大気圧プラズマによる無触媒脱硝および水素製造法の開発

(1)

Title

大気圧プラズマによる無触媒脱硝および水素製造法の開発(

_{本文(Fulltext) )}

Author(s)

早川, 幸男

Report No.(Doctoral

Degree)

博士(工学) 工博甲第525号

Issue Date

2017-03-25

Type

博士論文

Version

ETD

URL

http://hdl.handle.net/20.500.12099/56185

※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。

(2)

༤ ༤ ኈ ㄽ ᩥ

኱Ẽᅽࣉࣛࢬ࣐࡟ࡼࡿ

↓ゐ፹⬺◪࠾ࡼࡧỈ⣲〇㐀ἲࡢ㛤Ⓨ

Development of non-catalytic DeNOx treatment and hydrogen

production device by atmospheric pressure plasma

ᖹᡂ

28 ᖺᗘ

ᒱ㜧኱Ꮫ኱Ꮫ㝔 ᕤᏛ◊✲⛉ ༤ኈᚋᮇㄢ⛬

⎔ቃ࢚ࢿࣝࢠ࣮ࢩࢫࢸ࣒ᑓᨷ

(3)

┠ḟ

➨1 ❶ ᗎㄽ 1 -1.1 NOx࡟ࡼࡿ⎔ቃၥ㢟 1 -1.1.1 NOx࡟ࡼࡿ኱Ẽởᰁ 1 -1. -1. 2 NOxࡢ⏕ᡂᶵᵓ࡜᤼ฟ※ 1 -1. -1. 3 ᪥ᮏᅜෆ࡟࠾ࡅࡿ NOx᤼ฟつไࡢ⌧≧ 2 -1. -1. 4 ᪤Ꮡࡢ᤼↮⬺◪ᢏ⾡ 3 -1. -1. 5 SNCR ᛶ⬟ྥୖ࡟㛵ࡍࡿ᪤ ࡢ◊✲ 5 -1. 2 Ỉ⣲࢚ࢿࣝࢠ࣮♫఍ࡢᵓ⠏ 6 -1. 2. 1 Ỉ⣲࢚ࢿࣝࢠ࣮♫఍࡜ࡣ 6 -1. 2. 2 ᪤ᏑࡢỈ⣲〇㐀ᢏ⾡ 7 -1. 2. 3 Ỉ⣲࢟ࣕࣜ࢔࡬ࡢ㌿᥮ 11 -1. 2. 3. 1 Ỉ⣲࢟ࣕࣜ࢔࡜ࡣ 11 -1. 2. 3. 2 Ỉ⣲࢟ࣕࣜ࢔ࡢẚ㍑ 13 -1. 2. 3. 3 ࢔ࣥࣔࢽ࢔࠿ࡽࡢỈ⣲〇㐀࡟㛵ࡍࡿ᪤ ࡢ◊✲ 14 -1. 2. 3. 4 ኱Ẽᅽࣉࣛࢬ࣐ࢆ⏝࠸ࡓᢏ⾡ 14 -1. 3. ᮏ◊✲ࡢ┠ⓗ࠾ࡼࡧㄽᩥᵓᡂ 15 -1. 4. ཧ⪃ᩥ⊩ 17 -➨2 ❶ ኱Ẽᅽࣉࣛࢬ࣐࡟ࡼࡿᨵ㉁ NH3࢖ࣥࢪ࢙ࢡࢩࣙࣥ⬺◪ἲࡢ㛤Ⓨ 20 -2. 1 ⥴ゝ 20 -2. 2 ᐇ㦂⿦⨨࠾ࡼࡧ᪉ἲ 21 -2. -2. 1 ᐇ㦂⿦⨨࠾ࡼࡧ᪉ἲ 21 -2. -2. 2 ࣉࣛࢬ࣐㟁※≉ᛶ 22 -2. 3 ኱Ẽᅽࣉࣛࢬ࣐࡟ࡼࡿ NH3ᨵ㉁ 23 -2. 4 ບ㉳࢔ࣥࣔࢽ࢔ࡢ໬Ꮫ⤌ᡂ࡜⬺◪≉ᛶࡢ㛵ಀ 25 -2. 5 ⬺◪࡟ཬࡰࡍ H2ࡢᙳ㡪 27 -2. 6 ⣲཯ᛂゎᯒ࡟ࡼࡿ⬺◪ࢩ࣑࣮ࣗࣞࢩࣙࣥ 29 -2. 7 ᨵ㉁ NH3࢖ࣥࢪ࢙ࢡࢩࣙࣥἲ࡟࠾ࡅࡿ⬺◪࣓࢝ࢽࢬ࣒ 30 -2. 8 ⤖ゝ 31 -2. 9 ཧ⪃ᩥ⊩ 32 -➨3 ❶ ኱Ẽᅽࣉࣛࢬ࣐࡟ࡼࡿ NH3࠿ࡽࡢ᪂つỈ⣲〇㐀ࢹࣂ࢖ࢫࡢᇶᮏ≉ᛶゎ᫂ - 33 -3. 1 ⥴ゝ 33 -3. 2 ᐇ㦂⿦⨨࠾ࡼࡧ᪉ἲ 33 -3. 3 ኱Ẽᅽࣉࣛࢬ࣐࡟ࡼࡿ NH3ศゎ≉ᛶ 35

(4)

-3. 4 㧗⃰ᗘ NH3࡟࠾ࡅࡿỈ⣲⏕ᡂ≉ᛶ 39 -3. 5 ⤖ゝ 43 -3. 6 ཧ⪃ᩥ⊩ 44 -➨ 4 ❶ ࣉࣛࢬ࣐࣓ࣥࣈࣞࣥࣜ࢔ࢡࢱ࣮࡟ࡼࡿ NH3࠿ࡽࡢ㧗⣧ᗘỈ⣲㐃⥆〇㐀ࢹࣂ ࢖ࢫࡢ㛤Ⓨ 45 -4 .1 ⥴ゝ 45 -4. 2 ᐇ㦂⿦⨨࠾ࡼࡧᐇ㦂᪉ἲ 45 -4. 2. 1 ὶ㏻ᘧ཯ᛂჾ 45 -4. 2. 2 ࣂࢵࢳᘧ཯ᛂჾ 46 -4. 3 ᐇ㦂⤖ᯝ࠾ࡼࡧ⪃ᐹ 47 -4. 3. 1 ࣉࣛࢬ࣐࣓ࣥࣈࣞࣥࣜ࢔ࢡࢱ࣮ࡢ H2ศ㞳≉ᛶ㸦ᕪᅽࡢᙳ㡪㸧 47 -4. 3. 2 ࣉࣛࢬ࣐࣓ࣥࣈࣞࣥࣜ࢔ࢡࢱ࣮ࡢ H2ศ㞳≉ᛶ㸦Ỉ⣲⃰ᗘࡢᙳ㡪㸧 49 -4. 3. 3 ࣉࣛࢬ࣐࡟ࡼࡿ NH3ศゎ≉ᛶ㸦ࣂࢵࢳᘧ཯ᛂჾ㸧 50 -4. 3. 4 PMR ࡢ H2⏕ᡂ≉ᛶ 51 -4. 3. 5 PMR ࡢỈ⣲㏱㐣࣓࢝ࢽࢬ࣒ 54 -4. 4 ⤖ゝ 55 -4. 5 ཧ⪃ᩥ⊩ 56 -➨5 ❶ ⣲཯ᛂゎᯒ࡟ࡼࡿ኱Ẽᅽࣉࣛࢬ࣐ୗ࡛ࡢ NH3ศゎ཯ᛂ࣓࢝ࢽࢬ࣒ࡢゎ᫂ - 57 -5. 1 ⥴ゝ 57 -5. 2 ゎᯒ᪉ἲ࠾ࡼࡧ᮲௳ 57 -5. 3 ࣉࣛࢬ࣐཯ᛂሙ࡟࠾ࡅࡿ NH3ศゎ⣲཯ᛂゎᯒ 58 -5. 3. 1 ᭱㐺࡞Ẽ┦཯ᛂࣔࢹࣝࡢ㑅ᐃ 58 -5. 3. 2 NH3ศゎ཯ᛂࡢ⣲཯ᛂゎᯒ㸦NH3 conc. = 0.5 %㸧 59 -5. 3. 3 NH3ศゎ཯ᛂࡢ⣲཯ᛂゎᯒ㸦NH3 conc. = 50 %, 100 %㸧 61 -5. 3. 4 NH3ศゎ཯ᛂ࣓࢝ࢽࢬ࣒ 62 -5. 4 ⤖ゝ 63 -5. 5 ཧ⪃ᩥ⊩ 64 -➨6 ❶ ⥲ᣓ 65 -ᮏ◊✲࡟ಀࡿㄽᩥ࠾ࡼࡧⓎ⾲ 68 -ㅰ㎡ 71

(5)

-- 1 --

➨

1 ❶ ᗎㄽ

1.1 NO

x

࡟ࡼࡿ⎔ቃၥ㢟

1.1.1 NO

x

࡟ࡼࡿ኱Ẽởᰁ

❅⣲㓟໬≀㸦NOx㸧ࡣ◲㯤㓟໬≀㸦SOx㸧ࡸ᥹Ⓨᛶ᭷ᶵ໬ྜ≀㸦VOC㸧࡞࡝࡞࡝࡟௦

⾲ࡉࢀࡿ኱Ẽởᰁࢆᘬࡁ㉳ࡇࡍ᭷ᐖ࡞໬Ꮫ≀㉁ࡢ୍ࡘ࡛࠶ࡿ㸬NOx࡜ࡣ୍㓟໬❅⣲㸦NO㸧 ࡸ஧㓟໬❅⣲㸦NO2㸧㸪ள㓟໬❅⣲㸦N2O㸧㸪↓Ỉ◪㓟㸦N2O5㸧࡞࡝ࡢ❅⣲㓟໬≀ࡢ୰࡛ ࡶ኱Ẽởᰁ࡟ᙳ㡪ࢆ୚࠼ࡿNO ࡜ NO2ࢆ⥲⛠ࡋࡓࡶࡢ࡛࠶ࡿ1)㸬᫬࡜ࡋ࡚㸪NOx࡟N2O ࡀྵࡲࢀࡿሙྜࡶ࠶ࡿ㸬 NOxࡣ୺࡜ࡋ࡚⇞↝࡟࠾ࡅࡿ⏕ᡂ≀࡜ࡋ࡚᤼ฟࡉࢀࡿࡀ㸪ࡑࡢ࡯࡜ࢇ࡝ࡀNO ࡛࠶ࡿ㸬 ࡑࡋ࡚㸪኱Ẽ୰࡟ᨺฟࡉࢀࡓNO ࡢ୍㒊ࡀ㓟໬ࡉࢀ࡚ NO2࡟࡞ࡿ㸬NO2ࡣ⎔ቃၥ㢟࡛ ࠶ࡿග໬Ꮫࢫࣔࢵࢢࡢཎᅉ≀㉁ࡢ୍ࡘ࡛࠶ࡿ㸬ග໬Ꮫࢫࣔࢵࢢ࡜ࡣ㸪NO2ࡀ⣸እ⥺࡟ࡼ ࡾບ㉳ࡉࢀ࡚⏕ࡌࡿཎᏊ≧㓟⣲࡜኱Ẽ୰࡟ᨺฟࡉࢀࡓVOC ࡀ཯ᛂࡋ㸪ேయ࡟᭷ᐖ࡞࢔ ࣝࢹࣄࢻࡸ࣌ࣝ࢜࢟ࢩ࢔ࢭࢳࣝࢼ࢖ࢺ࣮ࣞࢺ㸦PAN㸧ࢆ⏕ᡂࡍࡿ኱Ẽởᰁ࡛࠶ࡿ2)_㸬 ࡲࡓ㸪ேయ࡟┤᥋୚࠼ࡿᙳ㡪࡜ࡋ࡚ࡣ㸪NO ࡣ⾑ᾮ୰ࡢ࣊ࣔࢢࣟࣅࣥ࡜⤖ྜࡋ㸪㓟⣲ Ḟஈ⑕ࢆᘬࡁ㉳ࡇࡍ㸬NO2ࡣேయ࡬྾ධࡍࡿ࡜⫵Ỉ⭘ࢆక࠺⣽Ẽ⟶ᨭ⅖ࢆⓎ⑕ࡍࡿཎᅉ ࡜࡞ࡿ1)_㸬

1. 1. 2 NO

x

ࡢ⏕ᡂᶵᵓ࡜᤼ฟ※

⇞↝࡟࠾ࡅࡿ NOxࡢ⏕ᡂᶵᵓ࡜᤼ฟ※࡟ࡼࡗ࡚ศ㢮ࡍࡿ࡜㸦1㸧Thermal NOx㸪㸦2㸧 Prompt NOx㸪㸦3㸧Fuel NOx࡟ࡢ୕ࡘ࡟኱ูࡉࢀࡿ3)㸬㸦1㸧Thermal NOx Thermal NOxࡣ✵Ẽ୰ࡢ N2ࡀ⇞↝ሙ࡟࠾࠸࡚㧗㓟໬ࡉࢀࡿࡇ࡜࡟ࡼࡗ࡚⏕ᡂࡉࢀ ࡿࡶࡢ࡛㸪௨ୗ࡟♧ࡍᣑ኱Zeldovich ᶵᵓ࡟ࡼࡗ࡚⏕ᡂࡍࡿ NOxࡀ1500 ºC ௨ୖࡢ㧗 ሙ࡟࠾࠸࡚⏕ᡂࡉࢀࡿ࠿ࡽThermal NOx࡜࿧ࡤࢀࡿ㸬 N2 + O = NO + N (1-1) N + O2 = NO + O (1-2) N + OH = NO + H (1-3) ࡇࡢ཯ᛂᶵᵓࡣ཯ᛂᘧ㸦1-1㸧࡟ࡼࡾ཯ᛂࡀ㛤ጞࡉࢀ㸪NO ࡀ⏕ᡂࡍࡿ㸬ࡲࡓ㸪཯ᛂᘧ 㸦1-1㸧ࡢ๪⏕ᡂ≀࡛࠶ࡿ N ࣛࢪ࢝ࣝࡀ O2࠾ࡼࡧOH ࣛࢪ࢝ࣝ࡜཯ᛂࡍࡿࡇ࡜࡛ࡉࡽ࡟ NO ࡀ⏕ᡂࡍࡿ࣓࢝ࢽࢬ࣒࡜࡞ࡗ࡚࠸ࡿ㸬ࡲࡓ㸪཯ᛂᘧ㸦1-1㸧ࡣάᛶ໬࢚ࢿࣝࢠ࣮ࡀᴟ ࡵ࡚㧗ࡃ㸪཯ᛂ㏿ᗘࡶ⇞↝཯ᛂ࡟ẚ࡭࡚㐜࠸ࡓࡵ㸪୺࡟ⅆ⅖ᖏᚋὶࡢ㧗 ᗘᇦ࡛⏕ᡂࡍ ࡿࡢࡀ≉ᚩ࡛࠶ࡿ㸬ࡇࡢThermal NOxࡢ⏕ᡂ㏿ᗘࡣ௨ୗࡢࡼ࠺࡟⾲ࡏࡿ㸬 ௗሾேைሿ ௗ௧

ൌ ʹ݇ሾܰ

ଶ

ሿሾܱሿ

(1-4)

(6)

- 2 - ࡇࡇ࡛㏿ᗘᐃᩘk = 1.8×1012_{exp(–38388/T)࡜࡞ࡾ㸪Thermal NO} xࡢ⏕ᡂࡣ཯ᛂ ᗘ㸪N2 ⃰ᗘ࠾ࡼࡧO2⃰ᗘ࡟౫Ꮡࡋ࡚࠸ࡿ4)㸬㸦2㸧Prompt NOx Thermal NOx࡜ྠࡌࡃ✵Ẽ୰ࡢN2ࢆ㉳※࡜ࡋ࡞ࡀࡽ㸪ⅆ⅖ࡢ⫼ᚋ࡛ࡣ࡞ࡃⅆ⅖ᖏࡢ୰ ࡛⏕ᡂࡍࡿPrompt NOx࡜࿧ࡤࢀࡿࡶࡢࡀ࠶ࡿ3)㸬ࡑࡢ⏕ᡂࡣⅣ໬Ỉ⣲ࡢศゎ㐣⛬࡛⏕ࡎ ࡿάᛶⅣ໬Ỉ⣲࡜N2࡜ࡢ㛫࡛㉳ࡇࡾ㸪⏕ᡂ཯ᛂࡣୗグࡢ࡜࠾ࡾ࡛࠶ࡿ㸬 CH + N2 = HCN + N (1-5) CH2 + N2 = HCN +NH (1-6) HCN + O = NCO + H (1-7) NCO + H = NH + CO (1-8) NH + H = N + H2 (1-9) N + OH = NO + H (1-10) ࡇࢀࡽࡢ཯ᛂࡣάᛶ໬࢚ࢿࣝࢠ࣮ࡀThermal NOxࡢࡑࢀ࡜ẚ࡭࡚ࡣࡿ࠿࡟ᑠࡉ࠸ࡓࡵ ẚ㍑ⓗప࠸ ᗘ(750 ºC ⛬ᗘ)࠿ࡽ⏕ᡂࡉࢀࡿ4)_㸬㸦3㸧Fuel NOx ✵Ẽ୰ࡢ❅⣲ࢆ㉳※࡜ࡏࡎ㸪⇞ᩱ୰࡟ྵࡲࢀࡿ❅⣲㓟໬≀ࢆ㉳※࡜ࡋ࡚⏕ᡂࡍࡿNO ࢆFuel NOx࡜࿧ࡪ4)㸬⇞ᩱ୰ࡢ❅⣲ࡣ୺࡟HCN㸪CN㸪NHiࢆ⤒⏤ࡋ࡚NO ࢆᙧᡂࡍࡿ㸬

1. 1. 3 ᪥

᪥ᮏᅜෆ࡟࠾ࡅࡿ

NO

x

᤼ฟつไࡢ⌧≧

ᵝࠎ࡞⇞↝཯ᛂ࡟క࠸Ⓨ⏕ࡍࡿ NOx࡛࠶ࡿࡀࡺ࠼࡟㸪ࡑࡢ᤼ฟ※ࡣᵝࠎ࡛࠶ࡿ㸬᪥ ᮏᅜෆ࡟࠾࠸࡚ࡶ᤼ฟ※ࡈ࡜࡟NOxつไ್ࡀタࡅࡽࢀ࡚࠸ࡿ㸬NOxつไ್࠾ࡼࡧࡑࢀ࡟ 㐺ᛂࡋࡓ⬺◪ᢏ⾡ࢆTable 1-1 ࡟ࡲ࡜ࡵࡓ5)-7)_㸬 ⅆຊⓎ㟁ᡤ࡟࠾ࡅࡿNOxつไ್ࡣ50 ppm ௨ୗ࡜ཝࡋ࠸ࡶࡢ࡜࡞ࡗ࡚࠾ࡾ㸪᤼↮⬺◪

ᢏ⾡࡜ࡋ࡚ࡣ⬺◪ゐ፹ࢆ⏝࠸ࡿ㑅ᢥⓗゐ፹㑏ඖ⬺◪ἲ㸦Selective Catalytic Reduction : SCR㸧ࡶࡋࡃࡣゐ፹ࢆ⏝࠸ࡎ⇕ࡢࡳ࡟ࡼࡗ࡚⬺◪ࢆ⾜࠺㑅ᢥⓗ↓ゐ፹㑏ඖ ⬺◪ἲ 㸦Selective Non-Catalytic Reduction : SNCR㸧ࡀ୍⯡ⓗ࡞ᢏ⾡࡜ࡋ࡚ᬑཬࡋ࡚࠸ࡿ㸬

Table 1-1 NOx regulations and DeNOx techniques in Japan

NOx᤼ฟ※ ᪥ᮏ䛻䛚䛡䜛NOxつไ್ 㻌 ᑐᛂ䛩䜛⬺◪タഛ ⅆຊⓎ㟁ᡤ 䠘50 ppm 㻌 SCR or SNCR ᬑ㏻஌⏝㌴(䜺䝋䝸䞁) 䠘0.08 g/km from 2005 ୕ඖゐ፹ 䝖䝷䝑䜽䠄䝕䜱䞊䝊䝹䠅䠘0.4 g/km from 2016 SCR+DPF ᗫᲠ≀↝༷⅔ 䠘250 ppm 䊻50–100 㻌 ᮍฎ⌮䊻ᑐᛂ⟇ᮍ☜❧㻌 ⯪⯧䠄䝕䜱䞊䝊䝹) 80 %๐ῶ䠄≉ᐃᾏᇦ䛾䜏䠅 from 2016 పNOx䜶䞁䝆䞁䊻ᮍ☜❧

(7)

- 3 - ࢞ࢯࣜࣥࢆ⇞ᩱ࡜ࡍࡿᬑ㏻஌⏝㌴࡟࠾ࡅࡿNOxつไ್ࡣ0.08 g/km ௨ୗ࡜࡞ࡗ࡚࠾ࡾ㸪 ⬺◪ᢏ⾡࡜ࡋ࡚ࡣⓑ㔠㸦 Pt 㸧㸪ࣃࣛࢪ࣒࢘㸦 Pd 㸧ࡸࣟࢪ࣒࢘㸦 Rh 㸧ࢆࡶࡕ࠸ࡓࢆ ཎᩱ࡜ࡋࡓ୕ඖゐ፹ࢆ⏝࠸ࡓ⬺◪ࢆ⾜ࡗ࡚࠸ࡿ㸬ࡋ࠿ࡋ࡞ࡀࡽ㸪୕ඖゐ፹࡛ຠ⋡ⓗ࡟㓟 ໬࣭㑏ඖࢆ⾜࠺ࡓࡵ࡟ࡣ⌮ㄽ✵⇞ẚࢆ⥔ᣢࡋࡓ㐠㌿ࡀᚲせ࡜࡞ࡿࡓࡵ㸪᤼࢞ࢫ୰ࡢ㓟⣲ ⃰ᗘࡀ㧗ࡃ࡞ࡗ࡚ࡋࡲ࠺ࢺࣛࢵࢡ➼ࡢࢹ࢕࣮ࢮ࢚ࣝࣥࢪࣥ᤼࢞ࢫ࡟ࡣ୕ඖゐ፹ࡣ㐺ᛂ ࡛ࡁ࡞࠸㸬ࡑࡇ࡛㸪⌧≧࡛ࡣ⮬ື㌴⏝ࢹ࢕࣮ࢮ࢚ࣝࣥࢪࣥ᤼࢞ࢫࡢ⬺◪タഛ࡜ࡋ࡚ࡣୖ ㏙ࡢ SCR ࡜㓟໬ゐ፹ࢆᦚ㍕ࡋࡓࢹ࢕࣮ࢮࣝᚤ⢏Ꮚᤕ㞟ࣇ࢕ࣝࢱ࣮㸦Diesel particulate filter : DPF㸧ࡢే⏝ࡀ᳨ウࡉࢀ࡚࠸ࡿ8)9)_㸬 ⎔ቃ┬ࡀᐃࡵࡿᗫᲠ≀↝༷⅔᤼࢞ࢫࡢNOx つไ್ࡣ 250 ppm ௨ୗ࡛࠶ࡾ㸪᤼↮⬺◪ タഛࢆタ⨨ࡏࡎ࡜ࡶప NOx ࣂ࣮ࢼ࣮ࡢ฼⏝ࡸ᤼࢞ࢫ෌ᚠ⎔ἲ㸪⇞↝ሙ࡟Ỉࡸ⵨Ẽࢆ྿ ࡁ㎸ࡴప ⇞↝ἲ࡞࡝⇞↝᪉ἲࡢᨵၿࢆ⾜࠺ࡇ࡜࡛ NOx つไ್ࢆ‶ࡓࡋ࡚ࡁࡓ 9)_㸬ࡋ ࠿ࡋ࡞ࡀࡽ㸪᫖௒࡟࠾ࡅࡿ⎔ቃၥ㢟࡬ࡢ㛵ᚰࡢ㧗ࡲࡾ࡟ࡼࡾ㸪㒔㐨ᗓ┴࠾ࡼࡧᕷ⏫ᮧ༢ ఩࡛⎔ቃ┬ࡀᐃࡵࡓNOxつไ್ࡼࡾࡶཝࡋ࠸NOxつไ್ࢆᐃࡵࡿ౛ࡀቑ࠼࡚ࡁ࡚࠸ࡿ㸬 ࡑࡢⅭ㸪SCR ➼ࡢ᤼↮⬺◪タഛࡢᑟධࢆవ൤࡞ࡃࡉࢀࡘࡘ࠶ࡿࡀ㸪୰ᑠつᶍࡢᗫᲠ≀↝ ༷⅔࡬ࡢ᤼↮⬺◪タഛࡢᑟධࡣ⌧≧㸪ᅔ㞴࡛࠶ࡿ㸬⌮⏤ࡣᚋ㏙ࡍࡿ㸬 ࡲࡓ㸪⯪⯧⏝ࢹ࢕࣮ࢮ࢚ࣝࣥࢪࣥ᤼࢞ࢫࡢ NOx つไ࡟㛵ࡋ࡚ࡶ㸪ᅜ㝿ᾏ஦ᶵ㛵

㸦International Maritime Organization㸸IMO㸧ࡀᐃࡵࡓᾏὒởᰁ㜵Ṇ᮲⣙㸦MARPOL73/78㸧

࡟࠾ࡅࡿNOxࡢ୕ḟつไ㸦Tier Ⅲ㸧ࡀ 2016 ᖺ࠿ࡽ᪋ᕤࡉࢀ࡚࠸ࡿ7㸧㸬ࡑࡢෆᐜࡣ≉ᐃ ᾏᇦ࡟࠾࠸୍࡚ḟつไ್࠿ࡽࡉࡽ࡟80 %๐ῶࡍࡿ࡜࠸࠺ࡶࡢ࡛࠶ࡾ㸪ࡑࢀ࡟ᑐᛂࡍࡿ ࡓࡵ࡟SCR ࡞࡝ࡢᑟධࡀ᳨ウࡉࢀ࡚࠸ࡿ㸬

1. 1. 4 ᪤

᪤Ꮡࡢ᤼↮⬺◪ᢏ⾡

᤼࢞ࢫ୰࡟ྵࡲࢀࡿNOxࡢᚋฎ⌮ᢏ⾡࡜ࡋ୍࡚⯡ⓗ࡞ࡶࡢࡣୖ㏙ࡋࡓ SCR ࡜ SNCR ࡛࠶ࡿ10㸧_㸬

㸦1㸧㑅ᢥⓗゐ፹㑏ඖ⬺◪ἲ㸦Selective Catalytic Reduction : SCR㸧

Fig. 1-1 ࡟♧ࡋࡓ SCR ࡢᴫせᅗ࡟࠶ࡿࡼ࠺࡟ゐ፹ᒙୖὶ࡛㑏ඖ๣㸦NH3㸧ࢆῧຍࡉࢀ ࡓฎ⌮࢞ࢫࡀ㸪㐺ᙜ࡞ ᗘᇦ࡛ゐ፹ᒙࢆ㏻㐣ࡍࡿࡇ࡜࡟ࡼࡾ㸪ୗグ࡟♧ࡍ໬Ꮫ཯ᛂᘧ࡟ ࡼࡾNOxࢆ↓ᐖ࡞N2࡜H2O ࡟ศゎࡍࡿࡶࡢ࡛࠶ࡿ11)㸬 4NO + 4NH3 + O2 Ѝ 4N2 + 6H2O (1-11) ࡲࡓ㸪࢞ࢫࢱ࣮ࣅࣥࡸࢹ࢕࣮ࢮ࢚ࣝࣥࢪࣥ࡞࡝ࡢ⇞↝✵Ẽẚࡢ㧗࠸᤼ฟ※࠿ࡽฟࡿ NO2ࢆ20 %⛬ᗘྵࢇࡔ᤼࢞ࢫ࡟࠾࠸࡚ࡶୗグࡢ⬺◪཯ᛂࡀ㐍⾜ࡋ㸪㧗࠸⬺◪ᛶ⬟ࢆⓎ ᥹ࡍࡿ㸬 NO + NO2 + 2NH3 Ѝ 2N2 + 3H2O (1-12)

(8)

- 4 -

Fig. 1-1 Basic concept of NOx removal process by SCR

౑⏝ࡉࢀࡿ⬺◪ゐ፹ࡣV2O5㸪WO3㸪MoO3࡞࡝ࢆ୺ᡂศ࡜ࡋࡓࣁࢽ࣒࢝≧ࡢࡶࡢࡀ୍ ⯡ⓗ࡛࠶ࡿ㸬୍⯡ⓗ࡞⬺◪ゐ፹ᛶ⬟ࡢάᛶ⠊ᅖࡣ350 ºC–400 ºC ࡛࠶ࡗࡓࡀ㸪㏆ᖺ࡛ࡣ 200 ºC ௜㏆࡟άᛶࢆᣢࡘప ⏝ゐ፹ࡸ 500 ºC ࢆ㉸࠼ࡿ㧗 ᇦ࡟ᑐᛂࡋࡓゐ፹3)_ࡢ㛤Ⓨࡀ ࡞ࡉࢀ࡚࠸ࡿ㸬ࡲࡓ㸪ࢹ࢕࣮ࢮ࢚ࣝࣥࢪࣥ⮬ື㌴ྥࡅ࡟⬺◪๣࡜ࡋ࡚ᒀ⣲Ỉࢆ⏝࠸ࡓᒀ ⣲SCR ࡢ㛤Ⓨࡶ⾜ࢃࢀ࡚࠸ࡿ12)_{㸬ࡋ࠿ࡋ࡞ࡀࡽ㸪SCR ࡟࠾࠸࡚ࡶゎỴࡍ࡭ࡁㄢ㢟ࡀ࠸} ࡃࡘ࠿࠶ࡿ㸬ⅆຊⓎ㟁ᡤ࡞࡝ࡢ኱つᶍ࡞⇞↝᪋タྥࡅ࡟ᾐ㏱ࡋ࡚࠸ࡿ SCR ࡛࠶ࡿࡀ㸪 ୰ᑠつᶍࡢᗫᲠ≀ฎ⌮᪋タࡸ⯪⯧࡟㐺ᛂࡍࡿୖ࡛ SCR ࡢタ⨨ࢫ࣮࣌ࢫࡢ኱ࡁࡉࡀࢿࢵ ࢡ࡜࡞ࡿ㸬ࡲࡓ㸪ฎ⌮࢞ࢫ୰࡟ SO3ࡀྵࡲࢀࡿሙྜ㸪㑏ඖ๣࡛࠶ࡿ NH3࡜SO3ࡀୗグ ࡟♧ࡍ໬Ꮫ཯ᛂࢆ㉳ࡇࡋ㸪཯ᛂ⏕ᡂ≀࡜ࡋ࡚◲㓟Ỉ⣲࢔ࣥࣔࢽ࣒࢘㸦㸦NH4㸧HSO4㸧ࡀ ⏕ࡌࡿ㸬ࡑࡢⅭ㸪350 ºC ௨ୗࡢప ᗘ㐠㌿࡛ࡣ㸦NH4㸧HSO4ࡀゐ፹⾲㠃࡟ᯒฟࡋ㸪㛢 ሰ࠾ࡼࡧ⭉㣗ࢆᘬࡁ㉳ࡇࡋ⬺◪ᛶ⬟ࡀపୗࡋ࡚ࡋࡲ࠺࡜࠸࠺ሗ࿌ࡶ࠶ࡿ13)_{㸬ࡲࡓ㸪400} ºC ௨ୖࡢ㧗 ࡟࡞ࡿ࡜ NH3ࡀ㓟໬ࡉࢀࠊࡑࢀ࡟క࠸NH3ࡀῶᑡࡋࠊ⬺◪ᛶ⬟ࡣపୗࡍ ࡿ㸬 ௨ୖࡢ⌮⏤࡟ࡼࡾ㸪ᗫᲠ≀↝༷Ⓨ㟁᪋タ࡬SCR ࢆᑟධࡍࡿ࡟ࡣ㸪࢔ࣝ࢝ࣜ㔠ᒓ࣭㓟 ᛶ◲Ᏻ➼࡟ࡼࡿゐ፹ຎ໬ࢆ㑊ࡅࡿࡓࡵ࡟ࠊSCR ୖὶഃ࡟タ⨨ࡍࡿࣂࢢࣇ࢕ࣝࢱࢆ 200 ºC ௨ୗ࡛㐠㌿ࡋࠊࢲ࢖࢜࢟ࢩࣥ㢮ࡢ㝖ཤ࣭㝖ሻ࣭⬺ሷ࣭⬺◲ࢆ⾜ࡗࡓ࠶࡜ࠊຍ⇕ჾ࡛ ෌ᗘ200 ºC ௨ୖ࡟᪼ ࡋ࡚࠿ࡽ⬺◪᧯సࢆ⾜࠺➼ࡢᚲせࡀ࠶ࡾ㸪SCR ࢆ඲࡚ࡢᗫᲠ≀ ↝༷⅔࡬ࡢ᤼↮⬺◪タഛࡢᑟධࡍࡿࡢࡣ⌧≧࡜ࡋ࡚ᅔ㞴࡛࠶ࡿ࡜࠸࠼ࡿ㸬

㸦2㸧㑅ᢥⓗ↓ゐ፹㑏ඖ⬺◪ἲ㸦Selective Non-Catalytic Reduction : SNCR㸧

SNCR ࡜ࡣࠊゐ፹ࢆ౑⏝ࡏࡎ࡟ࠊ㧗 ᤼࢞ࢫ୰࡟ NH3ࡸᒀ⣲࡞࡝ࡢ㑏ඖ๣ࢆ྿ࡁ㎸

ࡳࠊNOx ࢆ↓ᐖ࡞ N2࡜H2O ࡟㑏ඖࡍࡿᢏ⾡࡛࠶ࡿ14)㸬ࡇࡢ᪉ἲ࡛ࡣࠊゐ፹ࡀ୙せ࡛࠿

ࡘタഛࢥࢫࢺࡀప࠸฼Ⅼࢆ᭷ࡍࡿࡀࠊ࢞ࢫ ᗘ750 ºC㸦↝༷⅔ฟཱྀ᤼࢞ࢫ ᗘ┦ᙜ㸧㸪

NH3/NOx ࣔࣝẚ 1.5 ࡟࠾࠸࡚⬺◪⋡ࡣ 40 %⛬ᗘ࡜⬺◪ᛶ⬟ࡣప࠸㸬SNCR ࡛㧗࠸⬺◪

(9)

- 5 -

㸦900–1000 ºC㸧࡟྿ࡁ㎸ࡴࡇ࡜ࡀ㔜せ࡛࠶ࡿ㸦Fig. 1-2㸧15)_㸬_{Temperature window ࡟ᑐࡋ}

࡚ࠊ཯ᛂሙࡢ ᗘࡀప ᇦഃ࡛࠶ࡿ࡜㑏ඖ๣ࡀ཯ᛂࡋࡁࢀࡎࠊ⬺◪ᛶ⬟ࡀపୗࡋ࡚ᮍ཯ ᛂ NH3 ࡀⓎ⏕ࡋࠊ㏫࡟㧗 ᇦഃ࡟྿ࡁ㎸ࡴ࡜㑏ඖ๣ࡀ㓟໬ࡋ࡚ NOx࡟࡞ࡗ࡚ࡋࡲ࠺㸬 ୰ᑠつᶍࡢ⇞↝᪋タ࡛ࡣ᤼࢞ࢫ ᗘࡀ࠶ࡲࡾ㧗ࡃ࡞࠸ࡢ࡛ Temperature window ࡟࠾ࡅ ࡿ༑ศ࡞཯ᛂ᫬㛫ࡀྲྀࢀࡎ㸪༑ศ࡞⬺◪ᛶ⬟ࢆᚓࡽࢀ࡞࠸㸬ࡼࡗ࡚㸪Temperature window ࢆᣑ኱ࡶࡋࡃࡣప ഃ࡬ࢩࣇࢺࡉࡏࡿࡇ࡜ࡀ࡛ࡁࢀࡤ㸪SNCR ࡣ୰ᑠつᶍࡢ⇞↝᪋タ࡟ 㐺ᛂ࡛ࡁࡿྍ⬟ࡣ༑ศ࡟࠶ࡿ࡜⪃࠼ࡽࢀࡿ㸬

Fig. 1-2 Temperature window of SNCR process using NH3 at molar ratio (NH3/NOx) = 1.5

1. 1. 5 SNCR ᛶ

ᛶ⬟ྥୖ࡟㛵ࡍࡿ᪤ ࡢ◊✲

SNCR ࡢᛶ⬟ࢆྥୖࡍࡿࡓࡵ࡟ᵝࠎ࡞᪉ྥ࠿ࡽࡢ࢔ࣉ࣮ࣟࢳࡀヨࡳࡽࢀ࡚࠸ࡿ㸬౛࠼ ࡤ㸪⬺◪๣࡛࠶ࡿNH3࡟ῧຍ๣ࢆΰࡐࡿࡇ࡜࡛Temperature window ࡢప ໬ࢆヨࡳࡓ ◊✲ࡣ࠸ࡃࡘࡶሗ࿌ࡉࢀ࡚࠸ࡿ㸬Lyon ࡽࡣ⬺◪๣࡟ H2ࢆῧຍࡍࡿࡇ࡜࡛700 ºC ࡜࠸࠺ ప ᇦ࡛⬺◪཯ᛂࡀ㐍⾜ࡍࡿࡇ࡜ࢆぢฟࡋࡓ 14㸧_{㸬Wenli ࡽ࡟ࡼࡗ࡚ࡶ H} 2/NH3ࣔࣝẚ =

0.5㸪NH3/NOx ࣔࣝẚ = 1.6㸪㓟⣲⃰ᗘ 0.4 %࡟࠾࠸࡚ Temperature window ࡀ 145 ºC ప

ഃ࡟ࢩࣇࢺࡍࡿࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿ16㸧_{㸬ࡲࡓ㸪Azuhata ࡽ࡟ࡼࡗ࡚ H} 2O2ࢆῧຍࡍࡿ ࡇ࡜࡛OH ࣛࢪ࢝ࣝࡀ⏕ᡂࡋ㸪⬺◪཯ᛂࡀಁ㐍ࡉࢀࡿࡇ࡜ࡶ♧ࡉࢀࡓ17)_㸬ࡲࡓ㸪_Cooper ࡣH2O2ࢆῧຍࡋ㸪H2O2/NO ࣔࣝẚ = 0.7㸪᤼࢞ࢫ ᗘ 690–710 ºC ࡛⬺◪⋡ 70 %ࢆグ㘓 ࡋࡓࡇ࡜ࢆሗ࿌ࡋ࡚࠸ࡿ18)_{㸬ࡇࡢ௚࡟ࡶ㸪Wenli ࡽ࡟ࡼࡗ࡚ CH} 4ࡸC2H6ࡢῧຍࡸ H2O ࡢῧຍ19)_{㸪Lyon ࡜ Longwell ࡽ࡟ࡼࡾ CO ࡢῧຍࡀሗ࿌ࡉࢀ࡚࠸ࡿ}20)_㸬

(10)

- 6 -

ࡇࡢ௚࡟ࡶ⬺◪๣ࢆ௚ࡢ໬Ꮫ≀㉁࡟ኚ࠼࡚㸪⬺◪ᐇ㦂ࢆヨࡳࡓሗ࿌ࡶ࠸ࡃࡘ࠿࡞ࡉࢀ

࡚࠸ࡿ㸬Salimian ࡜ Hanson ࡽࡣᒀ⣲ࢆ⬺◪๣࡜ࡋ࡚⏝࠸࡚⬺◪ヨ㦂ࢆ⾜ࡗ࡚࠸ࡿ21)_㸬

Arand ࡽࡣᒀ⣲㸦CO(NH2)2㸧ࢆ⬺◪๣࡜ࡋ࡚⏝࠸࡚㸪ᒀ⣲/NOxࣔࣝẚ = 0.5㸪᤼࢞ࢫ

ᗘ1015–1060 ºC ࡟࠾࠸࡚⬺◪⋡ 67 %࡜࠸࠺⤖ᯝࢆᚓ࡚㸪ᒀ⣲ࢆ⏝࠸࡚ࡶ NH3࡜ྠ➼ࡢ ⬺◪ᛶ⬟ࢆᚓࡽࢀࡿࡇ࡜ࢆ♧ࡋࡓ22)_㸬ࡲࡓ㸪_{Perry ࡜ Siebers ࡣ⬺◪๣࡜ࡋ࡚ࢩ࢔ࢾࣝ㓟} 㸦C3H3N3O3㸧ࢆ⏝࠸ࡿࡇ࡜ࢆᥦ᱌ࡋ࡚࠸ࡿ 23)㸬ࡋ࠿ࡋ࡞ࡀࡽ㸪⬺◪๣࡟ῧຍ≀ࢆຍ࠼ ࡿ᪉ἲࡸ⬺◪๣ࡑࡢࡶࡢࢆูࡢ໬Ꮫ≀㉁࡟ኚ᭦ࡍࡿࡇ࡜ࡣ㸪⤖ᯝⓗ࡟⬺◪ࢥࢫࢺࡀୖࡀ ࡗ࡚ࡋࡲ࠸㸪ᐇ⏝໬ࡲ࡛ࡣ⮳ࡽ࡞࠿ࡗࡓ㸬 ࡑࡢᚋ㸪SNCR ༢య࡛㐠⏝ࡍࡿࡢ࡛ࡣ࡞ࡃ㸪௚ࡢᢏ⾡࡜ SNCR ࢆ⤌ࡳྜࢃࡏࡓ」ྜᆺ SNCR ࡢ◊✲ࡀ┒ࢇ࡟⾜ࢃࢀࡓ㸬Ἠ࡜ᮧୖࡽ࡟ࡼࡾ᤼࢞ࢫ୰࡬࢜ࢰࣥࢆ྿ࡁ㎸ࡴࡇ࡜࡟ ࡼࡗ࡚NO ࢆ NO2࡬㓟໬ࡋ㸪ࢫࢡࣛࣂ࣮࡛㝖ཤࡍࡿࡇ࡜ࡀᥦ᱌ࡉࢀࡓ 24)㸬࢜ࢰࣥࡢ౪ ⤥※࡜ࡋ࡚ࢥࣟࢼᨺ㟁࡟ࡼࡿ O2࠿ࡽ࢜ࢰࣥࢆ⏕ᡂࡍࡿ᪉ἲࡀ᥇⏝ࡉࢀࡓࡀ㸪⿦⨨ࡢつ ᶍࠊࢥࢫࢺ࡜ࡶ࡟ぢྜࢃࡎᐇ⏝໬࡟ࡣ⮳ࡽ࡞࠿ࡗࡓ㸬ࡲࡓ㸪NO ࢆ㓟໬ࡍࡿ᪉ἲ࡜ࡋ࡚ ࣓ࢱࣀ࣮ࣝࢆ᤼࢞ࢫ୰࡟౪⤥ࡍࡿࡇ࡜ࡀLyon ࡽ࡟ࡼࡾᥦ᱌ࡉࢀ࡚࠸ࡿ14)20)_㸬 ௚࡟ࡶWallace ࡽࡣ SNCR ࡜ SCR ࢆ⤌ࡳྜࢃࡏ࡚⬺◪ᛶ⬟࡜ࢥࢫࢺࡢ㠃࡛ࡢࣂࣛࣥ ࢫࢆᅗࡗ࡚࠸ࡿ25)_{㸬ࡲࡓ㸪Matzing ࡽࡣ᤼࢞ࢫ࡟㟁Ꮚࣅ࣮࣒ࢆ↷ᑕࡍࡿࡇ࡜࡛ࣛࢪ࢝ࣝ} ཯ᛂࢆㄏⓎࡋNOx㸪SOxࡢບ㉳࣭ศゎࢆ᳨ウࡋ࡚࠸ࡿ26)㸬ࡋ࠿ࡋ࡞ࡀࡽ㸪᤼࢞ࢫ඲య࡟ 㟁Ꮚࣅ࣮࣒ࢆ↷ᑕࡍࡿࡢࡣ㞴ࡋࡃ㸪ศゎ཯ᛂ࡟ࡶ᫬㛫ࡀ࠿࠿ࡿ࡞࡝ၥ㢟ࡀ࠶ࡿ㸬୍᪉࡛㸪 Boyles ࡣ࢔࣮ࢡᨺ㟁࡟ࡼࡾບ㉳ࡉࡏࡓ࢔ࣝࢦࣥࣉࣛࢬ࣐ࢆ⏝࠸࡚㸪⬺◪๣࡛࠶ࡿ NH3 ࢆࣛࢪ࢝ࣝ໬ࡉࡏ࡚㸪᤼࢞ࢫ୰࡬࡜ὶࡋ㎸ࡴ᪉ἲࢆᥦ᱌ࡋࡓ27)_㸬_{Boyle ࡽࡣࡇࡢ᪉ἲ࡟} ࡼࡾ㸪⬺◪⋡94 %ࡲ࡛ SNCR ࡢᛶ⬟ࢆ㧗ࡵࡿࡇ࡜ࢆド᫂ࡋ㸪ࣉࣛࢬ࣐ࢆ⿵ຓⓗ࡟⏝࠸ ࡿ᪉ἲࡢ᭷⏝ᛶࢆ♧ࡋࡓ㸬

1. 2 Ỉ

Ỉ⣲࢚ࢿࣝࢠ࣮♫఍ࡢᵓ⠏

1. 2. 1 Ỉ⣲࢚ࢿࣝࢠ࣮♫఍࡜ࡣ

ᮾ᪥ᮏ኱㟈⅏௨㝆㸪඲Ⓨ㟁㔞࡟ᑐࡍࡿⅆຊⓎ㟁ࡀ༨ࡵࡿ๭ྜࡀୖ᪼ࡋ࡚࠾ࡾ㸪ࡑࢀ࡟ క࠸ⅆຊⓎ㟁ࡢ⇞ᩱㄪ㐩ࢥࢫࢺࡢቑຍࡣ᪥ᮏ⤒῭࡟࡜ࡗ࡚ᕪࡋ㏕ࡗࡓㄢ㢟࡛࠶ࡿ㸬ࡲࡓ㸪 ⅆຊⓎ㟁ẚ⋡ࡢୖ᪼ࡣ CO2 ᤼ฟ㔞ࡢ኱ᖜ࡞ቑຍࢆࡶࡓࡽࡋ㸪ᡃࡀᅜࡢ᤼ฟ๐ῶ┠ᶆࡢ ᚋ㏥࡟ࡶࡘ࡞ࡀࡿ࡜⪃࠼ࡽࢀࡿ28)_{㸬ࡑࡢࡓࡵ㸬⌧ᅾ࡛ࡣ෌⏕ྍ⬟࢚ࢿࣝࢠ࣮࡟୍ᒙࡢᮇ} ᚅࡀᐤࡏࡽࢀ࡚ࡣ࠸ࡿࡶࡢࡢ㸪Ẽೃ࡟ࡼࡿⓎ㟁ኚືไࡸ㸪ཎᏊຊⓎ㟁ࡢ100 ศࡢ 1 ࡟‶ ࡓ࡞࠸࢚ࢿࣝࢠ࣮ຠ⋡࡞࡝㸪ᢏ⾡ⓗၥ㢟ࡸࢥࢫࢺୖࡢၥ㢟ࡀᏑᅾࡋ࡚࠸ࡿ㸬ࡇࡢ⌧≧࠿ ࡽ㸪෌⏕ྍ⬟࢚ࢿࣝࢠ࣮࡛ᚓࡓ㟁ຊࢆỈ⣲࡟ኚ᥮ࡉࡏࡓᚋ㸪ࡑࢀࢆᐙᗞ⏝⇞ᩱ㟁ụࡸ⇞ ᩱ㟁ụ⮬ື㌴࡟౑⏝ࡍࡿࡇ࡜࡛㸪෌⏕ྍ⬟࢚ࢿࣝࢠ࣮ࡢࢹ࣓ࣜࢵࢺࢆ⿵࠺ࡔࡅ࡛࡞ࡃ㸪 ᆅ⌫⎔ቃ࡟ඃࡋ࠸పⅣ⣲♫఍ࡢᵓ⠏ࢆ⾜࠾࠺࡜ࡍࡿ͆Ỉ⣲࢚ࢿࣝࢠ࣮♫఍͇ࡢᐇ⌧࡟ྥ ࡅ࡚ຍ㏿ࡋ࡚ࡁ࡚࠸ࡿ㸬 Fig. 1-3 ࡟♧ࡋࡓࡼ࠺࡟㸪᪥ᮏ࡟࠾ࡅࡿ㍺㏦㒊㛛࡜Ẹ⏕㒊㛛࡟࠾ࡅࡿ࢚ࢿࣝࢠ࣮౑⏝

(11)

- 7 - 㔞ࡣ඲యࡢ6 ๭ࢆ༨ࡵ࡚࠸ࡿ29)_{㸬ࡲࡓ㸪඲࡚ࡀ໬▼⇞ᩱࡢ౫Ꮡࡋ࡚࠸ࡿࡇ࡜࠿ࡽ㸪ࡇࡢ} 2 㒊㛛࡟࠾࠸࡚໬▼⇞ᩱ౫Ꮡయไ࠿ࡽ⬺༷ࡋ࡞࠸㝈ࡾ㸪᪥ᮏࡢᆅ⌫ ᬮ໬ࢆᢚไࡍࡿࡇ ࡜ࡣ࡛ࡁ࡞࠸ࡔࢁ࠺㸬๓㡯࡛㏙࡭ࡓ࡜࠾ࡾ㸪Ỉ⣲ࡣከᵝ࡞౪⤥※ࢆᣢࡘࡔࡅ࡛࡞ࡃ㸪༙ Ọஂ࠿ࡘࢡ࣮ࣜࣥ࡞࢚ࢿࣝࢠ࣮࡛࠶ࡿⅬࡀ㨩ຊⓗ࡛࠶ࡿ㸬1981 ᖺࡼࡾ㸪ᡃࡀᅜ࡛ࡣỈ ⣲ࢆ⇞ᩱ࡜ࡋ࡚౑⏝ࡍࡿ⇞ᩱ㟁ụࡢ㛤Ⓨ࣭ᐇドࢆ✚ᴟⓗ࡟⾜ࡗ࡚ࡁࡓ㸬Ỉ⣲ࡢ฼ά⏝㡿 ᇦࡀᖜᗈ࠸ࡇ࡜࠿ࡽ㸪ᐙᗞ⏝⇞ᩱ㟁ụ㸦࢚ࢿࣇ࢓࣮࣒㸧ࡢᬑཬࡸ㸪2015 ᖺ࠿ࡽࡣ⇞ᩱ 㟁ụ⮬ື㌴ࡢ㈍኎ࡀ㛤ጞࡍࡿẁ㝵ࡲ࡛㎺ࡾ╔࠸ࡓ㸬Ỉ⣲ࡢ฼ά⏝ࢆᣑ኱ࡍࢀࡤ㸪┬࢚ࢿ ࣝࢠ࣮㸪࢚ࢿࣝࢠ࣮ࢭ࢟ࣗࣜࢸ࢕ࡢྥୖࡔࡅ࡛࡞ࡃ㸪㐠㍺㒊㛛࣭Ẹ⏕㒊㛛࡟࠾ࡅࡿ ᐊ ຠᯝ࢞ࢫࡢ᤼ฟ㔞ࡣ኱ᖜ࡟๐ῶ࡛ࡁࡿ࡜⪃࠼ࡽࢀࡿ㸬ࡲࡓ㸪ᑗ᮶ⓗ࡟෌⏕ྍ⬟࢚ࢿࣝࢠ ࣮࠿ࡽ〇㐀ࡉࢀࡓỈ⣲ࢆ฼⏝ࡍࡿࡇ࡜࡛㸪ᡃࡀᅜࡢ࢚ࢿࣝࢠ࣮⮬⤥⋡ྥୖ࡟ࡘ࡞ࡀࡿࡓ ࡵ㸪Ỉ⣲࢚ࢿࣝࢠ࣮♫఍ࡢᑟධព⩏ࡣ኱ࡁ࠸࡜⪃࠼ࡽࢀࡿ㸬

Fig. 1-3 Energy consumption of the transport sector

1. 2. 2 ᪤ᏑࡢỈ⣲〇㐀ᢏ⾡

Ỉ⣲࢚ࢿࣝࢠ࣮ᢏ⾡ࡣ㸪〇㐀ẁ㝵࠿ࡽ㈓ⶶ࣭㍺㏦㸪౪⤥࣭฼⏝ẁ㝵࡜ከᒱ࡟ࢃࡓࡿ㸬 ᮏሗ࡛ࡣ㸪Ỉ⣲〇㐀࡟╔┠ࡋ✀ࠎࡢỈ⣲〇㐀ࣉࣟࢭࢫ࡟ࡘ࠸࡚௨ୗࡢTable 1-2 ࡟ࡲ࡜ ࡵࡿ㸬⌧ᅾ㸪୺࡞Ỉ⣲౪⤥※ࡣ㸪໬▼⇞ᩱ㸦ኳ↛࢞ࢫ㸪ࢼࣇࢧ㸧ࡢᨵ㉁࡟ࡼࡗ࡚ᕤᴗⓗ ࡟〇㐀ࡉࢀ࡚࠸ࡿ࡯࠿㸪〇㚩ᡤࡸࢯ࣮ࢲᕤᴗ࠿ࡽࡢ๪⏕Ỉ⣲࡛࠶ࡿ㸬ᑗ᮶ⓗ࡟ࡣ㸪ⅆຊ Ⓨ㟁ࡸ෌⏕ྍ⬟࢚ࢿࣝࢠ࣮࠿ࡽࡢ㟁ຊࢆ⏝࠸࡚〇㐀ࡉࢀࡿࡇ࡜ࡀᮇᚅࡉࢀࡿ࡯࠿㸪㛗ᮇ ⓗ࡟ᐇ⌧ࡀᮇᚅࡉࢀࡿࣂ࢖࣐࢜ࢫኚ᥮㸪Ỉ⇕ศゎ㸪ගゐ፹㸪IS ࣉࣟࢭࢫ࡞࡝ࡢపⅣ⣲Ỉ ⣲〇㐀ᢏ⾡ࡀ◊✲㛤Ⓨࡉࢀ࡚࠸ࡿ㸬

(12)

- 8 - 㸦1㸧Ỉ⵨Ẽᨵ㉁ἲ ୡ⏺࡛ࡣ㸪ᖺ㛫 5000 ୓ࢺࣥ௨ୖࡢỈ⣲ࡀኳ↛࢞ࢫ㸦࣓ࢱࣥ㸧ࡸࢼࣇࢧ࡞࡝ࡢ໬▼ ⇞ᩱ࠿ࡽ〇㐀ࡉࢀ࡚࠸ࡿ28)_{㸬✀ࠎࡢỈ⣲〇㐀ࣉࣟࢭࢫࡢ୰࡛ࡶ㸪ኳ↛࢞ࢫࡢỈ⵨Ẽᨵ㉁} ࡀ୺࡜ࡋ࡚ᕤᴗⓗ࡟ᐇ⏝໬ࡉࢀ࡚࠾ࡾ㸪඲Ỉ⣲⏕⏘㔞ࡢ50 %௨ୖࢆ༨ࡵ࡚࠸ࡿ㸬Ỉ⵨ Ẽᨵ㉁ἲࡣ㸪CO ࡸ CO2ࢆྵࡴỈ⣲ࣜࢵࢳ࡞ΰྜ࢞ࢫࢆ〇㐀ࡍࡿᨵ㉁ᕤ⛬࡜㸪ᨵ㉁࢞ࢫ ࠿ࡽ୙⣧≀ࢆྲྀࡾ㝖ࡁ⣧Ỉ⣲࢞ࢫࢆ⢭〇ࡋ㸪⏝㏵࡟ࡼࡗ୍࡚ᐃࡢH2 /CO ẚࢆᣢࡘΰྜ ࢞ࢫࢆᚓࡿศ㞳࣭⢭〇ᕤ⛬ࡢ஧ࡘࡢᕤ⛬࠿ࡽᵓᡂࡉࢀࡿ㸬ኳ↛࢞ࢫࡢỈ⵨Ẽᨵ㉁཯ᛂࡣ㸪 ୗグ࡟♧ࡍ཯ᛂᘧ࡟ᚑ࠸྾⇕཯ᛂ㸦ǼH = –206.2 kJ /mol㸧࡛࠶ࡾ㸪㧗 ࡛㌿᥮⋡ࡀୖ᪼ ࡍࡿ㸬 CH4 + H2O Ѝ CO + 2H2 㸦1-13㸧 ᕤᴗⓗ࡟ࡣ㸪Ni ⣔ゐ፹ࢆ඘ሸࡋࡓᅛᐃᗋ཯ᛂჾࢆ⇞↝ࣂ࣮ࢼ࣮࡟ࡼࡾ 700–900 ºC ࡜ ࠸࠺㧗 ࡟ຍ⇕ࡍࡿ㐠㌿᪉ἲࡀ୍⯡ⓗ࡛࠶ࡿ30)_{㸬ᨵ㉁཯ᛂ୰࡟ゐ፹࡬ࡢⅣ⣲ᯒฟࡸᴟᚤ} 㔞ࡢ◲㯤ศ⿕ẘ࡟ࡼࡿゐ፹ࡢኻάࢆ㑊ࡅࡿࡓࡵ㸪ᨵ㉁཯ᛂ࡟ᚲせ࡞໬Ꮫ㔞ㄽẚࡼࡾ㐣๫ ࡟Ỉ⵨Ẽࢆ౑⏝ࡍࡿࡇ࡜㸦Ỉ⵨Ẽ /Ⅳ⣲ࣔࣝẚࡀ 3.0 ௨ୖ㸧ࡸ㸪ᨵ㉁๓࡟⬺◲ᕤ⛬ࢆタ ࡅࡿࡇ࡜㸪ࡲࡓ᪂つ⪏◲㯤⿕ẘゐ፹ࢆ౑⏝ࡍࡿࡇ࡜࡛㸬ᨵ㉁཯ᛂࡢ཯ᛂ⋡ࢆྥୖࡉࡏ࡚ ࠸ࡿ31)_{㸬ᨵ㉁཯ᛂ࡛ᆅ⌫ ᬮ໬ࡢཎᅉ࡛࠶ࡿ஧㓟໬Ⅳ⣲ࡀ᤼ฟࡍࡿࢹ࣓ࣜࢵࢺࢆᣢࡘ㸬} 㸦2㸧㒊ศ㓟໬ἲ 㔜㉁Ἔࡢ࢞ࢫ໬ࡣ㸪ୗグ࡟♧ࡍ཯ᛂᘧࡢࡼ࠺࡟㸪ཎᩱⅣ໬Ỉ⣲ࡢ୍㒊ࢆ㓟⣲࠶ࡿ࠸ ࡣ✵Ẽ㞺ᅖẼୗ࡛1100–1500 ºC㸪ᅽຊ 2–6 MPa ࡢ཯ᛂ᮲௳࡛⇞↝ࡉࡏ㸪ࡑࡢⓎ⇕࡟ࡼࡾ ṧࡾࡢⅣ໬Ỉ⣲࡜Ỉ⵨Ẽࢆᨵ㉁཯ᛂࡉࡏ㸪CO ࡜ H2ࡢΰྜ࢞ࢫࢆ〇㐀ࡍࡿ᪉ἲ࡛࠶ࡿ 28)_㸬 CnHm + n/2 O2 Ѝ nCO + m/2 H2 㸦1-14㸧㒊ศ㓟໬ἲࡣ㸪ゐ፹ࢆᚲせ࡜ࡋ࡞࠸ࡓࡵཎᩱ୰ࡢ୙⣧≀࡟ࡼࡿไ⣙ࡀ࡯࡜ࢇ࡝࡞ࡃ㸪㍍㉁ࡢⅣ໬Ỉ⣲ࡢࡳ࡞ࡽࡎ▼Ⅳࡸ㔜㉁Ἔ࡞࡝ࡶཎᩱ࡜ࡋ࡚⏝࠸ࡿࡇ࡜ࡀྍ⬟࡛࠶ࡿ㸬ࡇ ࡢ〇㐀ࣉࣟࢭࢫ࡟ࡣ㸪㓟⣲〇㐀⿦⨨ࡀᚲせ࡛Ỉ⵨Ẽᨵ㉁ἲ࡟ẚ࡭࡚ࢥࢫࢺࡀ࠿࠿ࡿࡀ㸪 ↓ゐ፹᮲௳࡛࠶ࡿࡓࡵ◲㯤ศࡀከ࠸㔜㉁Ἔࡸ▼Ἔ⢭〇ṧ´ࢆ౑⏝ࡋ࡚ࡶ⿕ẘࡍࡿᜍࢀ ࡀ↓࠸࡜࠸࠺࣓ࣜࢵࢺࡀ࠶ࡿ㸬ࡲࡓ㸪H2 /CO = 2 ࡢྜᡂ࢞ࢫࡀ⏕ᡂࡍࡿࡢ࡛㸪࣓ࢱࣀ࣮ ࣝࡸFT ྜᡂ⏝ཎᩱ࢞ࢫࡢ〇㐀࡟ࡶ㐺ࡋ࡚࠾ࡾ㸪᭱ࡶ⤒῭ⓗ࡞᪉ἲ࡜ࡋ࡚ከࡃࡢὀ┠ࢆ 㞟ࡵ࡚࠸ࡿ31)_{㸬⌧≧࡛ࡣ㸪Ỉ⵨Ẽᨵ㉁ἲ࡜ྠᵝ࡟㸪ᕤᴗⓗ࡟ᢏ⾡ࡀ☜❧ࡉࢀ࡚࠸ࡿࡀ㸪} 㧗 ᧯ᴗ᮲௳ࡸ཯ᛂ᫬࡟ᯒฟࡍࡿᅛయⅣ⣲ࡢฎ⌮࡞࡝ࢥࢫࢺⓗ࡞ㄢ㢟ࡀከࡃᏑᅾࡍࡿ㸬

(13)

- 9 -

Table 1-2 Classification of hydrogen production technology.

㻌㻌 ᪉ἲ㻌 ཎᩱ㻌 ⏝䛔䜛䜶䝛䝹䜼䞊✀㻌 ᢏ⾡㛤Ⓨ䝺䝧䝹㻌 ໬▼㈨※฼⏝㻌 Ỉ⵨Ẽᨵ㉁ἲ㻌 ኳ↛䜺䝇㻌 ⇕㻌 ᐇ⏝໬䝺䝧䝹㻌㻸㻼㻳㻌䝘䝣䝃㻌㒊ศ㓟໬ἲ㻌㔜㉁Ἔ㻌 ⇕㻌 ᐇ⏝໬䝺䝧䝹㻌 ▼Ⅳ㻌 ᥋ゐᨵ㉁ἲ㻌㻸㻼㻳㻌 ⇕㻌 ᐇ⏝໬䝺䝧䝹㻌䝘䝣䝃㻌 ๪⏕䜺䝇฼⏝㻌 ▼Ⅳ㻌 ⇕㻌 ᐇ⏝໬䝺䝧䝹㻌㣗ሷ㻌㠀໬▼㈨※฼⏝㻌㟁Ẽศゎ㻌 Ỉ㻌㟁ຊ㻌 ᐇ⏝໬䝺䝧䝹㻌 ⇕໬Ꮫศゎ㻌 Ỉ㻌 ཎᏊຊ㻌 ᐇ⏝໬䝺䝧䝹㻌 ኴ㝧ග㻌䝞䜲䜸䝬䝇㌿᥮㻌䝞䜲䜸䝬䝇㻌 ⇕㻌 ᐇ⏝໬䝺䝧䝹㻌 ᚤ⏕≀㻌 ගศゎ㻌 Ỉ㻌 ኴ㝧ග㻌 ᇶ┙◊✲䝺䝧䝹㻌㻵㻿䝥䝻䝉䝇㻌 Ỉ㻌 ⇕㻌 ᇶ┙◊✲䝺䝧䝹㻌㸦3㸧ྛ✀ࣉࣟࢭࢫ࠿ࡽࡢ๪⏕࢞ࢫ ๪⏕Ỉ⣲ࡣ㸪ከᵝ࡞ᕤᴗࣉࣟࢭࢫ࠿ࡽ๪⏘≀࡜ࡋ࡚⏕⏘ࡉࢀࡿỈ⣲ࡢࡇ࡜࡛࠶ࡿ㸬ᡃ ࡀᅜ࡛ࡣ㸪〇㚩ᡤ࡛ࡢࢥ࣮ࢡࢫ〇㐀ࣉࣟࢭࢫ㸪ሷ⣲ࡸⱔᛶࢯ࣮ࢲ⏕⏘⏝ࡢ㣗ሷ㟁ゎࣉࣟ ࢭࢫ㸪▼Ἔ໬Ꮫࣉࣟࢭࢫࡀ࠶ࡿ29)_㸬㣗ሷ㟁ゎࣉࣟࢭࢫ࡛ࡣ㸪ୗグ࡟♧ࡍࡼ࠺࡟ሷ⣲࡜ⱔᛶࢯ࣮ࢲࢆ⏕⏘ࡍࡿ㸬⌧≧࡛ࡣ㸪 9 ୓ࢺࣥ㸦10 ൨ Nm3_{㸧⛬ᗘࡢỈ⣲ࡀ๪⏕ࡋ࡚࠸ࡿ㸬ࡇࡢỈ⣲ࡣ⣧ᗘࡀ㧗ࡃ㸪ࡍ࡛࡟እ} ㈍ࡉࢀ࡚Ỉ⣲࡜ࡋ࡚฼⏝ࡉࢀ࡚࠸ࡿ㸬

2NaCl + 2H2O + electricity Ѝ 2NaOH + H2 + Cl2 㸦1-15㸧

〇㚩ᡤ࠿ࡽࡢ๪⏕Ỉ⣲ࡣ㸪ୗグ࡟♧ࡍࡼ࠺࡟▼Ⅳࢆ 1000–1100 ºC ࡛஝␃ࡋ࡚ࢥ࣮ࢡ

ࢫࢆ〇㐀ࡍࡿ㐣⛬࡛⏕⏘ࡉࢀࡿ࢞ࢫ࡛㸪ࢥ࣮ࢡࢫ࣮࢜ࣈࣥ࢞ࢫ㸦COG㸧࡜࿧ࡤࢀࡿ㸬⌧

(14)

- 10 - ㈍ࡍࡿሙྜ࡟ࡣ௦᭰⇞ᩱࢆ☜ಖࡍࡿᚲせࡀ࠶ࡿ㸬 CH0.8O0.2 Ѝ 0.8C + 0.2CO + 0.4H2 㸦1-16㸧 ࡉࡽ࡟㸪〇Ἔᡤ࡟࠾ࡅࡿࢼࣇࢧᨵ㉁ࣉࣟࢭࢫ㸪࢚ࢳࣞࣥྜᡂࣉࣟࢭࢫ㸪▼Ἔ⢭〇᫬ ࡢ⬺◲ࣉࣟࢭࢫࢆࡣࡌࡵ࡜ࡍࡿ✀ࠎࡢ▼Ἔ໬Ꮫࣉࣟࢭࢫ࠿ࡽࡣ㸪Ỉ⣲ࢆ୺ᡂศ࡜ࡍࡿ࢜ ࣇ࢞ࢫࡀ〇㐀ࡉࢀࡿ㸬〇Ἔᡤ࡟࠾ࡅࡿᚲせ㔞࡟ᛂࡌ࡚㸪ࣈࢱࣥࡸࢼࣇࢧ࠿ࡽỈ⵨Ẽᨵ㉁ ࡟ࡼࡗ࡚〇㐀ࡉࢀ࡚࠾ࡾࠊ⌧≧࡛ࡣእ㈍ࡉࢀ࡚࠸࡞࠸ࡀࠊ〇㐀᪋タࡢᐜ㔞ࡣవ๫ࡀ࠶ࡿ ࡜ゝࢃࢀ࡚࠸ࡿ28)_{㸬ࡲࡓ㸪⤒῭ᛶࡸ࢖ࣥࣇࣛᩚഛࡢ㛵ಀୖ㸪࢜ࣇ࢞ࢫ୰ࡢỈ⣲ࡣᅇ཰ࡉ} ࢀ࡚ࡇ࡞࠿ࡗࡓࡀ㸪᫖௒ࡢỈ⣲࢚ࢿࣝࢠ࣮♫఍࡬ࡢὀ┠ࡢ㧗ࡲࡾ࠿ࡽ᪂ࡓ࡟ᅇ཰ࣉࣟࢭ ࢫࡢᑟධࡀண᝿ࡉࢀࡿ㸬㣗ሷ㟁ゎࣉࣟࢭࢫ࠿ࡽࡢ๪⏕Ỉ⣲ࡣ⣧ᗘࡀ㧗࠸ࡶࡢࡢ㸪ࢥ࣮ࢡࢫ〇㐀࠾ࡼࡧ▼Ἔ⢭ 〇ࣉࣟࢭࢫ࡟࠾ࡅࡿ๪⏕Ỉ⣲ࡣ⣧ᗘࡀప࠸࡜࠸࠺ࢹ࣓ࣜࢵࢺࢆᣢࡗ࡚࠸ࡿ 29㸧_㸬ࡇࡢࡓ ࡵ㸪᪂ࡓ࡟Ỉ⣲⢭〇⿦⨨ࡢᑟධ㸪ࡲࡓእ㈍⏝ࡢฟⲴ⿦⨨࡞࡝タഛᢞ㈨㈝⏝ࡀⓎ⏕ࡋ࡚ࡋ ࡲ࠺㸬ࡉࡽ࡟㸪ᑗ᮶ⓗ࡟ࡣỈ⣲〇㐀ࡢపⅣ⣲໬ࡀồࡵࡽࢀࡿࡓࡵ㸪ࢯ࣮ࢲ㟁ゎ⮬యࡣ CO2ࢆⓎ⏕ࡋ࡞࠸ࡶࡢࡢࠊ〇㚩ᡤࡸ〇Ἔᡤ࡛ࡢỈ⣲〇㐀ࣉࣟࢭࢫ࡛ࡣCO2ࡀⓎ⏕ࡍࡿࡓ ࡵ㸪኱つᶍࣉࣛࣥࢺࡢ฼Ⅼࢆ⏕࠿ࡋ࡚Ⅳ⣲㝸㞳ࡢ᳨ウࡶᚲせ࡟࡞ࡗ࡚ࡃࡿ㸬㸦4㸧ࣂ࢖࣐࢜ࢫ㌿᥮ ࣂ࢖࣐࢜ࢫࡣ✀㢮ࡀከᵝ࡛࠶ࡿࡀ㸪୍⯡࡟ࡣ⏕⏘⣔㸦ᮌ㉁㢮㸪⢾㉁㢮㸪࡛ࢇ࡫ࢇ㢮㸪 Ἔ⬡⣔㸪ᾏ⸴㢮࡞࡝㸧࡜ᗫᲠ≀⣔㸦㎰⏘≀⣔ᗫᲠ≀㸪␆⏘⣔ᗫᲠ≀㸪㛫ఆᮦ࣭ᗫᮌᮦ࣭ ᘓタᗫᮦ㸪Ỉ⏘⣔ᗫᲠ≀㸪ࢦ࣑㸪ୗỈởἾ࡞࡝㸧࡟ศ࠿ࢀࡿ32)_{㸬࣮࢝࣎ࣥࢽ࣮ࣗࢺࣛࣝ} ࡢ⪃࠼᪉࠿ࡽ㸪ࣂ࢖࣐࢜ࢫࡣᆅ⌫ ᬮ໬㐍⾜ࢆᢚไࡍࡿࡔࡅ࡛࡞ࡃ㸪㈓ⶶࡢᐜ᫆ᛶ㸪Ᏻ ᐃࡋࡓ࢚ࢿࣝࢠ࣮ኚ᥮ྍ⬟࡜࠸࠺฼Ⅼࡀ࠶ࡿࡓࡵ㸪㏆ᮍ᮶࡟࠾࠸࡚᭱ࡶᏳ౯࡞Ỉ⣲ཎᩱ ࡜ࡋ࡚ᮇᚅ࡛ࡁࡿ㸬 ࣂ࢖࣐࢜ࢫ࠿ࡽࡢỈ⣲〇㐀ἲ࡟ࡣ㸪໬▼㈨※࡜ྠᵝ࡞ࠕ⇕໬Ꮫⓗ࢞ࢫ໬ࣉࣟࢭࢫࠖ࡜㸪 ࠕ⏕≀໬Ꮫⓗ࢞ࢫ໬ࣉࣟࢭࢫࠖࡀᏑᅾࡍࡿ33)_{㸬๓⪅ࡣ㸪ࣂ࢖࣐࢜ࢫ࡟⇕ࢆ࠿ࡅ࡚⇕ศゎ㸪} 㒊ศ㓟໬㸪ຍỈศゎ࡞࡝ࡢ໬Ꮫ཯ᛂࢆ㐍⾜ࡉࡏ㸪㎿㏿࠿ࡘẚ㍑ⓗ᏶඲࡟࢞ࢫ໬ࡀ㐍⾜ࡍ ࡿ㧗 ࢞ࢫ໬ࣉࣟࢭࢫ㸪㉸⮫⏺Ỉ࢞ࢫ໬ࣉࣟࢭࢫࡀᣲࡆࡽࢀࡿ㸬ᚋ⪅ࡣ㸪ࣂ࢖࣐࢜ࢫ࡟ ᚤ⏕≀ࢆస⏝ࡉࡏ࡚Ⓨ㓝స⏝࡟ࡼࡗ࡚࢞ࢫ࡬ࡢኚ᥮ࢆ㐍ࡵࡿࡶࡢ࡛࠶ࡾ㸪㛗᫬㛫࠿ࡘᮍ ᏶඲࡞࢞ࢫ໬࡛ࡣ࠶ࡿࡀ㸪ẚ㍑ⓗ✜࿴᮲௳࡛ᐇ⌧࡛ࡁࡿ฼Ⅼࢆ᭷ࡋ㸪࣓ࢱࣥⓎ㓝ࣉࣟࢭ ࢫ㸪Ỉ⣲Ⓨ㓝ࣉࣟࢭࢫࡀᣲࡆࡽࢀࡿ㸬ࣂ࢖࣐࢜ࢫࡢ࢞ࢫ໬࡟ࡼࡗ࡚⏕ᡂࡍࡿ࢞ࢫࡣ㸪୺ ࡟Ỉ⣲㸪࣓ࢱࣥ㸪୍㓟໬Ⅳ⣲㸪஧㓟໬Ⅳ⣲ࢆ୺ᡂศ࡜ࡋ㸪⇞ᩱ࢞ࢫࡸ໬Ꮫཎᩱ࢞ࢫ࡜ࡋ ࡚฼⏝࡛ࡁࡿ㸬 ࡋ࠿ࡋ㸪ࣂ࢖࣐࢜ࢫ࡟ࡼࡗ࡚ࡣࢳ࣮ࣕ㸦Ⅳ໬≀㸧ࡀ኱㔞࡟Ⓨ⏕ࡋ㸪⿦⨨ෆ࡟ṧ␃ࡋ࡚ ࡋࡲ࠺ࡓࡵ࡟ࡑࡢᑐᛂࡀᚲせ࡜࡞ࡿ34)_{㸬ྜࢃࡏ࡚㸪ศ㞳࣭⢭〇ᢏ⾡ࡢ㛤Ⓨࡀᚲせ࡛࠶ࡿ㸬} ࡲࡓ㸪ࣂ࢖࣐࢜ࢫ࢞ࢫ໬ᢏ⾡࡟ࡼࡿỈ⣲ࢥࢫࢺࡣࣂ࢖࣐࢜ࢫࢥࢫࢺ࡟౫Ꮡࡍࡿࡓࡵ㸪཰ 㞟ࢥࢫࢺࢆྵࡵࡓࢥࢫࢺపῶࡀᚲせ࡛࠶ࡿ35)_㸬

(15)

- 11 - 㸦5㸧Ỉࡢ㟁Ẽ㸪⇕࠾ࡼࡧගศゎࣉࣟࢭࢫ Ỉ⣲※࡜ࡋ࡚Ỉࢆ฼⏝ࡍࢀࡤ㸪࢚ࢿࣝࢠ࣮࡜ࡋ࡚౑⏝ࡋࡓᚋ࡟ࡣ෌ࡧỈࡢᙧ࡛ᡠࡿ ࡇ࡜࡟࡞ࡿࡢ࡛㸪㈨※ⓗไ⣙ࡣᏑᅾࡏࡎ஧㓟໬Ⅳ⣲࡞࡝ࡢⓎ⏕ࡶ࡞࠸ࡢ࡛᭱ࡶࢡ࣮ࣜࣥ ࡞Ỉ⣲※࡛࠶ࡿ࡜ゝ࠼ࡿ㸬ࡺ࠼࡟㸪Ỉࢆཎᩱ࡜ࡋ࡚ࢡ࣮ࣜࣥ࡞Ỉ⣲ࢆ኱㔞࡟〇㐀ࡍࡿࣉ ࣟࢭࢫࢆᐇ⌧ࡍࡿࡇ࡜ࡀ୙ྍḞ࡛࠶ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿ㸬෌⏕ྍ⬟࢚ࢿࣝࢠ࣮ࢆ฼⏝ࡋ ࡚㸪Ỉ࠿ࡽỈ⣲ࢆ〇㐀ࡍࡿ୺࡞᪉ἲ࡜ࡋ࡚ࡣ㸪Ỉࡢ㟁Ẽศゎ㸪⇕ศゎ㸪ගศゎࡀᣲࡆࡽ ࢀࡿ29)_{㸬 Ỉࡢ㟁Ẽศゎ࡟㛵ࡋ࡚㸪ᐇ⏝໬ࡉࢀ࡚࠸ࡿࡢࡣ࢔ࣝ࢝ࣜỈ㟁ゎἲ࡛࠶ࡾ㸪⿦} ⨨ࡢᵓ㐀ࡀࢩࣥࣉࣝ࡜࠸࠺฼Ⅼࢆᣢࡘࡀ㸪࢚ࢿࣝࢠ࣮ຠ⋡ࡀపࡃ㟁ຊᩱ㔠ࡀỈ⣲〇㐀ࢥ ࢫࢺ࡟኱ࡁࡃᙳ㡪ࡋ࡚ࡋࡲ࠺㸬ຠ⋡ྥୖ࣭ࢥࢫࢺపῶࢆ┠ᣦࡋ࡚㸪⌧ᅾ㸪ᅛయ㧗ศᏊ㟁ゎ㉁Ỉ㟁ゎἲ࣭㧗 Ỉ⵨Ẽ㟁ゎἲࡢ㛤Ⓨࡀ㐍ࡵࡽࢀ࡚࠸ࡿ㸬Ỉࡢ⇕ศゎ࡟㛵ࡋ࡚㸪Ỉࢆ ⇕ⓗ࡟Ỉ⣲࡜㓟⣲࡟ศゎࡍࡿ࡟ࡣ㸪Ỉࡢศゎ཯ᛂࡢࢠࣈࢬ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬ࡀ0 ࡟࡞ ࡿ ᗘ࡜ࡋ࡚4000 ºC ௨ୖࡢ㧗 ࡀᚲせ࡟࡞ࡿ㸬ࡑࡇ࡛㸪」ᩘ௨ୖࡢ໬Ꮫ཯ᛂࢆ⤌ࡳྜ ࢃࡏ࡚ࢧ࢖ࢡࣝ࡜ࡋ㸪ࡑࡢࢧ࢖ࢡ࡛ࣝỈࢆศゎࡍࡿࢠࣈࢬ࢚ࢿࣝࢠ࣮ࢆศᢸࡋ㸪ࡼࡾప ࡛཯ᛂࢆ㐍⾜ࡉࡏ࡚Ỉࢆศゎࡍࡿࡼ࠺࡟ࡋࡓࣉࣟࢭࢫࡀỈࡢከẁ⇕໬Ꮫศゎ࡛࠶ࡿ㸬 ୍⯡࡟㸪ከẁ⇕໬Ꮫศゎࢧ࢖ࢡࣝ࡟ࡼࡾ㸪ỈࢆỈ⣲࡜㓟⣲࡟ศゎࡍࡿ᪉ἲࢆỈࡢ⇕໬Ꮫ ศゎἲ࡜࿧ࡪ㸬ࡇࡢ཯ᛂࡣ㸪྾⇕཯ᛂ࡟ࡼࡿ⇕࢚ࢿࣝࢠ࣮࡛໬Ꮫ཯ᛂࢆ㐍⾜ࡉࡏ࡚Ỉࢆ Ỉ⣲࡜㓟⣲࡟ศゎࡋ㸪Ⓨ⇕཯ᛂࡼࡾ⇕ࢆᨺฟࡍࡿ࡜࠸࠺୍✀ࡢ໬Ꮫ⇕ᶵ㛵࡜ぢࡿࡇ࡜ࡀ ࡛ࡁࡿ㸬IS ࢧ࢖ࢡࣝ 36)_ࡸ_{UT̽3 ࢧ࢖ࢡࣝ} 37)_{࡞࡝㸪ᩘᑡ࡞࠸⇕໬ᏛỈ⣲〇㐀ࢧ࢖ࢡࣝࡢ} ࡳࡀᐇ⌧ྍ⬟࡛࠶ࡿࡢࡀ⌧≧࡛࠶ࡿ㸬Ỉࡢගศゎ࡟㛵ࡋ࡚㸪ගゐ፹ࡀኴ㝧ග࢚ࢿࣝࢠ࣮ ࢆ྾཰ࡍࡿ࡜㸪౯㟁Ꮚᖏ࡟࠶ࡿ㟁Ꮚࡀఏᑟᖏ࡬࡜㑄⛣ࡋ㸪ఏᑟᖏ㟁Ꮚ࡜ṇᏍࢆ⏕ࡌࡿ㸬 ྛࠎࡢ࣏ࢸࣥࢩࣕࣝࡀ㸪Ỉࢆ㓟໬࣭㑏ඖ࡛ࡁࡿ‽఩࡟࠶ࢀࡤ㸪ఏᑟᖏ㟁ᏊࡣỈࢆ㑏ඖࡋ ࡚Ỉ⣲ࢆⓎ⏕ࡋ㸪ṇᏍࡣỈࢆ㓟໬ࡋ࡚㓟⣲ࢆⓎ⏕ࡍࡿ࡜࠸࠺࣓࢝ࢽࢬ࣒࡛࠶ࡿ 29㸧_㸬ࡇ ࢀࡲ࡛࡟㸪⣸እᇦࡢග࡟ᑐࡋ࡚཯ᛂࡍࡿගゐ፹ᮦᩱࡣከᩘⓎぢࡉࢀ࡚࠸ࡿࡀ㸪⣸እ⥺ࡣ ኴ㝧ගࡢධᑕ࢚ࢿࣝࢠ࣮ࡢࢃࡎ࠿ࢆ༨ࡵࡿ࡟㐣ࡂ࡞࠸㸬ࡺ࠼࡟㸪ኴ㝧ග࡟ࡼࡗ࡚Ỉ⣲ࢆ ຠ⋡ⓗ࡟⏕ᡂࡍࡿ࡟ࡣ㸪ධᑕ࢚ࢿࣝࢠ࣮ࡢ43 %ࢆ༨ࡵࡿྍどගࡢᗈ࠸Ἴ㛗⠊ᅖ࡟ᑐࡋ ࡚ᛂ⟅ࡍࡿගゐ፹ࡢ㛤Ⓨࡀᚲせ࡜࡞ࡿ㸬ࡑࡢࡓࡵ࡟ࡣ㸪ࣂࣥࢻࢠࣕࢵࣉࡀྍどගࢆ྾཰ ࡛ࡁࡿ࡯࡝ᑠࡉࡃ㸪࠿ࡘఏᑟᖏ࠾ࡼࡧ౯㟁Ꮚᖏࡢ‽఩ࡀỈ⣲࠾ࡼࡧ㓟⣲ࢆⓎ⏕࡛ࡁࡿࣞ ࣋ࣝ࡟࠶ࡾ㸪ගゐ፹⮬㌟ࡀᏳᐃ࡜࠸࠺᮲௳ࢆ‶ࡓࡍᚲせࡀ࠶ࡿ㸬㏆ᖺࠊ◊✲ᡂᯝࡣ࠸ࡃ ࡘ࠿ᣲࡆࡽࢀ࡚࠸ࡿࡶࡢࡢ㸪Ỉ⣲〇㐀࡬ࡢᛂ⏝࡜࠸࠺ほⅬ࠿ࡽࡳࡿ࡜㸪㛗࠸཯ᛂ᫬㛫ࢆ せࡋ㸪࢚ࢿࣝࢠ࣮ຠ⋡ࡀపࡃᐇ⏝໬࡟ࡣ⛬㐲࠸ẁ㝵࡛࠶ࡿ㸬

1. 2. 3 Ỉ⣲࢟ࣕࣜ࢔࡬ࡢ㌿᥮

1. 2. 3. 1 Ỉ⣲࢟ࣕࣜ࢔࡜ࡣ Ỉ⣲ࡣ㸪ࢡ࣮࡛ࣜࣥ࠶ࡿࡇ࡜࡟ຍ࠼㸪໬▼⇞ᩱࡔࡅ࡛࡞ࡃ෌⏕ྍ⬟࢚ࢿࣝࢠ࣮࠿ࡽࡶ 〇㐀ྍ⬟࡛࢚ࢿࣝࢠ࣮౪⤥※ࡢከᵝ໬࡟ᐤ୚࡛ࡁࡿ㸬ࡓࡔࡋ㸪௨ୖࡢ࣓ࣜࢵࢺࡔࡅ࡛ࡣ ኱つᶍ࡞ᬑཬࡣᐇ⌧࡛ࡁ࡞࠿ࡗࡓ㸬஦ᐇ㸪20 ᖺ๓࡟෌⏕ྍ⬟࢚ࢿࣝࢠ࣮࠿ࡽỈ⣲ࢆ〇

(16)

- 12 - 㐀㸪㍺㏦㸪㈓ⶶࡋ฼⏝ࡍࡿWE̽NET ᵓ᝿ࡀࢫࢱ࣮ࢺࡋࡓࡀ㸪Ỉ⣲฼⏝࡟㣕㌍ⓗ㐍ᒎࡀ ↓࠸ࡢࡀ⌧≧࡛࠶ࡿ 38㸧_{㸬ࡑࡢཎᅉࡢ} _{1 ࡘ࡜ࡋ࡚㸪๓㡯ࡲ࡛࡛㏙࡭࡚ࡁࡓỈ⣲〇㐀ࣉࣟ} ࢭࢫ࡟࠾ࡅࡿㄢ㢟ࡀᣲࡆࡽࢀࡿ㸬ࡲࡓ㸪㍺㏦ࡍࡿ㝿࡟ᩘ10 MPa ௨ୖࡢ㧗ᅽ࡜ᴟప ࡀ ᚲせ࡛㸪㈓ⶶࡍࡿ㝿࡟ࡣ㛗᫬㛫Ỉ⣲࡟ࡼࡿᮦᩱ⬤ᙅ໬ࡀ㉳ࡇࡽ࡞࠸᪂つᮦᩱ㛤Ⓨࡀᚲせ ࡞࡝㸪࢚ࢿࣝࢠ࣮ࣟࢫࡀⓎ⏕ࡋ࡚ࡋࡲ࠺㸬ࡺ࠼࡟㸪Ỉ⣲ࢆప౯᱁࡛࠶ࡾᏳ඲࠿ࡘከ㔞࡟ ㈓ⶶ࣭㍺㏦࡛ࡁࡿ᪉ἲࡀᏑᅾࡋ࡚࠸࡞࠸㸬㏆ᖺ࡛ࡣ㸪Ỉ⣲ࡢ௦ࢃࡾ࡟㈓ⶶ࣭㍺㏦ࡀᐜ᫆ ࡞Ỉ⣲ྵ᭷≀㉁㸦Ỉ⣲࢟ࣕࣜ࢔㸧ࢆ෌⏕ྍ⬟࢚ࢿࣝࢠ࣮࡛〇㐀ࡋ㸪Ỉ⣲ࢆᾘ㈝ࡍࡿ┤๓ ࡟ኚ᥮ࡍࡿ࡜࠸࠺᪂ࡓ࡞࢚ࢿࣝࢠ࣮ࢩࢫࢸ࣒ࡀ㸪Ỉ⣲࢚ࢿࣝࢠ࣮♫఍᪩ᮇᐇ⌧ࡢ㘽࡟࡞ ࡿ࡜⪃࠼ࡽࢀࡿ39)_{㸬ࡑࡢỈ⣲࢟ࣕࣜ࢔࡜ࡋ࡚㸪୺࡟ὀ┠ࡉࢀ࡚࠸ࡿࡶࡢ࡜ࡋ࡚࢔ࣥࣔࢽ} ࢔㸪࣓ࢳࣝࢩࢡࣟ࣊࢟ࢧࣥ㸦᭷ᶵࣁ࢖ࢻࣛ࢖ࢻ㸧㸪ࢠ㓟㸪࣓ࢱࣀ࣮ࣝࡀᣲࡆࡽࢀࡿ㸬㸦1㸧࢔ࣥࣔࢽ࢔ ࢔ࣥࣔࢽ࢔ࡣ㸪17.8 wt%ࡶࡢỈ⣲㔞ࢆ᭷ࡋ㸪Ỉ⣲ྵ᭷≀㉁ࡢ୰࡛ࡣⴭࡋࡃ኱ࡁ࡞್ ࢆ♧ࡍ40)_{㸬ᅽ⦰ࡍࡿࡇ࡜࡟ࡼࡗ࡚㸪ᐊ ࠿ࡘ}_{1 MPa ௨ୗ࡛ᐜ᫆࡟ᾮ໬ྍ⬟࡛࠶ࡿ㸬ᾮ} య࢔ࣥࣔࢽ࢔ࡢయ✚࢚ࢿࣝࢠ࣮ᐦᗘࡣ㸪ᾮయỈ⣲ࡢ1.5–2.2 ಸ࡛࠶ࡾ㸪Ỉ⣲࡜ẚ࡭࡚㧗 ᐦᗘ࡟࢚ࢿࣝࢠ࣮㍺㏦ࡀྍ⬟࡛࠶ࡿ㸬ఱࡼࡾࡶ࢔ࣥࣔࢽ࢔ࡢᣢࡘ฼Ⅼࡣ㈓ⶶ࣭㍺㏦ࡢࣀ ࢘ࣁ࢘ࡀ☜❧ࡉࢀ࡚࠸ࡿⅬ࡟࠶ࡿ㸬ࡲࡓ㸪࢔ࣥࣔࢽ࢔ࡣ㸦5㸧ᘧ࡟♧ࡍࡼ࠺࡟ᨵ㉁ࡍࡿ ࡇ࡜࡛࢚ࢿࣝࢠ࣮࡛࠶ࡿỈ⣲࡜❅⣲ࡢࡳࡀᚓࡽࢀࡿࡇ࡜࠿ࡽ㸪஧㓟໬Ⅳ⣲ࢆ᤼ฟࡋ࡞࠸ Ỉ⣲࢟ࣕࣜ࢔࡜ࡋ࡚ᮇᚅ࡛ࡁࡿ㸬 NH3 Ѝ 1.5 H2 + 0.5 N2 㸦1-17㸧 ࡋ࠿ࡶ㸪࢔ࣥࣔࢽ࢔ࢆศゎࡋ࡚Ỉ⣲ࢆᨺฟࡉࡏࡿࡢ࡟せࡍࡿ࢚ࢿࣝࢠ࣮ࡣ㸪௚ࡢỈ⣲ ࢟ࣕࣜ࢔࡟ẚ࡭࡚పࡃ㸪ຠ⋡ⓗ࡟Ỉ⣲࡟ኚ᥮࡛ࡁࡿ฼Ⅼࡶᣢࡘ㸬ࡋ࠿ࡋ㸪ཎᩱ࡜ࡋ࡚Ỉ ⣲ࢆ౑⏝ࡍࡿࡓࡵ㸪᪤Ꮡἲ࡛〇㐀ࡍࡿỈ⣲ࡼࡾࡶ〇㐀ࢥࢫࢺࡣୖ᪼ࡍࡿࡶࡢࡢ㸪㈓ⶶ࣭ ㍺㏦ᕤ⛬ࢆྵࡵࡿ࡜పࢥࢫࢺ࡟࡞ࡿ41)_㸬㸦2㸧࣓ࢳࣝࢩࢡࣟ࣊࢟ࢧࣥ 㸦᭷ᶵࣁ࢖ࢻࣛ࢖ࢻ㸧 Ỉ⣲໬཯ᛂ࡟ࡼࡾỈ⣲ࢆࢺ࢚ࣝࣥ࡟ᅛᐃࡉࡏ㸪࣓ࢳࣝࢩࢡࣟ࣊࢟ࢧࣥ࡜ࡋ࡚ᖖ ࣭ ᖖᅽ᮲௳࡛ᐜ᫆࡟㈓ⶶ࣭㍺㏦ࢆ⾜࠸ᾘ㈝᫬࡟⬺Ỉ⣲཯ᛂ࡟ࡼࡗ࡚Ỉ⣲ࢆྲྀࡾฟࡍ᪉ἲ 㸦᭷ᶵࣁ࢖ࢻࣛ࢖ࢻἲ㸧ࡀ୍⯡ⓗ࡛࠶ࡿ40)_{㸬ࢺ࢚ࣝࣥ࡜࣓ࢳࣝࢩࢡࣟ࣊࢟ࢧࣥࡣ㸪໬Ꮫ} ရ࡜ࡋ࡚኱ᆺࢣ࣑࢝ࣝࢱ࣮ࣥ࢝࡟ࡼࡿ኱㔞㍺㏦ࡔࡅ࡛࡞ࡃ㸪࣮࣮ࣟࣜࡸ㕲㐨㈌≀㌴୧ࡢ ᅜෆ㍺㏦ᶵჾ㸪ࢱࣥࢡ࡞࡝ࡢ኱ᆺ㈓ⶶタഛࡶᐇ⏝໬ࡉࢀ࡚࠸ࡿ㸬ࡺ࠼࡟㸪᪤Ꮡὶ㏻࢖ࣥ ࣇࣛࢆ᭱኱㝈࡟ά⏝ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࡓࡵࢫ࣒࣮ࢬ࡞⛣⾜ࡀᮇᚅ࡛ࡁࡿ42)_{㸬ຍ࠼࡚㸪㸫} 95–100 ºC ࡢᗈ࠸ ᗘ⠊ᅖ࡛ᾮయ≧ែࢆ⥔ᣢ࡛ࡁࡿࡓࡵ㸪ᆅ⌫ୖࡢ࠶ࡽࡺࡿ⎔ቃୗ࡛⁐ ፹ࡀ୙せ࡛㸪ࢺ࢚ࣝࣥࡣᕤᴗ⁐๣ࡸࣁ࢖࢜ࢡ࢞ࢯࣜࣥᇶᮦ࡜ࡋ࡚኱㔞࡟⏕⏘ࡉࢀ࡚࠾ࡾ㸪 ᬑཬ࡟㝿ࡋ࡚ࡢ኱㔞ㄪ㐩ࡀᐜ࡛᫆࠶ࡿ฼Ⅼࢆᣢࡘ㸬ࡲࡓ㸪ࡇࡢࣉࣟࢭࢫࡣྍ㏫཯ᛂࢆ฼ ⏝ࡋ࡚࠾ࡾࣜࢧ࢖ࢡࣝྍ⬟࡛࠶ࡿ㸬ࡇࢀࡲ࡛㸪ཎᩱࡀ࡜ࡶ࡟Ⅳ໬Ỉ⣲⣔໬ྜ≀࡛࠶ࡿࡇ

(17)

- 13 - ࡜࠿ࡽ㸪㛗ᮇ㛫㐠㌿࡟ࡼࡾゐ፹ୖ࡛Ⅳ⣲ࡀᯒฟࡍࡿ࡜࠸࠺ㄢ㢟ࡀᏑᅾࡋ࡚࠸ࡓ㸬Ẹ㛫௻ ᴗ࡟ࡼࡾ᪂つゐ፹ࡢ㛤Ⓨࡀᡂຌࡋ㸪ㄢ㢟࡛࠶ࡗࡓⅣ⣲ᯒฟࢆᢚไࡍࡿࡔࡅ࡛࡞ࡃ㸪㛗ᮇ 㛫Ᏻᐃⓗ࡟㧗⣧ᗘỈ⣲ࢆ〇㐀࡛ࡁ㸪ᐇドẁ㝵ࡲ࡛฿㐩ࡋࡓ43)-45)_㸬㸦3㸧ࢠ㓟࣭࣓ࢱࣀ࣮ࣝ ࢠ㓟࡜࣓ࢱࣀ࣮ࣝࡣ㸪࡜ࡶ࡟๓㡯ࡢ࣓ࢳࣝࢩࢡࣟ࣊࢟ࢧࣥ࡟ẚ࡭࡚య✚Ỉ⣲ᐦᗘࡀ 㧗࠸㸬ࡲࡓ㸪࣓ࢱࣀ࣮ࣝ࡟㛵ࡋ࡚ࡣ㸪ᕤᴗⓗ࡟Ỉ⵨Ẽᨵ㉁ἲࡀ☜❧ࡉࢀ࡚࠾ࡾᐇ⏝໬ࡢ Ⅼ࡟࠾࠸࡚ࡣ᭷⬟࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿ40)_{㸬ࡋ࠿ࡋ㸪ୗグࡢ཯ᛂ࡟ࡼࡾ㸪ࡇࢀࡽࡣỈ⣲ᨺ} ฟ᫬࡟஧㓟໬Ⅳ⣲ࢆ᤼ฟࡋ࡚ࡋࡲ࠺ࡓࡵ㸪Ỉ⣲〇㐀ࣉࣟࢭࢫ௨እ࡟ࡶ஧㓟໬Ⅳ⣲ᅇ཰ࣉ ࣟࢭࢫ࡞࡝ࢆᑟධࡋ࡞࠸㝈ࡾ㸪ᆅ⌫ ᬮ໬ࡢ㐍⾜ࡀᠱᛕࡉࢀࡿ㸬 HCOOH Ѝ H2 + CO2 㸦1-18㸧 CH3OH + O2 Ѝ 2 H2 + CO2 㸦1-19㸧 1. 2. 3. 2 Ỉ⣲࢟ࣕࣜ࢔ࡢẚ㍑⾲1̽2 ࡟㸪ᮏሗ࡛㏙࡭ࡓ 4 ✀㢮ࡢỈ⣲࢟ࣕࣜ࢔ࡢ≉ᛶ࡟ࡘ࠸࡚ࡲ࡜ࡵࡓࡶࡢࢆ♧ࡍ46)_㸬

Table 1-3 Comparison of physical properties for hydrogen carriers.

㻌㻌 ࢔ࣥࣔࢽ࢔ ࣓ࢳࣝࢩࢡࣟ ࣊࢟ࢧࣥ ࢠ㓟 ࣓ࢱࣀ࣮ࣝ ᾮయỈ⣲ ἛⅬ _[K] ₂₄₀ ₃₇₄ ₃₇₄ ₃₃₈ _20.3 ㉁㔞Ỉ⣲ᐦᗘ _[mass%] _17.8 _6.16 _4.38 _12.1 ₁₀₀ య✚Ỉ⣲ᐦᗘ _[kg/100L] _12.1 _4.73 _5.34 _10.3 _7.08 Ỉ⣲ᨺฟ࢚ࣥࢱࣝࣆ࣮ _[kJ/mol-H₂_] _67.5 _67.5 _31.6 _43.8 _0.899 ࢠ㓟࣭࣓ࢱࣀ࣮ࣝ࡟㛵ࡋ࡚ࡣ㸪࢔ࣥࣔࢽ࢔࡟⥆ࡁయ✚Ỉ⣲ᐦᗘࡀ㧗࠸࡜࠸࠺฼Ⅼࢆ ᭷ࡋ࡚࠸ࡿࡀ㸪Ỉ⣲ᨺฟ᫬࡟Ⓨ⏕ࡍࡿ஧㓟໬Ⅳ⣲ࡢᏑᅾࡸ࢚ࢿࣝࢠ࣮ຠ⋡ࡢపࡉࡀࢿࢵ ࢡ࡟࡞ࡿ㸬ࡲࡓ㸪Ỉ⣲ᨺฟ࢚ࣥࢱࣝࣆ࣮࡟╔┠ࡋ࡚࢔ࣥࣔࢽ࢔࡜࣓ࢳࣝࢩࢡࣟ࣊࢟ࢧࣥ ࢆẚ㍑ࡍࡿ࡜㸪࢔ࣥࣔࢽ࢔ࢆศゎࡋ࡚Ỉ⣲ࢆᨺฟࡉࡏࡿࡢ࡟ᚲせ࡞࢚ࢿࣝࢠ࣮ࡣ㸪Ỉ⣲ ࡢ⇞↝࢚ࢿࣝࢠ࣮㸦286 kJ/mol–H2㸧ࡢ10 %⛬ᗘ࡟␃ࡲࡿ㸬୍᪉㸪࣓ࢳࣝࢩࢡࣟ࣊࢟ࢧ ࣥࡢỈ⣲ᨺฟ࢚ࣥࢱࣝࣆ࣮ࡣ㸪࢔ࣥࣔࢽ࢔࡟ẚ࡭࡚2 ಸ௨ୖ࡟࡞ࡾ㸪Ỉ⣲ࡢ⇞↝࢚ࢿࣝ ࢠ࣮ࡢ24 %࡟┦ᙜࡍࡿ㸬Ỉ⣲ᨺฟ࡟㈝ࡸࡉࢀࡿ࢚ࢿࣝࢠ࣮ࡢ๭ྜࡀከ࠸࡯࡝Ỉ⣲ࡣ⏕ ᡂࡍࡿࡓࡵ㸪࢔ࣥࣔࢽ࢔ࡢ᪉ࡀ᭷฼࡛࠶ࡿ㸬ࡲࡓ㸪࢔ࣥࣔࢽ࢔࡜࣓ࢳࣝࢩࢡࣟ࣊࢟ࢧࣥ ࢆ෌⏕ྍ⬟࢚ࢿࣝࢠ࣮࡛〇㐀ࡍࡿ࡜௬ᐃࡋࡓ᫬㸪࣓ࢳࣝࢩࢡࣟ࣊࢟ࢧࣥࡢ〇㐀ࢥࢫࢺࡣ ࢔ࣥࣔࢽ࢔ࡢ100 ಸ࡟࡞ࡿ࡜ゝࢃࢀ࡚࠸ࡿ㸬Ỉ⣲࢚ࢿࣝࢠ࣮♫఍ࢆᐇ⌧ࡍࡿ࡟ࡣ㸪Ỉ⣲ ࢆ࠸࠿࡟Ᏻ౯࠿ࡘከ㔞࡟〇㐀࡛ࡁࡿ࠿ࡀ㔜せ࡛࠶ࡿࡓࡵ㸪୧ほⅬࡼࡾ࢔ࣥࣔࢽ࢔ࡢ᪉ࡀ Ỉ⣲࢟ࣕࣜ࢔࡜ࡋ࡚᭷ព࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿ㸬

(18)

- 14 - 1. 2. 3. 3 ࢔ࣥࣔࢽ࢔࠿ࡽࡢỈ⣲〇㐀࡟㛵ࡍࡿ᪤ ࡢ◊✲ ๓㡯ࡢ㸦1-17㸧ᘧࡢࡼ࠺࡟㸪⇕ࡢࡳࢆ฼⏝ࡋ࡚࢔ࣥࣔࢽ࢔࠿ࡽỈ⣲ࢆྲྀࡾฟࡍሙྜ ࡟ࡣ㧗 ࡀᚲせ࡟࡞ࡿ㸬ࡇࡢࡓࡵ㸪⌧ᅾࡣゐ፹ࢆ౑⏝ࡋࡓ࢔ࣥࣔࢽ࢔ᨵ㉁཯ᛂࡀ୺ὶ࡛ ࠶ࡿ 46)_㸬_{㸦1-17㸧ᘧࡢ཯ᛂࢆ⌧ᐇⓗ࡞཯ᛂ㏿ᗘ࡛㐍⾜ࡉࡏࡿ࡟ࡣ㸪ᶵᲔⓗᙉᗘࡀ㧗ࡃ⇕} Ᏻᐃᛶ࡟ඃࢀࡓ࢔࣑ࣝࢼᢸᣢࢽࢵࢣࣝゐ፹㸦Ni/Al2O3㸧ࡀ౑⏝ࡉࢀ࡚ࡁࡓ 47)㸬ࡓࡔࡋ㸪 ࢽࢵࢣࣝゐ፹࡛ࡣ800 ºC ௨ୖࡢศゎ ᗘࡀᚲせ࡛࠶ࡿ㸬ศゎ ᗘࢆୗࡆࡿࡓࡵ࡟㸪✀ࠎ ࡢゐ፹ࡀ᳨ウࡉࢀ㸪ࣝࢸࢽ࣒࢘ゐ፹ࡀ᭱ࡶ㧗࠸ゐ፹άᛶࢆ♧ࡍࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓ48)_㸬 ࢔࣑ࣝࢼᢸᣢࣝࢸࢽ࣒࢘ゐ፹㸦Ru/Al2O3㸧ࢆ౑⏝ࡍࡿࡇ࡜࡛㸪࢔ࣥࣔࢽ࢔ࢆ600㹼900 ºC ࡛ศゎࡋỈ⣲࡜❅⣲ࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡿ49)_{㸬࿘ᮇ⾲ୖ࡟࠾࠸࡚㸪ࣝࢸࢽ࣒࢘㸪ࢽࢵࢣࣝ} ࡟㏆࠸ࢥࣂࣝࢺ㸪㕲࡜࢔ࣥࣔࢽ࢔ศゎ≉ᛶ࡟ࡘ࠸࡚ẚ㍑ࡍࡿ࡜㸪ࣝࢸࢽ࣒࢘㸼ࢽࢵࢣࣝ 㸼ࢥࣂࣝࢺ㸼㕲ࡢ㡰␒࡛άᛶࡣῶᑡࡍࡿ㸬࢔ࣥࣔࢽ࢔ศゎ㐣⛬࡟࠾࠸࡚㸪❅⣲⬺㞳ࡣᚊ ㏿ẁ㝵࡛࠶ࡿࡇ࡜࠿ࡽ㸪ࡇࢀࡽ㔠ᒓゐ፹ࡢ࢔ࣥࣔࢽ࢔ศゎάᛶຊࡣ❅⣲⬺㞳᫬ࡢάᛶ࢚ ࢿࣝࢠ࣮࡟㛵ಀࡋ࡚࠸ࡿ࡜ሗ࿌ࡉࢀ࡚࠸ࡿ50)_㸬 ࡋ࠿ࡋ㸪㈗㔠ᒓ࡛࠶ࡿࣝࢸࢽ࣒࢘ゐ፹ࡣࢽࢵࢣࣝゐ፹࡟ẚ࡭࡚100 ಸࡢࢥࢫࢺࡀⓎ⏕ ࡋ࡚ࡋࡲ࠺㸬ࡲࡓ㸪࢜ࣥࢧ࢖ࢺ࡟࠾࠸࡚〇㐀ࡋࡓỈ⣲ࢆ⇞ᩱ㟁ụ࡟฼⏝ࡍࡿ㝿㸪㎿㏿࡟ ࢔ࣥࣔࢽ࢔࠿ࡽỈ⣲ࢆ〇㐀ࡍࡿࡇ࡜ࡀᮃࡲࢀࡿࡀ㸪ゐ፹࡟ࡼࡿ⇕ศゎ࡛ࡣゐ፹ࡢຍ⇕᫬ 㛫➼࡛Ỉ⣲〇㐀ࡀጞࡲࡿࡲ࡛࡟࠶ࡿ⛬ᗘࡢ᫬㛫ࡀᚲせ࡛࠶ࡿ㸬ࡑࡢⅭ㸪㎿㏿࡟࢔ࣥࣔࢽ ࢔࠿ࡽỈ⣲ࢆ〇㐀ࡍࡿ᪂つࣉࣟࢭࢫࡢ㛤Ⓨࡀᮃࡲࢀ࡚࠸ࡿ㸬 1. 2. 3. 4 ኱Ẽᅽࣉࣛࢬ࣐ࢆ⏝࠸ࡓᢏ⾡ ࣉࣛࢬ࣐࡜ࡣ㸪≀㉁ࡢ➨4 ≧ែ࡜࿧ࡤࢀࡿ㠀ᖖ࡟࢚ࢿࣝࢠ࣮ࡢ㧗࠸≧ែ࡛࠶ࡾ㸪㟁Ꮚ ࡜㝧Ꮚ࡟ศ࠿ࢀ࡚࠸ࡿ㸬ࣉࣛࢬ࣐ࡢ୰࡛ࡣ㸪ࡑࡢ㟁Ꮚࡢ୍㒊ࡢࡳࡀ㟁⏺࡛ຍ㏿ࡉࢀࡿࡇ ࡜࡛㧗࠸࢚ࢿࣝࢠ࣮ࢆ๰ᡂࡋ㸪⇕ⓗ࡟ࡣ㟁Ꮚ ᗘࡢࡳࡀᴟࡵ࡚㧗࠸≧ែ࡟࡞ࡿ㸬ࡑࡢ࢚ ࢿࣝࢠ࣮ࡀ࢞ࢫศᏊ࡟୚࠼ࡽࢀࡿࡇ࡜࡛㸪㟁㞳ࡸບ㉳㸪ゎ㞳཯ᛂࡀ㉳ࡇࡾ㸪ᬑẁ࡛ࡣ㉳ ࡇࡾ࠼࡞࠸໬Ꮫᖹ⾮ㄽࡢไ⣙ࢆ㉺࠼ࡿ཯ᛂࡀᮇᚅ࡛ࡁࡿ51㸧_㸬㏆ᖺ࡛ࡣ㸪ᖖ ࣭ᖖᅽ࡛ࣉࣛࢬ࣐ࡀᙧᡂࡉࢀࡿࡼ࠺࡟࡞ࡾ㸪኱Ẽởᰁ≀㉁࡛࠶ࡿVOC ࡢศゎ 52㸧_{㸪࢜ࢰࣥ⏕ᡂ≉ᛶࢆ฼⏝ࡋࡓ✵ẼὙίᶵ࡞࡝ࡢ⎔ቃί໬ศ㔝ࡸ㸪ᮦᩱࡢ❅໬} 53)_{ࡸ໬Ꮫ⵨╔཯ᛂ࡞࡝ࡢᮦᩱ㛤Ⓨศ㔝㸪ࡉࡽ࡟ࡣẅ⳦ࡸ⁛⳦࡞࡝ࡢ་⒪ศ㔝࡟ࡲ࡛ᛂ⏝} ࡢᖜࡀᣑ኱ࡉࢀ࡚ࡁ࡚࠸ࡿ㸬 ኱Ẽᅽࣉࣛࢬ࣐ࡢ୰࡛ࡶ㸪ᮏ◊✲࡛ࡣㄏ㟁యࣂࣜ࢔ᨺ㟁㸦DBD㸧࡟ὀ┠ࡋ࡚࠸ࡿ㸬ㄏ㟁యࣂࣜ࢔ᨺ㟁࡜ࡣ㸪㟁ᴟ㛫࡟࢞ࣛࢫ࡞࡝ࡢㄏ㟁యࢆᣳࡳ㸪஺ὶ㟁ᅽࢆ༳ຍࡍࡿࡇ࡜ ࡛✵㛫ⓗ࡟ᒁᅾ໬ࡋࡓ㐣Ώⓗ࡞ᚤ⣽ᨺ㟁㸦ࣉࣛࢬ࣐㸧ࢆᙧᡂࡍࡿᨺ㟁᪉ᘧࡢࡇ࡜࡛࠶ࡿ㸬ㄏ㟁య࡟ࡼࡗ࡚㸪ᨺ㟁㟁ὶࡀᛴ⃭࡟ᢚไࡉࢀࡿ࡜ྠ᫬࡟ㄏ㟁య࡟⵳✚ࡋࡓ㟁Ⲵࡀ㏫㟁⏺ ࢆᙧᡂࡍࡿࡓࡵ㸪࢞ࢫ ᗘࡣ࡯ࡰᖖ ࡟␃ࡲࡗࡓࡲࡲ㟁Ꮚ ᗘࡀ10000 ºC ࡟㉸࠼ࡿ㠀 ᖹ⾮ࣉࣛࢬ࣐ࡀᙧᡂࡉࢀ㸪ᵝࠎ࡞άᛶ✀ࢆᖖ ࣭ᖖᅽ࡛ᙧᡂ࡛ࡁࡿ51㸧_㸬

(19)

- 15 - ࡘࡲࡾ㸪኱Ẽᅽࣉࣛࢬ࣐ࢆ฼⏝ࡍࡿࡇ࡜࡛㸪እ㒊࠿ࡽࡢ⇕※ࡀ୙せ࡟࡞ࡿࡔࡅ࡛࡞ ࡃ㸪࢔ࣥࣔࢽ࢔ࢆ↓ゐ፹࠿ࡘప ᇦ࡛ศゎ࡛ࡁ㸪Ỉ⣲ࡀ〇㐀࡛ࡁࡿࡢ࡛ࡣ࡞࠸࠿࡜⪃࠼ ࡽࢀࡿࡀ㸪DBD ࡟ࡼࡿ኱Ẽᅽࣉࣛࢬ࣐ࢆ⏝࠸࡚࢔ࣥࣔࢽ࢔ࢆศゎࡍࡿ◊✲ࡣ࡯࡜ࢇ࡝ ⾜ࢃࢀ࡚࠸࡞࠸㸬

1. 3. ᮏ

ᮏ◊✲ࡢ┠ⓗ࠾ࡼࡧㄽᩥᵓᡂ

ࡇࡇࡲ࡛ NH3ࢆ⏝࠸ࡓ⬺◪ᢏ⾡ࡸ NH3࠿ࡽࡢỈ⣲〇㐀࡟㛵ࡋ࡚ゝཬࡋ࡚ࡁࡓ㸬⬺◪ ᢏ⾡࡟㛵ࡋ࡚ゝ࠼ࡤ㸪 SNCR ࡣゐ፹ࢆᚲせ࡜ࡏࡎᑟධࢥࢫࢺࡶప࠸ࡢ࡛ᵝࠎ࡞ NOx᤼ ฟ※࡟ᑐᛂ࡛ࡁࡿྍ⬟ᛶࢆ⛎ࡵࡓ᤼↮⬺◪ᢏ⾡࡛࠶ࡿࡀ㸪Temperature window ࡟ࡼࡿ ᗘⓗไ⣙࡟ࡼࡿᢏ⾡ⓗㄢ㢟ࢆゎᾘࡏࡡࡤ࡞ࡽ࡞࠸㸬ࡑࡢ᪉ἲ࡜ࡋ࡚㸪⌧ᅾ࡛ࡣࣉࣛࢬ࣐ ᢏ⾡ࢆ⏝࠸࡚⬺◪๣࡛࠶ࡿ NH3ࢆບ㉳ࡍࡿᡭἲࡀ᭷ຊ࡛࠶ࡾ㸪ᵝࠎ࡞◊✲ࡀ࡞ࡉࢀ࡚ ࠸ࡿࡀㄏ㟁యࣂࣜ࢔ᨺ㟁ࢆ⏝࠸࡚ NH3ࢆບ㉳ࡍࡿ◊✲ࡣᮍࡔ࡞ࡉࢀ࡚࠸࡞࠸㸬ࡲࡓ㸪 ୖ㏙ࡋࡓࡀNH3ࡣ⌧ᅾ㸪Ỉ⣲࢟ࣕࣜ࢔࡜ࡋ࡚ࡶὀ┠ࢆ㞟ࡵ࡚࠸ࡿ㸬⌧≧㸪NH3࠿ࡽỈ⣲ ࢆ〇㐀ࡍࡿ᪉ἲ࡜ࡋ࡚ࡣ㔠ᒓゐ፹ࢆ⏝࠸ࡓ⇕ศゎࡀ୍⯡ⓗ࡛࠶ࡿࡀ㸪⇞ᩱ㟁ụ࡜⤌ࡳྜ ࢃࡏ࡚࢜ࣥࢧ࢖ࢺ࡛⏝࠸ࡿሙྜ㸪Ỉ⣲〇㐀㛤ጞࡲ࡛ࡢ㉳ື᫬㛫ࡸᚓࡽࢀࡿỈ⣲ࡢ㧗⣧ᗘ ໬࡞࡝ゎỴࡍ࡭ࡁၥ㢟ࡣᑡ࡞ࡃ࡞࠸㸬኱Ẽᅽࣉࣛࢬ࣐࡟ࡼࡾㄏ㉳ࡉࢀࡿࣛࢪ࢝ࣝ཯ᛂࡣ ཯ᛂ㏿ᗘࡀ࡜࡚ࡶ㏿࠸ࡢ࡛㸪⬺◪ᢏ⾡ࡢ㛤Ⓨ࡛ᚓࡽࢀࡓ኱Ẽᅽࣉࣛࢬ࣐࡟ࡼࡿ NH3 ບ ㉳࣭ศゎᢏ⾡ࢆᛂ⏝ࡍࢀࡤNH3࠿ࡽ㎿㏿࡟H2ࢆᚓࡿᢏ⾡ࢆ㛤Ⓨ࡛ࡁࡿྍ⬟ᛶࡣ㠀ᖖ࡟ 㧗࠸࡜࠸࠼ࡿ㸬 ࡑࡇ࡛㸪ᮏ◊✲࡛ࡣㄏ㟁యࣂࣜ࢔ᨺ㟁࡟ࡼࡾⓎ⏕ࡉࡏࡓ኱Ẽᅽࣉࣛࢬ࣐ࢆ⏝࠸࡚NH3 ࢆບ㉳࣭ศゎࡉࡏࡓᨵ㉁ NH3 ࢞ࢫࢆ SNCR ෆ࡟྿ࡁ㎸ࡴࡇ࡜࡛ SNCR ࡟࠾ࡅࡿ Temperature window ࡢప ໬ࢆ≺࠺㸬ࡲࡓ㸪ࡑࡢ㝿࡟ᚓࡓ NH3ࡢບ㉳࣭ศゎᢏ⾡ࢆᛂ⏝ ࡋ࡚㸪NH3࠿ࡽ㐃⥆ⓗ࡟㧗⣧ᗘỈ⣲ࢆ㎿㏿࡟〇㐀ࡍࡿᢏ⾡ࡢ☜❧ࢆ┠ᶆ࡜ࡋࡓ㸬ୖグࡢ ᢏ⾡㛤Ⓨࢆ┠ⓗ࡜ࡋࡓᮏㄽᩥࡢᵓᡂࢆ௨ୗ࡟♧ࡍ㸬 ➨1 ❶࡛ࡣ NOx࡟ࡼࡿ⎔ቃၥ㢟࡟㛵ࡋ࡚㸪NOxฎ⌮ᢏ⾡࡟࠾ࡅࡿ SNCR ࡢ❧ࡕ఩⨨ ࡸSNCR ࡢᐇ⏝ᛶࢆ㧗ࡵࡿࡓࡵ࡟ゎỴࡍ࡭ࡁㄢ㢟Ⅼࢆㄽࡌࡓ㸬୍᪉࡛㸪࢚ࢿࣝࢠ࣮ศ㔝 ࡟࠾࠸࡚Ỉ⣲࢚ࢿࣝࢠ࣮♫఍ᐇ⌧࡬ྥࡅࡓືྥࢆㄪᰝࡋ㸪Ỉ⣲࢟ࣕࣜ࢔࡜ࡋ࡚ࡢ NH3 ࡢ㔜せᛶࢆㄽࡌࡓ㸬ࡑࡋ࡚㸪ࡑࡢ୧ࢸ࣮࣐࡟࠾࠸࡚኱Ẽᅽࣉࣛࢬ࣐ࢆ⏝࠸ࡓ NH3ᨵ㉁ ࡢ㔜せᛶࢆㄝࡁ㸪⌧ᅾ࠶ࡿᢏ⾡࡜᪤ ࡢ◊✲౛ࢆ᳨ウࡍࡿࡇ࡜࡛ᮏ◊✲ࡢព⩏ࢆ᫂☜໬ ࡋࡓ㸬 ➨ 2 ❶ࠕ኱Ẽᅽࣉࣛࢬ࣐ࢆ⏝࠸ࡓᨵ㉁ NH3࢖ࣥࢪ࢙ࢡࢩࣙࣥ⬺◪ἲࡢ㛤Ⓨ࡛ࠖࡣ㸪 ኱Ẽᅽࣉࣛࢬ࣐࡟ࡼࡾᨵ㉁ࡋࡓ NH3 ࢞ࢫࢆ⏝࠸ࡓ⬺◪ᐇ㦂࡜ᨵ㉁࢔ࣥࣔࢽ࢔࢞ࢫࡢ࢞ ࢫ⤌ᡂ ᐃࢆ⾜࠸㸪ࡑࡢ⤖ᯝࡼࡾ⬺◪཯ᛂࡢ⣲཯ᛂࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸㸪ᨵ㉁࢔ࣥ ࣔࢽ࢔࢖ࣥࢪ࢙ࢡࢩࣙࣥἲ࡟࠾ࡅࡿ཯ᛂᶵᵓࢆ᳨ウ࣭⪃ᐹࡋࡓ⤖ᯝࢆ㏙࡭ࡿ㸬 ➨3 ❶ࠕ኱Ẽᅽࣉࣛࢬ࣐ࢆ⏝࠸ࡓ NH3࠿ࡽࡢ᪂つỈ⣲〇㐀ࢹࣂ࢖ࢫࡢᇶᮏ≉ᛶゎ᫂ࠖ ࡛ࡣ㸪ࣉࣛࢬ࣐ࣜ࢔ࢡࢱ࣮ࢆ⏝࠸࡚ NH3ࡢ⬺Ỉ⣲ᐇ㦂ࢆ⾜࠸㸪ཎᩱ࢞ࢫ୰ࡢ NH3⃰ᗘ

(20)

- 16 - ࡸ⁫␃᫬㛫㸪ᾘ㈝㟁ຊࢆኚ໬ࡉࡏࡿࡇ࡜࡛㸪኱Ẽᅽࣉࣛࢬ࣐࡟ࡼࡿNH3࠿ࡽࡢH2〇㐀 ≉ᛶࢆㄪᰝࡋࡓ⤖ᯝࢆ㏙࡭ࡿ㸬 ➨ 4 ❶ࠕࣉࣛࢬ࣐࣓ࣥࣈࣞࣥࣜ࢔ࢡࢱ࣮ࢆ⏝࠸ࡓ NH3࠿ࡽࡢ㧗⣧ᗘỈ⣲㐃⥆〇㐀ࢹ ࣂ࢖ࢫࡢ㛤Ⓨ࡛ࠖࡣ㸪ࣉࣛࢬ࣐ࣜ࢔ࢡࢱ࣮࡜Ỉ⣲ศ㞳⭷ࢆ⤌ࡳྜࢃࡏࡓࣉࣛࢬ࣐࣓ࣥࣈ ࣞࣥࣜ࢔ࢡࢱ࣮㸦PMR㸧ࢆ⏝࠸࡚ NH3࠿ࡽࡢ⬺Ỉ⣲ᐇ㦂ࢆ⾜࠸㸪PMR ࡢỈ⣲ศ㞳≉ᛶ ࡜Ỉ⣲⏕ᡂ≉ᛶࢆㄪᰝࡋࡓ⤖ᯝࢆ㏙࡭ࡿ㸬 ➨5 ❶ࠕ⣲཯ᛂゎᯒࢆ⏝࠸ࡓ኱Ẽᅽࣉࣛࢬ࣐ୗ࡛ࡢ NH3ศゎ཯ᛂ࣓࢝ࢽࢬ࣒ࡢゎ᫂ࠖ ࡛ࡣ㸪PMR ࡢỈ⣲〇㐀≉ᛶࢆ㧗ࡵࡿ࡭ࡃ⣲཯ᛂゎᯒ࡟ࡼࡾࣉࣛࢬ࣐཯ᛂሙ࡟࠾ࡅࡿ NH3 ศゎ཯ᛂࡢ཯ᛂ࣓࢝ࢽࢬ࣒ࡢゎ᫂ࢆ⾜࠸㸪ࣈࣞ࢖ࢡࢫ࣮ࣝࣇ࢓ࢡࢱ࣮ࡢ᳨ウࢆࡋࡓ⤖ᯝ ࢆ㏙࡭ࡿ㸬 ➨6 ❶ࠕ⥲ᣓ࡛ࠖࡣ㸪ᮏㄽᩥࡢᡂᯝࢆ⥲ᣓࡍࡿ㸬

(21)

- 17 -

1. 4. ཧ

ཧ⪃ᩥ⊩

1) ୰ᓥὈ▱, ᴋᮏ⦾Ꮚ, ⧊⏣⫕: ❅⣲㓟໬≀࡟ࡼࡿ኱Ẽởᰁ࡜⏕యᙳ㡪, ⏕ά⾨⏕, 17, pp. 32-43, 1973. 2) SPM ࡜࢜࢟ࢩࢲࣥࢺࡢ⏕ᡂ࣓࢝ࢽࢬ࣒, ⎔ቃ┬㸬㸦http://www.env.go.jp/air/osen/voc/materials/101.pdf㸧 3) ᪂஭⣖⏨, ⇞↝⏕ᡂ≀ࡢⓎ⏕࡜ᢚไᢏ⾡, 1997 4) ᪂ᒸᔞ, Ἑ㔝㏻᪉, బ⸨㡰୍, ⇞↝⌧㇟ࡢᇶ♏, 2001. 5) ࡤ࠸ࡌࢇ࡜ NOxࡢ᤼ฟᇶ‽್୍ぴ, ⎔ቃ┬, 2012. 6) ᪂㌴࡟ᑐࡍࡿ᤼ฟ࢞ࢫつไ࡟ࡘ࠸࡚, ᅜᅵ஺㏻┬, 7) IMO ཬࡧḢᕞ࡟࠾ࡅࡿ⯪⯧⇞ᩱつไ࡟㛵ࡍࡿ᭱᪂ືྥ, ▼Ἔ࢚ࢿࣝࢠ࣮ᢏ⾡ࢭࣥ ࢱ࣮, 2013. 8) ᪥ᮏᶵᲔᏛ఍ㄅ, No.1061, vol. 110, pp. 308, 2007.

9) Journal of Society of Automotive Engineers of Japan, Vol. 59(4), pp. 128-132, 2005. 10) ᪥ᮏࡢࢡ࣮ࣜࣥࢥ࣮ࣝࢸࢡࣀࣟࢪ࣮, NEDO, JCOAL, 2006. 11) 㕥ᮌဴኵ㸪㣤ᒣᩗஅ㸪ᖾᮧ᫂᠇, ▼ᕝᓥ᧛☻ᢏሗ㸪vol. 33㸪➨ 5 ྕ㸪pp. 298̽301㸪 1993. 12) ᖹ⏣බಙ, ୖ㔝ᘯᶞ, ㉥ᕝஂ, ᪥ᮏᶵᲔᏛ఍ᇸ⋢ࣈࣟࢵࢡ኱఍ㅮ₇ㄽᩥ㞟, pp. 31-32, 2005. 13) ᳃⏣ᩔ, ⴗගᬕ, ᪥ᮏ࣐࢚ࣜࣥࣥࢪࢽ࢔ࣜࣥࢢᏛ఍➨ 56 ᅇ≉ูᇶ㔠ㅮ₇఍ண✏㞟, pp. 25-30, 2012.

14) R. K. Lyon, “Method for the reduction of the concentration of NO in combustion effluents using NH3”, US. Patent 3900554, 1975.

15) M. Jodal, C. Nielsen, T. Hulgaard, K. Dam-Johansen, 23rd Symposium (International) on Combustion, pp. 237–243, 1990.

16) Wenli, D., Dam-Johansen, K., Ostergaard, K., 23rd Symposium (International) on Combustion, The Combustion Institute, Pittsburgh, pp. 297–303, 1990.

17) Azuhata, S., Akimoto, H., Hishinuma, Y., AlChE Journal, Vol. 28, pp. 7–11, 1982. 18) Cooper, D.A., Journal of institute of Engineers, pp. 78–84, 1988.

19) Wenli, D., Dam-Johansen, K., Ostergaard, K., The influence of additives on selective non-catalytic reduction of nitric oxide with NH3. ACHEMASIA, Beijing, 1989. 20) Lyon, R.K., Longwell, J.P., The Proceedings of NOx Control Technology Seminar, San

Francisco, CA, pp. 237–256, 1976.

21) Salimian, S., Hanson, R.K., Combustion Science and Technology, Vol. 23, pp. 225–230, 1980.

22) Arand, J.K., Palos, R., Muzio, L.J., Sotter, J.G., “Urea reduction of NOx in combustion

(22)

- 18 - Alto, CA, 1980.

23) Perry, R.A., Siebers, D.L., Nature, Vol. 324, pp. 657–658, 1986.

24) Izumi, J., Murakami, N., “Process for controlling nitrogen oxides in exhaust gases.” US Patent 4350669, Assigned to Mitsubishi Jukogyo Kabushiki Kaisha, Tokyo, Japan, 1982. 25) Wallace, A., Huhmann, A. Boyle, J., Albanese, V., Fuel Tech Inc., report no. PP. 522. In:

Power-Gen ‘95, Anaheim, CA, 1995.

26) Matzing, H., Advances in Chemical Physics, Vol. 80, pp. 315–402, 1991.

27) Boyle, J., Russell, A., Yao, S-.C., Zhou, Q., Ekmann, J., Fu, Y., Mathur, M., Fuel, Vol. 72, pp. 1419–1427, 1993.

28) NEDO ෌⏕ྍ⬟࢚ࢿࣝࢠ࣮ᢏ⾡ⓑ᭩➨ 2 ∧, ⊂❧⾜ᨻἲே ᪂࢚ࢿࣝࢠ࣮࣭⏘ᴗ ᢏ⾡⥲ྜ㛤Ⓨᶵᵓ, 2014.

29) NEDO Ỉ⣲࢚ࢿࣝࢠ࣮ⓑ᭩, ⊂❧⾜ᨻἲே ᪂࢚ࢿࣝࢠ࣮࣭⏘ᴗᢏ⾡⥲ྜ㛤Ⓨᶵᵓ, 2015.

30) Eika W. QIAN: “Advance in Production Technology of Hydrogen via Steam Reforming”, Journal of the Japan Institute of Energy, Vol. 92, pp. 1034–1040, 2013.

31) C. Hulteberg: Int J Hydrogen Energy, Vol. 37, pp. 3978–3992, 2012

32) JosephJ. Romm (ⴭ), ᮏ㛫 ⌶ஓ (⩻ヂ), Ỉ⣲ࡣ▼Ἔ࡟௦ࢃࢀࡿ࠿, ࣮࣒࢜♫, 2005. 33) M. Yukihiko, Journal of Hydrogen Energy Systems Society of Japan, Vol. 29, pp. 7–12,

2004.

34) ຍ⸨㈗ྐ, ኱ཎ⪷⨾, ͇ᮌ㉁⣔ࣂ࢖࣐࢜ࢫ⤌ᡂᡂศࡢ⇕ศゎ≉ᛶ͇, ⚟ᒸ኱ᏛᕤᏛ 㞟ሗ, Vol. 78, 2007.

35) ♫ᅋἲே᪥ᮏ࢚ࢿࣝࢠ࣮Ꮫ఍⦅, ࣂ࢖࣐࢜ࢫࣁࣥࢻࣈࢵࢡ, ࣮࣒࢜♫, 2002. 36) K. Shinji, O. Masaru, Journal of the Japan Institute of Energy, Vol. 92, pp. 1041–1045,

2013.

37) S. Makoto, Journal of Japan Institute of Energy, Vol. 92, pp. 1046–1051, 2013.

38) F. Kenzo, Journal of Hydrogen Energy Systems Society of Japan, Vol. 19, No. 2, 1994. 39) ᡓ␎ⓗ࢖ࣀ࣮࣋ࢩࣙࣥ๰㐀ࣉࣟࢢ࣒࢚ࣛࢿࣝࢠ࣮࢟ࣕࣜ࢔◊✲㛤Ⓨ, ෆ㛶ᗓ,

2014.

40) K. Yoshitsugu, Journal of the Japan Institute of Energy, Vol. 93, pp. 378–385, 2014. 41) Bartels, J. R., ”A feasibility study of implementing an Ammonia Economy”, Graduate

Theses and Dissertations. Paper 11132, Iowa State University, 2008.

42) O. Yoshimi, I. Kenichi, K. Norihiko, M. Tomoyuki, Y. Makoto, Journal of the Japan Institute of Energy, Vol. 93, pp. 15–20, 2014.

43) O. Yoshimi, PETROTECH, Vol. 29, pp. 114–121, 2006.

44) O. Yoshimi, Journal of Hydrogen Energy Systems Society of Japan, Vol. 35, pp. 19–24, 2010.

(23)

- 19 -

45) O. Yoshimi, Journal of Fuel Cell, Vol. 11, pp. 56–61, 2012.

46) K. Yoshitsugu, I. Takayuki, Journal of Hydrogen Energy Systems Society of Japan, Vol. 36, pp. 34–41, 2011.

47) S. Takashi, N. Tetsuo, I. Shinji, ≉チ 2005̽145748 ྕ 48) S. Takashi, N. Tetsuo, O. Masaya, ≉チ 2009̽35458 ྕ

49) ⇕ᾏⰋ㍜, 㧗ᮌⱥ⾜, 㔝⏣⋹἞, ୰ᕝఙዲ, ㎷ཱྀᣅஓ, ಴ᮏᾈྖ, ໬ᏛᕤᏛ఍➨ 75 ᅇ኱఍せ᪨㞟, 2010.

50) S. F. Yin, B. Q. Xu, X. P. Zhou, C. T. Au, Journal of Applied Catalysis, Vol. 277, pp. 1–9, 2004.

51) ⚄ཎಙᚿ, ኱Ẽᅽࣉࣛࢬ࣐཯ᛂᕤᏛࣁࣥࢻࣈࢵࢡ, 2013.

52) Osman Karatum, Marc A. Deshusses, Chemical Engineering Journal, Vol. 294, pp. 308-315, 2016.

(24)

- 20 -

➨

2 ❶ ኱Ẽᅽࣉࣛࢬ࣐࡟ࡼࡿᨵ㉁ NH

3

࢖ࣥࢪ࢙ࢡࢩࣙ

ࣥ⬺◪ἲࡢ㛤Ⓨ

2. 1 ⥴ゝ

㏆ᖺࡢ⎔ቃၥ㢟࡟ᑐࡍࡿព㆑ࡢ㧗ࡲࡾ࠿ࡽ㸪୰ᑠつᶍࡢ⇞↝タഛ࡛ࡶ❅⣲㓟໬≀ 㸦NOx㸧ࡢཝࡋ࠸⃰ᗘつไࡀᆅᇦ༠ᐃ➼࡛ᐇ᪋ࡉࢀࡿࡼ࠺࡟࡞ࡾ㸪⬺◪タഛࡢタ⨨ࡀᚲ せ࡜࡞ࡗ࡚ࡁ࡚࠸ࡿ㸬኱つᶍ⇞↝タഛ࡛ࡣ㑅ᢥⓗゐ፹⬺◪ἲ㸦SCR㸧ࡀከࡃ⏝࠸ࡽࢀ࡚ ࠸ࡿࡀ㸪୰ᑠつᶍࡢ⇞↝⅔࡛ࡣタ⨨㠃✚ࡸタഛࢥࢫࢺࡢ㠃࡛㸪↓ゐ፹⬺◪ἲ㸦SNCR㸧 ࡀᮃࡲࢀ࡚࠸ࡿ㸬SNCR ࡜ࡣゐ፹ࢆ౑⏝ࡏࡎ࡟⬺◪๣࡛࠶ࡿ࢔ࣥࣔࢽ࢔ࢆ᤼࢞ࢫ୰࡬྿ ࡁ㎸ࡴ⬺◪᪉ἲ࡛࠶ࡿ 1)_{㸬ࡋ࠿ࡋ㸪SNCR ࡟࠾ࡅࡿ཯ᛂ ᗘ⠊ᅖࡣ 850–1175 ºC} 㸦Temperature window ࡜࠸࠺㸧ࡢ㧗 ᇦ࡟࠶ࡾ㸪୰ᑠつᶍࡢ⇞↝⅔࡛ࡣ཯ᛂ᫬㛫ࢆ༑ศ ☜ಖ࡛ࡁ࡞࠸ࡓࡵ㸪⬺◪⋡ࡀపୗࡍࡿ࡜࠸࠺ၥ㢟ࡀ࠶ࡿ 2)_{㸬ࡑࡢㄢ㢟ࡢゎỴ࡟ࡣ㸪} Temperature window ࢆప ഃ࡟ᣑ኱ࡍࡿᢏ⾡ࡀᚲせ࡛࠶ࡿ㸬࢔ࣥࣔࢽ࢔࡟ᵝࠎ࡞໬Ꮫ≀ ㉁ࢆῧຍࡍࡿࡇ࡜࡛ Temperature window ࢆప ഃ࡟ᣑ኱࡛ࡁࡿ࡜࠸࠺ሗ࿌ࡀከᩘࡉࢀ ࡚࠸ࡿ3)_{ࠋῧຍࡍࡿ໬Ꮫ≀㉁࡜ࡋ࡚}_H 2ࠊH2O2ࠊⅣ໬Ỉ⣲ࠊCOࠊࢩ࢔ࢾࣝ㓟ࠊ࢔ࣝ࢝ࣜ ሷࠊ࢚ࢫࢸࣝࠊࣇ࢙ࣀ࣮ࣝࠊ࢝ࣝ࣎ࣥ㓟ࠊ࢔ࣝࢹࣄࢻࠊ࢚࣮ࢸࣝཬࡧ࢔ࣝࢥ࣮ࣝ࡞࡝࡟ ࡘ࠸࡚ࡣࡍ࡛࡟◊✲ࡀ࡞ࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀࡽ㸪ῧຍ≀ࢆ౑⏝ࡍࡿࡇ࡜࡛㏣ຍࡢᏳ ඲タഛࡀᚲせ࡜࡞ࡿࡢ࡛㸪⤖ᯝⓗ࡟⬺◪ࢥࢫࢺࡀୖࡀࡗ࡚ࡋࡲ࠺ࡓࡵ㸪ᐇ⏝ⓗ࡜ࡣゝ࠼ ࡞࠸ࠋ ࡑࡇ࡛㸪SNCR ࡟࠾࠸࡚ Temperature window ࢆప ഃ࡟ᣑ኱ࡍࡿ᪉ἲ࡜ࡋ࡚኱Ẽᅽࣉ ࣛࢬ࣐ࢆ⏝࠸ࡓ᪂つ SNCR ἲࢆ╔᝿ࡋࡓࠋㄏ㟁యࣂࣜ࢔ᨺ㟁㸦 Dielectric Barrier Discharge : DBD㸧࡛Ⓨ⏕ࡉࡏࡓ኱Ẽᅽࣃࣝࢫࣉࣛࢬ࣐ࢆ⏝࠸ࡓ⬺◪᪉ἲࡣࡇࢀࡲ࡛࡟ࡶ ◊✲ሗ࿌ࡀ࡞ࡉࢀ࡚࠸ࡿ 4)5)_{㸬ࡋ࠿ࡋ࡞ࡀࡽ㸪௒ᅇࡣ⬺◪๣࡛࠶ࡿ࢔ࣥࣔࢽ࢔࢞ࢫࡢࡳ} ࢆᨵ㉁ࡋ㸪⇞↝᤼࢞ࢫ࡟྿ࡁ㎸ࡴ㸦௨ୗ㸪ᨵ㉁ NH3࢖ࣥࢪ࢙ࢡࢩࣙࣥἲ࡜࿧ࡪ㸧࡜࠸ ࠺᪂ࡓ࡞ᡭἲࢆヨࡳࡓ6)7)_{㸬ࡑࡢᢏ⾡࡟ࡼࡾ}_{Temperature window ࡀప ഃ࡟ 150–200 ºC} ᣑ኱ࡍࡿࡇ࡜ࢆぢฟࡋࡓ8)9)_{㸬ࡋ࠿ࡋ࡞ࡀࡽ㸪ᨵ㉁} _NH 3࢖ࣥࢪ࢙ࢡࢩࣙࣥἲ࡟ࡼࡿ⬺◪ ཯ᛂᶵᵓࡣゎ᫂ࡉࢀ࡚࠸࡞࠸㸬 ➨஧❶࡛ࡣ㸪ࡲࡎ SNCR ࡟ᑐࡍࡿᨵ㉁ NH3࢖ࣥࢪ࢙ࢡࢩࣙࣥἲࡢ᭷⏝ᛶࡢ☜ㄆࢆ⾜ ࡗࡓ㸬⥆࠸࡚㸪ᨵ㉁NH3࢖ࣥࢪ࢙ࢡࢩࣙࣥἲ࡟ࡼࡿ⬺◪཯ᛂᶵᵓࢆゎ᫂ࡍࡿࡓࡵ࡟DBD ࣃࣝࢫࣉࣛࢬ࣐࡟ࡼࡾᚓࡽࢀࡿᨵ㉁NH3࢞ࢫ୰ࡢᏳᐃ໬Ꮫ✀ࡢ⤌ᡂ㸦NH3, H2, N2㸧ࢆᐃ 㔞ࡋ㸪ᨵ㉁NH3࢞ࢫࡢ⤌ᡂ ᐃࢆ⾜ࡗࡓ㸬ḟ࡟㸪ᨵ㉁NH3࢞ࢫࡢᶍᨃ࢞ࢫࢆ⏝࠸࡚SNCR ⬺◪ᐇ㦂ࢆ⾜࠸㸪ᨵ㉁ NH3࢖ࣥࢪ࢙ࢡࢩࣙࣥἲ࡟ࡼࡿᐇ㦂⤖ᯝ࡜ẚ㍑ࡋࡓ㸬ࡑࡋ࡚㸪 ᭱⤊ⓗ࡟⬺◪཯ᛂࡢ⣲཯ᛂࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸㸪ᨵ㉁ NH3࢖ࣥࢪ࢙ࢡࢩࣙࣥἲ࡟ ࠾ࡅࡿ཯ᛂᶵᵓࢆ⪃ᐹࡋࡓ㸬

(25)

- 21 -

2. 2 ᐇ

ᐇ㦂⿦⨨࠾ࡼࡧ᪉ἲ

2. 2. 1 ᐇ㦂⿦⨨࠾ࡼࡧ᪉ἲ

ᨵ㉁NH3࢖ࣥࢪ࢙ࢡࢩࣙࣥ⬺◪ἲ࡟⏝࠸ࡓᐇ㦂⿦⨨ࡢᴫせࢆFig. 2-1 ࡟♧ࡋࡓ㸬 ࣉࣛࢬ࣐ࣜ࢔ࢡࢱ࣮ࡣ▼ⱥ〇෇⟄஧㔜⟶ᵓ㐀࡛㸪እ⟶እᚄ61 mm㸦ཌࡉ t = 2 mm㸧㸪 ෆ⟶እᚄ54 mm㸦t = 2 mm㸧㸪㛗ࡉ 490 mm ࡛࠶ࡾ㸪ࢠࣕࢵࣉ㛗㸦እ⟶࡜ෆ⟶ࡢ㝽㛫㸧 ࡣ1.5 mm ࡛࠶ࡿ㸬㧗㟁ᅽ㟁ᴟ㸦SUS316㸧ࢆෆ⟶ෆഃ࡟タ⨨ࡋ㸪᥋ᆅ㟁ᴟ㸦SUS316 ࣃ ࣥࢳࣥࢢ࣓ࢱࣝ㸧ࡣእ⟶࿘ᅖ࡟ᕳࡁ௜ࡅ࡚࠸ࡿ㸬 ᥋ᆅ㟁ᴟࡢ㛗ࡉࡣ 360 mm ࡛࠶ࡿ㸬࢞ࢫࣈࣞࣥࢲ࣮௜ࡁࡢ࣐ࢫࣇ࣮ࣟࢥࣥࢺ࣮ࣟࣛ ࣮࡛ὶ㔞ㄪᩚࡋࡓNH3/Ar ΰྜ࢞ࢫࢆࢠࣕࢵࣉ㒊࡟ὶࡋ㸪⃝⸨㟁ᶵ〇㧗㟁ᅽࣃࣝࢫ㟁※ ࢆ⏝࠸࡚㸪ㄏ㟁యࣂࣜ࢔ᨺ㟁࡟ࡼࡾ኱Ẽᅽࣉࣛࢬ࣐ࢆⓎ⏕ࡉࡏࡓ㸬኱Ẽᅽࣉࣛࢬ࣐࡛ᨵ ㉁ࡋࡓNH3ࢆࣉࣛࢬ࣐ࣜ࢔ࢡࢱ࣮ฟཱྀ࡛ࢧࣥࣉࣜࣥࢢࡋ㸪FT-IR㸦GASERA F10㸧࡛ NH3 ⃰ᗘࢆ㸪࢞ࢫࢡ࣐ࣟࢺࢢࣛࣇ㸦Agilent 3000A㸧࡛ H2, N2 ⃰ᗘࢆ ᐃࡋࡓ㸬୍᪉㸪ࣔࢹ ࣝ࢞ࢫ㸦NO/O2/N2㸧ࡣෆᚄ46 mm ࡢ▼ⱥ⟶࡟౪⤥ࡋ㸪㟁Ẽࣄ࣮ࢱ࣮࡛ 500|C ࡟ண⇕ࡋ ࡓ㸬ࣔࢹࣝ࢞ࢫ࡜ᨵ㉁NH3ࡣΰྜᐊ࡛ྜὶࡋࡓᚋ㸪㛗ࡉ600 mm ࡢ▼ⱥ཯ᛂ⟶ෆ࡟ὶ ධࡍࡿ㸬཯ᛂ⟶ࡢ ᗘࢆ500㸫800 ºC ࡟ኚ໬ࡉࡏ㸪཯ᛂᚋࡢ࢞ࢫ⤌ᡂࢆ ᐃࡋ㸪⬺◪⋡

ࡢኚ໬ࢆㄪ࡭ࡓ㸬࢞ࢫ⤌ᡂࡣ㸪NOx㸦HORIBA VIA510㸧㸪N2O㸦HORIBA VIA510㸧㸪O2

㸦(SHIMAZU NOA-7000㸧ศᯒィࢆ⏝࠸࡚㐃⥆ศᯒࢆ⾜ࡗࡓ㸬

(26)

- 22 -

Table 2-1 Experimental conditions For measurements of chemical compositions

Flow rate of NH3/Ar gas 0.2, 0.4, 0.8 L/min

NH3 concentration 4840 ppm by volume

Applied voltage 0–15 kV For de-Nox experiments

Flow rate of NH3/Ar gas 0.8 L/min

Flow rate of model gas 2.2 L/min

NOx concentration 500 ppm by volume NH3 concentration 750 ppm by volume O2 concentration 8.3 % by volume Applied voltage 0–15 kV Reaction temperatures 500–750 ºC ᐇ㦂᮲௳ࢆTable 2-1 ࡟♧ࡍ㸬ᨵ㉁ NH3࢞ࢫ⤌ᡂ ᐃᐇ㦂࡛ࡣNH3/Ar ࢞ࢫὶ㔞࡜༳ ຍ㟁ᅽࢆኚ໬ࡉࡏ࡚ᨵ㉁࢔ࣥࣔࢽ࢔ࡢ⤌ᡂኚ໬ࢆㄪ࡭ࡓ㸬ḟ࡟㸪ᨵ㉁NH3࢖ࣥࢪ࢙ࢡ ࢩࣙࣥ⬺◪ᐇ㦂࡛ࡣNH3/Ar ὶ㔞㸪NO/O2/N2 ὶ㔞㸪㓟⣲⃰ᗘࢆ୍ᐃ࡜ࡋ㸪༳ຍ㟁ᅽ࡜ ཯ᛂ ᗘࢆኚ໬ࡉࡏ㸪⬺◪⋡ࢆㄪ࡭ࡓ㸬ࡲࡓ㸪ᶍᨃ᤼࢞ࢫࡢண⇕ ᗘࡣ⬺◪཯ᛂࡀ㉳ࡇ ࡽ࡞࠸500 ºC ࡜ࡋࡓ㸬ࣉࣛࢬ࣐㟁※ࡢ࿘Ἴᩘࡣ 10 kHz ࡟ᅛᐃࡋࡓ㸬

2. 2. 2 ࣉࣛࢬ࣐㟁※≉ᛶ

ࣛࢪ࢝ࣝ࢖ࣥࢪ࢙ࢡࢱ࣮࡟౪⤥ࡉࢀࡿ⬺◪๣ࡣNH3࡛࠶ࡾ㸪࢟ࣕࣜ࢔࢞ࢫࡣప㟁ᅽ ࡛ࣉࣛࢬ࣐ࡀⓎ⏕ࡍࡿAr ࢆ⏝࠸ࡓ㸬⬺◪๣୰ࡢ NH3⃰ᗘࡣ㸪࢟ࣕࣜ࢔࢞ࢫ࡜ࡢศ⋡ࢆ ㄪᩚࡍࡿࡇ࡜࡛ኚ໬ࡉࡏࡓ㸬ࣉࣛࢬ࣐ࢆⓎ⏕ࡉࡏࡿ㧗࿘Ἴ㟁※࡜ࡋ࡚㸪ṇᘻἼ2 Ἴ࠿ࡽ ࡞ࡿOCS㸦One-Cycle Sinusoidal㸧㟁※㸦⃝⸨㟁ᶵ♫〇㸧ࢆ⏝࠸㸪Fig. 2-2 ࡟♧ࡍࡼ࠺࡞ ṇᘻἼࡢࣃࣝࢫ㟁ᅽࢆ୍ᐃࡢ⧞ࡾ㏉ࡋ࿘ᮇT1࡛༳ຍࡋࡓ㸬T1ࡢ㏫ᩘࡣ࿘Ἴᩘ࡟┦ᙜࡍ ࡿ⧞ࡾ㏉ࡋᩘRR ࡜ࡋ࡚ᐃ⩏ࡋࡓ㸬㟁※⿦⨨ࡢ≉ᛶ࡜ࡋ࡚༳ຍ㟁ᅽࡢṇᘻἼࣃࣝࢫࡣ㸪 ṇࡢ༙Ἴࡢࣆ࣮ࢡ㟁ᅽࡼࡾ㈇ࡢ༙Ἴࡢࣆ࣮ࢡࡢ᪉ࡀ኱ࡁ࠸Ἴᙧ࡜࡞ࡿ㸬ࡇࡢࡓࡵ༳ຍ㟁 ᅽ್ࡣ㸪ṇᘻἼࣃࣝࢫ㟁ᅽࡢ᭱኱್࡜᭱ᑠ್ࡢᕪ࡛࠶ࡿVPPࢆ⏝࠸ࡓ㸬 ࡲࡓ㸪Ἴᙧಖ ᣢ᫬㛫T0ࡀᴟࡵ࡚▷࠸᫬㛫㸦10 μs㸧࡛࠶ࡾ㸪ࣛࢪ࢝ࣝࢆຠ⋡ࡼࡃ⏕ᡂ࡛ࡁࡿࡇ࡜ࢆ≉ ᚩ࡜ࡋ࡚࠸ࡿ10)㸬 Ἴᙧࡢ ᐃ࡟ࡣ4ch ࢹࢪࢱࣝ࢜ࢩࣟࢫࢥ࣮ࣉ㸦Tektronix, TDS3034B㸧ࢆ⏝࠸㸪㟁ᅽࡢ ᐃ࡟ࡣ㧗㟁ᅽࣉ࣮ࣟࣈ㸦Tektronix, P6015A㸧㸪㟁ὶࡢ ᐃ࡟ࡣ㟁ὶࣉ࣮ࣟࣈ㸦Tektronix, P6021㸧ࢆࡑࢀࡒࢀ⏝࠸ࡓ㸬

(27)

- 23 -

Fig. 2-2 Schematic waveform of voltage supplied from a one-cycle sinusoidal power source.

2. 3 ኱Ẽᅽࣉࣛࢬ࣐࡟ࡼࡿ NH

3

ᨵ㉁

Fig. 2-3 ࡟㸪༳ຍ㟁ᅽ࡟ᑐࡍࡿ NH3 ศゎ⋡ࡢኚ໬ࢆ NH3/Ar ࢞ࢫὶ㔞ࢆࣃ࣓࣮ࣛࢱ࡜ ࡋ࡚♧ࡍ㸬NH3 ศゎ⋡ DNH3 [%]ࡣ㸪ḟᘧ࡛ồࡵࡓ㸬 DNH3 = ([NH3]IN − [NH3]OUT) / [NH3]IN × 100 (2-1) ࡇࡇ࡛㸪[NH3]INࡣࣉࣛࢬ࣐ࣜ࢔ࢡࢱ࣮ධཱྀࡢNH3ึᮇ⃰ᗘ[ppm]㸪[NH3]OUTࡣࣉࣛࢬ ࣐ࣜ࢔ࢡࢱ࣮ฟཱྀࡢNH3⃰ᗘ[ppm]࡛࠶ࡿ㸬 NH3ศゎ⋡ࡣ㸪༳ຍ㟁ᅽࡢቑຍ࠾ࡼࡧ࢞ࢫὶ㔞ࡢῶᑡ࡟࡜ࡶ࡞ࡗ࡚ቑຍࡋࡓ㸬NH3 ࡢ N-H ⤖ྜ࢚ࣥࢱࣝࣆ࣮ࡣ 450 kJ/mol ࡛࠶ࡿࡀ㸪ࣉࣛࢬ࣐ࡢ㟁Ꮚ࢚ࢿࣝࢠ࣮e-_࡟ࡼࡾ

(28)

- 24 -

Fig. 2-3 Variation in NH3 decomposition as functions of applied voltage and flow rate of

NH3/Ar gas. ࡑࢀ௨ୖࡢ࢚ࣥࢱࣝࣆ࣮ࡀࣃࣝࢫⓗ࡟୚࠼ࡽࢀࡿࡇ࡜࡛ᘧ(2-2)㸫(2-4)ࡢ཯ᛂ࡟ࡼࡾ NH3ࡀゎ㞳ࡍࡿ࡜⪃࠼ࡽࢀࡿ㸬༳ຍ㟁ᅽࡢቑຍ࡜࢞ࢫὶ㔞ࡢῶᑡࡣ㸪༢఩ࣔࣝ㸪༢఩᫬ 㛫࡟࢔ࣥࣔࢽ࢔࢞ࢫࡀཷࡅࡿ㟁Ꮚ࢚ࢿࣝࢠ࣮[kJ∙mol−1∙s−1]ࢆቑຍࡉࡏࡿࡓࡵ㸪NH3ศゎ ⋡ࡀቑຍࡋࡓ࡜ㄝ࡛᫂ࡁࡿ㸬࢞ࢫὶ㔞0.2 L/min㸪༳ຍ㟁ᅽ 15 kV ࡛ NH3 ࡣ᏶඲࡟ศゎ ࡋࡓ㸬 NH3 + e- Ѝ NH2 + H + e- (2-2) NH3 + e- Ѝ NH + H + H + e- (2-3) NH3 + e- Ѝ N + H + H + H + e- (2-4) H + H + M Ѝ H2 + M (2-5) Fig. 2-4 ࡣ㸪ศゎࡋࡓ NH3ࡀH2࡟㌿᥮ࡋࡓ๭ྜ㸦H2㌿᥮⋡㸧ࢆ࢞ࢫὶ㔞ࢆࣃ࣓࣮ࣛ ࢱ࡜ࡋ࡚༳ຍ㟁ᅽ࡟ᑐࡋࣉࣟࢵࢺࡋࡓᅗ࡛࠶ࡿ㸬ࡇࡇ࡛㸪H2㌿᥮⋡CH2 [%]ࡣᘧ(2-6)ࡢ ⥲ᣓ཯ᛂᘧ࡟ᇶ࡙ࡁ㸪ᘧ(2-7)࡛⟬ฟࡋࡓ㸬ྠᵝ࡟㸪N2㌿᥮⋡ࡣᘧ(2-8)࡛ồࡵࡓ㸬CH2ࡣ㸪 ༳ຍ㟁ᅽࡸ࢞ࢫὶ㔞ࡀ኱ࡁࡃኚ໬ࡋ࡚ࡶ82㸫91%ࡢ㧗࠸㌿᥮⋡ࢆ♧ࡋࡓ㸦Fig. 2-4㸧㸬ࡇ ࢀࡣ㸪ᘧ(2-2)㸫(2-4)࡛⏕ᡂࡋࡓ H ࣛࢪ࢝ࣝࡀᘧ(2-5)ࡢ෌⤖ྜ཯ᛂ࡟ࡼࡗ࡚㸪㑅ᢥⓗ࡟ H2ࢆ⏕ᡂࡋ࡚࠸ࡿ⤖ᯝ࡛࠶ࡿ࡜⌮ゎ࡛ࡁࡿ㸬୍᪉㸪CH2ࡣ༳ຍ㟁ᅽࡢቑຍ࡟ࡘࢀ࡚ᚎࠎ ࡟ῶᑡࡋࡓࡀ㸪ࡇࡢせᅉࢆ❅⣲㌿᥮⋡CN2ࡢኚ໬ᣲື࠿ࡽ⪃ᐹࡍࡿ㸬 0 20 40 60 80 100 0 4 8 12 16 0.2L/min 0.4L/min 0.8L/min

NH

3

decom

posi

ti

on

[

%

]

Applied voltage, V

_pp

[kV]

R_R= 10 kHz [NH₃]₀ = 4840 ppm

(29)

- 25 - NH3 + e- Ѝ 1.5 H2 + 0.5 N2 + e- (2-6) CH2 = [H2]/(1.5 × [NH3]IN× DNH3) (2-7) CN2 = [N2]/(0.5 × [NH3]IN× DNH3) (2-8) [H2], [N2]ࡣࡑࢀࡒࢀࣉࣛࢬ࣐ࣜ࢔ࢡࢱ࣮ฟཱྀ࡛ ᐃࡋࡓ H2⃰ᗘ[ppm]㸪N2⃰ᗘ[ppm] ࡛࠶ࡿ㸬 Fig. 2-5 ࡣ㸪༳ຍ㟁ᅽ࡟ᑐࡍࡿ N2㌿᥮⋡CN2 ࡢኚ໬ࢆ࢞ࢫὶ㔞ࢆࣃ࣓࣮ࣛࢱ࡜ࡋ࡚ ♧ࡋࡓᅗ࡛࠶ࡿ㸬CN2ࡣ㸪༳ຍ㟁ᅽࡀቑຍࡍࡿ࡯࡝㸪ࡲࡓ࢞ࢫὶ㔞ࡀῶᑡࡍࡿ࡯࡝ẚ౛ ⓗ࡟ቑຍࡋࡓ㸬༳ຍ㟁ᅽࡢቑຍ࡜࢞ࢫὶ㔞ࡢῶᑡࡣ㸪ᘧ (2-4) ࡟ࡼࡿ N ࣛࢪ࢝ࣝ⏕ᡂ 㔞ࢆቑຍࡉࡏࡿࡓࡵ㸪ࡑࢀ࡟క࠸N2 ㌿᥮⋡ࡶቑຍࡋࡓ࡜⪃࠼ࡽࢀࡿ㸬ࡋ࠿ࡋ࡞ࡀࡽ㸪 N2㌿᥮⋡ࡣ20 %௨ୗ࡜పࡃ㸪ゎ㞳ࡋࡓ NH3୰ࡢN ศ㸦NH2, NH, N㸧ࡢ࡯࡜ࢇ࡝ࡀ N2 ௨እࡢ࡞ࢇࡽ࠿ࡢ໬ྜ≀㸦NmHn㸧࡟㌿᥮ࡋࡓ࡜⪃࠼ࡽࢀࡿ㸬ࡇࢀࡼࡾ㸪༳ຍ㟁ᅽࡀ㧗 ࡃ࡞ࡿ࡯࡝N ศ࡜ H ࣛࢪ࢝ࣝ࡜ࡢ཯ᛂࡶ㉳ࡇࡿࡼ࠺࡟࡞ࡾ㸪ࡑࡢ⤖ᯝ H2㌿᥮⋡ࡀῶᑡ

ࡋࡓ㸦Fig. 2-4㸧࡜⪃࠼ࡽࢀࡿ㸬Fig. 2-6 ࡣ㸪NH3/Ar ὶ㔞 0.8 L∙min−1 ࡢ᫬ࡢࣉࣛࢬ࣐

ࣜ࢔ࢡࢱ࣮ฟཱྀ࢞ࢫࡢ୺࡞໬Ꮫ⤌ᡂ㸦ᮍ཯ᛂNH3, H2, N2㸧ࢆ༳ຍ㟁ᅽẖ࡟♧ࡋࡓᅗ࡛࠶ ࡿ㸬ୖグࡢ⤖ᯝ࠿ࡽண᝿࡛ࡁࡿࡼ࠺࡟㸪༳ຍ㟁ᅽࡢቑຍ࡟࡜ࡶ࡞࠸NH3ࡢ๭ྜࡣῶᑡ ࡋ㸪H2࡜N2ࡢ๭ྜࡣቑຍࡍࡿ㸬ࡲࡓ㸪ࡇࡢ≀㉁཰ᨭ㸦100 %ࡢⅬ⥺ࣛ࢖ࣥ࡜⤌ᡂ๭ྜ ྜィࡢᕪ㸧࠿ࡽ㸪࠾ࡼࡑ0.8㸫3.8%ࡢ NmHn ໬ྜ≀ࡀᏑᅾࡍࡿ࡜᥎ᐃ࡛ࡁࡿ㸬

2. 4 ບ㉳࢔ࣥࣔࢽ࢔ࡢ໬Ꮫ⤌ᡂ࡜⬺◪≉ᛶࡢ㛵ಀ

Fig. 2-7 ࡟ࡣ㸪኱Ẽᅽࣉࣛࢬ࣐࡛࢔ࣥࣔࢽ࢔ࢆບ㉳ࡋ㸦ὶ㔞 0.8 L/min㸧㸪ࡑࢀࢆࣔࢹ ࣝ࢞ࢫNO/O2/N2㸦ὶ㔞2.2 L/min㸧࡟྿ࡁ㎸ࡳ㸪཯ᛂ ᗘࢆ 500㸫750ºC ࡟ኚ໬ࡉࡏࡓ ᫬ࡢ⬺◪≉ᛶࢆ♧ࡋࡓ㸬࡝ࡢ཯ᛂ ᗘ࡟࠾࠸࡚ࡶ⬺◪⋡ࡀ᭱኱࡜࡞ࡿ༳ຍ㟁ᅽ㸦᭱㐺㟁 ᅽ㸧ࡀᏑᅾࡋ㸪཯ᛂ ᗘࡀ㧗ࡃ࡞ࡿ࡯࡝᭱㐺㟁ᅽࡣపࡃ࡞ࡗࡓ㸬 ౛࠼ࡤ㸪600 ºC ࡛ࡣ᭱㐺㟁ᅽ 12 kV㸪750 ºC ࡛ࡣ᭱㐺㟁ᅽ 3.0 kV ࡛࠶ࡗࡓ㸬Lyon ࡽ 1) 11)_ࡣ㸪_{SNCR ࡟࠾࠸࡚ H} 2ࢆῧຍࡍࡿ࡜Temperature window ࡀ⣙ 150 ºC ప ഃ࡟ࢩࣇ ࢺࡍࡿࡇ࡜ࢆ♧ࡋࡓ㸬ࡲࡓ㸪Muzio ࡽ12)_ࡣ_{Lyon ࡽ࡜ྠᵝࡢ⤖ᯝࢆᚓࡓ࠺࠼࡛㸪཯ᛂ} ᗘ࡜NH3/NO ࣔࣝẚࡢ㐪࠸࡟ࡼࡗ࡚㸪᭱኱⬺◪⋡ࢆᚓࡿࡓࡵ࡟᭱㐺࡞ H2/NO ࣔࣝẚࡀ Ꮡᅾࡍࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓ㸬Muzio ࡽࡣ཯ᛂ ᗘ 700 ºC㸪NH3/NO ࣔࣝẚ=1.0 ࡢ᫬㸪 H2/NO ࣔࣝẚ=2.4 ࡛᭱኱⬺◪⋡ 92 %ࢆᚓ࡚࠸ࡿ㸬 Fig. 2-6 ࡜ Fig. 2-7 ࢆẚ㍑ࡍࡿ࡜㸪཯ᛂ ᗘࡀప࠸᫬㸪౛࠼ࡤ 600 ºC ࡛᭱㐺㟁ᅽ 12 kV ࡢ᫬ࡣH2⃰ᗘࡀ㧗࠸᮲௳࡛᭱኱⬺◪⋡ࡀᚓࡽࢀ㸪ࡲࡓ㏫࡟཯ᛂ ᗘࡀ㧗࠸᫬ࡣH2⃰ᗘ ࡀప࠸᮲௳࡛᭱኱⬺◪⋡ࡀᚓࡽࢀࡿࡇ࡜ࡀࢃ࠿ࡿ㸬ࡍ࡞ࢃࡕ㸪཯ᛂ ᗘࡢ㐪࠸࡟ࡼࡗ࡚ ᭱㐺࡞H2/NO ࣔࣝẚࡀኚ໬ࡍࡿ㸬ᮏᐇ㦂᮲௳࡛ࡣ㸪཯ᛂ ᗘ 700 ºC㸪NH3/NO ࣔࣝẚ=1.5 ࡢ᫬㸪H2/NO ࣔࣝẚ= 0.35 ࡛᭱኱⬺◪⋡ 60 %ࢆᚓࡓ㸬

(30)

- 26 -

Fig. 2-4 H2 conversion at the ranges from 3.5 to 15 kV as a parameter of flow rates of NH3/Ar gas.

Fig. 2-5 N2 conversion at the ranges from 3.5 to 15 kV as a parameter of flow rates of NH3/Ar gas.

60 70 80 90 100 0 4 8 12 16 0.2 L/min 0.8 L/min

H

2

conv

er

si

on [

%

]

Applied voltage, V

_pp

[kV]

R_R = 10 kHz [NH₃]₀ = 4840 ppm 0 10 20 30 40 0 4 8 12 16 0.2 L/min 0.4 L/min 0.8 L/min

N

O

x

re

m

oval

[

%

]

Applied voltage, V

_pp

[kV]

R_R = 10 kHz [NH₃]₀ = 4840 ppm

(31)

- 27 -

Fig. 2-6 Gas composition of reforming ammonia at the plasma reactor exit.

ࡇࢀࡽࡢ⤖ᯝࡣ㸪⬺◪⋡ࡸH2/NO ࣔࣝẚࡢ⤯ᑐ್ࡣ␗࡞ࡿࡶࡢࡢ㸪Muzio ࡽࡢ⤖ᯝ࡜ ഴྥࡀ୍⮴ࡍࡿࡶࡢ࡛࠶ࡿ㸬ࡇࢀࡼࡾ㸪ᨵ㉁࢔ࣥࣔࢽ࢔࢖ࣥࢪ࢙ࢡࢩࣙࣥἲ࡟࠾࠸࡚⬺ ◪཯ᛂ ᗘࡀప ഃ࡟ᣑ኱ࡍࡿ⌮⏤ࡣ㸪࢔ࣥࣔࢽ࢔ࢆ኱Ẽᅽࣉࣛࢬ࣐࡛ບ㉳ࡋࡓ᫬࡟⏕ ᡂࡍࡿH2࡟ࡼࡿຠᯝ࡛࠶ࡿ࡜᥎ᐃ࡛ࡁࡿ㸬H2ࡀ⬺◪཯ᛂ ᗘࡢపୗ࡟ᐤ୚ࡍࡿ཯ᛂᶵ ᵓࡣ㸪Muzio ࡽ࡟ࡼࡗ࡚ࡍ࡛࡟⪃ᐹࡉࢀ࡚࠸ࡿ12)_㸬 Fig. 2-8 ࡟ࡣ㸪ࣛࢪ࢝ࣝ࢖ࣥࢪ࢙ࢡࢩࣙࣥἲ࡟࠾ࡅࡿ᭱኱⬺◪⋡࡜᭱㐺 H2/NO ࣔࣝẚ ࢆ཯ᛂ ᗘ࡟ᑐࡋ࡚♧ࡋࡓ㸬ẚ㍑ࡢࡓࡵ࡟SNCR ࡢ⬺◪⋡ࡢኚ໬ࡶᅗ୰࡟♧ࡋࡓ㸬᭱ 㐺H2/NO ࣔࣝẚࡣ㸪཯ᛂ ᗘ 600㸫800 ºC ࡛ 1.06㸫0 ࡢ⠊ᅖ࡟࠶ࡾ㸪཯ᛂ ᗘࡀపࡃ ࡞ࡿ࡯࡝᭱㐺H2/NO ࣔࣝẚࡣ㧗ࡃ࡞ࡗࡓ㸬

2. 5 ⬺◪࡟ཬࡰࡍ H

2

ࡢᙳ㡪

Fig. 2-6 ࠿ࡽ㸪ᨵ㉁࢔ࣥࣔࢽ࢔ࡢ⤌ᡂࡣ୺࡟ H2࡜ᮍ཯ᛂNH3࡛࠶ࡿࡇ࡜ࡀุ᫂ࡋࡓ㸬 ࡑࡇ࡛㸪Fig. 2-6 ࡛ᚓࡽࢀࡓ⤌ᡂ㸦NH3+H2㸧࡟ᚑ࠸࣎ࣥ࣋࢞ࢫࢆ⏝࠸࡚సᡂࡋ㸦௨ୗࠊ ᨵ㉁NH3ᶍᨃ࢞ࢫ࡜ࡍࡿ㸧㸪ࡑࢀࢆᶍᨃ᤼࢞ࢫࣛ࢖ࣥ࡟┤᥋྿ࡁ㎸ࢇ࡛⬺◪ᐇ㦂ࢆ⾜ࡗ ࡓ㸬 Fig. 2-9 ࡣᨵ㉁ NH3࠾ࡼࡧᨵ㉁NH3ᶍᨃ࢞ࢫࡢ࢖ࣥࢪ࢙ࢡࢩࣙࣥ࡟ࡼࡿ⬺◪⋡ࡢኚ໬ ࢆ཯ᛂ㒊 ᗘ650 ºC ࠾ࡼࡧ 750 ºC ࡟ࡘ࠸࡚ẚ㍑ࡋࡓᅗ࡛࠶ࡿ㸬NH3ࡢࡳࢆ྿ࡁ㎸ࢇࡔ ሙྜ㸪ࡇࡢ ᗘ⠊ᅖ࡛ࡣ⬺◪཯ᛂࡣ㉳ࡇࡽ࡞࠸ࡀ㸪ᨵ㉁NH3ᶍᨃ࢞ࢫ㸦NH3/H2/Ar㸧ࢆ ྿ࡁ㎸ࡴ࡜⬺◪ࡀ㉳ࡇࡿࡇ࡜ࡀุ᫂ࡋࡓ㸬ࡍ࡞ࢃࡕ㸪Temperature Window ࡢప ᗘᇦᣑ

0

20

40

60

80

100

120

140

0

3.5

6

9

12

15 NH

₃

H

₂

N

₂

C

hem

ical

co

m

pos

it

ion [%

]

Applied voltage, V

_pp

[kV]

F₀ = 0.8 L/min [NH₃]₀ = 4840 ppm

(32)

- 28 -

኱࡟ࡣH2ࡀᐤ୚ࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓ㸬

Fig. 2-7 Characteristics of NOx removal by reforming ammonia generated by pulsed plasma.

Fig. 2-8 Variation in H2/NO ratios at maximum NOx removal with reaction temperatures.

0 20 40 60 80 100 0 4 8 12 16 750ӣC 700ӣC 650_ӣC 600ӣC 500ӣC

N

O

x

re

m

oval

[

%

]

Applied voltage, V

_pp

[kV]

NH₃/NO = 1.5 O₂ = 8.3 % 0 20 40 60 80 100 0 0.5 1 1.5 2 2.5 400 500 600 700 800 900

NO

x

r

em

ov

al

[

%

]

H

2

/N

O

m

ola

r

ra

ti

o

[-]

Temperature [

ӣC]

NO₀ = 500 ppm NH₃/NO = 1.5 O₂ = 8.3 % Reforming NH₃ Injection Thermal DeNOx

(33)

- 29 -

Fig.2-9 Comparison of DeNOx performances between radical injection and DBD model gas.

2. 6 ⣲཯ᛂゎᯒ࡟ࡼࡿ⬺◪ࢩ࣑࣮ࣗࣞࢩࣙࣥ

ᨵ㉁NH3࢖ࣥࢪ࢙ࢡࢩࣙࣥἲࡢ཯ᛂ࣓࢝ࢽࢬ࣒ࢆゎ᫂ࡍࡿࡓࡵ㸪⣲཯ᛂࢩ࣑࣮ࣗࣞ ࢩࣙࣥࢆ⾜ࡗࡓ㸬NO ࡟㛵ࡍࡿ⏕ᡂ࠾ࡼࡧ㑏ඖ࣓࢝ࢽࢬ࣒ࡣᵝࠎ࡞࢔ࣉ࣮ࣟࢳ࡛◊✲ࡋ ࡓࡶࡢࡀሗ࿌ࡉࢀ࡚࠸ࡿ㸬௒ᅇࡣ㸪❅⣲㸪㓟⣲࠾ࡼࡧỈ⣲ࢆྵࡴSkreiberg ࡢ໬Ꮫ཯ᛂ ㏿ᗘࣔࢹࣝࢆ⏝࠸࡚㸪ᨵ㉁࢔ࣥࣔࢽ࢔࢖ࣥࢪ࢙ࢡࢩࣙࣥ཯ᛂ࡟ࡘ࠸࡚⣲཯ᛂィ⟬ࢩ࣑ࣗ ࣮ࣞࢩࣙࣥࢆ⾜ࡗࡓࠋࢩ࣑࣮ࣗࣞࢩࣙࣥ₇⟬࡟ࡣ㸪ỗ⏝ࡢ໬Ꮫ཯ᛂᶵᵓゎᯒࢯࣇࢺ࢙࢘ ࢔࡛࠶ࡿCHEMKIN-PRO ࢆ౑⏝ࡋࡓࠋ཯ᛂჾࣔࢹࣝ࡟ࡣࣉࣛࢢࣇ࣮ࣟࣜ࢔ࢡࢱ࣮(PFR) ࢆ⏝࠸㸪ึᮇ᮲௳࡜ࡋ࡚NO㸪N2㸪O2㸦ࣔࢹࣝ࢞ࢫ㸧㸪NH3㸪H2㸪Ar㸦ᨵ㉁࢔ࣥࣔࢽ࢔࢞ ࢫ㸧໬Ꮫ✀ࡢ⃰ᗘࢆ୚࠼ࡓ㸬Table 2 ࡟㸪タᐃࡋࡓᨵ㉁࢔ࣥࣔࢽ࢔࢞ࢫࡢ࢞ࢫ⤌ᡂࢆ༳ ྍ㟁ᅽࡈ࡜࡟グࡋࡓ㸬 Fig. 2-10 ࡣ㸪⬺◪ィ⟬⤖ᯝࢆ Fig. 2-7 ࡢ཯ᛂ ᗘ 750 ºC ࡢᐇ㦂⤖ᯝ࡜ẚ㍑ࡋࡓࡶࡢ࡛ ࠶ࡿࠋィ⟬⤖ᯝࡣࣛࢪ࢝ࣝ࢖ࣥࢪ࢙ࢡࢩࣙࣥ࠾ࡼࡧNH3/H2/Ar ┤᥋ᢞධ⬺◪ࢆྠࡌᣲື ࡜♧ࡋ࡚࠾ࡾ㸪H2ࡀTemperature window ࡢᣑ኱࡟ᐤ୚ࡋ࡚࠸ࡿࡇ࡜ࡀࢩ࣑࣮ࣗࣞࢩࣙ ࣥ࠿ࡽࡶ᫂ࡽ࠿࡟࡞ࡗࡓ㸬ࡲࡓ㸪ᨵ㉁NH3࡟ࡼࡿ⬺NOx཯ᛂᶵᵓࡣSkreiberg ࡀᵓ⠏ࡋ ࡓ໬Ꮫ཯ᛂ㏿ᗘㄽࣔࢹࣝ13)_{ࢆ⏝࠸ࡿࡇ࡜࡛཯ᛂᶵᵓࡢゎ᫂ࡀྍ⬟࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗ} ࡓ㸬 0 20 40 60 80 100 0 4 8 12 16 Plasma-750_ӣC H 2-750ӣC Plasma-650_ӣC H 2-650ӣC

大気圧プラズマによる無触媒脱硝および水素製造法の開発

Title