39

沼津工業高等専門学校研究報告
第 52 号，2018 年 1 月ᾮ┦࢚ࢱࣀ࣮ࣝ࠿ࡽࡢ┤᥋Ỉ⣲〇㐀ࢩࢫࢸ࣒ࡢ๰〇࠾ࡼࡧホ౯኱ᓥ୍┿*㸪຾ཪ⁞ᖹ*
Characterization and development of a system ofdirect hydrogen production from liquid ethanol
Kazumasa Oshima*, Kohei Katsumata*Abstract: Direct conversion of liquid ethanol is a promising way of hydrogen production for acompact society. In our laboratory, an efficient conversion system using an electrical assistance(< 100 V) and loaded metal particles, has been developed. In this study, we evaluated thissystem in order to apply for water splitting and direct ethanol conversion, and investigated thefactors for an effective hydrogen production. From results, Pt/Al2O3 was a suitable material as
the loaded metal particle charged between the electrodes, and showed a high efficiency for thewater splitting. The volume of gas formation and the conversion efficiency depended on thenumber of particles and the imposed voltage. The maximum efficiency for the water splitting
on Pt/Al2O3 reached 210 % at the 65 V of imposed voltage. And from the investigation of thedirect ethanol conversion, it was found that the suitable concentration of liquid ethanol was 60
wt%, and NaOH addition as an electrolyte increased the efficiency.
Key Words:

Hydrogen production, Direct ethanol conversion, Electrochemical processᮏࣉࣟࢭࢫࡣ㟁Ẽ໬Ꮫ཯ᛂࢆ⏝࠸࡚࠸ࡿࡓࡵ㸪ᖖ ࡛㥑ື䠍䠊⥴㻌 ゝࡍࡿࡇ࡜ࡀྍ⬟࡛࠶ࡿࡀ㸪ᘧ 3,4 ࡢ༙཯ᛂᘧ࡟♧ࡍ㏻ࡾ㸪㏆ᖺ㸪࢚ࢿࣝࢠ࣮㞟୰ᆺࡢ⏘ᴗᙧែ࠿ࡽ㸪࢚ࢿࣝࢠ࣮ศᩓᆺ࡬ࡢ♫఍ࢩࢫࢸ࣒ࡢ⛣⾜ࡀ㐍ࢇ࡛࠸ࡿ㸬࢚ࢿࣝࢠ࣮ࡢ⏕ᡂ㔞࡜㟁Ꮚᩘ࡟㔞ㄽ㛵ಀࡀᡂ❧ࡍࡿࡓࡵ㸪༑ศ࡞⏕ᡂ㏿ᗘࡀ㐩ᡂ࡛ࡁ࡞࠸㸬ᆅ⏘ᆅᾘ࡟ࡼࡾᡂ❧ࡍࡿ࢚ࢿࣝࢠ࣮ศᩓᆺ♫఍࡟࠾࠸࡚ࡣ㸪ྛᆅᇦࡢ≉ᛶ࡟ྜࢃࡏࡓཎᩱ࡟ᑐࡋ࡚㸪㐺ษ࡞࢚ࢿࣝࢠ࣮ኚ᥮࠾ࡼࡧ≀㉁ኚ᥮ࢩࢫࢸ࣒ࢆᵓ⠏ࡋ࡞ࡅࢀࡤ࡞ࡽ

Anode
Cathode4H+ + 4e– Ѝ 2H2
2H2O Ѝ O2(ᘧ 3)+ 4H+ + 4e–(ᘧ 4)࡞࠸㸬ࡑࡢୖ࡟ࡣ⿦⨨ୖࡢไ⣙ࡀከࡃᏑᅾࡋ㸪⇕஺᥮ჾࢆタ⨨࡛ࡁ࡞࠸ࡓࡵ᤼⇕ᅇ཰ࡀฟ᮶࡞࠸㸪ᚠ⎔ࢩࢫࢸ࣒ࢆタ ከᵝ࡞ཎᩱ࠾ࡼࡧ㐠㌿᮲௳࡟ᑐᛂ࡛ࡁࡿࣉࣟࢭࢫࢆタ⨨࡛ࡁ࡞࠸ࡓࡵ㧗㌿໬⋡ࡀせồࡉࢀࡿ㸪࡜࠸ࡗࡓᑠᆺࣉࣟィ࣭ᵓ⠏ࡍࡿࡓࡵ࡟ࡣ㸪ࡇࢀࡽࡢ฼Ⅼࢆවࡡഛ࠼ࡓࠕప ࠖࢭࢫ㐠⏝ࡀせồࡉࢀࡿ㸬࠿ࡘࠕ㧗࠸⏕ᡂ㏿ᗘࠖࢆ᭷ࡋࡓ཯ᛂࢩࢫࢸ࣒ࡀ᭷ຠ࡜࡞ࡿ㸬Ỉ⣲〇㐀ࢆ౛࡟⪃࠼ࡿ࡜㸪࢚ࢿࣝࢠ࣮㞟୰ᆺࡢ⏘ᴗ࡟࠾ࡑࡇ࡛ᮏ◊✲࡟࠾࠸࡚ࡣ㸪㟁Ẽ໬Ꮫ཯ᛂࡢ⏕ᡂ㔞ቑ኱ࢆ≺࠸࡚ࡣ㸪ኳ↛࢞ࢫ(࣓ࢱࣥ)ࢆཎᩱ࡜ࡋࡓỈ⵨Ẽᨵ㉁ἲ(ᘧ 1)࠸㸪ᅗ 1 ࡟♧ࡍ཯ᛂࢩࢫࢸ࣒ࢆᥦ᱌ࡍࡿ㸬஧㟁ᴟᘧ㟁Ẽ໬࡟ࡼࡾ〇㐀ࡉࢀࡿ㸬Ꮫࢭࣝࡢ㟁ᴟ㛫࡟㸪ᅗ 1 ࡟♧ࡍࡼ࠺࡞㔠ᒓᚤ⢏Ꮚࢆ㧗ศᩓ

CH4 + H2O Ѝ CO + 3H2(ᘧ 1)'H = 206 kJ mol-1ࡉࡏࡓᢸᣢ㔠ᒓ⢏Ꮚࢆ඘ሸࡉࡏࡿ㸬㟁ᴟୖ࡟ຍ࠼࡚㸪඘ሸࡋࡓᢸᣢ㔠ᒓ⢏Ꮚୖ࡛ࡶ཯ᛂࢆ㐍⾜ࡉࡏࡿࡇ࡜࡛㸪ᅇ㊰㛫ᮏࣉࣟࢭࢫࡣ㸪ᅛయゐ፹ࢆ⏝࠸࡚࠸ࡿࡓࡵ㸪㧗࠸Ỉ⣲⏕ᡂࡢ㟁Ꮚ࠶ࡓࡾࡢ⏕ᡂ㔞ࢆቑ኱ࡉࡏࡿࡇ࡜ࢆ≺࠺㸬㏿ᗘࢆ㐩ᡂ࡛ࡁࡿࡀ㸪኱ࡁ࡞྾⇕཯ᛂ࡛࠶ࡿࡓࡵ 600 ºC ௨ୖࡢ㧗 ࡀᚲせ࡜࡞ࡿ㸬୍᪉࡛㧗 ࢆせࡋ࡞࠸ᑠᆺࡢỈ⣲Feed〇㐀ἲ࡜ࡋ࡚㸪Ỉࡢ㟁Ẽศゎ(ᘧ 2)ࡀᣲࡆࡽࢀࡿ㸬
2H2O → 2H2 + O2(ᘧ 2)

Productਃਤ᣿‫ޓ‬ቩ‫܇‬e–e–*≀㉁ᕤᏛ⛉Department of Chemistry and Biochemistryᅗ 1 ᮏ◊✲࡛ᥦ᱌ࡍࡿ㟁Ẽ໬Ꮫ཯ᛂࢩࢫࢸ࣒40沼津工業高等専門学校研究報告第 52 号

Ỉࡢ㟁Ẽ໬Ꮫ཯ᛂࢆ౛࡟⪃࠼ࡿ࡜㸪ᘧ 3,4 ࡼࡾ 4 㟁Ꮚ࠶ࡓ㸰㸬㸰 ࢩࢫࢸ࣒ホ౯ヨ㦂ࡾࡢ࢞ࢫ(H2+O2)Ⓨ⏕㔞ࡣ 3 ศᏊ࡜࡞ࡿ㸬ࡇࡢ㟁Ẽ໬Ꮫ㔞ㄽ ࢩࢫࢸ࣒ࡢᛶ⬟ホ౯ࡣᅗ 2 ࡟♧ࡍ⿦⨨ࢆ⏝࠸࡚ᐇ᪋ࡋࡓ㸬࡟ᇶ࡙ࡃ࢞ࢫⓎ⏕㔞ࢆ 100 %࡜ᐃ⩏ࡋ㸪඘ሸࡋࡓᢸᣢ㔠ᒓ࢞ࣛࢫ〇཯ᛂ⟶ࡢ୧➃࠿ࡽ㟁ᴟ(Anode㸸Copper (2.0 mmI)㸪

⢏Ꮚୖ࡛」ᩘᅇࡢ཯ᛂࢆ㐍⾜ࡉࡏࡿࡇ࡜࡛㸪ຠ⋡ 100 %ࢆ

Cathode㸸Carbon (2.0 mmI))ࢆᤄධࡋ㸪㟁ᴟ㛫(4.0 cm)࡟ㄪ

ୖᅇࡿࢩࢫࢸ࣒ࡢᵓ⠏ࢆ┠ᣦࡍ㸬ලయⓗ࡟ࡣ㸪Ỉࡢ㟁Ẽศ〇ࡋࡓᢸᣢ㔠ᒓ⢏Ꮚࢆ඘ሸࡋࡓ㸬ཎᩱ࡛࠶ࡿỈ࠾ࡼࡧ࢚ࢱ

ゎ(ᘧ 2)࠾ࡼࡧ࢚ࢱࣀ࣮ࣝࡢ㟁ゎ㓟໬(ᘧ 5)࡟ࡼࡿ≀㉁ኚ᥮

ࣀ࣮ࣝỈ⁐ᾮࡣ㸪㟁ゎᾮ࡜ࡋ࡚㐣ሷ⣲㓟(HClO4)ࡶࡋࡃࡣỈࢆᮏ཯ᛂࢩࢫࢸ࣒࡟࡚ᐇ᪋ࡋ㸪㟁Ẽⓗ≉ᛶࡸ඘ሸ⢏Ꮚࡀ࢞㓟໬ࢼࢺ࣒ࣜ࢘(NaOH)ࢆ 0.05 M ࡜࡞ࡿࡼ࠺࡟ῧຍࡋ㸪࣌ࢫⓎ⏕࠾ࡼࡧ⏕ᡂຠ⋡࡟ཬࡰࡍຠᯝࢆ᳨ウࡍࡿ㸬ࣜࢫࢱ࣏ࣥࣉ࡟࡚ 90 mL min-1 ࡛౪⤥ࡋࡓ㸬㟁Ꮚࡢᢞධࡣ㟁

CH3CH2OH Ѝ CH3CHO + H2ᅽไᚚ(CV)࡟࡚⾜࠸㸪㟁ὶࣔࢽࢱ࣮ࢆ⏝࠸࡚཯ᛂ୰ࡢᢞධ(ᘧ 5)Ỉࡢ㟁Ẽศゎࡸ࢚ࢱࣀ࣮ࣝࡢ㟁ゎ㓟໬࡟ࡣ㸪Pt 㟁ᴟࡀ᭷ຠ㟁Ꮚᩘࢆ⟬ฟࡋࡓ㸬⏕ᡂ࢞ࢫࡣỈୖ⨨᥮ἲ࡟ࡼࡾ᥇㞟࣭ᐃ࡛࠶ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿ[1]㸬ᮏ◊✲࡛ࡣᢸᣢ㔠ᒓ⢏Ꮚ࡜㔞ࡋ㸪GC-TCD ࡟࡚ᐃᛶࢆ⾜ࡗࡓ㸬࡞࠾Ỉࡢ㟁Ẽศゎ࡟࠾ࡋ࡚ Pt ࢆ⏝࠸࡚㸪⤯⦕య࡛࠶ࡿ࢔࣑ࣝࢼ࣮࣎ࣝ࡟ᢸᣢࡋࡓ࠸࡚ࡣ㸪඲࡚㸪Ỉ⣲࡜㓟⣲ࡀ 2㸸1 ࡛⏕ᡂࡋ࡚࠸ࡿࡇ࡜ࢆᢸᣢ㔠ᒓ⢏Ꮚ Pt/Al2O3 ࢆ⏝࠸᳨࡚ウࢆ⾜࠺㸬☜ㄆࡋ࡚࠸ࡿ㸬ࡲࡓ⏕ᡂຠ⋡ࡣ㸪ᘧ 3,4 ࡢ㟁Ẽ໬Ꮫ㔞ㄽ࡟ ࡞࠾ࡇࡢࡼ࠺࡞㟁Ẽ࡟ࡼࡿ཯ᛂ࢔ࢩࢫࢺࡢඛ⾜◊✲౛๎ࡿ࢞ࢫⓎ⏕㔞ࢆ 100 %࡜ࡋ㸪࢚ࢱࣀ࣮ࣝ㟁ゎ㓟໬࡟࠾࠸࡜ࡋ࡚㸪ࣉࣛࢬ࣐࢔ࢩࢫࢺ[2,3]ࡸ NEMCA(Non-Faradaic࡚ࡶྠᵝࡢ⟬ฟ᪉ἲࢆ᥇⏝ࡋࡓ㸬

Electrochemical Modification on Catalytic Activity)[4,5]ࡀᣲࡆ
ࡽࢀࡿ㸬㧗࠸࢚ࢿࣝࢠ࣮ᐦᗘࢆ᭷ࡍࡿࣉࣛࢬ࣐ࡣ㸪ᖖ ࡛㥑ືࡉࡏࡿࡇ࡜ࡀྍ⬟࡛࠶ࡿࡀ㸪1.0 kV ௨ୖࡢ㧗࠸༳ຍ㟁䠏䠊⤖ᯝ䛚䜘䜃⪃ᐹᅽࢆᚲせ࡜ࡋ㸪࢚ࢿࣝࢠ࣮ຠ⋡ࡀ㧗ࡃ࡞࠸㸬ࡲࡓ NEMCA㸱㸬㸯 Ỉࡢ㟁Ẽศゎ࡛ࡢ᳨ウࡣ㸪ᩘ V ࡢప㟁ᅽ࢔ࢩࢫࢺ࡛཯ᛂಁ㐍ࡀ㐩ᡂࡉࢀࡿࡀ㸪ࡑ ࡲࡎỈࡢ㟁Ẽศゎ(ᘧ 2)࡟࠾࠸࡚㸪ᮏࢩࢫࢸ࣒ࡀ⏕ᡂຠࡢࢩࢫࢸ࣒ࢆ㥑ືࡍࡿࡢ࡟ 600 ºC ௨ୖࡢ㧗 ࢆᚲせ࡜ࡍ⋡ 100 %ࢆୖᅇࡿࡇ࡜ࡀྍ⬟࡞ࢩࢫࢸ࣒࡛࠶ࡿ࠿ࢆ᳨ウࡋࡿ㸬ᮏ◊✲࡟ࡼࡾᥦ᱌ࡍࡿࢩࢫࢸ࣒ࡣ୧⪅ࡢ≉ᛶࢆවࡡഛࡓ㸬ᅗ 3 ࡟ྛ⢏Ꮚࢆ඘ሸࡋࡓሙྜࡢ㸪㟁ὶ࡟ᑐࡍࡿ࢞ࢫⓎ࠼ࡓ㸪ప㟁ᅽ(< 100 V)࣭ᖖ 㥑ືࡀ㐩ᡂࡉࢀࡿ཯ᛂࢩࢫࢸ⏕㔞ࢆ♧ࡍ㸬࡞࠾ᅗ୰ࡢᐇ⥺ࡣ㟁Ẽ໬Ꮫ㔞ㄽ(ᘧ 3,4)࡟๎ࡗ

࣒ࢆ┠ᶆ࡜ࡍࡿ㸬ࡓሙྜࡢ㸪㟁ὶ(㟁Ꮚ)࡟ᑐࡍࡿ࢞ࢫ(H2+O2)⏕ᡂ㏿ᗘࢆ♧ࡋ࡚࠸ࡿ㸬㟁ᴟ㛫࡟⢏Ꮚࢆ඘ሸࡋ࡚࠸࡞࠸ Blank㸪࠾ࡼࡧ㔠ᒓࢆᢸᣢࡋ࡚࠸࡞࠸ Al2O3 ࣮࣎ࣝࡢࡳࢆ඘ሸࡋࡓ Al2O3 ࡛䠎䠊ᐇ㦂᧯సࡣ㸪࢞ࢫ⏕ᡂ㏿ᗘࡀ㟁Ẽ໬Ꮫ㔞ㄽ(ᐇ⥺)࡟㐩ࡏࡎ㸪⏕ᡂຠ㸰㸬㸯 ᢸᣢ㔠ᒓ⢏Ꮚࡢㄪ〇⋡ࡀ⣙ 80 %࡟␃ࡲࡗࡓ㸬ࡇࢀ࡟ᑐࡋ࡚㸪άᛶⅬ࡜࡞ࡿ Pt ඘ሸࡍࡿᢸᣢ㔠ᒓ⢏Ꮚࡣ㸪ྵᾐἲ࡟ࡼࡾㄪ〇ࡋࡓ㸬ᢸయࢆ Al2O3 ࣮࣎ࣝ࡟ᢸᣢࡉࡏࡓ Pt/Al2O3 ࢆ㟁ᴟ㛫࡟඘ሸࡋࡓ࡟ࡣ࢔࣑ࣝࢼ࣮࣎ࣝ(Al2O3, 2 mmI)ࢆ⏝࠸㸪ⓑ㔠ࡢ๓㥑య࡟ሙྜ㸪⏕ᡂຠ⋡ࡀ 100 %ࢆୖᅇࡾ㸪᭱኱࡛⣙ 110 %࡟㐩ࡋࡣࢸࢺࣛ࢔࣑ࣥࣥ◪㓟ⓑ㔠(Pt(NH3)3(NO2)3)ࢆ⏝࠸ࡓ㸬ᢸᣢࡓ㸬ࡇࡢ⤖ᯝࡼࡾ㸪㟁ᴟୖ࡟ຍ࠼࡚㸪㔠ᒓᢸᣢ⢏Ꮚୖ࡛ࡶ㔠ᒓ㔞ࡣ࢔࣑ࣝࢼ࣮࣎ࣝ࡟ᑐࡋ࡚ 0.36 wt%࡜ࡋ㸪↝ᡂࡣ཯ᛂࡀ㐍⾜ࡍࡿࡇ࡜࡛㸪⏕ᡂຠ⋡ 100 %ࢆୖᅇࡿࢩࢫࢸ࣒

500 ºC ࡛ 3 h ⾜ࡗࡓ㸬ࡀᵓ⠏ࡉࢀࡓࡇ࡜ࡀ♧ࡉࢀࡓ㸬

Metal loading particles

PotentioStat

Electrode

8QNVCIG

Feed pumpLiquid flow
Gas flowᅗ 2 ᐇ㦂⿦⨨ᅗᴫせGas samplingGas formation rate / mL min -1

1.2
1

Pt/Al2O3
Al2O3

0.8Blank

0.6
0.4
0.2
0020

4060

Cuurent / mA

80100

ᅗ 3 ᮏࢩࢫࢸ࣒࡟࠾ࡅࡿỈࡢ㟁Ẽศゎࡢ⤖ᯝ

41

液相エタノールからの直接水素製造システムの創製および評価 ᭦࡞ࡿ࢞ࢫⓎ⏕㔞࠾ࡼࡧ⏕ᡂຠ⋡ࡢྥୖࢆ≺࠸㸪඘ሸࡍ

25010020080

1506010040ቑ኱ࡋ㸪⏕ᡂຠ⋡ࡶྥୖࡋࡓ㸬⢏Ꮚᩘ 30 ⢏㸪༳ຍ㟁ᅽ 65 Vࡢ㝿࡟᭱ࡶ㧗࠸⏕ᡂຠ⋡ࢆ♧ࡋ㸪ࡑࡢ್ࡣ 200 %ࢆୖᅇࡗࡓ㸬200 %ࢆୖᅇࡿࡓࡵ࡟ࡣ㸪ᅗ 1 ࡟♧ࡍࢩࢫࢸ࣒࡟࠾࠸࡚㸪」ᩘࡢ⢏Ꮚୖ࡛཯ᛂࡀ㐍⾜ࡋ࡞ࡅࢀࡤ࡞ࡽ࡞࠸㸬ࡍ࡞

Efficiency / %ᯝࢆᅗ 4 ࡟♧ࡍ㸬඘ሸ⢏Ꮚᩘࡢቑຍ࡟క࠸㸪࢞ࢫⓎ⏕㔞ࡀࢃࡕ㸪」ᩘࡢ㔠ᒓᢸᣢ⢏Ꮚࡀ཯ᛂ࡟㛵୚ࡋ㸪┠ⓗ࡛࠶ࡿ㟁

45 V50Current / mAࡿ㔠ᒓᢸᣢ⢏Ꮚࡢ඘ሸ⢏Ꮚᩘࡢ౫Ꮡᛶࢆ ᐃࡋࡓ㸬ࡑࡢ⤖2065 Vᴟ㛫࡛ࡢ」ᩘᅇࡢ཯ᛂࡀ㐩ᡂࡉࢀࡓ㸬࡞࠾ᅗ 4 ࡢⓑᢤࡁࣉ0ࣟࢵࢺ࡟♧ࡍ㏻ࡾ㸪඘ሸ⢏Ꮚᩘࡢቑ኱࡟క࠸㸪㟁ὶ್ࡀῶ

0

0.2

0.4

0.6

0.8

10ᑡࡍࡿഴྥࡀ♧ࡉࢀࡓ㸬ࡇࢀࡣ඘ሸ⢏Ꮚᩘࡢቑ኱࡟క࠸⏕Pt loading / wt%ᡂ࢞ࢫࡀ⁫␃ࡋࡸࡍࡃ࡞ࡗࡓࡓࡵ㸪㟁ᴟ㛫ࡢ᢬ᢠࡀቑ኱ࡋ

ᅗ 5 Ỉ㟁ゎ࡟࠾ࡅࡿ⏕ᡂຠ⋡ࡢᢸᣢ㔠ᒓ㔞౫Ꮡᛶࡓࡶࡢ࡜⪃࠼ࡽࢀࡿ㸬ࡓࡔࡋ⏕ᡂຠ⋡࡟኱ࡁࡃᙳ㡪ࢆཬࡰࡍ࡯࡝ࡢኚ໬࡛ࡣ࡞ࡃ㸪ᅗ 4 ࡟♧ࡍࡢ⏕ᡂຠ⋡ྥୖࡣ࢞ࢫ㸱㸬㸰 ࢚ࢱࣀ࣮ࣝࡢ㟁Ẽ໬Ꮫ཯ᛂ࡛ࡢ᳨ウⓎ⏕㔞ࡢቑ኱࡟ࡼࡗ࡚㐩ᡂࡉࢀࡓࡶࡢ࡛࠶ࡿ㸬 ๓⠇ࡢỈࡢ㟁Ẽศゎࢆ⏝࠸ࡓࢩࢫࢸ࣒ホ౯ࡼࡾ㸪⏕ᡂຠ

250

10020080150

6010040⋡ࡀ 100 %ࢆୖᅇࡿ㟁Ẽ໬Ꮫⓗ≀㉁ኚ᥮ࢩࢫࢸ࣒ࡢᵓ⠏ࡀ

45 V50ࡢỈ⣲〇㐀࡟ࡘ࠸࡚ホ౯ࡋࡓ㸬✀ࠎࡢ࢚ࢱࣀ࣮ࣝ⃰ᗘ࠾ࡼ

Current / mA

Efficiency / %㐩ᡂࡉࢀࡓ㸬ࡑࡇ࡛࢚ࢱࣀ࣮ࣝ㟁ゎ㓟໬࡟ࡼࡿ┤᥋㌿᥮࡛

2065 V00102030ࡧῧຍ㟁ゎᾮ࡟ᑐࡍࡿ࢞ࢫⓎ⏕㔞࠾ࡼࡧ㟁ὶ್ࢆᅗ 6 ࡟♧ࡍ㸬࢚ࢱࣀ࣮ࣝ⃰ᗘࡢቑຍ࡟క࠸㸪ሷᇶᛶ᮲௳࠾ࡼࡧ㓟ᛶ᮲௳࡜ࡶ࡟㸪࢚ࢱࣀ࣮ࣝࡢప࠸㟁Ẽఏᑟ⋡ࡢࡓࡵ࡟㟁ὶ್ࡀῶᑡࡋࡓ㸬୍᪉࡛࢞ࢫⓎ⏕㔞ࡣ㸪20 wt%࠿ࡽ 60 wt%ࡢ㛫࡛࡯ࡰྠࡌ್ࢆ♧ࡋࡓ㸬Ỉࡢ㟁Ẽศゎࡢࡳࡀ㐍⾜ࡋࡓሙྜ㸪ᅗ 3 ࡟♧ࡍ㏻ࡾ㟁ὶ್ࡀῶᑡࡍࢀࡤ㸪ࡑࢀ࡟కࡗ࡚࢞

0ࢫⓎ⏕㔞ࡶῶᑡࡍࡿࡣࡎ࡛࠶ࡿ㸬ࡇࡢࡇ࡜࠿ࡽ㸪࢚ࢱࣀ࣮

Number of particles / -ࣝ⃰ᗘ 20 wt%࠿ࡽ 60 wt%ࡢ㡿ᇦ࡟࠾࠸࡚ࡣ㸪Ỉࡢ㟁Ẽศᅗ 4 Ỉ㟁ゎ࡟࠾ࡅࡿ⏕ᡂຠ⋡ࡢ඘ሸ⢏Ꮚᩘ౫Ꮡᛶゎ࡟ຍ࠼࡚㸪࢚ࢱࣀ࣮ࣝࡢ㟁Ẽ໬Ꮫ཯ᛂࡶ㐍⾜ࡋ࡚࠸ࡿྍ⬟ᛶࡀ࠶ࡿ㸬ࡇࡢ⤖ᯝ࡟ࡘ࠸࡚ヲ⣽࡟᳨ウࡍࡿࡓࡵ㸪࢚ࢱ ᭦࡟㸪άᛶⅬ࡜࡞ࡿ Pt ࡢᢸᣢ㔞ࡘ࠸᳨࡚ウࡍࡿࡓࡵ㸪㔠ࣀ࣮ࣝ⃰ᗘ࡟ᑐࡍࡿ⏕ᡂຠ⋡౫Ꮡᛶࢆồࡵࡓ㸬ࡑࡢ⤖ᯝࢆᒓᢸᣢ㔞ࡢ౫Ꮡᛶࢆ ᐃࡋࡓ㸬ࡑࡢ⤖ᯝࢆᅗ 5 ࡟♧ࡍ㸬ᅗ

ᅗ 7 ࡟♧ࡍ㸬࡞࠾⏕ᡂຠ⋡ࡢ⟬ฟ᪉ἲࡣ㸪๓⠇ࡢỈࡢ㟁Ẽ5 ࡟♧ࡍ㏻ࡾ㸪ᮏ⣔࡟࠾࠸࡚ࡣᢸᣢ㔠ᒓ㔞࡟౫Ꮡࡏࡎ࢞ࢫศゎ࡜ྠᵝࡢィ⟬ᘧࢆ⏝࠸ࡓ㸬ࡀቑຍࡍࡿࡓࡵ㸪࢞ࢫⓎ⏕㔞࠾ࡼࡧ⏕ᡂຠ⋡ࡣྥୖࡍࡿࡣࡎ࡛࠶ࡿ㸬ࡇࡢཎᅉࢆ᳨ウࡍࡿࡓࡵ࡟㸪ᢸᣢ㔠ᒓ⢏Ꮚࡢ
SEM ほᐹࢆᐇ᪋ࡋࡓ㸬ࡑࡢ⤖ᯝ㸪ᢸᣢࡋࡓⓑ㔠ࡀ Al2O3࣮࣎ࣝୖ࡟඲యⓗ࡟ⷧࡃそ࠺ࡼ࠺࡟Ꮡᅾࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓ㸬ᮏࢩࢫࢸ࣒ࡢ≺࠸ࡀ㐩ᡂࡉࢀࡿࡓࡵ࡟ࡣ㸪ᅗ 1࡟♧ࡍࡼ࠺࡞㔠ᒓ⢏Ꮚࡀ༑ศ࡟ᙧᡂࡉࢀ࡚࠸ࡿᚲせࡀ࠶ࡿ㸬ࡋ࠿ࡋ࡞ࡀࡽᮏㄪ〇ἲ࡛ࡣ㸪ᢸᣢ㔠ᒓ⢏Ꮚࡀ኱ࡁ࡞ 1ࡘࡢ㔠ᒓ⢏Ꮚ࡜ࡋ࡚Ꮡᅾࡋ࡚࠸ࡓࡓࡵ㸪ᢸᣢ㔠ᒓ㔞ቑຍ࡟క࠺⏕ᡂ㔞ቑຍࡀ㐩ᡂࡉࢀࡓ࠿ࡗࡓ࡜⪃࠼ࡽࢀࡿ㸬᭦࡟⏕ᡂ㔞ࢆቑ኱ࡍࡿࡓࡵ࡟ࡣ㸪ᮏࢩࢫࢸ࣒ࡢ≺࠸࡟ἢࡗࡓᢸᣢ
㔠ᒓ⢏Ꮚࢆㄪ〇ࡍࡿᡭἲࢆ᳨ウࡋ࡞ࡃ࡚ࡣ࡞ࡽ࡞࠸㸬

Gas formation rate / mL min -1

ࢭࢫࡢ≺࠸ࢆ⪃៖ࡍࡿ࡜㸪ᢸᣢ㔠ᒓ㔞ࡢቑ኱࡟క࠸άᛶⅬ80

0.6

NaOH (Base)HClO4 (Acid)

0.560

0.40.3

400.2

Current / mAⓎ⏕㔞࠾ࡼࡧ⏕ᡂຠ⋡ࡣ୍ᐃ࡜࡞ࡗࡓ㸬ᅗ 1 ࡟♧ࡍᮏࣉࣟ

200.1
00204060

80

Ethanol concentration / wt%0100ᅗ 6 ࢚ࢱࣀ࣮ࣝ㟁ゎ㓟໬࡟࠾ࡅࡿ࢚ࢱࣀ࣮ࣝ⃰ᗘࡀ࢞ࢫⓎ⏕㔞࠾ࡼࡧ㟁ὶ࡟ཬࡰࡍᙳ㡪

42

沼津工業高等専門学校研究報告

第 52 号௨ୖࡢ⤖ᯝࡼࡾ㸪ᮏࢩࢫࢸ࣒ࡣᖖ 㥑ື࡛㧗࠸⏕ᡂຠ⋡ࢆ᭷ࡍࡿỈࡢ㟁Ẽศゎ࠾ࡼࡧ࢚ࢱࣀ࣮ࣝࡢ㟁ゎ㓟໬࡟ࡼࡿ160

Efficiency / %Ỉ⣲〇㐀ࢩࢫࢸ࣒࡜ࡋ࡚᭷ຠ࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓ㸬
120

䠑䠊ཧ⪃ᩥ⊩

80

NaOH (Base)HClO (Acid)40[1] H. Hitmi, E.M. Belgsir, J.M. Leger, C. Lamy, R.O. Lezna,
Electrochemica Acta, 39 (1994) 407.

4[2] A. Marafee, C. Liu, G. Xu, R. Mallinson, L. Lobban, Ind. Eng.
0020

4060

80

Ethanol concentration / wt%100ᅗ 7 ࢚ࢱࣀ࣮ࣝ㟁ゎ㓟໬࡟࠾ࡅࡿ⏕ᡂຠ⋡ࡢ⃰ᗘ౫ᏑᛶChem. Res., 36 (1997) 632.
[3] K. Oshima, T. Shinagawa, Y. Sekine, J. Jpn. Petrol. Inst., 56(2013) 11.
[4] G.C. Vayenas, S. Bebelis, S. Ladas, Nature, 343 (1990) 625

 㟁ὶ್ῶᑡ࡟క࠺࢞ࢫⓎ⏕㔞ࡢῶᑡࡀぢࡽࢀ࡞࠿ࡗࡓ࢚ࢱࣀ࣮ࣝ⃰ᗘ 40 wt%࠾ࡼࡧ 60 wt%࡟࠾࠸࡚ࡣ㸪ᅗ 7 ࡟♧ࡍ㏻ࡾ㸪Ỉࡢ㟁Ẽศゎ(࢚ࢱࣀ࣮ࣝ⃰ᗘ 0 wt%)࡜ẚ㍑ࡋ
࡚⏕ᡂຠ⋡ࡀྥୖࡋࡓ㸬ࡇࡢ⤖ᯝ࠿ࡽỈࡢ㟁Ẽ໬Ꮫ཯ᛂ࡟ຍ࠼࡚㸪࢚ࢱࣀ࣮ࣝ㟁Ẽ໬Ꮫ཯ᛂࡶ㐍⾜ࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓ㸬࢚ࢱࣀ࣮ࣝࡢ㟁Ẽ໬Ꮫ཯ᛂ࡜ࡋ࡚ࡣ㸪㟁ゎ㓟໬࡟ࡼࡿ࢔ࢭࢺ࢔ࣝࢹࣄࢻ⏕ᡂࡀ⪃࠼ࡽࢀࡿ㸬
CH3CH2OH Ѝ CH3CHO + H2(ᘧ 6)ࡇࡢ཯ᛂࡀ㐍⾜ࡋ࡚࠸ࡿሙྜ㸪Ỉ⣲ࡢࡳࡀ⏕ᡂࡍࡿࡓࡵ㸪⏕ᡂ≀ࡢỈ⣲๭ྜࡀቑ኱ࡍࡿࡣࡎ࡛࠶ࡿ㸬ᐇ㝿㸪GC-TCD࡟ࡼࡿ⏕ᡂ࢞ࢫࡢ⤌ᡂศᯒࡢ⤖ᯝ㸪Ỉ⣲ࡀ㓟⣲࡟ᑐࡋ࡚ 2ಸ௨ୖ⏕ᡂࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓ㸬ࡇࡢ⤖ᯝࡼࡾ㸪ᮏࢩࢫࢸ࣒ࢆ⏝࠸ࡿࡇ࡜࡛ᾮ┦࢚ࢱࣀ࣮ࣝࡢ┤᥋㌿᥮ࡀ㐩ᡂࡉࢀ㸪࢚ࢱࣀ࣮ࣝ࠿ࡽỈ⣲ࢆ〇㐀࡛ࡁࡿࡇ࡜ࡀ♧ࡉࢀࡓ㸬࡞࠾᭦࡞ࡿỈ⣲⏕ᡂ㔞ࡢቑ኱ࢆ㐩ᡂࡍࡿࡓࡵ࡟ࡣ㸪๓⠇ࡢỈࡢ㟁Ẽศゎࡢ⤖ᯝ࡜ྠᵝ࡟㸪ᮏࢩࢫࢸ࣒࠾ࡼࡧ཯ᛂ࡟㐺ࡋࡓ඘ሸ⢏Ꮚࢆタィ࣭ㄪ〇ࡍࡿࡇ࡜ࡀ㔜せ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿ㸬䠐䠊⤖㻌 ㄽ 㟁ᴟ㛫࡟ᢸᣢ㔠ᒓ⢏Ꮚࢆ඘ሸࡋࡓࢩࢫࢸ࣒ࢆᵓ⠏ࡋ㸪
Pt/Al2O3 ୖ࡛Ỉࡢ㟁Ẽศゎ࠾ࡼࡧ࢚ࢱࣀ࣮ࣝࡢ㟁ゎ㓟໬ࢆ⾜ࡗࡓ⤖ᯝ㸪㟁Ẽ໬Ꮫ㔞ㄽࡢไ⣙ࢆぢ࠿ࡅᅇ㑊ࡋࡓ㧗࠸࢞ࢫⓎ⏕㔞ࢆ㐩ᡂࡋࡓ㸬Ỉࡢ㟁Ẽศゎࡢ⤖ᯝࡼࡾ㸪༳ຍ㟁ᅽ࠾ࡼࡧ඘ሸ⢏Ꮚᩘࡀ࢞ࢫⓎ⏕㔞࡟኱ࡁࡃᐤ୚ࡋ㸪㟁Ẽ໬Ꮫ㔞ㄽ࡟ᚑ࠺࢞ࢫⓎ⏕㔞ࢆ 100 %࡜ࡍࡿ࡜㸪ᮏࢩࢫࢸ࣒࡛ࡣ
᭱኱࡛ 200 %ࢆୖᅇࡿ⏕ᡂຠ⋡ࢆ㐩ᡂࡋࡓ㸬ࡲࡓ࢚ࢱࣀ࣮ࣝỈ⁐ᾮࢆཎᩱࡢ⏝࠸ࡓሙྜ㸪Ỉࡢ㟁Ẽศゎ࡟ຍ࠼㸪࢚ࢱࣀ࣮ࣝࡢ㟁ゎ㓟໬࡟ࡼࡗ࡚Ỉ⣲Ⓨ⏕㔞ࡀቑ኱ࡋࡓ㸬ཎᩱ࡜
ࡋ࡚ࡣ 60 wt%࢚ࢱࣀ࣮ࣝỈ⁐ᾮ࡛᭱ࡶ㧗࠸⏕ᡂຠ⋡ࢆ♧ࡋ㸪㟁ゎ᮲௳࡜ࡋ࡚ࡣሷᇶᛶࡀ᭷ຠ࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓ㸬

[5] S. Bebelis, G.C. Vayenas, J. Catal., 118 (1989) 125.