7 75.7 83.6 77.1 70.0 78.7 77.5 75.9 82.0 75.8 68.5 78.7 74.9 77.7 81.8 78.1 68.2 78.6 77.0 76.0 81.3 78.8 58.9 74.1 71.0 78.2 82.3 73.2 46.5 78.4 68.0 81.1 82.5 77.7 5.4 5.1 4.6 5.3 6.5 5.0 5.2 5.5 4.6 5.1 7.6 5.2 5.2 5.1 4.1 4.9 7.1 4.9 5.0 5.1 3.9 4.9 7.5 5.2 4.6 4.9 4.0 4.7 6.4 4.7 4.9 5.3 4.4 5.6 7.7 5.0 5.6 6.2 4.9 5.3 6.8 6.0 1.9 1.5 1.5 1.9 1.2 1.3 1.5 1.8 2.1 2.0 1.0 1.8 1.7 1.2 1.3 1.2 0.9 1.2 1.0 1.2 1.5 1.4 0.7 1.2 0.6 0.9 1.1 1.2 0.7 0.9 3.3 2.6 2.7 3.6 2.4 3.4 0.4 1.1 0.9 1.4 1.2 0.8 11.2 9.2 10.6 8.8 5.4 11.7 20.2 13.7 15.7 17.3 7.8 15.9 23.2 15.0 17.1 18.0 10.0 18.1 25.5 15.0 19.6 16.0 10.0 15.4 26.5 15.6 18.0 18.1 11.6 15.6 32.9 18.0 21.9 12.6 7.6 18.4 47.5 14.4 26.2 12.2 9.6 15.5 Atomic ratio Yield [ʊ] H/C O/C [kg/kg d. a. f.] 0.78 0.72 0.65 0.75 0.89 0.73 0.85 0.83 0.70 0.80 1.08 0.81 0.88 0.77 0.64 0.76 1.03 0.77 0.88 0.77 0.63 0.75 1.09 0.80 0.81 0.74 0.61 0.73 0.93 0.72 0.99 0.85 0.74 0.85 1.12 0.82 1.44 0.94 0.86 0.78 0.98 0.93 0.10 0.08 0.10 0.08 0.05 0.11 0.21 0.13 0.15 0.17 0.07 0.15 0.25 0.14 0.17 0.18 0.09 0.18 0.28 0.14 0.20 0.15 0.09 0.15 0.29 0.15 0.18 0.18 0.11 0.15 0.42 0.18 0.23 0.12 0.07 0.19 0.77 0.14 0.29 0.11 0.09 0.15 73 ʊ 1.040 0.704 0.107 0.229 0.988 ʊ 0.992 0.614 0.106 0.272 0.901 ʊ 0.888 0.538 0.084 0.266 0.875 ʊ 0.888 0.589 0.025 0.252 0.716 ʊ 0.888 0.479 0.059 0.332 0.733 ʊ 0.679 0.488 0.016 0.174 0.630 ʊ 0.448 0.124 0.031 0.293 0.446 HHV HHV [MJ/kg-product] [MJ/kg-raw sample] 33.4 34.1 33.0 34.5 37.7 33.0 29.6 32.4 27.3 26.6 36.7 31.1 27.0 31.0 28.7 29.4 36.2 29.9 26.7 31.0 29.6 30.9 36.6 31.5 25.9 30.6 29.0 29.6 34.7 31.0 22.5 29.9 27.1 32.4 37.6 29.2 18.0 31.9 22.1 32.5 35.9 32.5 33.4 35.5 23.2 3.7 8.6 32.6 29.6 32.1 16.7 2.8 10.0 28.0 27.0 27.5 15.4 2.5 9.6 26.1 26.7 27.4 17.4 0.8 9.2 22.6 25.9 27.4 13.9 1.7 11.5 22.7 22.5 20.3 13.2 0.5 6.5 18.4 18.0 14.3 2.7 1.0 10.5 14.5 ๋дϼྸඥ↝Ꮾ൦∝ોឋ⇁ˤⅵᐯႆ້৮Сඥ↗ↆ↕↝МဇӧᏡࣱ ྍ⁐ᡂศ䛷䛒䜛 Deposit 䛿Ⅳ⣲ྵ᭷⋡䛜 75 ~ 84 wt%䠈㓟⣲ྵ᭷⋡䛜 8 ~ 18 wt%䠈 Soluble 䛿Ⅳ⣲ྵ᭷⋡䛜 82 ~ 87 wt%䠈㓟⣲ྵ᭷⋡䛜 5 ~ 12 wt%䛷䛒䜚䠈ཎᩱ䛻䜘䜛㐪䛔 䛿䛒䜎䜚䜏䜙䜜䛺䛛䛳䛯䠊ฎ⌮ヨᩱᇶ‽䛾Ⓨ⇕㔞䛿 Residue 䛷䛿 30 MJ/kg ௨ୗ䛷ཎᩱ䛾 ㉁䛜㧗䛟䛺䜛䜋䛹Ⓨ⇕㔞䛜ቑຍ䛧䛯䛜䠈Deposit 䛷䛿 26 ~ 33 MJ/kg 䛷ཎᩱ䛾㉁䛜㧗䛟䛺䜛 䜋䛹Ⓨ⇕㔞䛜ῶᑡ䛩䜛ഴྥ䛜䜏䜙䜜䛯䠊୍᪉䠈Soluble 䛷䛿 35 MJ/kg ௨ୖ䛷䛒䜚䠈ཎᩱ䛻 䜘䜛㐪䛔䛿䛒䜎䜚䜏䜙䜜䛺䛛䛳䛯䠊 㻌 Batch Char 䛷䛿Ⅳ⣲ྵ᭷⋡䛜 73 ~ 82 wt%䠈㓟⣲ྵ᭷⋡䛜 11 ~ 18 wt%䛷䛒䜚䠈STP 䛸 ẚ䜉䛶Ⅳ⣲ྵ᭷⋡䛜ᑠ䛥䛟䠈㓟⣲ྵ᭷⋡䛜䛝䛟䛺䛳䛯䠊ฎ⌮ヨᩱᇶ‽䛾Ⓨ⇕㔞䛿 29 ~ 33 MJ/kg 䛸ள℡㟷Ⅳ⛬ᗘ䛻ᨵ㉁䛥䜜䛯䛜䠈ཎᩱᇶ‽䛾Ⓨ⇕㔞䛿ཎᩱ䜘䜚䜒ᑠ䛥䛟䛺䜚䠈 Tar 䛾⏕ᡂ䛻క䛔䜶䝛䝹䜼䞊䝻䝇䛜⏕䛨䛯䛸⪃䛘䜙䜜䜛䠊 㻌 ᅗ 3. 5 ~ 3. 11 䛻ྛฎ⌮䛻䛚䛡䜛ඖ⣲ᨭ䜢♧䛩䠊ᅗ୰䛾㯮Ⰽ◚⥺䛿ཎᩱ䛾Ⅳ⣲䠈Ỉ ⣲䠈㓟⣲䛾್䜢⾲䛩䠊Ⅳ⣲⋡䛿䠈㉁䛾㧗䛔ཎᩱ䛷䛿 Residue 䛜䛝䛟䠈㉁䛾ప䛔ཎᩱ 䛷䛿 Soluble 䛜䛝䛟䛺䛳䛯䠊RS 䛷䛿 Soluble 䛾Ⅳ⣲⋡䛜 52 %䛸༙ศ௨ୖ䜢༨䜑䛯䠊 ୍᪉䠈ᅛయ⏕ᡂ≀䛾㓟⣲⋡䛿ᑠ䛥䛟䠈STP 䛻䛴䛔䛶ẚ㍑䛩䜛䛸䠈Residue 䛾㓟⣲⋡䛜 䛝䛟䠈Soluble䠈Deposit 䛾㓟⣲⋡䛿ᑠ䛥䛟䛺䛳䛯䠊㓟⣲ᨭ䜢ẚ㍑䛩䜛䛸䠈⁐ฎ⌮䛷 䛿 H2O 䛜ከ䛟⏕ᡂ䛧䠈⇕ศゎฎ⌮䛷䛿 CO2 䛜ከ䛟⏕ᡂ䛧䛯䠊▼Ⅳ䛚䜘䜃䝞䜲䜸䝬䝇䛻䛿 䜹䝹䝪䜻䝅䝹ᇶ 2 ศᏊ䛛䜙䛺䜛㔜Ỉ⣲⤖ྜ䛜䛒䜚䠈⇕ศゎฎ⌮䛷䛿䛭䛾 2 ศᏊ㛫䛷ศ ゎᛂ䛜㉳䛣䜚䠈㓟⣲ᯫᶫ䛾ᙧᡂ䛸 CO2 䛾⏕ᡂ䛜㐍⾜䛧䠈⁐ฎ⌮䛷䛿䠈䛭䛾⤖ྜ䛾㛫 䛻⁐䛜ᾐ㏱䛧䠈䜹䝹䝪䜻䝅䝹ᇶྠኈ䛾㊥㞳䛜㞳䜜䜛䛣䛸䛷䠈㓟⣲ᯫᶫ䛜ᢚไ䛥䜜䠈1 䛴 䛾䜹䝹䝪䜻䝅䝹ᇶ䛷ศゎ䛜㉳䛣䜚 H2O 䛜⏕ᡂ䛧䛯䛸⪃䛘䜙䜜䜛䠊 74 ᇹ3ᇘ 8 8 Elemental distribution [kmol/100 kg-sample] Elemental distribution [kmol/100 kg-sample] 6 TH WH STP H2O Tar Soluble 4 2 Deposit Residue Batch Char CO2 0 H 6 H2O Tar Soluble 4 Deposit 2 Residue Batch Char CO2 0 Solvent Batch Solvent Batch Solvent Batch treat. pyro. treat. pyro. treat. pyro. C STP Solvent Batch Solvent Batch Solvent Batch treat. pyro. treat. pyro. treat. pyro. C O 3.5. WH ໗↝Ψእӓૅ H O 3. 6. TH ໗↝Ψእӓૅ 8 8 PD STP 6 H2O 4 2 0 Elemental distribution [kmol/100 kg-sample] Elemental distribution [kmol/100 kg-sample] AD Tar Soluble Deposit Residue CO2 Batch Char H STP H2O Tar 4 Soluble 2 3. 7. AD ໗↝Ψእӓૅ Residue Solvent Batch Solvent Batch Solvent Batch treat. pyro. treat. pyro. treat. pyro. C O Deposit Batch Char CO2 0 Solvent Batch Solvent Batch Solvent Batch treat. pyro. treat. pyro. treat. pyro. C 6 H O 3. 8. PD ໗↝Ψእӓૅ 75 ๋дϼྸඥ↝Ꮾ൦∝ોឋ⇁ˤⅵᐯႆ້৮Сඥ↗ↆ↕↝МဇӧᏡࣱ 8 8 BP 6 Elemental distribution [kmol/100 kg-sample] Elemental distribution [kmol/100 kg-sample] LY STP H2O 4 2 Tar Batch Char Soluble Deposit Residue CO2 0 H O Elemental distribution [kmol/100 kg-sample] RS 6 STP Tar Soluble Deposit Batch Char CO2 Residue 0 Solvent Batch Solvent Batch Solvent Batch treat. pyro. treat. pyro. treat. pyro. C H Soluble 2 Deposit Residue Batch Char CO2 Solvent Batch Solvent Batch Solvent Batch treat. pyro. treat. pyro. treat. pyro. H O 3. 10. BP ↝Ψእӓૅ 8 2 Liquid 4 C 3. 9. LY ໗↝Ψእӓૅ 4 STP 0 Solvent Batch Solvent Batch Solvent Batch treat. pyro. treat. pyro. treat. pyro. C 6 O 3. 11. RS ↝Ψእӓૅ 76 ᇹ3ᇘ 㻌 ᅗ 3. 12 䛻ཎᩱ䛚䜘䜃ྛ⏕ᡂ≀䛾 H/C ẚ䛸 O/C ẚ䛾㛵ಀ䜢♧䛩䠊ᅗ୰䛾ᐇ⥺䛚䜘䜃◚ ⥺䛿⬺Ỉ䠈⬺Ⅳ㓟䠈⬺䝯䝍䞁䛻ᑐᛂ䛩䜛ඖ⣲ẚ䛾ኚ䜢⾲䛧䛶䛔䜛䠊䜎䛯䠈ᩳ⥺㒊䛿䝁䞊 䝹䝞䞁䝗䛸䜘䜀䜜䜛䜒䛾䛷䠈▼Ⅳ䛾ඖ⣲⤌ᡂ䛿▼Ⅳ䛾㐍⾜䛻క䛔䠈⬺Ỉ䞉⬺Ⅳ㓟䛻䜘䜚 䝁䞊䝹䝞䞁䝗䛾ྑഃ䛛䜙ᕥୖ䛾ྥ䛝䛻ኚ䛧䠈䛭䛾ᚋ䠈⬺䝯䝍䞁ᛂ䛻䜘䜚䠈ཎⅬ᪉ྥ䜈 ኚ䛧䛶䛔䛟䛣䛸䛜▱䜙䜜䛶䛔䜛[4]䠊䜎䛯䠈䝞䜲䜸䝬䝇(RS)䛛䜙〓Ⅳ(LY)䛻䛺䜛㐣⛬䛻䛚䛡 䜛⤌ᡂኚ䛾᪉ྥ䛿⬺Ỉ䛻䜘䜛⤌ᡂኚ䛸⬺Ⅳ㓟䛻䜘䜛⤌ᡂኚ䛾⥺䛾㛫䛻䛝䛶䛚䜚䠈 䝞䜲䜸䝬䝇䛿䛻⬺Ỉᛂ䛸⬺Ⅳ㓟ᛂ䛻䜘䜚〓Ⅳ䛻䛺䜛䛣䛸䛜䛖䛛䛜䛘䜛䠊ཎᩱ䛿ඖ⣲ ẚ䛜䛝䛟␗䛺䜛䛜䠈ฎ⌮ᚋ䛾ヨᩱ䛿 Residue䜢㝖䛝䛭䜜䛮䜜䛾ᡂศྠኈ䛿ఝ䛯䜘䛖䛺ඖ ⣲ẚ䛷䛒䛳䛯䠊Soluble 䛿 H/C 䛜䝁䞊䝹䝞䞁䝗䛛䜙䛝䛔䜋䛖䜈䠈Residue 䛿䝁䞊䝹䝞䞁䝗 䛛䜙 H/C 䛜ᑠ䛥䛔䜋䛖䜈䛪䜜䛶䛔䛯䛜䠈Deposit䠈STP 䛚䜘䜃 Batch Char 䛾ඖ⣲⤌ᡂ䛿℡ 㟷Ⅳ䛷䛒䜛 WH 䛻㏆䛵䛔䛶䛚䜚䠈䝁䞊䝹䝞䞁䝗㏆ഐ䛻ศᕸ䛧䛶䛔䛯䠊䛣䛾䛣䛸䛛䜙䠈⁐ ฎ⌮䛻䜘䛳䛶䠈䛔䛪䜜䛾ヨᩱ䜒ள℡㟷Ⅳ⛬ᗘ䜎䛷ᨵ㉁䛩䜛䛣䛸䛜䛷䛝䠈䛣䛾䛸䛝⮬↛⏺䛷 䛾▼Ⅳ䛾㐣⛬䛸ྠ䛨䜘䛖䛺ᛂ䛷䛒䜛⬺Ỉᛂ䛚䜘䜃⬺Ⅳ㓟ᛂ䛜㐍⾜䛧䛯䛣䛸䛜♧ ၀䛥䜜䜛䠊 1.4 Batch Char STP 1.2 H/C [-] WH 1 BP AD PD TH 0.8 LY RS Raw Soluble îCO2 îH2O îCH4 Residue 0.6 Deposit 0.4 Coal band 0.2 0 0 0.2 0.4 0.6 O/C [-] 0.8 3. 12. Ӳᛦᙌᚾ૰↝Ψእൔ 77 1.0 ๋дϼྸඥ↝Ꮾ൦∝ોឋ⇁ˤⅵᐯႆ້৮Сඥ↗ↆ↕↝МဇӧᏡࣱ 3. 3. 3. ᐁ⬟ᇶ㔞䛾ኚ 㻌 ᅗ 3. 13 ~ 3. 19 䛻ཎᩱ䠈STP 䛚䜘䜃 Batch Char 䛾 IR 䝇䝨䜽䝖䝹䜢♧䛩䠊WH Ⅳ䛷䛿⁐ ฎ⌮䠈⇕ศゎฎ⌮䛻䜘䜛ኚ䛜䜋䛸䜣䛹ぢ䜙䜜䛺䛛䛳䛯䛜䠈䛭䜜௨እ䛾ヨᩱ䛷䛿 STP䠈 Batch Char 䛸䜒䛻䜹䝹䝪䜻䝅䝹ᇶ䛻ᑐᛂ䛩䜛 1750 cm䌦1 䛾䝢䞊䜽䛚䜘䜃Ỉ㓟ᇶ䛻ᑐᛂ䛩 䜛 2500 ~ 3600 cm䌦1 䛻䛒䜛䝤䝻䞊䝗䛺䝢䞊䜽䛜ῶᑡ䛧䛯䠊䜎䛯䠈STP 䛷䛿 1600 cm䌦1 䛻䛒䜛 ⰾ㤶᪘Ⅳ⣲䛻ᑐᛂ䛩䜛䝢䞊䜽䛜ቑຍ䛧䛯䛜䠈Batch Char 䛷䛿ⰾ㤶᪘Ⅳ⣲䛻ᑐᛂ䛩䜛䝢䞊 䜽䛜ῶᑡ䛧䛯䠊䛣䛾䛣䛸䛛䜙䠈⁐ฎ⌮䛷䛿䠈〓Ⅳ䛰䛡䛷䛺䛟ள℡㟷Ⅳ䛛䜙䝞䜲䜸䝬䝇䜎䛷 䛾ᖜᗈ䛔ཎᩱ䛻䛴䛔䛶䠈๓❶䛷♧䛧䛯䜘䛖䛺ྵ㓟⣲ᐁ⬟ᇶ䛜ศゎ䛧ⰾ㤶᪘Ⅳ⣲䛜⏕ᡂ 䛩䜛ᛂ䛜㐍⾜䛧䛯䛸⪃䛘䜙䜜䜛䠊୍᪉䠈⇕ศゎฎ⌮䛷䛿ⰾ㤶᪘Ⅳ⣲䛾ቑຍ䛜䜏䜙䜜䛪䠈 ⰾ㤶᪘Ⅳ⣲䜢᭷䛩䜛పศᏊ㔞ᡂศ䛜 Tar 䛸䛧䛶⏕ᡂ䛧䛯䛸⪃䛘䜙䜜䜛䠊 TH 4000 -OH aromatic C=C aliphatic CH Absorbance [a. u.] Absorbance [a. u.] WH carboxyl Raw STP Batch Char 3000 2000 -1 1000 Wavenumber [cm ] aromatic C=C -OH aliphatic CH carboxyl Raw STP Batch Char 4000 3000 2000 -1 Wavenumber [cm ] 3. 13. WH ໗↗ϼྸ໗↝ FT-IR ⇟∀⇕⇮∑ 3. 14. WH ໗↗ϼྸ໗↝ FT-IR ⇟∀⇕⇮∑ 78 1000 ᇹ3ᇘ PD aromatic C=C -OH aliphatic CH Absorbance [a. u.] Absorbance [a. u.] AD carboxyl Raw STP aromatic C=C -OH aliphatic CH Raw STP Batch Char Batch Char 4000 3000 2000 -1 1000 4000 Wavenumber [cm ] -OH carboxyl Raw STP Batch Char 4000 3000 2000 -1 1000 Absorbance [a. u.] aromatic C=C aliphatic CH carboxyl Raw STP Batch Char 2000 -1 Raw STP Batch Char 3000 2000 -1 Wavenumber [cm ] RS 3000 carboxyl 3. 18. BP ↗ϼྸᚾ૰↝ FT-IR ⇟∀⇕⇮∑ 3. 17. LY ໗↗ϼྸ໗↝ FT-IR ⇟∀⇕⇮∑ 4000 1000 aliphatic CH 4000 Wavenumber [cm ] -OH -1 aromatic C=C BP Absorbance [a. u.] Absorbance [a. u.] aliphatic CH 2000 3. 16. PD ໗↗ϼྸ໗↝ FT-IR ⇟∀⇕⇮∑ aromatic C=C -OH 3000 Wavenumber [cm ] 3. 15. AD ໗↗ϼྸ໗↝ FT-IR ⇟∀⇕⇮∑ LY carboxyl 1000 Wavenumber [cm ] 3. 19. RS ↗ϼྸᚾ૰↝ FT-IR ⇟∀⇕⇮∑ 79 1000 ๋дϼྸඥ↝Ꮾ൦∝ોឋ⇁ˤⅵᐯႆ້৮Сඥ↗ↆ↕↝МဇӧᏡࣱ 3. 3. 4. 㓟⣲྾╔ᣲື(LY Ⅳ䠈PD Ⅳ) 㻌 ᅗ 3. 20 䛚䜘䜃ᅗ 3. 21 䛻 LY Ⅳ䛚䜘䜃 PB Ⅳ䛛䜙ㄪ〇䛧䛯ྛヨᩱ䛾 65 °C 䛻䛚䛡䜛㓟 ⣲྾╔㔞䛾⤒ኚ䜢♧䛩䠊65 °C 䛻䛚䛡䜛㓟㐣⛬䛷䛿䜺䝇䛾⏕ᡂ䛿ほ 䛥䜜䛪䠈㔜 㔞ቑຍ䛾䜏䛜⏕䛨䛯䠊䛭䛾䛯䜑䠈䛣䛾㐣⛬䛷䛿䠈䜺䝇䛾⏕ᡂ䜢క䛖㓟䛿㉳䛣䜙䛪䠈㓟⣲ qO 2h [mg-O/g-sample d. a. f.] Oxygen adsorption [mg-O/g-sample d. a. f.] 2.5 2.0 65C, 22 % O2/He 1.5 2.3 2.2 Residue STP 1.6 Raw coal 1.0 1.1 1.0 Soluble 0.5 0 0 Char 0.3 Deposit 30 60 Time [min] 90 120 3. 20. LY ໗ⅺ↸ᛦᙌↆᚾ૰↝ᣠእԈბਫѣ qO 2h [mg-O/g-sample d. a. f.] Oxygen adsorption [mg-O/g-sample d. a. f.] 20 15 10 6 19.3 Char 65C, 22 % O2/He Residue 5.1 4 STP 2 00 0 Soluble Raw coal Deposit 30 60 Time [min] 90 2.7 2.4 2.3 1.2 120 3. 21. PD ໗ⅺ↸ᛦᙌↆᚾ૰↝ᣠእԈბਫѣ 80 ᇹ3ᇘ ྾╔䛾䜏䛜㐍⾜䛧䛯䛣䛸䜢♧䛧䛶䛔䜛䠊ཎⅣ䠈STP䠈䛚䜘䜃 Char 䛻䛴䛔䛶 qO, 2h 䛾್䜢ẚ ㍑䛩䜛䛸䠈LY Ⅳ䠈PD Ⅳ䛸䜒䛻ཎⅣ䛜᭱䜒ᑠ䛥䛟䠈Char 䛜᭱䜒䛝䛟䛺䛳䛯䠊䛣䛾䛣䛸䜘䜚䠈 STP 䛿 Char 䜘䜚䜒ྲྀ䜚㎸䜣䛰㓟⣲䛾㔞䛜ᑡ䛺䛟䠈ప 䛻䛚䛡䜛㓟⣲䛸䛾ᛂᛶ䛜ᑠ䛥䛔䛣 䛸䜢♧၀䛧䛶䛔䜛䠊䛔䛪䜜䛾ཎⅣ䜒ᶍᨃ✵Ẽ㞺ᅖẼ䛻ษ䜚᭰䛘䛶䛛䜙 30 ศ䛷䜋䜌୍ᐃ䛾 ್䛻䛺䜚䠈Char 䛿ᶍᨃ✵Ẽ㞺ᅖẼ䛻ษ䜚᭰䛘䛯䛒䛸䛩䛠䠈㎿㏿䛻㓟⣲䛜྾╔䛧䠈30 ศ௨ 㝆䜒⦆䜔䛛䛻㓟⣲྾╔㔞䛜ቑຍ䛧䛯䠊STP 䛾ྛ䝣䝷䜽䝅䝵䞁䛻䛴䛔䛶ཎⅣ䛾 qO, 2h 䛸ẚ㍑ 䛩䜛䛸䠈Deposit 䛷䛿༙ศ⛬ᗘ䜎䛷ᑠ䛥䛟䠈Soluble 䛷䛿ྠ⛬ᗘ䛻䛺䜚䠈Residue 䛷䛿 2 ಸ⛬ ᗘ䜎䛷䛝䛟䛺䛳䛯䠊⁐ྍ⁐ᡂศ䛷䛒䜛 Deposit 䛚䜘䜃 Soluble 䛿䠈ᶍᨃ✵Ẽ㞺ᅖẼ䛻 ษ䜚᭰䛘䛶䛩䛠䛾㓟⣲྾╔㏿ᗘ䛜ᑠ䛥䛟䠈30 ศ௨㝆䛷䛿 Deposit 䛾㓟⣲྾╔㏿ᗘ䛜⦆䜔 䛛䛻䛺䛳䛯䛜䠈Soluble 䛾㓟⣲྾╔㔞䛿༢ㄪ䛻ቑຍ䛧䛯䠊STP 䛾㓟⣲྾╔ᣲື䛿 Residue䠈 Deposit 䛚䜘䜃 Soluble 䛾㓟⣲྾╔ᣲື䜢㊊䛧ྜ䜟䛫䛯䜘䛖䛺ᣲື䜢♧䛧䠈Residue 䜘䜚 qO, 2h 䛜ᑠ䛥䛟䛺䛳䛯䛜 Deposit 䛚䜘䜃 Soluble 䜘䜚䛿 qO, 2h 䛜䛝䛟䛺䛳䛯䠊⁐ྍ⁐ᡂศ䛷䛒 䜛 Deposit 䛚䜘䜃 Soluble 䛿ᖜ䛻㓟⣲䛾ྲྀ䜚㎸䜏㔞䛜ῶᑡ䛧䛶䛔䜛䛣䛸䛛䜙䠈⁐ฎ⌮ 䛻䜘䜚ᚓ䜙䜜䛯⁐ྍ⁐ᡂศ䛿ప 䛻䛚䛡䜛㓟⣲䛸䛾ᛂᛶ䛜ప䛔䛸⪃䛘䜙䜜䜛䠊 㻌 ప 㓟䛾せᅉ䛿✀䚻䛾䜒䛾䛜ᥦ䛥䜜䛶䛚䜚䠈Ꮫⓗ䛺せᅉ䛾୍䛴䛸䛧䛶⬡⫫᪘Ⅳ ⣲䛾㔞[5]䛜䠈≀⌮ⓗ䛺せᅉ䛾୍䛴䛸䛧䛶⣽Ꮝ⾲㠃✚[6]䛜ᣲ䛢䜙䜜䜛䠊⾲ 3. 3 䛻 LY Ⅳ䛛䜙 ㄪ〇䛧䛯ྛヨᩱ䛾㓟⣲྾╔㔞䠈⬡⫫᪘Ⅳ⣲ྵ᭷⋡䛚䜘䜃⣽Ꮝ⾲㠃✚䜢♧䛩䠊⬡⫫᪘Ⅳ ⣲ྵ᭷⋡䛿 13C-NMR 䝇䝨䜽䝖䝹䜘䜚⟬ฟ䛧䛯䠊⬡⫫᪘Ⅳ⣲ྵ᭷⋡䛿 Residue 䛷᭱䜒ᑠ䛥䛟䠈 Soluble 䛜᭱䜒䛝䛟䛺䛳䛯䠊➨ 1 ❶䛷᫂䜙䛛䛻䛧䛯䜘䛖䛻䠈⬡⫫᪘Ⅳ⣲䛿㓟⣲䛸䛾ᛂᛶ 䛜㧗䛔䛾䛷䠈⬡⫫᪘Ⅳ⣲ྵ᭷⋡䛾䜏䛷ẚ㍑䛩䜛䛸䠈Soluble 䛾 qO, 2h 䛜᭱䜒䛝䛟䛺䜛䛸ᛮ 䜟䜜䜛䠊୍᪉䠈Soluble 䜔 Deposit 䛿⣽Ꮝ⾲㠃✚䛜㠀ᖖ䛻ᑠ䛥䛟䛺䛳䛯䠊䛣䜜䛿⁐ྍ⁐ ᡂศ䛾᭷䛩䜛㌾⁐⼥ᛶ䛻㉳ᅉ䛩䜛䜒䛾䛰䛸⪃䛘䜙䜜䜛䠊⣽Ꮝ⾲㠃✚䛜ᑠ䛥䛟䛺䜛䛸䠈䛭 䛾ศ㓟⣲䛾䜰䜽䝉䝇䛜ᢚไ䛥䜜䠈㓟⣲䛸䛾ᛂᛶ䛜ᑠ䛥䛟䛺䜛䛸⪃䛘䜙䜜䜛䠊䛧䛯䛜䛳䛶䠈 ⣽Ꮝ⾲㠃✚䛾䜏䛷ẚ㍑䛩䜛䛸䠈⁐ྍ⁐ᡂศ䛾 qO, 2h 䛜ᑠ䛥䛟䛺䜛䛸ᛮ䜟䜜䜛䠊䜎䛯䠈STP 䛿 Residue 䜔 Char 䜘䜚䜒⣽Ꮝ⾲㠃✚䛜ᑠ䛥䛟䛺䛳䛯䠊䛣䜜䛿䠈ฎ⌮ ᗘ䛷䛿⁐⼥䛧䛶䛔䛯 81 ๋дϼྸඥ↝Ꮾ൦∝ોឋ⇁ˤⅵᐯႆ້৮Сඥ↗ↆ↕↝МဇӧᏡࣱ ᘙ 3. 3. LY ໗ⅺ↸ᛦᙌↆӲᚾ૰↝ᣠእԈბ≏ᏢᏆଈ໗እԃஊྙ ⅹ↷↢ኬ܉ᘙ᩿ᆢ Deposit 䜔 Soluble 䛜 Residue 䛾⣽Ꮝ䜢ሰ䛔䛰䛯䜑䛷䛒䜛䛸⪃䛘䜙䜜䜛䠊௨ୖ䜘䜚䠈ฎ⌮Ⅳ Oxygen adsorption, qO 2h [mg-O/g-sample] Aliphatic carbon concentration, Cal [mol-C/kg-sample] Pore surface area Sp [m2/g-sample] Raw coal 1.1 19.1 174.1 STP 1.6 11.9 66.0 Residue 2.2 6.6 151.8 Deposit 0.3 13.8 30.3 Soluble 1.0 22.2 18.7 Char 2.3 14.5 206.2 䛾㓟⣲䛾ྲྀ䜚㎸䜏㔞䛻䛿⣽Ꮝ⾲㠃✚䛾ᐤ䛜䛝䛔䛸⪃䛘䜙䜜䜛䠊Soluble 䛿⬡⫫᪘Ⅳ ⣲䜢ከ䛟᭷䛩䜛䛜⣽Ꮝ⾲㠃✚䛜㠀ᖖ䛻ᑠ䛥䛟㓟⣲䛾䜰䜽䝉䝇䛜ᢚไ䛥䜜䛯䛯䜑䛻 qO, 2h 䛜 ᑠ䛥䛟䛺䜚䠈Deposit 䛿⬡⫫᪘Ⅳ⣲ྵ᭷⋡䠈⣽Ꮝ⾲㠃✚䛾䛹䛱䜙䜒ᑠ䛥䛟䛺䛳䛯䛾䛷 qO, 2h 䛜ⴭ䛧䛟ᑠ䛥䛟䛺䛳䛯䛸⪃䛘䜙䜜䜛䠊䜎䛯䠈STP 䛾 qO, 2h 䛜 Residue 䛚䜘䜃 Char 䜘䜚ᑠ䛥䛟䛺 䛳䛯䛾䛿䠈⁐ྍ⁐ᡂศ䛻䜘䜚⣽Ꮝ䛜㛢ሰ䛧䠈㓟⣲䛾䜰䜽䝉䝇䜢ᢚไ䛧䛯䛯䜑䛸⪃䛘䜙䜜 䜛䠊䜎䛯䠈PD Ⅳ䜘䜚ㄪ〇䛧䛯ヨᩱ䛾㓟⣲྾╔ᣲື䜒 LY Ⅳ䛸ྠᵝ䛾ㄝ᫂䛜ᙜ䛶䛿䜎䜛䠊 㻌 䛺䛚䠈ᮏᐇ㦂䛷䛿๓❶䜘䜚䜒ప 䛻䛚䛡䜛㓟⣲䛸䛾ᛂᛶ䜢 ᐃ䛧䠈㓟⣲྾╔䛾䜏䛜 ほᐹ䛥䜜䛯䛜䠈ᮏ㡯䛷ほᐹ䛥䜜䛯㓟⣲྾╔䛾⏕ᡂ≀䛜Ᏻᐃ䛷䛒䜛䛛䛹䛖䛛䛻䛴䛔䛶䛿༊ ู䛷䛝䛺䛔䠊䛩䛺䜟䛱䠈ᮏᐇ㦂䛷䛿ప 䛷 ᐃ䛧䛶䛔䜛䛯䜑㓟⣲྾╔䛻⥆䛟ᛂ䛾㏿ᗘ 䛜㠀ᖖ䛻ప䛟䠈ᑡ䛧 ᗘ䛜ୖ᪼䛧䛯㝿䛻䛭䛾⏕ᡂ≀䛜䛥䜙䛻㓟䛥䜜䜛䛛䛹䛖䛛䛜䜟䛛䜙 䛺䛔䠊๓❶䛷㆟ㄽ䛧䛯 200 °C ௨ୗ䛻䛚䛡䜛ཎⅣ䛾㓟䛿㓟⣲྾╔䛻ຍ䛘 H2O 䛾⏕ᡂ䜒 ྵ䜐䛯䜑㓟⣲ᾘ㈝㔞䛜⁐ฎ⌮ヨᩱ䜘䜚䜒䛝䛟䛺䜚䠈ᮏᐇ㦂䛷䛿㓟⣲྾╔䛾䜏䛷 H2O 䛾⏕ᡂ䛜ྵ䜎䜜䛶䛔䛺䛔䛯䜑 qO, 2h 䛜 STP 䜘䜚䜒ᑠ䛥䛟䛺䛳䛯䛸⪃䛘䜙䜜䜛䠊䜎䛯䠈⮬↛Ⓨ ⅆᛶ䛾㆟ㄽ䛻䛿㓟⣲䛸䛾ᛂᛶ䛰䛡䛷䛺䛟䠈ᛂ䛻క䛖Ⓨ⇕䛜㔜せ䛷䛒䜛䛯䜑䠈ᮏ㡯䛾 㓟⣲྾╔㔞䛾䜏䛷䛾⮬↛Ⓨⅆᛶ䛾㆟ㄽ䛿ᅔ㞴䛷䛒䜛䠊⮬↛Ⓨⅆᛶ䛾㆟ㄽ䜢⾜䛖䛯䜑䛻 䛿䠈ᛂึᮇ䛷䛾Ⓨ⇕㏿ᗘ䛾ᐃᘧ䠈䛩䛺䜟䛱ప 䛷⏕䛨䜛㓟䛾ᛂ㏿ᗘ䛾ᐃᘧ 82 ᇹ3ᇘ 䛚䜘䜃䛭䛾ᛂ䜶䞁䝍䝹䝢䞊䛾ᑟฟ䛜㔜せ䛷䛒䜛䠊 3. 4. ⤖ゝ 㻌 ⮬↛Ⓨⅆᢚไἲ䛸䛧䛶䛾⏝ྍ⬟ᛶ䛜♧၀䛥䜜䛯⁐ฎ⌮ἲ䛻䛴䛔䛶✀䚻䛾▼Ⅳ䛚 䜘䜃䝞䜲䜸䝬䝇䛻ᑐ䛧䛶䛣䛾ฎ⌮䜢䛧䠈⁐ฎ⌮ἲ䛜ᖜᗈ䛔Ⅳ⣲㈨※䛻ᑐ䛧䛶䠈⮬↛ Ⓨⅆᢚไ䛸⬺Ỉ䞉ᨵ㉁䛸䜢ྠ䛻ᐇ⌧䛷䛝䜛䛛䜢᳨ウ䛧䛯䠊ᮏ◊✲䛷⏝䛔䛯⁐ฎ⌮䛾 ᮲௳䛷䛿䠈䛩䜉䛶䛾ヨᩱ䛻ᑐ䛧䛶⬺Ỉ䛚䜘䜃ᨵ㉁ຠᯝ䛜䜏䜙䜜䛯䠊䛺䛛䛷䜒䝞䜲䜸䝬䝇䠈 ἾⅣ䛚䜘䜃〓Ⅳ䜢ள℡㟷Ⅳ䛸ྠ⛬ᗘ䛾Ⓨ⇕㔞䛻ᨵ㉁䛷䛝䜛䛣䛸䛜䜟䛛䛳䛯䠊䜎䛯䠈〓Ⅳ 䜔ள℡㟷Ⅳ䠈℡㟷Ⅳ䛷䛿䠈Ⅳ⣲䛚䜘䜃Ỉ⣲䛾䝻䝇䛜ᑡ䛺䛟䠈㓟⣲䛜ᖜ䛻㝖ཤ䛥䜜䜛䛯 䜑䠈⁐ฎ⌮ヨᩱ䛾ཎᩱᇶ‽䛾Ⓨ⇕㔞䛿ཎᩱ䛾Ⓨ⇕㔞䜘䜚䜒䛝䛟䠈ຠ⋡ⓗ䛺ᨵ㉁䛜ᐇ ⌧䛥䜜䛯䠊⁐ฎ⌮ヨᩱ䜢ศ㞳䛧ᚓ䜙䜜䛯 3 ✀㢮䛾䝣䝷䜽䝅䝵䞁䛷䛒䜛 Residue䠈Deposit 䛚䜘䜃 Soluble 䛻䛴䛔䛶ẚ㍑䛩䜛䛸䠈㉁䛾ప䛔ཎᩱ䜋䛹ᐊ 䛻䛚䛔䛶䜒⁐ྍ⁐䛺 Soluble 䛾ྜ䛜ቑຍ䛧䠈⁐⁐ᡂศ䛷䛒䜛 Residue 䛾ྜ䛜ῶᑡ䛧䛯䠊ฎ⌮Ⅳ䛾 FT-IR 䝇䝨䜽䝖䝹䜢ẚ㍑䛩䜛䛣䛸䛷ฎ⌮୰䛾ᅛయ⏕ᡂ≀䛾ᵓ㐀ኚ䜢ㄪ䜉䛯⤖ᯝ䠈⁐ ฎ⌮䛚䜘䜃⇕ศゎฎ⌮䛸䜒䛻Ỉ㓟ᇶ䛚䜘䜃䜹䝹䝪䜻䝅䝹ᇶ䛜ῶᑡ䛧䛶䛚䜚䠈⁐ฎ⌮䛷 䛿ⰾ㤶᪘Ⅳ⣲䛜ቑຍ䛧䠈⇕ศゎฎ⌮䛷䛿ⰾ㤶᪘Ⅳ⣲䛾䝢䞊䜽䛜ῶᑡ䛧䛯䠊䛣䛾䛣䛸䛛䜙 ⁐ฎ⌮䛿ฎ⌮୰䛷ⰾ㤶⎔䛜⏕ᡂ䛧䠈⇕ศゎฎ⌮䛷䛿ⰾ㤶᪘Ⅳ⣲䜢ྵ䜐 Tar 䛜⏕ᡂ䛩 䜛䛣䛸䛜ศ䛛䛳䛯䠊 㻌 䜎䛯䠈2 ✀㢮䛾〓Ⅳ䛚䜘䜃䛭䜜䜙䛛䜙ㄪ〇䛧䛯ヨᩱ䛻䛴䛔䛶 65 °C 䛻䛚䛡䜛㓟⣲྾╔ᣲ ື䜢ほᐹ䛧䛯䠊⁐ฎ⌮ヨᩱ䛿⇕ศゎヨᩱ䜘䜚䜒 2 㛫ᚋ䛾㓟⣲྾╔㔞 qO, 2h 䛜ᑠ䛥䛟䛺 䛳䛯䛜䠈ཎⅣ䜘䜚䜒䜟䛪䛛䛻䛝䛟䛺䛳䛯䠊䜎䛯䠈⁐ྍ⁐ᡂศ䛷䛒䜛 Soluble 䛚䜘䜃 Deposit 䛿 qO, 2h 䛜ᖜ䛻ᑠ䛥䛟䛺䛳䛯䠊䛣䜜䛿⁐ྍ⁐ᡂศ䛜㌾⁐⼥ᛶ䜢᭷䛧䠈⣽Ꮝ ⾲㠃✚䛜㠀ᖖ䛻ᑠ䛥䛟䛺䜛䛯䜑㓟⣲䛾䜰䜽䝉䝇䛜ᢚไ䛥䜜䛯䛯䜑䛷䛒䜛䠊䜎䛯䠈⁐ฎ⌮ ヨᩱ䛿⁐ྍ⁐ᡂศ䛜⣽Ꮝ䜢㛢ሰ䛥䛫䜛䛣䛸䛷⣽Ꮝ⾲㠃✚䜢ᑠ䛥䛟䛧䠈㓟⣲䛾䜰䜽䝉䝇䜢 83 ๋дϼྸඥ↝Ꮾ൦∝ોឋ⇁ˤⅵᐯႆ້৮Сඥ↗ↆ↕↝МဇӧᏡࣱ ᢚไ䛧䛯䛯䜑䛻 Residue 䜔⇕ศゎヨᩱ䜘䜚䜒 qO, 2h 䛜ప䛟䛺䛳䛯䛣䛸䛜᫂䜙䛛䛸䛺䛳䛯䠊䛣䛾 䛣䛸䛛䜙䠈⁐ฎ⌮ヨᩱ䛿⣽Ꮝ⾲㠃✚䛜ῶᑡ䛧䛯䛣䛸䛷ప 䛻䛚䛡䜛㓟⣲䛸䛾ᛂᛶ䛜 ᢚไ䛥䜜䛯䛣䛸䛜♧၀䛥䜜䛯䠊௨ୖ䜘䜚䠈⁐ฎ⌮䛿పရⅣ⣲㈨※䜢ຠ⋡ⓗ䛻⬺Ỉ䞉ᨵ ㉁䛷䛝䠈ప 㓟ᛶ䜢⇕ศゎฎ⌮䜘䜚䜒ᢚไ䛷䛝䜛పရⅣ䛾᭷ຠ⏝䛾䛯䜑䛾᭷⏝䛺 ฎ⌮䛷䛒䜛䛣䛸䛜♧䛥䜜䛯䠊 ཧ⪃ᩥ⊩ [1] Miura, K., Hasegawa, Y., Ashida, R., Upgrading of brown coal using solvent extraction at high temperature, American Chemical Society Division of Fuel Chemistry, 2009, 54-2, 870-871. [2] Li, X., Hasegawa, Y., Morimoto, M., Ashida, R., Miura, K., Conversion of low-rank coals into upgraded coals and extracts having similar chemical and physical properties using degradative solvent extraction, American Chemical Society Division of Fuel Chemistry, 2010, 552, 212214. [3] Mott, R. A., Spooner, C. E., The calorific value of carbon in coal: The Dulong relationship, Fuel, 1949, 10, 226231, 242251. [4] van Kleveren, D. W., “Coal”, 3rd Edition, Elsevier 1993. [5] Wang, H., Dlugogorski, B. Z., Kennedy, E. M., Coal oxidation at low temperatures: oxygen consumption, oxidation products, reaction mechanism and kinetic modelling, Progress in Energy and Combustion Science, 2003, 29, 487513. [6] Kaji, R., Hishinuma, Y., Nakamura, Y., Low temperature oxidation of coal. Effects of pore structure and coal composition, Fuel, 1985, 64, 297302. 84 ᇹ4ᇘ ➨ 4 ❶㻌 ▼Ⅳప 㓟䛾ᛂ㏿ᗘゎᯒ 4. 1. ⥴ゝ 㻌 ▼Ⅳ䛾ప 㓟䛿༢୍ᛂ䛷䛿䛺䛟䠈ᛂ䛾㐍⾜䛻䜘䛳䛶␗䛺䜛ᛂ䛜㉳䛣䜛䠊䛭䛾 䛯䜑䠈▼Ⅳ䛾㓟㐣⛬䛾ᩘ್䝅䝭䝳䝺䞊䝅䝵䞁䛻䛿䛭䛾ᶵᵓ䛻ᇶ䛵䛔䛯㏿ᗘゎᯒ䛜ᚲせ 䛸䛺䜛䠊䛧䛛䛧䛺䛜䜙䠈▼Ⅳ䛾㓟䛻䛴䛔䛶䠈ᛂ䛾㐍⾜䛻క䛖ᛂ㏿ᗘ䝟䝷䝯䞊䝍䞊䛾 ኚ䜢ゎᯒ䛧䛯◊✲䛿㠀ᖖ䛻ᑡ䛺䛟䠈༢୍ᛂ䜢௬ᐃ䛧䛯ゎᯒ䛜䛻⾜䜟䜜䛶䛔䜛䠊 㻌 」ྜᛂ䛾ゎᯒἲ䛾୍䛴䛸䛧䛶䠈୪ิ୍ḟᛂ䝰䝕䝹(Distributed Activation Energy Model, DAEM)[1]䛜䛒䜛䠊䛣䛾䝰䝕䝹䛿䠈▼Ⅳ䛾⇕ศゎ䛾㏿ᗘゎᯒ䛺䛹䛻⏝䛔䜙䜜䛶䛚䜚䠈 ྛᛂ⋡䛻䛚䛡䜛㏿ᗘ䝟䝷䝯䞊䝍䞊䜢 3 䛴௨ୖ䛾᪼ ㏿ᗘ䛻䛚䛡䜛㔜㔞ῶᑡ䜘䜚ồ䜑䜛 䛣䛸䛜䛷䛝䜛䠊䛧䛛䛧䠈DAEM ἲ䜢▼Ⅳ䛾㓟䛻⏝䛔䛯䛿ぢ䛒䛯䜙䛪䠈㐺⏝ྍ⬟ᛶ䛻䛴 䛔䛶᳨ウ䛩䜛ᚲせ䛜䛒䜛䠊䛭䛣䛷䠈ᮏ❶䛷䛿䠈䜎䛪 DAEM ἲ䜢▼Ⅳ㓟䛻㐺⏝ྍ⬟䛻䛴 䛔䛶᳨ウ䛧䛯䠊ḟ䛻 DAEM ἲ䛻䜘䜛ᛂ㏿ᗘゎᯒ䜢⾜䛔䠈ᛂ㏿ᗘ䝟䝷䝯䞊䝍䞊䜢Ỵᐃ 䛧䠈䛭䛾ᛂ䛾㐍⾜䛻క䛖ኚ䜢⪃ᐹ䛧䛯䠊 㻌 䛥䜙䛻䠈ᚓ䜙䜜䛯㏿ᗘ䝟䝷䝯䞊䝍䞊䜢⏝䛔䛶䠈᩿⇕㐣⛬䛻䛚䛡䜛 LY ཎⅣ䛾 ᗘୖ᪼䛾 ᩘ್䝅䝭䝳䝺䞊䝅䝵䞁䜢⾜䛳䛯䠊ᮏ◊✲䛷䛿㔜㔞ῶᑡ㐣⛬䛻䛾䜏 DAEM ἲ䜢㐺⏝䛩䜛䛯 䜑䠈➨ 1 ❶䛾 AL Ⅳ䜔➨ 2 ❶䛾⁐ฎ⌮Ⅳ䛚䜘䜃⇕ศゎⅣ䛷䛿㓟ึᮇ䛾㔜㔞ቑຍ䜢 ⾲⌧䛷䛝䛺䛔䛜䠈AL Ⅳ䛻䛴䛔䛶䜒᩿⇕㐣⛬䛻䛚䛡䜛 ᗘୖ᪼䛾ᩘ್䝅䝭䝳䝺䞊䝅䝵䞁䜢 ⾜䛳䛯䠊 4. 2. ᐇ㦂䛚䜘䜃ゎᯒ 4. 2. 1. 㔜㔞ኚ䛚䜘䜃䜺䝇⏕ᡂ㏿ᗘ 85 ჽ໗˯ภᣠ҄↝Ӓࣖᡮࡇᚐௌ 㻌 1. 2. 1 㡯䛾ᅗ 1. 1 䛸ྠᵝ䛻䝬䜲䜽䝻䜺䝇䜽䝻䝬䝖䜾䝷䝣䜢┤⤖䛧䛯⇕ኳ⛗䜢⏝䛔䠈ヨᩱ⣙ 2 mg-d. a .f.䜢䝦䝸䜴䝮㞺ᅖẼୗ 110 °C 䛷 30 ศ㛫ಖᣢ䛩䜛䛣䛸䛷⇱䛥䛫䛯䛾䛱䠈ᶍᨃ✵ Ẽ㞺ᅖẼୗ䛷 40 ~ 700 °C 䜎䛷᪼ 䛧䠈㓟䛥䛫䛯䠊᪼ ㏿ᗘ䛿 1䠈2䠈5䠈10 K/min 䛾 4 ✀㢮䜢⏝䛔䛯䠊 4. 2. 2. Ⓨ⇕㏿ᗘ 㻌 1. 2. 2 㡯䛸ྠᵝ䛻 DSC 䜢⏝䛔䠈ヨᩱ⣙ 4 mg-d. a .f.䜢ᶍᨃ✵Ẽ㞺ᅖẼୗ䛷 40 ~ 450 °C 䜎䛷᪼ 䛧䛯䠊᪼ ㏿ᗘ䛿 2䠈5䠈10 K/min 䛾 3 ✀㢮䜢⏝䛔䛯䠊 4. 2. 3. ᛂ㏿ᗘゎᯒ 㻌 DAEM ἲ䛻䜘䜛㏿ᗘゎᯒ䜢ヨ䜏䛯䠊䛣䛾䝰䝕䝹䛷䛿䠈」ྜᛂ䛜↓㝈ಶ䛾୍ḟᛂ 䛛䜙ᵓᡂ䛥䜜䠈௵ព䛾ᛂ⋡䛻䛚䛔䛶䠈↓㝈ಶ䛾ᛂ䛾䛖䛱䛾୍䛴䛾䜏䛜㉳䛣䜛䛸䛔䛖௬ ᐃ䜢⏝䛔䜛䠊䛴䜎䜚ᛂ i 䛾ᛂ㏿ᗘ䛿ᛂ⋡ Xi䠈㢖ᗘᅉᏊ k’0,i䠈䛚䜘䜃άᛶ䜶䝛䝹䜼 䞊Ei 䜢⏝䛔䛶(4. 1)ᘧ䛷⾲䛥䜜䜛䠊 dX i dt k 0,i e Ei / RT 1 X i k '0,i g ( pO2 )e Ei / RT 1 X i (4. 1) 㻌 g(pO2)䛿㓟⣲ศᅽ䛻㛵䛩䜛㛵ᩘ䛷䛒䜚䠈㓟⣲ศᅽ䛜୍ᐃ䛺䜙䜀䠈䜏䛛䛡䛾㢖ᗘᅉᏊ k0,i 䛾୰䛻ྵ䜎䜜䜛䠊䛩䜉䛶䛾ᛂ䛾㏿ᗘ䜢㊊䛧ྜ䜟䛫䜛䛣䛸䛷య䛾ᛂ⋡ X 䛸㛫 t 䛾 㛵ಀ䛜(4. 2)ᘧ䛸⾲䛩䛣䛸䛜䛷䛝䜛䠊 1 X dX dt ³ f 0 t exp§¨ k 0 ³ e E / RT dt ' ·¸ f E dE 0 ¹ © f t ³ ®k0 e E / RT exp ª k0 ³ e E / RT dt 'º f E ½¾dE «¬ »¼ 0 ¯ 0 ¿ 86 (4. 2) ᇹ4ᇘ 䛣䛣䛷䠈f(E)䛿つ᱁䛥䜜䛯άᛶ䜶䝛䝹䜼䞊䛾ศᕸ㛵ᩘ䛷䛒䜛䠊䛭䜜䛮䜜䛾ᛂ䛜䝇 䝔䝑䝥ୖ䛻㐍⾜䛩䜛䛸䜏䛺䛩䛸䠈ಶ䚻䛾ᛂ䛻ᑐ䛩䜛ᛂ⋡ Xi = 0.58 䛾䛸䛝䛻㉳䛣䜛䛣䛸 䛻䛺䜛[2, 3]䠊䛭䛾䛯䜑㢖ᗘᅉᏊ䛚䜘䜃άᛶ䜶䝛䝹䜼䞊䛻䛿䠈(4. 3)ᘧ䛾䜘䛖䛺㛵ಀ䛜ᡂ䜚 ❧䛱䠈3 䛴௨ୖ䛾␗䛺䜛᪼ ㏿ᗘ a 䛻䛴䛔䛶ྠ୍䛾ᛂ⋡䛻䛚䛡䜛 ᗘ䜢⏝䛔䛶䠈1/T 䛸 ln(a2/T)䛾䜰䝺䝙䜴䝇䝥䝻䝑䝖䜢⾜䛖䛣䛸䛷㏿ᗘ䝟䝷䝯䞊䝍䞊䜢ồ䜑䜛䛣䛸䛜䛷䛝䜛䠊 E1 § a · §k R· ln¨ 2 ¸ # ln¨ 0 ¸ 0.6075 RT ©T ¹ © E ¹ (4. 3) ᮏㄽᩥ䛷䛿 LY Ⅳ䛚䜘䜃 PRB Ⅳ䛿 X = 0.01 ~ 0.12 䜎䛷䜢 0.01 㛫㝸䛷 12 Ⅼ䛚䜘䜃 X = 0.13 ~ 0.99 䜎䛷䜢 0.02 㛫㝸䛷 44 Ⅼ䛾 56 ಶ䠈AL Ⅳ䛿 X = 0.00 ~ 0.11 䜎䛷䜢 0.01 㛫㝸䛷 12 Ⅼ䛚䜘䜃 X = 0.12 ~ 0.98 䜎䛷䜢 0.02 㛫㝸䛷 44 Ⅼ䛾 56 ಶ䛾ᛂ䛷▼Ⅳయ䛾ᛂ䜢 ⾲⌧䛧䛯䠊 㻌 ➨ 1 ❶䜘䜚䠈▼Ⅳ㓟䛾ึᮇẁ㝵䛷䛿ྵ㓟⣲ᐁ⬟ᇶ䛾㓟䛜㏲ḟⓗ䛻㐍⾜䛧䛶䛔䜛䛣 䛸䛛䜙䠈䜎䛯䠈⏕ᡂ䜺䝇䛾䝰䝹ẚ䛜 ᗘ䛻䜘䛳䛶ኚ䛩䜛䛣䛸䛛䜙䠈ྛᛂ䛻ᑐ䛩䜛ᛂ ⋡䜢ᐃ⩏䛩䜛䛣䛸䛿ᅔ㞴䛷䛒䜛䠊䛭䛾䛯䜑䠈ᮏ◊✲䛷䛿▼Ⅳ䛾㔜㔞ῶᑡ䛻ᑐ䛧䛶 DAEM ἲ䜢㐺⏝䛧䠈㓟ึᮇ䛾▼Ⅳ㔜㔞䛻ᑐ䛩䜛㔜㔞ῶᑡ䛛䜙ᛂ⋡䜢ồ䜑䛯䠊䜎䛯䠈䛒䜛 ᛂ⋡䛻䛚䛔䛶୍䛴䛾ᛂ䛾䜏䛜㐍⾜䛩䜛䛸䛔䛖௬ᐃ䛿ཝᐦ䛻䛿ᡂ䜚❧䛯䛺䛔䛜䠈ᮏ◊✲ 䛷䛿ྛᛂ⋡䛻䛚䛡䜛䜏䛛䛡䛾ᛂ㏿ᗘ䝟䝷䝯䞊䝍䞊䜢ᑟฟ䛩䜛䛣䛸䛸䛧䛯䠊 4. 2. 4. ᩿⇕ ᗘୖ᪼ᩘ್䝅䝭䝳䝺䞊䝅䝵䞁 㻌 ᩿⇕ ᗘୖ᪼䛾ᩘ್䝅䝭䝳䝺䞊䝅䝵䞁䛷䛿⇱䛧䛯▼Ⅳ 1 kg 䜢㔝✚䜏䛻䛧䠈䛒䜛ึᮇ ᗘ䛛䜙୍ᐃ㔞䛾✵Ẽ䛻ᭀ㟢䛥䛫䛶ᛂ䛥䛫䛯ሙྜ䜢ᐃ䛧䛯䠊ィ⟬䛻⏝䛔䛯௬ᐃ䜢 ௨ୗ䛻♧䛩䠊 䞉 X 0.10 䛻䛚䛡䜛ึᮇ䛾 10 ಶ䛺䛔䛧 11 ಶ䛾ᛂ㏿ᗘ䜢⏝䛧䠈䛭䜜௨㝆䛾 ᛂ䛿⪃៖䛧䛺䛔䠊 87 ჽ໗˯ภᣠ҄↝Ӓࣖᡮࡇᚐௌ 䞉 ྛᛂ䛾ᐤ⋡䛿➼䛧䛟䠈f (Ei) ¨Ei = 0.01 䛸䛩䜛䠊 䞉 ▼Ⅳ䛸✵Ẽ䛾㛫䛻 ᗘᕪ䛿䛺䛔䠊 䞉 ▼Ⅳ䛚䜘䜃✵Ẽ䛾⇕ᐜ㔞䛿 ᗘ䛻䜘䜙䛪୍ᐃ䛷䛒䜛䠊 䞉 ᛂ䛻క䛖✵Ẽ䛾⤌ᡂኚ䛿↓ど䛷䛝䜛䠊 䛣䛾௬ᐃ䛾䜒䛸䛷䛿≀㉁ᨭ䛿▼Ⅳ䛾㔜㔞ῶᑡ䛾䜏䛸䛺䜛䠊ᛂ㏿ᗘᘧ䛿(4. 2)ᘧ䜢ᚤ ᑠ༊㛫¨Ei 䛾㊊䛧ྜ䜟䛫䛻᭩䛝䛘䛯(4. 4)ᘧ䜢⏝䛔䛯䠊 dX dt n t ¦ k 0,i e Ei / RT exp ª k 0,i ³ e Ei / RT dt 'º f ( Ei )'Ei «¬ »¼ 0 i 1 (4. 4) 䜎䛯䠈⇕ᨭ䛿(4. 5)ᘧ䛸䛺䜛䠊 ^c dT ¦ ri ' r H i p,coal 1 X Jc p,air ` dt n (4. 5) 0 䛣䛣䛷J䛿✵Ẽ䛸▼Ⅳ䛾㔜㔞ẚ[kg-air/kg-coal]䜢⾲䛩䠊cp,coal䠈cp,air 䛿䛭䜜䛮䜜▼Ⅳ䛚䜘䜃 ✵Ẽ䛾⇕ᐜ㔞[kJ/(kg K)]䛷䛒䜛䠊ri䠈¨rHi 䛿ᛂ i 䛾ᛂ㏿ᗘ[kg/(kg-coal min)]䛚䜘䜃 ᛂ䜶䞁䝍䝹䝢䞊[kJ/g]䛷䛒䜛䠊ri 䛿(4. 6)ᘧ䛾䜘䛖䛻⾲䛥䜜䜛䠊 ri t k 0,i e Ei / RT 1 X i k 0,i e Ei / RT exp§¨ k0,i ³ e Ei / RT dt ' ·¸ 0 © ¹ (4. 6) ᗘ T䠈▼Ⅳ䛾ᛂ⋡ X䠈䛚䜘䜃ྛᛂ䛾ᛂ㏿ᗘ ri 䛻ᑐ䛩䜛㐃❧ᚤศ᪉⛬ᘧ䜢 RKG ἲ䜢⏝䛔䛶✚ศ䛧䠈䛭䜜䜙䛾ኚᩘ䛾㛫ኚ䜢ィ⟬䛧䛯䠊✵Ẽ䛸▼Ⅳ䛾㔜㔞ẚ䛿J = 0, 4 䛾 2 䛴䜢⏝䛔䛯䠊J = 0 䛷䛿䠈ᛂ䛷⏕䛨䛯⇕䛜▼Ⅳ䛾 ᗘୖ᪼䛾䜏䛻⏝䛥䜜䜛䛯䜑䠈 ᭱䜒▼Ⅳ䛾 ᗘ䛜ୖ䛜䜚䜔䛩䛔䠈䛩䛺䜟䛱᭱䜒Ⓨⅆ䛜㉳䛝䜔䛩䛔᮲௳䛷䛒䜛䠊 88 ᇹ4ᇘ 4. 3. ⤖ᯝ䛸⪃ᐹ 4. 3. 1. ᪼ ㏿ᗘ䛾ᙳ㡪 㻌 ᅗ 4. 1 ~ 4. 3 䛻 LY Ⅳ䠈PRB Ⅳ䠈䛚䜘䜃 AL Ⅳ䛻䛴䛔䛶䠈␗䛺䜛᪼ ㏿ᗘ䛷䛾㔜㔞ኚ 䜢♧䛩䠊᪼ ㏿ᗘ䛜ᑠ䛥䛔䜋䛹ྠ䛨ᛂ⋡䛻䛺䜛 ᗘ䛜ప䛟䛺䜛䠊 Relative weight [kg/kg-daf] 1 LY 0.8 10 K/min 0.6 0.4 5 K/min 2 K/min 1 K/min 0.2 0 100 200 300 400 500 Temperature [°C] 600 700 Relative weight [kg/kg-raw coal daf] 4. 1. LY ໗↝ᣠ҄↝҄٭ 1 PRB 0.8 10 K/min 0.6 5 K/min 2 K/min 1 K/min 0.4 0.2 0 100 200 300 400 500 Temperature [°C] 600 700 4. 2. PRB ໗↝ᣠ҄↝҄٭ 89 ჽ໗˯ภᣠ҄↝Ӓࣖᡮࡇᚐௌ Relative weight [kg/kg-daf] 1 AL 0.8 10 K/min 5 K/min 0.6 2 K/min 1 K/min 0.4 0.2 0 100 200 300 400 500 Temperature [°C] 600 700 25 20 Loy Yang 20 15 10 K/min 15 5 K/min 2 K/min 10 10 10 K/min 5 K/min 5 2 K/min 5 0 Weight change rate [mg/(g-sample•K)] Accumulation of heat generation [kJ/g-sample] 4. 3. AL ໗↝ᣠ҄↝҄٭ 0 0.2 0.4 0.6 Conversion, X [-] 0.8 4. 4. LY ໗↝ถݲᡮࡇ↗ႆ༏ 90 1 0 25 20 PRB 20 15 2 K/min 5 K/min 10 K/min 15 10 10 K/min 5 K/min 2 K/min 10 5 5 0 0 0.2 Weight change rate [mg/(g-sample•K)] Accumulation of heat generation [kJ/g-sample] ᇹ4ᇘ 0.4 0.6 Conversion, X [-] 0.8 1 0 25 20 Alabama 2 K/min 20 15 5 K/min 2 K/min 15 10 K/min 10 10 5 K/min 10 K/min 5 0 Weight change rate [mg/(g-sample•K)] Accumulation of heat generation [kJ/g-sample] 4. 5. PRB ໗↝ถݲᡮࡇ↗ႆ༏ 0 0.2 0.4 0.6 Conversion, X [-] 5 0.8 4. 6. AL ໗↝ถݲᡮࡇ↗ႆ༏ 91 1 0 ჽ໗˯ภᣠ҄↝Ӓࣖᡮࡇᚐௌ 㻌 DAEM ἲ䜢㐺⏝䛩䜛䛯䜑䛻䛿䠈ྛᛂ⋡䛻䛚䛔䛶㉳䛝䛶䛔䜛ᛂ䛚䜘䜃ᅛయ䛾ᛶ≧ 䛿᪼ ㏿ᗘ䛻䜘䜙䛪ྠ䛨䛷䛒䜛䛸䛔䛖᮲௳䜢‶䛯䛥䛺䛡䜜䜀䛺䜙䛺䛔䠊䛭䛣䛷䠈䛭䜜䛮䜜 䛾᪼ ㏿ᗘ䛻ᑐ䛧䠈ྛᛂ⋡ X 䛻䛚䛡䜛 ᗘ䛻ᑐ䛩䜛㔜㔞ῶᑡ㏿ᗘ䛚䜘䜃Ⓨ⇕㔞䛾✚ ⟬್䜢ồ䜑䠈ᅗ 4. 4 ~ 4. 6 䛻♧䛧䛯䠊䛔䛪䜜䛾▼Ⅳ䜒 ᗘ䛻ᑐ䛩䜛㔜㔞ῶᑡ㏿ᗘ䛚䜘䜃 Ⓨ⇕㔞䛾✚⟬್䛿䛚䛚䜐䛽ᛂ⋡䛻䜘䜙䛺䛔䛣䛸䛛䜙䠈ྠ୍ᛂ⋡䛻䛚䛔䛶䛿᪼ ㏿ ᗘ䛻䜘䜙䛪ྠ䛨ᛂ䛜㉳䛝䛶䛔䜛䛸䜏䛺䛩䛣䛸䛜䛷䛝䜛䛸䛧䛯䠊10 K/min 䛷䛾 AL Ⅳ䛾㓟 䛷䛿䠈ᛂ⋡䛜 0.2 ~ 0.4 䛾⠊ᅖ䛷ᛴ⃭䛺㔜㔞ῶᑡ䛜ᩘ䛛ᡤ䜏䜙䜜䛯䛯䜑䠈 ᗘ䛻ᑐ䛩 䜛㔜㔞ῶᑡ㏿ᗘ䛜䛝䛟䜜䛶䛔䛯䠊䛣䜜䛿䠈10 K/min 䛷᪼ 䛧䛯㝿䛻䛿㛫䛻ᑐ䛩䜛 㔜㔞ῶᑡ㏿ᗘ䛜㧗䛟䛺䜛䛯䜑䠈ヨᩱ䛾⇕䛜↓ど䛷䛝䛺䛟䛺䛳䛯ྍ⬟ᛶ䛜䛒䜛䠊 㻌 ᅗ 4. 4 ~ 4. 6 ୰䛾Ⓨ⇕㔞᭤⥺䛾ഴ䛝䛿䛭䛾ᛂ⋡䛻䛚䛡䜛ᛂ䜶䞁䝍䝹䝢䞊䛾⤯ᑐ್ 䛻ᑐᛂ䛩䜛䠊LY Ⅳ䛸 PRB Ⅳ䛷䛿 X = 0.1 ௨ୗ䛷Ⓨ⇕㔞᭤⥺䛾ഴ䛝䛜ᛴ䛻䛺䛳䛶䛚䜚䠈 ᛂึᮇ䛾䜋䛖䛜ᛂ䜶䞁䝍䝹䝢䞊䛾⤯ᑐ್䛜䛝䛔䛣䛸䜢♧䛧䛶䛔䜛䠊䜎䛯䠈X = 0.4 ௨ୖ 䛷䛿䜋䜌ഴ䛝䛜୍ᐃ䛸䛺䛳䛶䛔䜛䠊➨ 1 ❶䛷♧䛧䛯ᛂᶵᵓ䜘䜚䠈X = 0.4 ௨ୖ䛷䛿▼Ⅳ 㦵᱁䛾㓟䛜㉳䛣䛳䛶䛚䜚䠈䛭䜜௨ୗ䛷䛿䠈▼Ⅳ୰䛾⬡⫫᪘Ⅳ⣲䜔ྵ㓟⣲ᐁ⬟ᇶ䛜 䛻ᛂ䛧䛶䛔䜛䠊䛣䛾䛣䛸䛛䜙䠈⬡⫫᪘Ⅳ⣲䛚䜘䜃ྵ㓟⣲ᐁ⬟ᇶ䛾㓟䛿▼Ⅳ㦵᱁䛾㓟 䜘䜚䜒ᛂ䜶䞁䝍䝹䝢䞊䛜䛝䛔䛣䛸䜢⾲䛧䛶䛔䜛䠊X = 0.4 ௨ୖ䛷䛾ᛂ䜶䞁䝍䝹䝢䞊 䛿 í 18 MJ/kg-sample 䛷䛒䜚䠈Ⅳ⣲䛾⇞↝䛻䜘䜚 CO2 䛚䜘䜃 CO 䛜⏕ᡂ䛩䜛ᛂ䛾ᛂ 䜶䞁䝍䝹䝢䞊䛿䛭䜜䛮䜜 í32.8 MJ/kg-C (í393.52 kJ/mol-C)䛚䜘䜃 í9.21 MJ/kg-C (í110.54 kJ/mol-C)䛷䛒䜛䛣䛸䛛䜙䠈▼Ⅳ㦵᱁䛾㓟䛷䛿 CO 䛸 CO2 䛾⏕ᡂ䜶䞁䝍䝹䝢䞊 䛾㛫䛾್䜢ྲྀ䜛䠊䜎䛯䠈⬡⫫᪘Ⅳ⣲䛚䜘䜃ྵ㓟⣲ᐁ⬟ᇶ䛾ᛂ䜶䞁䝍䝹䝢䞊䛿 í30 ~ í40 MJ/kg-sample 䛷䛒䜚䠈䝯䝍䞁䛾⇞↝䛾ᛂ䜶䞁䝍䝹䝢䞊 í55.5 MJ/kg-CH4 (í890.36 kJ/mol-CH4)䜔䝧䞁䝊䞁䛾⇞↝䛾ᛂ䜶䞁䝍䝹䝢䞊 í41.8 MJ/kg-C6H6 (í3267.6 kJ/mol-C6H6)䛸䛔䛳䛯 CO2 䛸 H2O 䛜⏕ᡂ䛩䜛䜘䛖䛺ᛂ䛾䜶䞁䝍䝹䝢䞊䛸ఝ䛯್ 䛷䛒䛳䛯䠊 㻌 ୍᪉䠈AL Ⅳ䛷䛿Ⓨ⇕㔞᭤⥺䛾 X = 0 ㏆ഐ䛷䛾ഴ䛝䛜 LY Ⅳ䜔 PRB Ⅳ䜘䜚ᑠ䛥䛟䛺䛳䛯䠊 92 ᇹ4ᇘ 䛣䜜䛿⬡⫫᪘Ⅳ⣲䜔ྵ㓟⣲ᐁ⬟ᇶ䛾㓟䛿ᛂึᮇ䛾㔜㔞ቑຍ䛜㉳䛝䛶䛔䜛 ᗘ䛷 ⏕䛨䛶䛚䜚䠈㔜㔞ῶᑡ㐣⛬䛾䜏䜢♧䛧䛯ᅗ 4. 6 䛷䛿䠈䛔䛪䜜䛾ᛂ⋡䛷䜒▼Ⅳ㦵᱁㒊ศ 䛾㓟䛜䛻㐍⾜䛧䛶䛔䜛䛯䜑䛷䛒䜛䛸⪃䛘䜙䜜䜛䠊 4. 3. 2. ᛂ㏿ᗘゎᯒ 㻌 4. 2. 3 㡯䛷㏙䜉䛯䜘䛖䛻 56 Ⅼ䛻䛚䛔䛶㏿ᗘゎᯒ䜢⾜䛳䛯䠊(4. 3)ᘧ䛻䜒䛸䛵䛝䠈a2/T 䛸 1/T 䛾䜰䝺䝙䜴䝇䝥䝻䝑䝖䜢ᅗ 4. 7 ~ 4. 9 䛻♧䛩䠊┤⥺䛾ഴ䛝䛿䛚䛚䜐䛽ᛂ⋡䛜䛝䛟䛺 䜛䜋䛹ᛴ䛻䛺䛳䛯䠊ᅗ 4. 7 ~ 4. 9 䜘䜚ồ䜑䛯άᛶ䜶䝛䝹䜼䞊䜢ᅗ 4. 10 䛻♧䛩䠊䛔䛪䜜 䛾▼Ⅳ䜒άᛶ䜶䝛䝹䜼䞊䛜 100 ~ 180 kJ/mol 䛻ศᕸ䛧䛶䛚䜚䠈୍⯡ⓗ䛻ゝ䜟䜜䛶䛔䜛 άᛶ䜶䝛䝹䜼䞊䛾್䜘䜚䜒䛝䛟䛺䛳䛯䠊LY Ⅳ䛚䜘䜃 PRB Ⅳ䛷䛿䠈ᛂ⋡䛜䛝䛟䛺䜛 䛻䛴䜜䛶άᛶ䜶䝛䝹䜼䞊䛜䛝䛟䛺䜚䠈X = 0.5 ௨ୖ䛷䛿䜋䜌୍ᐃ䛸䛺䛳䛯䛜䠈AL Ⅳ䛷 䛿 X = 0.2 ㏆䛷άᛶ䜶䝛䝹䜼䞊䛜᭱䛸䛺䜚䠈䛭䜜௨ୖ䛷䛿ᛂ⋡䛜䛝䛟䛺䜛䛻䛴 䜜䛶άᛶ䜶䝛䝹䜼䞊䛜ᑠ䛥䛟䛺䛳䛯䠊 10 -4 8 LY 6 2 10 -5 10 K/min 8 5 K/min 6 2 a/T [1/(min K)] 4 4 2 K/min 2 10 1 K/min -6 1.0 1.2 1.4 1.6 1.8 -1 î1 1000/T 1/T [K[K] ] 2.2 -3 2.0 2.2x10 4. 7. LY ໗↝⇈−⇱⇌⇟⇽∓⇩⇮ 93 ჽ໗˯ภᣠ҄↝Ӓࣖᡮࡇᚐௌ 10 -4 8 PRB 6 2 10 K/min 10 -5 5 K/min 8 6 2 a/T [1/(min K)] 4 2 K/min 4 1 K/min 2 10 -6 1.0 1.2 2.2 -3 2.0 2.2x10 1.4 1.6 1.8 -1 î1 1000/T 1/T [K[K] ] 4. 8. PRB ໗↝⇈−⇱⇌⇟⇽∓⇩⇮ 10 -4 8 AL 6 a/T [1/(min K)] 4 5 K/min -5 8 2 K/min 6 2 10 10 K/min 2 4 1 K/min 2 10 -6 1.0 1.2 1.4 -1 î1 1000/T 1/T [K[K] ] 1.6 4. 9. AL ໗↝⇈−⇱⇌⇟⇽∓⇩⇮ 94 1.8 -3 1.8x10 ᇹ4ᇘ Activation energy [kJ/mol] 200 0 11 16 Number, i [-] 26 36 46 56 LY 150 AL PB PRB 100 50 0 0.2 0.4 0.6 0.8 1 Selected conversion, Conversion, X [-] X [-] 4. 10. Ӳჽ໗↝ࣱ҄⇎⇳∑⇔∞↝҄٭ 10 -1 Frequency factor, ki [min ] 10 10 10 10 14 LY 13 12 11 10 10 10 10 10 PRB 9 8 AL 7 6 100 120 140 160 Activaiton Energy, Ei [kJ/mol] 180 4. 11. Ӳჽ໗↝ࣱ҄⇎⇳∑⇔∞↗᫁ࡇ̞᧙↝܇׆ 95 ჽ໗˯ภᣠ҄↝Ӓࣖᡮࡇᚐௌ 㻌 㢖ᗘᅉᏊ䛸άᛶ䜶䝛䝹䜼䞊䛾㛵ಀ䜢ᅗ 4. 11 䛻♧䛩䠊㢖ᗘᅉᏊ䛿 106 ~ 1014 miní1 ⛬ ᗘ䛷ኚ䛧䛶䛚䜚䠈k0 = D exp(EE) (D䠈E䛿ṇ䛾ᐃᩘ)䛾䜘䛖䛺⿵ൾ㛵ಀ䛿୍㒊䛾ᛂ⋡䛾 ⠊ᅖ䛷䛧䛛ぢ䜙䜜䛺䛛䛳䛯䠊䛣䛣䛷ồ䜑䛯㢖ᗘᅉᏊ䛿㓟⣲ศᅽ౫Ꮡᛶ䜔⣽Ꮝ⾲㠃✚䠈ึ ᮇᛂ≀⃰ᗘ䜒ྵ䜎䜜䛯㢖ᗘᅉᏊ䛷䛒䜚䠈ᛂ⋡䛻䜘䛳䛶㓟⣲ศᅽ䛾ḟᩘ䜔ึᮇᛂ ≀⃰ᗘ䛜ኚ䛩䜛䛯䜑⿵ൾ㛵ಀ䛜ぢ䜙䜜䛺䛛䛳䛯䛸⪃䛘䜙䜜䜛䠊䜎䛯䠈ྠ୍ᛂ⋡䛷ẚ ㍑䛩䜛䛸䠈㢖ᗘᅉᏊ䛿 LY Ⅳ䛜᭱䜒䛝䛟䠈PRB Ⅳ䜔 AL Ⅳ䜘䜚䜒ప 䛻䛚䛡䜛㓟⣲䛸䛾 ᛂᛶ䛜㧗䛔䛣䛸䛜ᫎ䛥䜜䛶䛔䜛䠊 㻌 ᅗ4. 11 䛻♧䛧䛯㏿ᗘ䝟䝷䝯䞊䝍䞊䜢⏝䛔䛶䠈䛭䜜䛮䜜䛾▼Ⅳ䛾㔜㔞ῶᑡ᭤⥺䜢ィ⟬ 䛧䛯⤖ᯝ䜢ᅗ 4. 12 ~ 4. 14 䛻♧䛩䠊▼Ⅳ㓟䛾⾲⌧䛻⏝䛔䛯䛩䜉䛶䛾ᛂ䠈ᐇ㦂䛷⏝䛔 䛯䛩䜉䛶䛾᪼ ㏿ᗘ䛻䛴䛔䛶䠈ィ⟬್䛸ᐇ ್䛾ㄗᕪ䛾⤯ᑐ್䛿᭱䛷䜒 10 °C 䛷䛒䜚䠈 90 %௨ୖ䛿 2 °C ௨ෆ䛷䛒䛳䛯䠊䛣䛾䛣䛸䛛䜙䠈ᮏゎᯒ䛷ᚓ䜙䜜䛯ᛂ㏿ᗘ䝟䝷䝯䞊䝍䞊䛻 䜘䜚ᐇ㦂⤖ᯝ䜢Ⰻዲ䛻⌧䛷䛝䜛䛣䛸䛜♧䛥䜜䛯䠊 㻌 䛔䛟䛴䛛䛾ᛂ⋡䛻䛚䛡䜛䜏䛛䛡䛾ᛂ㏿ᗘᐃᩘ ki = k0,i exp (íEi / RT)䛾 ᗘ౫Ꮡᛶ 䜢䜰䝺䝙䜴䝇䝥䝻䝑䝖䛾ᙧ䛷ᅗ 4. 15 ~ 4. 17 䛻♧䛧䛯䠊200 °C 䛷ẚ㍑䛩䜛䛸䠈䛔䛪䜜䛾▼Ⅳ 䜒ᛂ⋡䛜䛝䛔䜋䛹䠈䛴䜎䜚ᛂ䛜㐍⾜䛩䜛䜋䛹䠈䜏䛛䛡䛾ᛂ㏿ᗘᐃᩘ䛜ᑠ䛥䛟䛺䛳 䛯䠊LY Ⅳ䛚䜘䜃 PRB Ⅳ䛻䛚䛔䛶⬡⫫᪘Ⅳ⣲䜔ྵ㓟⣲ᐁ⬟ᇶ䛾㓟䛜⏕䛨䛶䛔䜛 X = 0.03 䛻䛚䛡䜛䜏䛛䛡䛾ᛂ㏿ᗘᐃᩘ䛿䠈LY Ⅳ䛿 5.42×10í3 miní1 䛷䛒䜚䠈PRB Ⅳ䛾 1.01×10í3 miní1䠈ALⅣ䛾 1.19×10í5 miní1 䜘䜚䜒䛝䛟䛺䛳䛯䠊୍᪉䠈▼Ⅳ㦵᱁㒊ศ䛾㓟 䛜⏕䛨䛶䛔䜛䛸⪃䛘䜙䜜䜛 X = 0.50 䜒䛧䛟䛿 0.51 䛻䛚䛡䜛䜏䛛䛡䛾ᛂ㏿ᗘᐃᩘ䛿䠈LY Ⅳ䛾ሙྜ䛿 5.10×10í6 miní1䠈PRB Ⅳ䛷䛿 6.27×10í6 miní1䠈AL Ⅳ䛷䛿 8.75×10í8 miní1 䛷䛒䜚䠈㓟ึᮇ䛾 X = 0.03 䛻䛚䛡䜛䜏䛛䛡䛾ᛂ㏿ᗘᐃᩘ䜘䜚䜒ᑠ䛥䛟䛺䛳䛯䠊≉䛻 LY Ⅳ䛷䛿䜏䛛䛡䛾㏿ᗘᐃᩘ䛾ᕪ䛜㢧ⴭ䛷䛒䜚䠈㓟ึᮇ䛾䜏䛛䛡䛾ᛂ㏿ᗘ䛿▼Ⅳ㦵᱁ 㓟䛾䜏䛛䛡䛾ᛂ㏿ᗘ䜘䜚⣙ 1000 ಸ䛝䛟䛺䛳䛯䠊 96 ᇹ4ᇘ Relative weight [kg/kg-raw coal daf] 1.1 LY 1 0.9 1 K/min 0.8 2 K/min 10 K/min 5 K/min 0.7 0.6 Measured Calculated 0.5 100 200 300 Temperature [°C] 400 4. 12. LY ໗↝ถ↝ݲϐᚘም Relative weight [kg/kg-raw coal daf] 1.1 PRB 1 0.9 1 K/min 0.8 10 K/min 5 K/min 2 K/min 0.7 0.6 0.5 100 Measured Calculated 200 300 Temperature [°C] 400 4. 13. PRB ໗↝ถ↝ݲϐᚘም 97 ჽ໗˯ภᣠ҄↝Ӓࣖᡮࡇᚐௌ Relative weight [kg/kg-raw coal daf] 1.1 AL 1 0.9 1 K/min 10 K/min 2 K/min 0.8 5 K/min 0.7 0.6 Measured Calculated 0.5 100 200 300 400 Temperature [°C] 500 4. 14. AL ໗↝ถ↝ݲϐᚘም -1 Rate constant, ki [min ] 10 10 10 10 10 10 10 10 1 0 -1 LY i=3 i = 16 (X = 0.21) i = 26 (X = 0.03) i=1 (X = 0.01) (X = 0.41) i = 31 -2 (X = 0.51) i = 21 i = 11 (X = 0.31) (X = 0.11) -3 -4 -5 -6 1.2 1.4 1.6 1.8 -1 1000/T 1/T [K[K]î1] 2.0 2.2x10 2.2 -3 4. 15. LY ໗↝↮ⅺↀ↝Ӓࣖᡮࡇܭૠ 98 ᇹ4ᇘ 10 -1 Rate constant, ki [min ] 10 10 10 10 10 10 10 1 i=3 i = 16 0 i =26 PRB (X = 0.03) (X = 0.41) (X = 0.21) i=2 (X = 0.02) -1 i = 31 (X = 0.51) -2 i = 11 i = 21 -3 (X = 0.11) (X = 0.31) -4 -5 -6 1.2 1.4 1.6 1.8 -1 î1 1000/T 1/T [K[K] ] 2.2 -3 2.0 2.2x10 4. 16. PRB ໗↝↮ⅺↀ↝Ӓࣖᡮࡇܭૠ 10 -1 Rate constant, ki [min ] 10 10 10 10 10 10 10 1 i = 17 0 (X = 0.20) AL i = 11 (X = 0.10) i=4 -1 (X = 0.03) i=3 -2 (X = 0.02) i = 32 (X = 0.50) i = 27 -3 (X = 0.40) i = 22 -4 (X = 0.30) -5 -6 1.2 1.4 1.6 1.8 -1 1000/T 1/T [K[K]î1] 2.2 -3 2.0 2.2x10 4. 17. AL ໗↝↮ⅺↀ↝Ӓࣖᡮࡇܭૠ 99 ჽ໗˯ภᣠ҄↝Ӓࣖᡮࡇᚐௌ 4. 3. 3. ᩿⇕ ᗘୖ᪼ᩘ್䝅䝭䝳䝺䞊䝅䝵䞁 㻌 ⾲ 4. 1 䛚䜘䜃⾲ 4. 2 䛻 LY Ⅳ䛚䜘䜃 AL Ⅳ䛾 ᗘୖ᪼䛾ᩘ್䝅䝭䝳䝺䞊䝅䝵䞁䛻⏝䛔䛯 䝟䝷䝯䞊䝍䞊䜢♧䛩䠊ᩘ್ィ⟬䛻⏝䛔䛯≀㉁ᨭᘧ䠈⇕ᨭᘧ䜢௨ୗ䛻♧䛩䠊 ≀㉁ᨭ䠖 dX dt n t ¦ k 0,i e Ei / RT exp ª k 0,i ³ e Ei / RT dt 'º f ( Ei )'Ei «¬ »¼ 0 i 1 (4. 4) ⇕ᨭ䠖 ^cp,coal 1 X Jcp,air `dT dt n ¦ r ' H r i i (4. 5) 0 䛯䛰䛧 ri t k 0,i e Ei / RT 1 X i k 0,i e Ei / RT exp§¨ k0,i ³ e Ei / RT dt ' ·¸ 0 © ¹ (4. 6) 㻌 ✀䚻䛾ึᮇ ᗘ䛻ᑐ䛧䛶 30 ᪥㛫䛷䛾 ᗘୖ᪼䜢ᩘ್䝅䝭䝳䝺䞊䝅䝵䞁䛧䛯⤖ᯝ䜢♧䛩䠊 ᭱䜒Ⓨⅆ䛜䛧䜔䛩䛔᮲௳䛷䛒䜛J = 0 䛾ሙྜ䛜ᅗ 4. 18 䛚䜘䜃ᅗ 4. 19䠈J = 4 䛾ሙྜ䛜ᅗ 4. 20 䛚䜘䜃ᅗ 4. 21 䛷䛒䜛䠊LY Ⅳ䛷䛿J = 0 䛾ሙྜ䛿ึᮇ ᗘ䛜 75 °C ௨ୖ䛷䠈J = 4 䛾 ሙྜ䛿ึᮇ ᗘ䛜 90 °C ௨ୖ䛷䛭䜜䛮䜜ᛴ⃭䛺 ᗘୖ᪼䛜䜏䜙䜜䠈▼Ⅳ䛜Ⓨⅆ䛧䛯䠊 ▼Ⅳ✵Ẽ㔜㔞ẚ䛾ኚ䛻䜘䜚䠈▼Ⅳ䛜Ⓨⅆ䛩䜛ึᮇ ᗘ䛜 15 °C 䜋䛹㧗䛟䛺䛳䛯䠊䜎䛯䠈 Ⓨⅆ䛜㉳䛝䛯䛸䛝䛾▼Ⅳ䛾 ᗘ䛿J = 0 䛾ሙྜ䛿 100 °C ⛬ᗘ䛷䛒䜚J = 4 䛾ሙྜ䛿 120 °C ⛬ᗘ䛷䛒䛳䛯䠊୍᪉䠈AL Ⅳ䛷䛿J = 0 䛾ሙྜึᮇ ᗘ䛜 140 °C ௨ୖ䛷▼Ⅳ䛾Ⓨⅆ䛜 30 ᪥௨ෆ䛻䜏䜙䜜䛯䛜䠈J = 4 䛾䛸䛝䛿ึᮇ ᗘ䛜 160 °C ௨ୗ䛷䛿 30 ᪥௨ෆ䛻Ⓨⅆ䛜䜏䜙 䜜䛺䛛䛳䛯䠊䛣䛾䜘䛖䛻▼Ⅳ✵Ẽ㛫䛷䛾⇕⛣ື䛻䜘䜛ᙳ㡪䛜㢧ⴭ䛻䜏䜙䜜䛯䠊 㻌 ᮏ◊✲䛷⏝䛔䛯᮲௳䛷䛿䠈▼Ⅳ୰䛾 ᗘศᕸ䠈䛚䜘䜃✵Ẽ▼Ⅳ㛫䛾 ᗘᕪ䜢⪃៖䛧 䛶䛔䛺䛔䛯䜑䠈௵ព䛾▼Ⅳ㔜㔞䛻ᑐ䛧䛶ྠ䛨⤖ᯝ䛜ᚓ䜙䜜䜛䠊ᐇ㝿䛻▼Ⅳ䜢㔝✚䜏䛻䛧 䛯ሙྜ䛻䛿䠈ᒁᡤⓗ䛺⇕䛻䜘䜚䠈Ⓨⅆ䛜㉳䛣䜛 ᗘ䛻㐩䛩䜛䜒䛾䛸⪃䛘䜙䜜䜛䠊J = 0 䛾 100 ᇹ4ᇘ ሙྜ䛿䠈ᛂ䛻䜘䜛Ⓨ⇕䛜䛩䜉䛶▼Ⅳ䛾 ᗘୖ᪼䛻䜟䜜䜛䛯䜑䠈᭱䜒Ⓨⅆ䛜䛧䜔䛩䛔 ᮲௳䛷䛒䜛䠊䛧䛯䛜䛳䛶䠈J = 0 䛷Ⓨⅆ䛜⏕䛨䛺䛔䜘䛖䛺 ᗘ䠈䛘䜀 LY Ⅳ䛷䛿 65 °C ௨ ୗ䠈䛻▼Ⅳ䛾 ᗘ䜢ಖ䛴䛣䛸䛜䛷䛝䜜䜀䠈30 ᪥㛫䛿ᛴ⃭䛺 ᗘୖ᪼䜢ᢚ䛘䜛䛣䛸䛜䛷䛝 䜛䠊䛣䛾䜘䛖䛻ᮏ◊✲䛷䛾᩿⇕ ᗘୖ᪼䛾ᩘ್䝅䝭䝳䝺䞊䝅䝵䞁䛿Ᏻ䜺䜲䝗䛸䛧䛶⏝䛷 䛝䜛䠊 ᘙ 4. 1. LY ໗↝ᡮࡇ⇷∏∇∞⇥∞ Number i [-] 1 2 3 4 5 6 7 8 9 10 X [-] 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10 k0 [min-1] ʊ 1.73⁷1013 5.41⁷1011 1.07⁷1011 5.87⁷1010 4.42⁷1010 3.05⁷1010 2.43⁷1010 1.98⁷1010 1.60⁷1010 1.39⁷1010 LY E [kJ/mol] ʊ 130.7 124.7 120.6 120.7 120.9 121.0 121.1 121.3 121.4 121.6 ¨rH [kJ/g] ʊ í53.3 í56.2 í55.0 í44.4 í46.3 í41.8 í40.3 í36.6 í32.6 í34.4 ᘙ 4. 2. AL ໗↝ᡮࡇ⇷∏∇∞⇥∞ Number i [-] X [-] 0 1 2 3 4 5 6 7 8 9 10 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10 [min-1] k0 3.39⁷109 8.42⁷108 2.88⁷108 1.92⁷108 1.58⁷108 1.53⁷108 1.73⁷108 2.22⁷108 3.11⁷108 4.59⁷108 7.30⁷108 101 AL E [kJ/mol] 130.8 125.4 121.2 120.3 120.3 121.1 122.6 124.8 127.4 130.1 133.3 ¨rH [kJ/g] í43.9 í41.5 í38.8 í37.4 í32.7 í31.1 í31.9 í29.8 í25.4 í27.7 í21.1 ჽ໗˯ภᣠ҄↝Ӓࣖᡮࡇᚐௌ 200 Loy Yang 90°C 150 80°C Temperature [°C] 75°C 100 70°C 65°C 60°C 50 40°C 25°C 0 0 5 10 15 20 Time [day] 25 30 4. 18. LY ໗↝ૺ༏ภࡇɥଞ(J = 0) 200 160°C Alabama 150°C 140°C 150 Temperature [°C] 130°C 120°C 100 100°C 80°C 50 60°C 40°C 25°C 0 0 5 10 15 20 Time [day] 25 4. 19. AL ໗↝ૺ༏ภࡇɥଞ(J = 0) 102 30 ᇹ4ᇘ 200 120°C Loy Yang 100°C 90°C Temperature [°C] 150 100 80°C 70°C 60°C 50 40°C 25°C 0 0 5 10 15 20 Time [day] 25 30 4. 20. LY ໗↝ૺ༏ภࡇɥଞ(J = 4) 200 Alabama 160°C 150 Temperature [°C] 150°C 140°C 130°C 120°C 100 100°C 80°C 50 60°C 40°C 25°C 0 0 5 10 15 20 Time [day] 25 4. 21. AL ໗↝ૺ༏ภࡇɥଞ(J = 4) 103 30 ჽ໗˯ภᣠ҄↝Ӓࣖᡮࡇᚐௌ 㻌 ᅗ 4. 22 䛻 LY Ⅳ䛾J = 0䠈ึᮇ ᗘ 75 °C 䛻䛚䛡䜛ᛂ⋡䛾⤒ኚ䜢♧䛩䠊ᛂ ⋡䛻ᑐ䛧䛶䠈1 ~ 3 ␒┠(X = 0.01䠈0.02 䛚䜘䜃 0.03)䛾ᛂ䛾ᐤ䛜 90 %௨ୖ䜢༨䜑䛶䛔 䜛䠊10 ␒┠(X = 0.10)䛾ᛂ䛾ᐤ䛿 1 %௨ୗ䛷䛒䜛䛣䛸䛛䜙䠈㠀ᖖ䛻ึᮇ䛾ᛂ䛜 ᗘ ୖ᪼䛻䛝䛟ᙳ㡪䛧䛶䛚䜚䠈ึᮇ䛾 10 ಶ䛾ᛂ䛰䛡䛷▼Ⅳయ䛾 ᗘୖ᪼䜢༑ศ䛻⾲ ⌧䛷䛝䛶䛔䜛䛸⪃䛘䜙䜜䜛䠊J = 0 䛾ሙྜ䠈75 °C 䛛䜙 100 °C 䛻㐩䛩䜛䜎䛷䛾▼Ⅳయ䛾 ᛂ⋡䛿 6.0×10í4 䛷䛒䜚䠈J = 4 䛾ሙྜ䠈90 °C 䛛䜙 115 °C 䛻㐩䛩䜛䜎䛷䛾▼Ⅳయ䛾ᛂ ⋡䛿 2.1×10í3 䛷䛒䛳䛯䠊᩿⇕ ᗘୖ᪼䛾ᩘ್䝅䝭䝳䝺䞊䝅䝵䞁䛻䜘䜚䠈䛭䛾䜘䛖䛺ᑠ䛥䛺 ᛂ⋡䛰䛡䛷䜒༑ศ䛻⮬↛Ⓨⅆ䛜㉳䛣䜛ྍ⬟ᛶ䛜♧䛥䜜䛯䠊 Relative weight [kg/kg-daf] 1 i=1 i=2 i=3 0.999 Relative weight 0.998 0.997 LY 0.996 0 5 10 15 20 Time [day] 25 4. 22. LY ໗↝ӲӒࣖ↝Ӓࣖྙ (J = 0≏Иภࡇ 75 °C) 104 30 ᇹ4ᇘ 4. 4. ⤖ゝ 㻌 DAEM ἲ䜢⏝䛔䛶䠈▼Ⅳ䛾ప 㓟䛾ᛂ㏿ᗘゎᯒ䜢⾜䛳䛯䠊ྛᛂ⋡䛻䛚䛡䜛㔜 㔞ῶᑡ㏿ᗘ䠈Ⓨ⇕㏿ᗘ䛿᪼ ㏿ᗘ䛻䜋䛸䜣䛹䜘䜙䛪䠈⬡⫫᪘Ⅳ⣲䛚䜘䜃ྵ㓟⣲ᐁ⬟ᇶ 䛾㓟䛷䛿䠈ᛂ䜶䞁䝍䝹䝢䞊䛜 í30 ~ í40 MJ/kg 䛸▼Ⅳ㦵᱁䛾㓟䛾ᛂ䜶䞁䝍䝹䝢 䞊䜘䜚䜒䛝䛟䛺䛳䛯䠊DAEM ἲ䛾㐺⏝䛻䜘䜚䠈ᛂ䛾㐍⾜䛻క䛖ᛂ㏿ᗘ䝟䝷䝯䞊䝍䞊 䛾ኚ䛜⾲⌧䛷䛝䠈䜏䛛䛡䛾άᛶ䜶䝛䝹䜼䞊䛿 100 ~ 180 kJ/mol 䛸▼Ⅳ䛻䜘䜙䛪ఝ䛯 䜘䛖䛺್䜢ྲྀ䛳䛯䛜䠈䜏䛛䛡䛾㢖ᗘᅉᏊ䛿 106 ~ 1014 miní1 䛸䛝䛟␗䛺䛳䛯䠊ᛂ䛾㐍⾜ 䛻క䛳䛶䠈ᛂ㏿ᗘ䛾㓟⣲ศᅽ౫Ꮡᛶ䜔⣽Ꮝ⾲㠃✚䠈ᛂ≀⃰ᗘ䛜␗䛺䜛䛯䜑䠈㢖ᗘ ᅉᏊ䛸άᛶ䜶䝛䝹䜼䞊䛸䛾㛫䛻⿵ൾ㛵ಀ䛜ぢ䜙䜜䛺䛛䛳䛯䠊䜏䛛䛡䛾ᛂ㏿ᗘᐃᩘ 䛿⬡⫫᪘Ⅳ⣲䛚䜘䜃ྵ㓟⣲ᐁ⬟ᇶ䛾㓟䛾䜋䛖䛜䛝䛟䠈LY Ⅳ䛾ሙྜ 200 °C 䛻䛚䛔䛶䠈 ▼Ⅳ㦵᱁䛾㓟䛾⣙ 1000 ಸ䛸䛺䛳䛯䠊 㻌 ᚓ䜙䜜䛯㏿ᗘ䝟䝷䝯䞊䝍䞊䜢⏝䛔䛶䠈ᵝ䚻䛺ึᮇ ᗘ䛻ᑐ䛩䜛᩿⇕ ᗘୖ᪼ᩘ್䝅䝭 䝳䝺䞊䝅䝵䞁䛜ྍ⬟䛻䛺䛳䛯䠊LY Ⅳ䛷䛿▼Ⅳ✵Ẽ㔜㔞ẚJ = 0 䛾ሙྜ䛿ึᮇ ᗘ䛜 75 °C ௨ୖ䛷䠈J = 4 䛾ሙྜ䛿ึᮇ ᗘ䛜 90 °C ௨ୖ䛷䛭䜜䛮䜜 30 ᪥௨ෆ䛻ᛴ⃭䛺 ᗘ ୖ᪼䛜㉳䛝䠈▼Ⅳ䛜Ⓨⅆ䛧䛯䠊Ⓨⅆ䛜⏕䛨䜛ึᮇ ᗘ䛜 15 °C 䜋䛹㧗䛟䛺䛳䛯䠊▼Ⅳ✵Ẽ 㛫䛷䛾⇕⛣ື䛻䜘䜛ᙳ㡪䛜㢧ⴭ䛻䜏䜙䜜䛯䠊୍᪉䠈AL Ⅳ䛷䛿J = 0 䛾ሙྜึᮇ ᗘ䛜 140 °C ௨ୖ䛾䛸䛝 30 ᪥௨ෆ䛻Ⓨⅆ䛜䜏䜙䜜䛯䛜䠈J = 4 䛾䛸䛝䛿ึᮇ ᗘ䛜 160 °C ௨ୗ 䛷䛿 30 ᪥௨ෆ䛻Ⓨⅆ䛜䜏䜙䜜䛺䛛䛳䛯䠊䜎䛯䠈LY Ⅳ䛷䛿ᛂ⋡䛻ᑐ䛧䛶䠈X = 0.01䠈 0.02 䛚䜘䜃 0.03 䛻䛚䛡䜛ᛂ䛾ᐤ䛜 90 %௨ୖ䜢༨䜑䛶䛚䜚䠈㠀ᖖ䛻ึᮇ䛾ᛂ䛜 ᗘୖ᪼䛻䛝䛟ᐤ䛧䛶䛔䛯䠊J = 0 䛾ሙྜ䠈75 °C 䛛䜙 100 °C 䛻㐩䛩䜛䜎䛷䛾▼Ⅳయ 䛾ᛂ⋡䛿 6.0×10í4 䛷䛒䜚䠈䛭䛾䜘䛖䛺ึᮇ䛾ᛂ䛾䜏䛷䜒⮬↛Ⓨⅆ䛜㉳䛣䜛䛣䛸䜢᫂䜙 䛛䛻䛧䛯䠊䛣䛾䜘䛖䛻䠈DAEM ἲ䛻䜘䜚ồ䜑䛯ᛂ㏿ᗘ䝟䝷䝯䞊䝍䞊䜢⏝䛔䛶䠈⮬↛Ⓨⅆ 䛻⮳䜛 ᗘୖ᪼䜢ண 䛷䛝䜛䜘䛖䛻䛺䜚䠈᭱䜒Ⓨⅆ䛧䜔䛩䛔᮲௳䛻䛚䛡䜛 ᗘୖ᪼䛾ᩘ ್䝅䝭䝳䝺䞊䝅䝵䞁䛾⤖ᯝ䛿▼Ⅳ䜢⟶⌮䛩䜛㝿䛾Ᏻ䜺䜲䝗䛸䛧䛶⏝䛷䛝䜛䠊 105 ჽ໗˯ภᣠ҄↝Ӓࣖᡮࡇᚐௌ ཧ⪃ᩥ⊩ [1] Vand, V., A theory of the irreversible electrical resistance changes of metallic films evaporated in vacuum, Proceedings of the Physical Society (London), 1943, A55, 222-246. [2] Miura, K., A new and simple method to estimate f(E) and k0(E) in the distributed activation model from three sets of experimental data, Energy & Fuels, 1995, 9, 302-307. [3] Miura, K., Maki, T., A new and simple method for estimating f(E) and k0(E) in the distributed activation model, Energy & Fuels, 1998, 12, 864-869. 106 ዮᛯ ⥲ㄽ 㻌 㟂せ䛾㐕㏕䛻క䛔䠈ᚋపရⅣ䛾⏝䛜ᚲせ䛸䛺䜛䛜䠈䛭䛾䛯䜑䛻䛿䠈⬺Ỉ䞉ᨵ㉁䛸 䛸䜒䛻⮬↛Ⓨⅆᛶ䛾ᢚไ䛜ᚲせྍḞ䛷䛒䜛䠊ᮏ◊✲䛷䛿䠈పရⅣ䛾ప 㓟ᶵᵓ 䜢ヲ⣽䛻᳨ウ䛩䜛䛣䛸䛷⮬↛Ⓨⅆᶵᵓ䛾ゎ᫂䜢ヨ䜏䠈䛭䛾ᶵᵓ䛻ᇶ䛵䛝⮬↛Ⓨⅆᢚไ ἲ䛾᳨ウ䛺䜙䜃䛻ᛂ㏿ᗘゎᯒ䜢⾜䛳䛯䠊 㻌 ➨ 1 ❶䛷䛿䠈〓Ⅳ䛷䛒䜛 Loy Yang Ⅳ (LY Ⅳ)䠈ள℡㟷Ⅳ䛷䛒䜛 Powder River Basin Ⅳ (PRB Ⅳ)䠈℡㟷Ⅳ䛷䛒䜛 Alabama Ⅳ (AL Ⅳ)䜢᪼ 䛧䛺䛜䜙㓟䛥䛫䠈䛭䛾㐣⛬䛻䛚䛡䜛 㔜㔞ኚ䠈䜺䝇⏕ᡂ㏿ᗘ䠈ᅛయ⏕ᡂ≀䛾ᵓ㐀ኚ䛚䜘䜃Ⓨ⇕㏿ᗘ䜢䛭䛾ሙ ᐃ䛩䜛䛣䛸 䛷▼Ⅳ䛾ప 㓟ᶵᵓ䛾᳨ウ䜢⾜䛔䠈▼Ⅳ䛾ప 㓟䛻䛿 3 䛴䛾ẁ㝵䛜䛒䜛䛣䛸䜢᫂䜙 䛛䛻䛧䛯䠊1 ẁ㝵┠䛿⬡⫫᪘Ⅳ⣲ୖ䛻㓟⣲䛜྾╔䛧㐣㓟≀䛜⏕ᡂ䛩䜛㐣⛬䛷䛒䜚䠈2 ẁ㝵┠䛿ᐁ⬟ᇶ㒊ศ䛜㓟䛥䜜ྵ㓟⣲ᐁ⬟ᇶ䛜⏕ᡂ䛧䠈䛭䛾ྵ㓟⣲ᐁ⬟ᇶ䛜㏲ḟⓗ䛻 㓟䛥䜜䜛㐣⛬䛷䛒䜛䠊3 ẁ㝵┠䛿▼Ⅳ㦵᱁䛾㓟䛷䛒䜛䠊䜎䛯䠈200 °C 䜎䛷䛾㓟⣲ᾘ㈝ 㔞䛸Ⓨ⇕㏿ᗘ䜢ẚ㍑䛩䜛䛸䠈LY Ⅳ䛾㓟⣲ᾘ㈝㔞䛿Ⅳ⣲ཎᏊ 100 mol 䛒䛯䜚㓟⣲ཎᏊ 4.6 mol 䛷᭱䜒䛝䛟䠈㓟⣲䛸䛾ᛂᛶ䛜㧗䛔䛣䛸䛜♧䛥䜜䛯䠊୍᪉䠈㉁䛾ప䛔▼Ⅳ䜋䛹䜏䛛 䛡䛾ᛂ䜶䞁䝍䝹䝢䞊䛾⤯ᑐ್䛜䛝䛟䛺䛳䛯䠊200 °C ௨ୗ䛻䛚䛡䜛Ⓨ⇕㔞䜘䜚᩿⇕ ᗘୖ᪼䜢᥎⟬䛩䜛䛸 LY Ⅳ䛷䛿 317 °C 䛸䛺䜚᭱䜒⮬↛Ⓨⅆᛶ䛜㧗䛔䛣䛸䛜♧䛥䜜䛯䠊䜎䛯䠈 䛔䛪䜜䛾▼Ⅳ䜒᩿⇕ ᗘୖ᪼䛜 180 °C 䜢㉸䛘䛶䛚䜚䠈200 °C ௨ୗ䛷⏕䛨䜛ᛂ䠈䛴䜎䜚䠈 ⬡⫫᪘Ⅳ⣲䜈䛾㓟⣲䛾྾╔䛸䜹䝹䝪䜻䝅䝹ᇶ䛾⏕ᡂᛂ䛜⮬↛Ⓨⅆᛶ䛻䛝䛟ᐤ䛧 䛶䛚䜚䠈㓟⣲䛸䛾ᛂᛶ䛜㧗䛔䛣䜜䜙䛾㒊ศ䜢ྲྀ䜚㝖䛟䛣䛸䛜⮬↛Ⓨⅆᢚไἲ䛸䛧䛶᭷ຠ 䛷䛒䜛ྍ⬟ᛶ䛜♧䛥䜜䛯䠊 㻌 ➨ 2 ❶䛷䛿䠈⬡⫫᪘Ⅳ⣲䜔䜹䝹䝪䜻䝅䝹ᇶ䜢ྲྀ䜚㝖䛟䛣䛸䛜䛷䛝䜛ฎ⌮䛸䛧䛶⁐ฎ⌮ 䛸⇕ศゎฎ⌮䛻╔┠䛧䠈ฎ⌮Ⅳ䛾ప 㓟ᣲື䜢ほᐹ䛧䠈ྛฎ⌮䛾ప 㓟ᣲື䛻ཬ 䜌䛩ᙳ㡪䛻䛴䛔䛶᳨ウ䛧䛯䠊⁐ฎ⌮䛚䜘䜃⇕ศゎฎ⌮䛷䛿⬡⫫᪘Ⅳ⣲㔞䛜ῶᑡ䛧䠈 䜹䝹䝪䜻䝅䝹ᇶ䛜ศゎ䞉㝖ཤ䛥䜜䛯䛜䠈⁐ฎ⌮䛷䛿⣽Ꮝ⾲㠃✚䛜ῶᑡ䛧䠈⇕ศゎฎ⌮ 107 䛷䛿⣽Ꮝ⾲㠃✚䛜ቑຍ䛩䜛䛸䛔䛖㐪䛔䛜ぢ䜙䜜䛯䠊䛭䜜䛮䜜䛾ฎ⌮Ⅳ䛿 350 °C ௨ୗ䛷 䛾ప 㓟ᣲື䛻㐪䛔䛜ぢ䜙䜜䠈200 °C 䜎䛷䛾㓟⣲ᾘ㈝㔞䛿⇕ศゎⅣ䛾䜋䛖䛜䛝䛟䛺 䜚䠈䜎䛯䠈ᛂ䜶䞁䝍䝹䝢䞊䛾⤯ᑐ್䜒⇕ศゎⅣ䛾䜋䛖䛜䛝䛟䛺䛳䛯䠊㓟⣲ᾘ㈝㔞䛾㐪 䛔䛿䠈⣽Ꮝ⾲㠃✚䛾㐪䛔䛻䜘䛳䛶ㄝ᫂䛷䛝䠈ᛂ䜶䞁䝍䝹䝢䞊䛾⤯ᑐ್䛾ᑠ䛿㓟⣲྾ ╔䛜 H2O 䛾⏕ᡂᛂ䜘䜚䜒㑅ᢥⓗ䛻㉳䛣䜛䛛䛹䛖䛛䛻㉳ᅉ䛩䜛䠊䛣䜜䜙䜘䜚䠈⁐ฎ⌮Ⅳ 䛿㓟䛥䜜䜔䛩䛔㒊ศ䜢ྲྀ䜚㝖䛟䛰䛡䛷䛺䛟䠈⣽Ꮝ⾲㠃✚䜢ῶ䜙䛩䛣䛸䛷㓟⣲䛾䜰䜽䝉䝇 䛜ᢚไ䛥䜜䠈⮬↛Ⓨⅆᛶ䛾ᢚไ䛻䛴䛺䛜䛳䛯䛣䛸䛜᫂䜙䛛䛻䛺䛳䛯䠊 㻌 ➨ 3 ❶䛷䛿䠈⮬↛Ⓨⅆᢚไἲ䛸䛧䛶᭷ຠ䛷䛒䜛ྍ⬟ᛶ䛜♧䛥䜜䛯⁐ฎ⌮䛻䛴䛔䛶䠈 䛭䛾⬺Ỉ䛚䜘䜃ᨵ㉁ຠᯝ䛻ὀ┠䛧䠈℡㟷Ⅳ䛛䜙䝞䜲䜸䝬䝇䜎䛷䛾ᖜᗈ䛔㉁䛾Ⅳ⣲㈨※ 䛻ᑐ䛧䛶ฎ⌮䜢⾜䛔䠈⁐ฎ⌮䛜పရⅣ䛾⮬↛Ⓨⅆᢚไἲ䛸䛧䛶䛰䛡䛷䛺䛟䠈⬺Ỉ䞉 ᨵ㉁䜢ྠ䛻ᐇ⌧䛷䛝䜛䜘䛖䛺ฎ⌮䛷䛒䜛䛛䜢᳨ウ䛩䜛䛸䛸䜒䛻䠈⁐ฎ⌮ヨᩱ䜢䛥䜙䛻 3 䛴䛾䝣䝷䜽䝅䝵䞁䛻ศ㞳䛧䠈⁐ฎ⌮ヨᩱ䛾ᛶ≧䜢䜘䜚ヲ⣽䛻᳨ウ䛧䛯䠊〓Ⅳ䜔䝞䜲䜸䝬 䝇䜘䜚ㄪ〇䛧䛯⁐ฎ⌮ヨᩱ䛿ள℡㟷Ⅳ⛬ᗘ䜎䛷ᨵ㉁䛥䜜䛶䛚䜚䠈ᮏ◊✲䛷⏝䛔䛯᮲௳ 䛷䛿ள℡㟷Ⅳ䜘䜚ຎ㉁䛾ཎᩱ䛻ᑐ䛧䛶᭷ຠ䛷䛒䜛䛣䛸䛜♧䛥䜜䛯䠊䜎䛯䠈㉁䛾ప䛔ヨᩱ䜋 䛹⁐ྍ⁐ᡂศ䛾ྜ䛜ቑຍ䛧䠈䝞䜲䜸䝬䝇䛷䛿⁐ྍ⁐ᡂศ䛾Ⅳ⣲⋡䛜 50 %௨ୖ 䛸䛺䛳䛯䠊ᐁ⬟ᇶ㔞䛾ኚ䜘䜚䠈ள℡㟷Ⅳ䜘䜚ຎ㉁䛾ཎᩱ䛛䜙ㄪ〇䛧䛯⁐ฎ⌮ヨᩱ䛷䛿 䜹䝹䝪䜻䝅䝹ᇶ䛾ῶᑡ䛸ⰾ㤶᪘Ⅳ⣲䛾ቑຍ䛜ぢ䜙䜜䠈⁐ฎ⌮୰䛷䛿ྵ㓟⣲ᐁ⬟ᇶ䛾 ศゎ㝖ཤ䛸䛸䜒䛻ⰾ㤶⎔䛾ᙧᡂ䛜㉳䛣䛳䛶䛔䜛䛣䛸䛜ศ䛛䛳䛯䠊〓Ⅳ䛚䜘䜃䛭䛾⁐ฎ ⌮ᡂศ䛾㓟⣲྾╔ᣲື䜢ほᐹ䛧䛯⤖ᯝ䠈⁐ฎ⌮ヨᩱ䛾㓟⣲྾╔㔞䛿⇕ศゎヨᩱ䜘䜚 䜒ᑡ䛺䛟ཎᩱ䜘䜚䛿䜔䜔ከ䛟䛺䛳䛯䠊䜎䛯䠈⁐ྍ⁐ᡂศ䛿㌾⁐⼥ᛶ䜢᭷䛧䠈⣽Ꮝ⾲㠃 ✚䛜ᖜ䛻ῶᑡ䛧䛯䛯䜑㓟⣲྾╔㔞䛜ᖜ䛻ᑡ䛺䛟䛺䛳䛯䠊䛣䜜䜙䜘䜚䠈⁐ฎ⌮䛻䜘䜛 ⮬↛Ⓨⅆᛶ䛾ᢚไ䛻䛿⣽Ꮝ⾲㠃✚䛾ῶᑡ䛜ᐤ䛧䛶䛚䜚䠈䛭䜜䛿⁐ྍ⁐ᡂศ䛻䜘䜚 ⣽Ꮝ䛜㛢ሰ䛩䜛䛣䛸䛷ᐇ⌧䛥䜜䛯䛣䛸䛜♧䛥䜜䛯䠊 㻌 ➨ 4 ❶䛷䛿䠈▼Ⅳ㓟䛻䜘䜛㔜㔞ῶᑡ䛻䛴䛔䛶ᛂ㏿ᗘゎᯒ䜢⾜䛳䛯䠊㓟䛾㐍⾜䛻 క䛔㉳䛣䜛ᛂ䛜ኚ䜟䜛䛯䜑䠈ྛᛂ⋡䛻䛚䛔䛶⏕䛨䛶䛔䜛ᛂ䛜᪼ ㏿ᗘ䛻䜘䜙䛪ྠ 108 ዮᛯ 䛨䛷䛒䜛䛣䛸䜢☜ㄆ䛧䛯䛖䛘䛷୪ิ୍ḟᛂ䝰䝕䝹(Distributed activation energy model, DAEM ἲ)䜢㐺⏝䛧䛯䠊ᚓ䜙䜜䛯άᛶ䜶䝛䝹䜼䞊䛿 100 ~ 180 kJ/mol 䛷䛒䜚䠈LY Ⅳ䠈 PRB Ⅳ䛷䛿㓟䛾㐍⾜䛻క䛔άᛶ䜶䝛䝹䜼䞊䛜ቑຍ䛧䛯䛜䠈AL Ⅳ䛷䛿ᛂ⋡ X = 0.2 ㏆䛷್᭱䜢ྲྀ䛳䛯䠊䜏䛛䛡䛾㢖ᗘᅉᏊ䛿 106 ~ 1014 miní1 ⛬ᗘ䛻ศᕸ䛧䠈䛚䛚䜐 䛽㉁䛾ప䛔▼Ⅳ䛾䜋䛖䛜䛝䛺್䜢ྲྀ䛳䛯䠊ྵ㓟⣲ᐁ⬟ᇶ䛾㓟䛜㉳䛝䜛 X = 0.03 䛻䛚 䛡䜛ᛂ䛻䛴䛔䛶 200 °C 䛷ẚ㍑䛩䜛䛸 LY Ⅳ䛾ᛂ㏿ᗘᐃᩘ䛿 5.42 ×10í3 miní1 䛷䛒䜚䠈 PRB Ⅳ䛾⣙ 5 ಸ䠈AL Ⅳ䛾⣙ 500 ಸ䛸ཎᩱ䛻䜘䛳䛶䛝䛺㐪䛔䛜ぢ䜙䜜䛯䠊୍᪉䠈▼Ⅳ㦵 ᱁䛾㓟䛜㉳䛝䛶䛔䜛 X = 0.50 䛺䛔䛧 0.51 䛻䛚䛡䜛ᛂ䜢 200 °C 䛷ẚ㍑䛩䜛䛸䠈LY Ⅳ 䛾ᛂ㏿ᗘᐃᩘ䛿 5.10 ×10í6 miní1 䛷䛒䜚䠈PRB Ⅳ䜔 AL Ⅳ䛾ᛂ㏿ᗘᐃᩘ䛸䛾ᕪ䛿䠈X = 0.03 䛾䛸䛝䜘䜚䜒ᑠ䛥䛟䛺䛳䛯䠊LY Ⅳ䛿ึᮇ䛾㓟㏿ᗘ䛜ᛂᚋᮇ䛾㏿ᗘ䜘䜚 1000 ಸ 㧗䛔䛣䛸䛜ศ䛛䛳䛯䠊䛣䛾䜘䛖䛻㓟䛾㐍⾜䛻క䛖㏿ᗘ䝟䝷䝯䞊䝍䞊䛾ኚ䜢⾲⌧䛩䜛䛣䛸 䛜䛷䛝䛯䠊䜎䛯䠈䛣䜜䜙䛾䝟䝷䝯䞊䝍䞊䜢⏝䛔䛶᩿⇕᮲௳ୗ䠈ᵝ䚻䛺ึᮇ ᗘ䛻䛚䛡䜛 ᗘୖ᪼䛾ᩘ್䝅䝭䝳䝺䞊䝅䝵䞁䛜ྍ⬟䛸䛺䜚䠈⮬↛Ⓨⅆ䛻⮳䜛䜎䛷䛾 ᗘୖ᪼䛜ண ྍ⬟ 䛸䛺䛳䛯䠊▼Ⅳ✵Ẽ㛫䛷⇕⛣ື䛜䛺䛟᭱䜒Ⓨⅆ䛜䛧䜔䛩䛔᮲௳(✵Ẽ▼Ⅳ㔜㔞ẚJ = 0)䛿䠈 ▼Ⅳ✵Ẽ㛫䛷⇕⛣ື䛜䛒䜛᮲௳(✵Ẽ▼Ⅳ㔜㔞ẚJ = 4)䜘䜚 15 ~ 20 °C ప䛔ึᮇ ᗘ䛷 ᛴ⃭䛺 ᗘୖ᪼䛜⏕䛨Ⓨⅆ䛜㉳䛣䜛䛣䛸䜢᫂䜙䛛䛻䛧䛯䠊䛣䜜䛻䜘䜚▼Ⅳ䛾Ⓨⅆ䜢ᢚ䛘䜙 䜜䜛ୖ㝈 ᗘ䛜ᩘ್ィ⟬䛷ồ䜑䜛䛣䛸䛜䛷䛝䠈▼Ⅳ䜢⟶⌮䛩䜛㝿䛾Ᏻ䜺䜲䝗䛻䛺䜚䛖䜛 ᣦᶆ䛸䛭䛾ᑟฟἲ䜢☜❧䛧䛯䠊䜎䛯䠈LY Ⅳ䛷䛿䠈200 °C 䛻㐩䛧䛯䛸䛝䛾ᛂ⋡䛜 6.0 ×10í4 䛸䛺䜚䠈⮬↛Ⓨⅆ䛿䛭䛾䜘䛖䛺㠀ᖖ䛻ᑠ䛥䛺ᛂ⋡䛷䜒⏕䛨䜛䛣䛸䜢᫂䜙䛛䛻䛧䛯䠊 㻌 ௨ୖ䠈ᮏㄽᩥ䛷䛿䠈ప 㓟ᣲື䛻ᇶ䛵䛟⮬↛Ⓨⅆᶵᵓ䛾᳨ウ䛻䜘䜚䠈⮬↛Ⓨⅆ䛿⬡ ⫫᪘Ⅳ⣲ୖ䜈䛾㓟⣲྾╔䛚䜘䜃 H2O 䛾⏕ᡂ䜢క䛖ྵ㓟⣲ᐁ⬟ᇶ䛾⏕ᡂᛂ䛻䜘䜛Ⓨ⇕ 䛷⏕䛨䠈⁐ฎ⌮ἲ䛿⬡⫫᪘Ⅳ⣲䜔ྵ㓟⣲ᐁ⬟ᇶ䜢ྲྀ䜚㝖䛝䠈䜎䛯⣽Ꮝ⾲㠃✚䜢ᑠ䛥䛟 䛩䜛䛣䛸䛷㓟⣲䛾䜰䜽䝉䝇䜢ᢚไ䛩䜛䛣䛸䛷⮬↛Ⓨⅆᛶ䜢ᢚไ䛷䛝䜛䛣䛸䛜᫂䜙䛛䛸䛺䛳䛯䠊 ⁐ฎ⌮ἲ䛿⮬↛Ⓨⅆᢚไἲ䛸䛧䛶᭷ຠ䛺䛰䛡䛷䛺䛟పရⅣ⣲㈨※䜢䛻⬺Ỉ䛧 ள℡㟷Ⅳ䛸ྠ⛬ᗘ䜎䛷ᨵ㉁䛩䜛䛣䛸䛜䛷䛝䠈పရⅣ䜢᭷ຠ⏝䛩䜛䛯䜑䛾ฎ⌮䛸䛧䛶 109 ᭷ຠ䛷䛒䜛䠊ᚋ䠈䛣䛾⁐ฎ⌮ἲ䛜ᐇ䝥䝻䝉䝇䜈䛸ᒎ㛤䛥䜜䠈పရⅣ䛾᭷ຠ⏝䛾 ୍ຓ䛻䛺䜛䛣䛸䛜ᮇᚅ䛥䜜䜛䠊䜎䛯䠈DAEM ἲ䛾㐺⏝䛻䜘䜚䠈▼Ⅳ㓟䛾ᛂ㏿ᗘ䜢ᛂ 䛾㐍⾜䛻క䛔㏿ᗘ䝟䝷䝯䞊䝍䞊䛜ኚ䛩䜛ᙧ䛷䛾ᐃᘧ䛻ᡂຌ䛧䠈▼ⅣⓎⅆ⌧㇟䛾ᐃ 㔞ⓗ䛺⾲⌧䜢ྍ⬟䛻䛧䛯䠊䛣䛾ᡭἲ䛜䠈⮬↛Ⓨⅆ䛾ண 䛺䜙䜃䛻⮬↛Ⓨⅆᛶ䛾ホ౯ᣦ ᶆ䛾㛤Ⓨ䛾୍ຓ䛸䛺䜛䛣䛸䛜ᮃ䜎䜜䜛䠊 110 ᜓᠴ ㅰ㎡ 㻌 ᮏ◊✲䛿䠈⚾䛜 2009 ᖺ䛻ᛂᕤᏛ◊✲ᐊ䛻㓄ᒓ䛥䜜䛶௨᮶䠈2010 ᖺ䛛䜙 2012 ᖺ 䛿䜶䝛䝹䜼䞊䝥䝻䝉䝇ᕤᏛ◊✲ᐊ䛻䛶䠈2013 ᖺ䛛䜙䛿䜃ᛂᕤᏛ◊✲ᐊ䛻䛶ィ 5 ᖺ㛫⾜䛳䛯䜒䛾䛷䛒䜚䜎䛩䠊䛭䛾㛫䠈2012 ᖺ䜎䛷䛿ᣦᑟᩍဨ䛸䛧䛶⇕ᚰ䛻䛤ᣦᑟ䜢㈷ 䛳䛯䛾䜏䛷䛺䛟䠈ᖺ㏥⫋䛥䜜䛯ᚋ䜒᠓ษᑀ䛻䛤ᣦᑟ䛤㠴᧡䜢㈷䜚䠈◊✲䛻ᑐ䛩䜛 ⇕ᚰ䛺ጼໃ䜢♧䛧䛶䛔䛯䛰䛝䜎䛧䛯⌧ி㒔Ꮫ䜶䝛䝹䜼䞊⌮ᕤᏛ◊✲ᡤ≉௵ᩍᤵ䛷 䛔䜙䛳䛧䜓䜛୕ᾆ㻌 Ꮥ୍ྡᩍᤵ䛻ᚰ䜘䜚ឤㅰ⏦䛧ୖ䛢䜎䛩䠊䜎䛯䠈ᛂᕤᏛ◊✲ᐊ ᅾ⡠䜘䜚㗦䛔䛤ᣦ䜔᪂䛧䛔Ⓨ䜢㈷䜚䠈2013 ᖺ䛛䜙䛿ᣦᑟᩍဨ䛸䛧䛶䛤ᣦᑟ䛔䛯 䛰䛔䛯ᛂᕤᏛ◊✲ᐊᩍᤵ䛾Ἑ℩㻌 ඖ᫂ඛ⏕䛻ᚰ䜘䜚ឤㅰ⏦䛧ୖ䛢䜎䛩䠊䜎䛯䠈ᮏㄽ ᩥ䜢䜎䛸䜑䜛䛻䛒䛯䜚䠈ᏛᕤᏛ䛾❧ሙ䛛䜙᰾ᚰ䜢✺䛔䛯䛤ຓゝ䜔䛤ᣦ䜢㈷䜚䜎䛧䛯 ศ㞳ᕤᏛ◊✲ᐊ䛾⏣㛛㻌 ⫕ᩍᤵ䠈⎔ቃ䝥䝻䝉䝇ᕤᏛ◊✲ᐊ䛾๓㻌 ୍ᘅᩍᤵ䛻ཌ䛟ᚚ ♩⏦䛧ୖ䛢䜎䛩䠊◊✲䛻㛵䛩䜛ᵝ䚻䛺䛤ຓゝ䜢㈷䜛䛰䛡䛷䛺䛟䠈ல⣽䛺ၥ䛻䜒䛔䛴 䜒᎘䛺㢦୍䛴䛫䛪ᑀ䛻䛚⟅䛘䛔䛯䛰䛔䛯ᛂᕤᏛ◊✲ᐊຓᩍ䛾⸼⏣㻌 㝯୍ඛ⏕ 䛻ឤㅰ⏦䛧ୖ䛢䜎䛩䠊䝊䝭䛷䛾䛤ᣦ䜔ㄽᩥᢞ✏䛷䛾䛤ຓゝ䜢䛔䛯䛰䛔䛯ᛂᕤ Ꮫ◊✲ᐊຓᩍ䛾ୖ㻌 ඖඛ⏕䛻ឤㅰ⮴䛧䜎䛩䠊䜶䝛䝹䜼䞊䝥䝻䝉䝇ᕤᏛ◊✲ᐊᅾ⡠ 䛻◊✲䛾᪂䛧䛔䜰䜲䝕䜱䜰䜔ᐇ㦂ᡭἲ䛻䛴䛔䛶ከ䛟䛾ຓゝ䜢㈷䛳䛯➲ᒸ㻌 ⱥྖᒸᒣ Ꮫྡᩍᤵ䠈⌧⳹୰⛉ᢏᏛᩍᤵ䛾 Li Xian ඖຓᩍ䠈༤ኈ◊✲ဨ䛾 Janewit Wannapeera Ặ䛻ឤㅰ⏦䛧ୖ䛢䜎䛩䠊䜎䛯䠈◊✲ᐊ⏕ά䜢䛔䜝䛔䜝䛺㠃䛛䜙ᨭ䛘䛶䛔䛯 䛰䛔䛯ඖ䜶䝛䝹䜼䞊䝥䝻䝉䝇ᕤᏛ◊✲ᐊ⛎᭩䛾ୖ㻌 ᏹᏊ䛥䜣䠈ᛂᕤᏛ◊✲ᐊ◊ ✲ဨ䛾ᙳᒣ㻌 ⨾ᕹ䛥䜣䛻ឤㅰ䛔䛯䛧䜎䛩䠊 㻌 䜎䛯䠈ᮏ◊✲䛾ඛ⾜◊✲䜢䛥䜜䛶䛔䛯ᆏ⏣㻌 ṊẶ(⌧᪥ᰴᘧ♫)䠈ᒸᓥ㻌 ுኴ Ặ(⌧᪂᪥㚩ఫ㔠ᰴᘧ♫)䛚䜘䜃⮳䜙䛺䛔⚾䛸ඹ䛻◊✲䠈ゎᯒ䜢⾜䛳䛯㒯㻌 ᛅ㉸Ặ (⌧ಟኈㄢ⛬)䜢䛿䛨䜑䛸䛧䛯ᛂᕤᏛ◊✲ᐊ䛚䜘䜃䜶䝛䝹䜼䞊䝥䝻䝉䝇ᕤᏛ◊✲ᐊ䛾 Ꮫ⏕䛺䜙䜃䛻༞ᴗ⏕䛻ឤㅰ䛔䛯䛧䜎䛩䠊⚾䛜༤ኈㄢ⛬䛻㐍Ꮫ䛧䛶௨᮶䠈䛸䜒䛻ບ䜎䛧 111 ྜ䛔㡹ᙇ䛳䛶䛝䛯ྠᮇ䛾ཱྀ㻌 㑈ᖹẶ䠈㔠㻌 ᑦᘯẶ䠈⚟⏣㻌 ㈗ྐẶ䛻ឤㅰ䛔䛯䛧䜎 䛩䠊 㻌 ᭱ᚋ䛻䛺䜚䜎䛧䛯䛜䠈䛣䜜䜎䛷 27 ᖺ㛫䛔䛴䜒ᬮ䛛䛟ぢᏲ䛳䛶䛟䜜䛯ẕ䛻ᚰ䜘䜚ឤㅰ⏦ 䛧ୖ䛢䜎䛩䠊 112 㻌㻌㻌㻌 㻌㻌㻌㻌 ᮏㄽᩥ䛻㛵䛩䜛ⴭ⪅䛾Ⓨ⾲ㄽᩥ Fujitsuka, H., Ashida, R., Motoaki, K., Miura, K., Examination of low temperature oxidation of low rank coals aiming at understanding their self-ignition tendency, submitted to Energy & Fuels. (➨ 1 ❶䛻ᑐᛂ) Fujitsuka, H., Ashida, R., Kawase, M., Miura, K., Kinetic analysis of low temperature oxidation of low rank coals solvent-treated or pyrolyzed for suppressing self-ignition, in preparation. (➨ 2 ❶䛻ᑐᛂ) Fujitsuka, H., Ashida, R., Miura, K., Upgrading and dewatering of low rank coals through solvent treatment at around 350 °C and low temperature oxygen reactivity of the treated coal, Fuel, 2013, 114, 16-20. (➨ 3 ❶䛻ᑐᛂ) Fujitsuka, H., Ashida, R., Kawase, M., Miura, K., Analysis of Low temperature oxidation of coals with the aim of understanding self-ignition mechanism of coals, in preparation. (➨ 4 ❶䛻ᑐᛂ) ᮏㄽᩥ䛻㛵䛩䜛ⴭ⪅䛾ᅜ㝿㆟Ⓨ⾲ㄽᩥ Fujitsuka, H., Ashida, R., Miura, K., Suppression of self-ignition tendency of upgraded products obtained by a solvent treatment of low rank coals, 29th Annual International Pittsburgh Coal Conference, 2012 Pittsburgh, USA, Oral Presentation. (➨ 3 ❶䛻ᑐᛂ) 113 Fujitsuka, H., Ashida, R., Miura, K., Self-ignition tendency of upgraded products obtained by a solvent treatment of low rank coals, 19th Regional Symposium on Chemical Engineering (RSCE2012), Bali, Indonesia, Oral Presentation. (➨ 3 ❶䛻ᑐᛂ) Fujitsuka, H., Kishimoto, T., Ashida, R., Miura, K., Analysis of low temperature oxidation of coal aiming at examining the self-ignition mechanism of coal, 9th World Congress of Chemical Engineering & 15th Asian Pacific Confederation of Chemical Engineering Congress, Seoul, Korea, Poster Presentation. (➨ 1䠈4 ❶䛻ᑐᛂ) Fujitsuka, H., Ashida, R., Kawase, M., Miura, K., Kinetic analysis of low temperature oxidation of low rank coals solvent-treated or pyrolyzed for suppressing self-ignition, The 12th Japan-China Symposium on Coal and C1 Chemistry, 2013, Fukuoka, Japan, Oral Presentation. (➨ 2 ❶䛻ᑐᛂ) Fujitsuka, H., Ashida, R., Kawase, M., Miura, K., Analysis of Low temperature oxidation of coals with the aim of understanding self-ignition mechanism of coals, 20th Regional Symposium on Chemical Engineering (RSCE2013), Bohol, Philippines, Oral Presentation. (➨ 1䠈4 ❶䛻ᑐᛂ) 114