A Proposal for Reformulation of Heavy Fuel Oil through Sonochemistry and Phase-Equilibrium Theory

A Proposal for Reformulation of Heavy Fuel Oil through Sonochemistry and Phase-Equilibrium Theory

Kazuo UEDA*, Shunichi HANADA**, Koichi TANAHASHI*,Jiro SENDA*** and Yoshiaki WATANABE****

(Received February 1, 2007)

In this study, authors aim to convert heavy fuel oils or solid fuels into lighter liquid fuel with high quality and propose new fuel reformulation method through sonochemistry approach and Phase-Equilibrium theory approach. The origen of sonochemistry is acoustic cavitation; nucleation, growth, and violent collapse. Here, instantaneous hot spot region with local temperature of several thousand Kelvin and pressure of several hundred Mega-Pascal is generated by the cavitaion bubble collapse. The other approach is phase equilibrium for pure or multi-component fuel. The vapor characteristics of heavy fuel oil mixed with lower boiling point fuel is improved by this approach. In this paper, the application of sonochemistry into heavy fuel or mixed fuel with two-component is reported.

-G[YQTFU Cavitation Bubble, Heavy Fuel Oil, Mixed Fuel, Sonochemistry, New Fuel Reformulation Method

ࠠ࡯ࡢ࡯࠼ࠠࡖࡆ࠹࡯࡚ࠪࡦ᳇ᵃ㧘㊀⾰♽Άᢱ㧘ᷙวΆᢱ㧘࠰ࡁࠤࡒࠬ࠻࡝࡯㧘ᣂΆᢱᡷ⾰ᚻᴺ

㊀⾰♽Άᢱߩ⋧ᐔⴧℂ⺰࡮࠰ࡁࠤࡒࠬ࠻࡝࡯૬↪ဳΆᢱᡷ⾰ᚻᴺߩឭ᩺

਄↰ ৻↢࡮⧎↰ ବ৻࡮᫜ᯅ ᤩ৻࡮ජ↰ ੑ㇢࡮ᷰㄝ ᅢ┨

㧚ߪߓ߼ߦ

⍹ᴤᨗᷢ߿ⅣႺ଻ోߩⷰὐ߆ࠄ㧘⍹ᴤઍᦧࠛࡀ࡞ࠡ

ߩ㐿⊒^(1)-(3)ߪ⃻࿷ߩ㊀ⷐ⺖㗴ߩ৻ߟߢߪ޽ࠆ߽ߩߩ㧘

㒢ࠄࠇߚ⍹ᴤ⾗Ḯࠍ᦭ല೑↪ߔࠆߎߣ߽㊀ⷐߢ޽ࠆ㧚

⍹ᴤ♖⵾ᤨߦ߅޿ߡ೽↢ᚑߐࠇࠆ㊀ᴤ߿ࠕࠬࡈࠔ࡞

࠻ߪ㧘ߘߩഠᖡߥᕈ⁁᡿ߦࠛࡀ࡞ࠡḮߣߒߡߩ㔛ⷐ߇

ᷫዋߒ㧘૛೾௑ะߦ޽ࠆ㧚߹ߚ㧘ߘߩઁߦ߽㊀ᴤߣห

⒟ᐲ߹ߚߪߘࠇࠃࠅഠᖡߥᕈ⁁ࠍ᦭ߔࠆࠝࠗ࡞ࠨࡦ

࠼߿࠲࡯࡞ࠪࠚ࡞ߥߤߩ⾗Ḯ߇਎⇇ਛߦၒ⬿ߒߡ߅ ࠅ㧘ߘߩၒ⬿㊂ߪ⍹ᴤ♽Άᢱߩ3.5୚ߦ߽਄ࠆߣ⸒ࠊ ࠇߡ޿ࠆ㧚ߎࠇࠄ㊀⾰♽Άᢱߪ᦭ല೑↪ߩⷰὐ߆ࠄ㧘

㔛ⷐ߇ᄙ޿シ⾰ᶧ૕Άᢱ߳ߩᡷ⾰߇᦭ᦸⷞߐࠇࠆ㧚 ߘߎߢᧄ⎇ⓥߢߪ㧘㊀⾰♽Άᢱߩシ⾰ᶧ૕Άᢱ߳ߩ ᡷ⾰ࠍ⋡⊛ߣߒߚ⋧ᐔⴧℂ⺰࡮࠰ࡁࠤࡒࠬ࠻࡝࡯૬↪

ဳΆᢱᡷ⾰ᚻᴺࠍឭ᩺ߒߡ޿ࠆ㧚⋧ᐔⴧℂ⺰ߣߪ㧘ൻ ቇᾲജቇߦࠃࠅⷙቯߐࠇࠆṁᶧߩ⋧ᄌൻߦ㑐ߔࠆℂ

⺰ߢ޽ࠆ㧚଀߃߫㧘㜞ᴣὐΆᢱߦૐᴣὐΆᢱࠍᷙวߔ ࠆߣ㧘㜞ᴣὐΆᢱߩ⫳⊒․ᕈߪ⋧ᐔⴧℂ⺰ߦࠃࠅะ਄

ߒ㧘ߐࠄߦ㧘☼ᕈ߿⴫㕙ᒛജߥߤߩャㅍ‛ᕈ߽ᡷༀߔ ࠆ⁽⁴⁾㧚৻ᣇ㧘࠰ࡁࠤࡒࠬ࠻࡝࡯ߣߪ㧘⿥㖸ᵄࠠࡖࡆ࠹

࡯࡚ࠪࡦߩൻቇ૞↪ࠍᗧ๧ߒ⁽⁵⁾㧘ߎࠇࠍΆᢱ߳ㆡ↪ߔ ࠆߣ㧘Άᢱਛߩ὇⚛⚿ว߇㐿ⵚߒ㧘὇⚛ᢙߩૐ޿ૐಽ

* Graduate Student, Department of Mechanical Engineering, Doshisha University, Kyoto Telephone: +81-774-65-7742, FAX: +81-774-65-7743, E-mail: [email protected]

** TOYOTA MOTOR Co.,Ltd.

*** Department of Mechanical Engineering, Doshisha University, Kyoto Telephone/FAX: +81-774-65-6405

**** Department of Electrical Engineering, Doshisha University, Kyoto Telephone/FAX: +81-774-65-6268

ሶ㊂ᚑಽ߳ߣᡷ⾰ߔࠆ㧚ߣߎࠈ߇㧘࠰ࡁࠤࡒࠬ࠻࡝࡯

ߦࠃࠆΆᢱᡷ⾰ߩലᨐߪ㧘ṁᶧߩ⫳᳇࿶ߦଐሽߔࠆߣ ᜰ៰ߐࠇߡ߅ࠅ^(6-7)㧘ૐ㘻๺⫳᳇࿶ߢ޽ࠆ㊀⾰♽Άᢱߢ ߪᡷ⾰ലᨐ߇ૐ޿㧚ߘߎߢ㧘వㅀߩ⋧ᐔⴧℂ⺰ߦၮߠ ߈㧘㊀⾰♽ΆᢱߦૐᴣὐΆᢱࠍᷙวߒ㧘⫳⊒․ᕈߩะ

਄ߣ޿߁ᷙวΆᢱߩ․ᕈࠍ೑↪ߔࠆߎߣࠍ⹜ߺࠆ㧚 ᧄ⺰ᢥߢߪ㧘⒳ޘߩනᚑಽΆᢱ߅ࠃ߮ߘࠇࠄߩᷙว Άᢱࠍଏ⹜Άᢱߣߒ㧘᳇ᵃ᜼േߩⷰኤ߅ࠃ߮⿥㖸ᵄΆ ᢱᡷ⾰ࠍⴕߥߞߚ㧚ߘߒߡ㧘නᚑಽΆᢱ߅ࠃ߮ᷙวΆ ᢱ෺ᣇߩ࠰ࡁࠤࡒࠬ࠻࡝࡯ߦࠃࠆΆᢱᡷ⾰ߩലᨐߦ ߟ޿ߡᬌ⸽ߒߚ㧚

㧚Άᢱᡷ⾰ᚻᴺߩឭ᩺

ᧄ⎇ⓥߢឭ᩺ߔࠆΆᢱᡷ⾰ᚻᴺߩⷐ⚂ࠍએਅߦ⸥

ߔ㧚

ૐᴣὐΆᢱᷙวߦࠃࠆ‛ℂ․ᕈߩᡷༀ

‛ᕈ߇⇣ߥࠆ⋧੕ṁ⸃น⢻ߥΆᢱห჻ࠍᷙวߔࠆ ߣ㧘ಽሶ㑆⋧੕૞↪ߦࠃࠅ㧘ฦ‛ℂ․ᕈ߇ᄌൻߔࠆ㧚 ߘߩ৻଀ߣߒߡ㧘ᷙวΆᢱߩ⫳⊒․ᕈߪవㅀߩ⋧ᐔⴧ ℂ⺰ߦࠃࠅⷙቯߐࠇ㧘࿑1ߦ␜ߔࠃ߁ߦ෺ᣇߩΆᢱߩ

᳇ᶧ⋧߇ᷙ࿷ߔࠆੑ⋧㗔ၞࠍᒻᚑߔࠆ㧚ߎࠇߦࠃࠅ㧘 㜞ᴣὐΆᢱߢ޽ࠆ㊀⾰♽Άᢱߩ⫳⊒․ᕈߪᡷༀߔࠆ㧚 ߥ߅㧘ᧄ⺰ᢥߢߪߎࠇએ㒠㧘ᷙวΆᢱߩ⫳᳇࿶ߪ㘻๺

ᶧ૕ᦛ✢਄ߩ࿶ജߣߒߡ޿ࠆ㧚

࠰ࡁࠤࡒࠬ࠻࡝࡯ߦࠃࠆΆᢱᡷ⾰

࠰ࡁࠤࡒࠬ࠻࡝࡯ߣߪ㧘⿥㖸ᵄᾖ኿ߦࠃࠅ↢ᚑߒߚ

ࠠࡖࡆ࠹࡯࡚ࠪࡦ᳇ᵃߩ፣უ⃻⽎߇ᒁ߈⿠ߎߔൻቇ

෻ᔕࠍᜰߔ㧚଀߃߫㧘Άᢱߥߤߩṁᶧਛߦ㜞ᒝᐲߥ⿥

㖸ᵄࠍᾖ኿ߔࠆߣ㧘࿑2ߦ␜ߔࠃ߁ߦ↢ߓߚ❑ᵄߦࠃ ࠅ๟ᦼ⊛ߦ࿶ജᄌേ߇↢ߓࠆ㧚ߎߩ࿶ജ߇ṁᶧߩ㘻๺

⫳᳇࿶એਅߦߥࠆߣ㧘ṁሽ᳇૕ߥߤࠍᩭߦࠠࡖࡆ࠹࡯

࡚ࠪࡦ᳇ᵃ߇↢ᚑߔࠆ㧚ߎߩ᳇ᵃߪ㧘๟࿐ߩ࿶ജᄌേ

ߦᔕߓߡ⤘ᒛ࡮෼❗ࠍ➅ࠅ㄰ߒ㧘߿߇ߡ޽ࠆᄢ߈ߐߦ

㆐ߔࠆߣᕆỗߦ፣უߔࠆ㧚ߎߩ፣უߩ㓙㧘᳇ᵃߪḰᢿ ᾲ࿶❗ߐࠇ㧘ߘߩౝㇱߪ 5000[K]㧘100[MPa]એ਄ߩ㜞

᷷࡮㜞࿶႐߇ᒻᚑߐࠇࠆ⁽⁸⁾㧚ߎߩ፣უ⃻⽎ࠍΆᢱ߳ㆡ

↪ߔࠆߣ㧘ᾲಽ⸃෻ᔕ߇↢ߓ㧘὇⚛⚿ว߇㐿ⵚߔࠆ㧚 ߘߩ⚿ᨐ㧘Άᢱߪ὇⚛ᢙߩૐ޿ૐಽሶ㊂ᚑಽ߳ߣᡷ⾰

ߐࠇࠆ㧚߹ߚޔ㊀⾰♽Άᢱਛߦᄙߊ฽᦭ߐࠇࠆ⓸⚛߿

⧐㚅ᣖᚑಽࠍ㒰෰ߔࠆߎߣ߽น⢻ߢ޽ࠅ⁽⁹⁾㧘࠰ࡁࠤࡒ

ࠬ࠻࡝࡯ߪΆᢱᡷ⾰ߦ߅޿ߡ᦭ലߥᚻᴺߢ޽ࠆ㧚

GasPhase Region Dew Point

Curve Saturated Vapor

Curve of Low

B.P. Solution Two Phase Region LiquidPhase Region

Bubble Point curve Critical Point

Pressure

Temperature Critical Pressure

B.P. = Boiling Point Saturated Vapor

Curve of High B.P. Solution

Fig. 1 Pressure-Temperature diagram of two-component fuel and pure fuel

Ultrasound Wave

Evaporation of Fuel

Nucleation Growth Collapse

Sound Pressure P

t

Ambient Pressure Vapor Pressure

Rebound Ultrasound Wave

Evaporation of Fuel

Nucleation Growth Collapse

Sound Pressure P

t

Ambient Pressure Vapor Pressure

Rebound

Fig. 2 Acoustic cavitation growth process from nucleation to collapse

Temperature

Pressure

(b) Sound Pressure Time Mixed Fuel

Low Boiling

Point Fuel Bubble

Collapse

Rebound Area Growth

Area

Improvement of Bubble growth time High Boiling

Point Fuel

Fig. 3 Concept of applying of sonochemistry into fuel with two-component

ૐᴣὐΆᢱᷙวߦࠃࠆ࠰ࡁࠤࡒࠞ࡞෻ᔕߩ㜞ല

₸ൻ

਄ㅀߒߚ᳇ᶧᐔⴧߩ᭎ᔨࠍ೑↪ߔࠆߣ㧘࿑3ߦ␜ߔ ࠃ߁ߦ㧘⿥㖸ᵄߩ㖸࿶߿๟ᵄᢙࠍᄌൻߔࠆߎߣߥߊ㧘

޽ࠆ╬ߒ޿᷷ᐲߦߡᶧ૕ߩ࿶ജ߇ṁᶧߩ⫳᳇࿶એਅ ߣߥࠆ⽶࿶ᦼ㑆ࠍᡷༀߔࠆߎߣ߇น⢻ߣߥࠆ㧚⽶࿶ᦼ 㑆ߪ᳇ᵃߩ↢ᚑ㧘ᚑ㐳ߦᓇ㗀ࠍਈ߃ࠆߎߣ߆ࠄ㧘࠰ࡁ

Table 1 Pure fuel properties

1.450 1.354 1.341 1.340 1.30 Specific heat ratio N

4720 20.9 414 684 100 C7H16

0.658 2.15 35.7 278K

0.117 300K

0.311 14.2 35.8 344 308K

0.0460 3.45 9.74 120 293K

27.6 26.1 25.0 Surface Tension^* 23.4

V·10³[N/m]

3450 1880 1490 Viscosity^*Kl[PPa·s] 943

323K 867 111 48.6 1.59

773 226 C16H34

Vapor Pressure

Pv[Pa]

739 142 C10H22

756 184 C13H28

749 170 C12H26

Density^* Ul[kg/m³] Molecular Weight

Test Fuel

1.450 1.354 1.341 1.340 1.30 Specific heat ratio N

4720 20.9 414 684 100 C7H16

0.658 2.15 35.7 278K

0.117 300K

0.311 14.2 35.8 344 308K

0.0460 3.45 9.74 120 293K

27.6 26.1 25.0 Surface Tension^* 23.4

V·10³[N/m]

3450 1880 1490 Viscosity^*Kl[PPa·s] 943

323K 867 111 48.6 1.59

773 226 C16H34

Vapor Pressure

Pv[Pa]

739 142 C10H22

756 184 C13H28

749 170 C12H26

Density^* Ul[kg/m³] Molecular Weight

Test Fuel

*at 293K, 0.1MPa

Table 2 C16/C10 fuel properties

1731 27.00 42.56 769 1.385

0.6

2203 28.16 20.27 739 1.406

0.4

1312 25.96 72.95 756 1.365

0.8

3214 30.43 0.61

792 1.445

0.05

3049 30.08 2.03 791 1.439

0.1

2892 29.75 3.8 790 1.433

0.15

2742 29.42 6.08

788 1.428

0.2

Vapor Pressure Pv[Pa]

Density U_l[Kg/m³] Specific heat

ratio N

Viscosity K_l䊶10⁶[Pa䊶s]

Surface Tension V_l䊶10³[N/m]

Mole Fraction of C10H22

1731 27.00 42.56 769 1.385

0.6

2203 28.16 20.27 739 1.406

0.4

1312 25.96 72.95 756 1.365

0.8

3214 30.43 0.61

792 1.445

0.05

3049 30.08 2.03 791 1.439

0.1

2892 29.75 3.8 790 1.433

0.15

2742 29.42 6.08

788 1.428

0.2

Vapor Pressure Pv[Pa]

Density U_l[Kg/m³] Specific heat

ratio N

Viscosity K_l䊶10⁶[Pa䊶s]

Surface Tension V_l䊶10³[N/m]

Mole Fraction of C10H22

Table 3 C16/C7 fuel properties

2454 28.66 0.71 785 1.41 0.2

1743 26.54 1.52

772 1.37 0.4

1194 24.42 2.53 753 1.35 0.6

758 22.31

3.65 725 1.32 0.8

Vapor Pressure*P_v[kPa]

Density*U[Kg/m³] Specific heat ratio N

Viscosity*K䊶10⁶[Pa䊶s]

Surface Tension**

V䊶10³[N/m]

Mole Fraction of C₇H₁₆

2454 28.66 0.71 785 1.41 0.2

1743 26.54 1.52

772 1.37 0.4

1194 24.42 2.53 753 1.35 0.6

758 22.31

3.65 725 1.32 0.8

Vapor Pressure*P_v[kPa]

Density*U[Kg/m³] Specific heat ratio N

Viscosity*K䊶10⁶[Pa䊶s]

Surface Tension**

V䊶10³[N/m]

Mole Fraction of C₇H₁₆

Table 4 Experimental conditions for photographing of cavitation behavior

0.101 Ambient Pressure Pb[MPa]

Mole Fraction of C₁₆H₃₄for each Mixed Fuel

C₁₆H₃₄/C₁₀H₂₂, C₁₆H₃₄/C₇H₁₆ Mixed Fuel

Pure Fuel

293 Ambient Temperature Tamb[K]

31 , 62 , 93, 124 Probe Amplitude Gprove[Pm]

13 Probe Diameter dprobe[mm]

20 Ultrasonic Frequency f[kHz]

150 Test Fuel Volume Vfuel[cm³]

0.2, 0.4, 0.6, 0.8 C₇H₁₆, C₁₀H₂₂, C₁₃H₂₈, C₁₆H₃₄ Test Fuel

0.101 Ambient Pressure Pb[MPa]

Mole Fraction of C₁₆H₃₄for each Mixed Fuel

C₁₆H₃₄/C₁₀H₂₂, C₁₆H₃₄/C₇H₁₆ Mixed Fuel

Pure Fuel

293 Ambient Temperature Tamb[K]

31 , 62 , 93, 124 Probe Amplitude Gprove[Pm]

13 Probe Diameter dprobe[mm]

20 Ultrasonic Frequency f[kHz]

150 Test Fuel Volume Vfuel[cm³]

0.2, 0.4, 0.6, 0.8 C₇H₁₆, C₁₀H₂₂, C₁₃H₂₈, C₁₆H₃₄ Test Fuel

ࠤࡒࠞ࡞෻ᔕߩലᨐࠍᡷༀߢ߈ࠆ㧚㊀⾰㊂♽Άᢱߢߪ㧘

᳇ᵃߩ↢ᚑ㊂߿ᚑ㐳ഀว߇ૐ޿ߚ߼㧘⫳᳇࿶ߩะ਄ߣ

޿߁ᷙวΆᢱߩ․ᕈࠍ೑↪ߔࠆߎߣߢ㧘㜞ല₸ߥ෻ᔕ ߇ᦼᓙߢ߈ࠆ㧚߹ߚ㧘ᧄᚻᴺߩࠕࡊࡠ࡯࠴ߢߪ㧘㜞ല

₸ߥ෻ᔕߩઁ㧘หᤨߦඨ࿕૕⁁ߢ޽ࠆ㊀⾰♽Άᢱߩಝ

࿕ὐ㒠ਅ߇↢ߓ㧘ૐ᷷ᵹേᕈߩะ਄ലᨐ߽ᓧࠄࠇࠆ㧚

㧚ታ㛎ⵝ⟎㧘ᣇᴺ߅ࠃ߮᧦ઙ

ଏ⹜Άᢱ

ᧄ⎇ⓥߢ૶↪ߒߚଏ⹜Άᢱߪn-ࡋࡊ࠲ࡦ㧘n-࠺ࠞࡦ㧘

n-࠼࠺ࠞࡦ㧘n-࠻࡝࠺ࠞࡦ㧘n-ࡋࠠࠨ࠺ࠞࡦߩ 5 ⒳㘃

ߩනᚑಽΆᢱߣ㧘ૐ㘻๺⫳᳇࿶Άᢱߢ޽ࠆn-ࡋࠠࠨ࠺

ࠞࡦࠍࡌ࡯ࠬߦ㧘Ყセ⊛㘻๺⫳᳇࿶߇㜞޿n-࠺ࠞࡦ߹

ߚߪn-ࡋࡊ࠲ࡦࠍᷙวߒߚΆᢱ(એਅ㧘C16/C10߅ࠃ߮

C16/C7ߣ⴫⸥ߔࠆ)ߢ޽ࠆ㧚ߎࠇࠄΆᢱߩ‛ᕈࠍ⴫1㧘

2㧘3ߦߘࠇߙࠇ␜ߔ㧚නᚑಽΆᢱߪߘߩ⒳㘃ߣ㔓࿐᳇

᷷ᐲࠍ㧘ᷙวΆᢱߪᷙวഀว߅ࠃ߮⚵ᚑࠍߘࠇߙࠇᄌ ᦝߔࠆߎߣߢ㧘છᗧߩ‛ℂ․ᕈࠍᜬߟΆᢱߣߒߚ㧚ߥ ߅㧘C16/C10ߩᷙวഀวߪ࠺ࠞࡦߩࡕ࡞ಽ₸XC10=0.05㧘 0.1㧘0.15㧘0.2㧘0.4㧘0.6㧘0.8 ߣߒ㧘C16/C7 ߩᷙวഀ

วߪࡋࡊ࠲ࡦߩࡕ࡞ಽ₸XC7=0.2㧘0.4㧘0.6㧘0.8ߣߒߚ㧚

߹ߚ㧘ᷙวΆᢱߩ᷷ᐲߪ293[K]৻ቯߢ޽ࠆ㧚 ᳇ᵃ⟲᜼േⷰኤߩታ㛎ᣇᴺ߅ࠃ߮᧦ઙ

නᚑಽ㧘ᷙวΆᢱ෺ᣇߦ߅ߌࠆࠠࡖࡆ࠹࡯࡚ࠪࡦ᳇

ᵃ⟲ߩ᜼േࠍᛠីߔࠆߚ߼ߦ㧘ࠠࡖࡆ࠹࡯࡚ࠪࡦ᳇ᵃ ߩ⢛᥊శ᠟ᓇࠍⴕߥߞߚ㧚శቇ♽ߩ᭎⇛ࠍ࿑4ߦ㧘ታ 㛎᧦ઙࠍ⴫4ߦߘࠇߙࠇ␜ߔ㧚⿥㖸ᵄⵝ⟎ߦߪนᄌ಴

ജဳ⿥㖸ᵄࡎࡕࠫ࠽ࠗࠩ࡯(SONICS & MATERIALS VC750㧘⊒ᝄ๟ᵄᢙ㧦20[kHz])ࠍ૶↪ߒߚ㧚శḮߣߒ ߡࡂࡠࠥࡦ࡜ࡦࡊࠍ㧘᠟ᓇ♽ߦߪ㜞ㅦᐲࡆ࠺ࠝࠞࡔ࡜

(PHOTRON㧘FASTCAM-APX RS 250K㧘᠟ᓇㅦᐲ㧦 10000[fps])ࠍߘࠇߙࠇ↪޿ߚ㧚ଏ⹜Άᢱࠍࠕࠢ࡝࡞ߢ

૞ᚑߒߚኈེౝ(60[mm]˜60[mm]˜105[mm]㧘378[cc]) ߦలႯߒ㧘ߘߩኈེࠍਛᔃߦశḮߣࠞࡔ࡜ࠍߘࠇߙࠇ

෻ኻߩ૏⟎ߦߥࠆࠃ߁ߦ⸳⟎ߒ㧘⢛᥊శ᠟ᓇࠍⴕߥߞ ߚ㧚ߥ߅㧘᠟ᓇ㗔ၞߪ㧘ᝄേሶవ┵߆ࠄ㋦⋥ᣇะߦ

59[mm]㧘ᝄേሶߩਛᔃゲ߆ࠄඨᓘᣇะߦ12.25[mm]ߢ

޽ࠆ㧚߹ߚ㧘ᤨೞtauiߣߪ㧘↹௝਄ߦߡᦨೋߦࠠࡖࡆ࠹

࡯࡚ࠪࡦ᳇ᵃࠍ⏕⹺ߒߡ߆ࠄߩᤨ㑆ߢ޽ࠆ㧚ߥ߅㧘ᝄ

േሶߩᝄ᏷G_probeࠍ31㧘62㧘93㧘124[Pm]ߣᄌ߃ߚ㧚

⿥㖸ᵄΆᢱᡷ⾰ߩታ㛎ᣇᴺ߅ࠃ߮᧦ઙ

නᚑಽ㧘ᷙวΆᢱߘࠇߙࠇߦ߅ߌࠆߘߩࠤࡒࠬ࠻࡝

࡯ߦࠃࠆΆᢱᡷ⾰ߩലᨐࠍᛠីߔࠆߚ߼ߦ㧘⿥㖸ᵄಽ

⸃ታ㛎ࠍⴕߥߞߚ㧚ታ㛎ⵝ⟎ߩ᭎⇛ࠍ࿑5ߦ㧘ታ㛎᧦

ઙࠍ⴫5ߦߘࠇߙࠇ␜ߔ㧚⿥㖸ᵄ⊒↢ⵝ⟎߆ࠄᝄേሶ

߳㔚ജࠍଏ⛎ߒ㧘ṁᶧߦ⋥ធ⿥㖸ᵄࠍᾖ኿ߔࠆ㧚ߘߩ 㓙㧘ࠟ࡜ࠬ⵾ߩኈེౝ(⋥ᓘ㧦22[mm]㧘㜞ߐ㧦83.5[mm]㧘

31.7[cc])ߦ㧘੍߼ᲧᾲᲧ߇㜞޿ࠕ࡞ࠧࡦ(એਅ㧘Arߣ⴫

⸥ߔࠆ)ࠍࡃࡉ࡝ࡦࠣߒߚΆᢱࠍኽ౉ߒ㧘ኒ㐽ߦߒߚ㧚 ߎߎߢ㧘ࡃࡉ࡝ࡦࠣߦࠃࠅΆᢱߩṁሽ᳇૕ߪࠕ࡞ࠧࡦ ߣߥࠅ㧘ߎߩലᨐࠍ⺞ߴࠆߚ߼ߦ㧘⓸⚛(એਅ㧘N2ߣ⴫

⸥ߔࠆ)ࠍࡃࡉ࡝ࡦࠣߒߚΆᢱߣᲧセߒߚ㧚߹ߚ㧘ࡃࡉ

࡝ࡦࠣߪᵹ㊂100[l/min]ߢ30ಽ㑆ⴕߥߞߚ㧚ߘߒߡ㧘 3ಽᲤߦ㧘ᝄേሶઃㄭߩΆᢱࠍ1[Pl]ࠨࡦࡊ࡞ߣߒߡណ ขߒ㧘ࠟࠬࠢࡠࡑ࠻ࠣ࡜ࡈࠍ↪޿ߡᚑಽಽᨆࠍⴕߥߞ ߚ㧚ߥ߅㧘⢛᥊శ᠟ᓇห᭽㧘⿥㖸ᵄᝄേሶߩᝄ᏷ࠍ31㧘

62㧘93㧘124[Pm]ߣᄌ߃㧘✚ᾖ኿ᤨ㑆ߪ12ಽߣߒߚ㧚

㧚ታ㛎⚿ᨐ߅ࠃ߮⠨ኤ ᳇ᵃ⟲᜼േߩⷰኤታ㛎

⿥㖸ᵄᒝᐲߩቯ⟵

⿥㖸ᵄᒝᐲI[W/cm²]ߪ㧘㖸ᵄߩㅴⴕᣇะߦኻߒߡု

⋥ᣇะߦන૏㕙Ⓧ㧘න૏ᤨ㑆ᒰߚࠅߦㅢㆊߔࠆࠛࡀ࡞

ࠡߣߒߡቯ⟵ߐࠇࠆ⁽¹⁰⁾㧚⿥㖸ᵄᒝᐲߪ㧘⿥㖸ᵄᝄേሶ ߦଏ⛎ߒߚᶖ⾌㔚ജ㊂߆ࠄᰴᑼߢ⴫ߔߎߣ߇ߢ߈ࠆ㧚

4 ^solution2 ^air

probe

W W

I Sd

(1)

ߎߎߢ㧘Wsolution㧘Wair[W]ߪߘࠇߙࠇଏ⹜Άᢱ߅ࠃ߮ⓨ

᳇ਛߢ⿥㖸ᵄࠍ⊒ᝄߒߚ㓙ߩᶖ⾌㔚ജ㊂ࠍ␜ߔ㧚ߥ߅㧘

⿥㖸ᵄߩᝄേሶ߇31㧘62㧘93㧘124[Pm]ߩ႐ว㧘⿥㖸 ᵄᒝᐲߪ⚂10㧘19㧘31㧘50[W/cm²]ߣߥࠆ㧚

Άᢱ‛ᕈߩ᳇ᵃ↢ᚑ㊂ၞ߳ߩᓇ㗀

I=19㧘50[W/cm²]㧘taui=0.3[s]ߢߩฦනᚑಽΆᢱ߅ࠃ߮

ฦC16/C10ᷙวΆᢱߦ߅ߌࠆ᳇ᵃ↹௝ࠍ࿑6㧘࿑7ߦ ߘࠇߙࠇ␜ߔ㧚ߥ߅㧘ฦ↹௝ߣ߽ߦtaui=0.2[s]ߢ޽ࠅ㧘 ᓧࠄࠇߚ↹௝߆ࠄߎࠇએ㒠ߢߪ㧘Ꮒⷞ⊛ߦߪ᳇ᵃ↢ᚑ

㊂ߩᄌൻߪ⷗ࠄࠇߥ޿㧚࿑6ࠃࠅ㧘⿥㖸ᵄᒝᐲߦࠃࠄ ߕ㧘㘻๺⫳᳇࿶߇㜞޿Άᢱߩ᳇ᵃ↢ᚑ㊂߇ᄙ޿㧚߹ߚ㧘

࿑7߽ห᭽ߦ㧘ૐᴣὐΆᢱߩᷙวഀว߇Ⴧടߔࠆߔߥ ࠊߜ⫳᳇࿶߇Ⴧടߔࠆߦ઻ߥ޿᳇ᵃ↢ᚑ㊂߇ᄙ޿㧚ߎ ࠇߪ㧘⫳᳇࿶߇㜞ߊߥࠆߦߟࠇ㧘⫳᳇࿶એਅߩᦼ㑆ߟ

߹ࠅᷫ࿶ᤨ㑆߇Ⴧടߒߚߎߣߦ⿠࿃ߔࠆ㧚߹ߚ㧘ᩭ↢

ᚑℂ⺰߆ࠄ㧘ᶧ૕ߦਈ߃ߚㆊᾲᐲߩჇടߦ઻ߥ޿⊒ᵃ

᳇ᵃᢙ߇ᜰᢙ㑐ᢙ⊛ߦჇടߔࠆ⁽¹¹⁾㧚ߎߎߢ㧘ㆊᾲᐲߣ ߪ㖸࿶ߣ⫳᳇࿶ߩᏅ࿶ߦࠃࠅⷙቯߐࠇࠆߎߣ߆ࠄ㧘⫳

᳇࿶ߩჇടߪㆊᾲᐲߩჇᄢߦ❬߇ࠅ㧘⊒ᵃ᳇ᵃᢙ߇ᄙ

ߊߥࠆ㧚એ਄ࠃࠅ㧘නᚑಽΆᢱ߅ࠃ߮ᷙวΆᢱߣ߽ߦ㧘

⫳᳇࿶ߩჇടߦ઻ߥ޿᳇ᵃ↢ᚑ㊂ࠍჇടߔࠆߎߣ߇ น⢻ߢ޽ࠆ㧚

Table 5 Experimental conditions for fuel reformulation

Mole Fraction of C10H22

C16H34/C10H22

Mixed Fuel Pure Fuel

12 Total Irradiation Time ttotal[min]

Ar(1.67), N2(1.40), Air(1.40) Dissolved Gas (Specific Heat Ration*)

30 Bubbling Time** tbub[min]

279, 293, 300, 308, 323 Ambient Temperature Tamb[K]

31 , 62 , 93, 124 Probe Amplitude G_prove[Pm]

13 Probe Diameter dprobe[mm]

20 Ultrasonic Frequency f[kHz]

15 Test Fuel Volume Vfuel[cm³]

0.05 , 0.1 , 0.15 0.2 , 0.4 C10H22,C12H26, C13H28, C16H34

Test Fuel

Mole Fraction of C10H22

C16H34/C10H22

Mixed Fuel Pure Fuel

12 Total Irradiation Time ttotal[min]

Ar(1.67), N2(1.40), Air(1.40) Dissolved Gas (Specific Heat Ration*)

30 Bubbling Time** tbub[min]

279, 293, 300, 308, 323 Ambient Temperature Tamb[K]

31 , 62 , 93, 124 Probe Amplitude G_prove[Pm]

13 Probe Diameter dprobe[mm]

20 Ultrasonic Frequency f[kHz]

15 Test Fuel Volume Vfuel[cm³]

0.05 , 0.1 , 0.15 0.2 , 0.4 C10H22,C12H26, C13H28, C16H34

Test Fuel

*at 298K, 0.1MPa ^**100ml/min, at 293K, 0.1MPa

*at 298K, 0.1MPa ^**100ml/min, at 293K, 0.1MPa

Hi-speed Video Camera Halogen Lamp

Diffuser

Converter (Ultrasound Transducer :PZT )

Probe Power Supply

Shunichi Hanad a Sonochemistr y Time 1 : 20 : 30 Pulse 4.0 2.0 Ampl100%

123

6 5 4

78

0 9

ClearEnter StartTimerPulse

PC

Hi-speed Video Camera Halogen Lamp

Diffuser

Converter (Ultrasound Transducer :PZT )

Probe Power Supply

Shunichi Hanad a Sonochemistr y Time 1 : 20 : 30 Pulse 4.0 2.0 Ampl100%

123

6 5 4

78

0 9

ClearEnter StartTimerPulse

PC PC

Fig. 4 Schematic diagram of transmitted light method for observation of cavitation behavior

Temperature-Controlled Bath Converter (Ultrasonic Transducer :PZT) Ultrasonic

Generator

Temperature-Control Unit Gas Chromatogram

(Detector : FID)

Sampling Bubbling

Ar Bomb

Probe

Shunichi Hanad a Sonochemistr y Time 1 : 20 : 30 Pulse 4.0 2.0 Ampl100%

12536 4

78

0 9 ClearEnter StartTimerPulse

Temperature-Controlled Bath Converter (Ultrasonic Transducer :PZT) Ultrasonic

Generator

Temperature-Control Unit Gas Chromatogram

(Detector : FID)

Sampling Bubbling

Ar Bomb

Probe

Shunichi Hanad a Sonochemistr y Time 1 : 20 : 30 Pulse 4.0 2.0 Ampl100%

12536 4

78

0 9 ClearEnter StartTimerPulse

Shunichi Hanad a Sonochemistr y Time 1 : 20 : 30 Pulse 4.0 2.0 Ampl100%

12536 4

78

0 9 ClearEnter StartTimerPulse

Fig. 5 Schematic diagram of experimental apparatus for fuel reformulation

⿥㖸ᵄᒝᐲߩ᳇ᵃ↢ᚑ㊂ၞ߳ߩᓇ㗀

taui=0.3[s]㧘n-࠺ࠞࡦߣn-ࡋࠠࠨ࠺ࠞࡦ߅ࠃ߮ߘࠇࠄ

ߩᷙวΆᢱC16/C10(X_C10=0.6㧘0.2)ߦ߅ߌࠆ⿥㖸ᵄᒝᐲ ߣࡏࠗ࠼₸ߩ㑐ଥࠍ࿑8ߦ␜ߔ㧚ߥ߅㧘ࡏࠗ࠼ߪᓧࠄ ࠇߚ↹௝ࠍ⊕㤥ߩ2୯ൻ↹௝ߦᄌ឵ߒ㧘᠟ᓇ㗔ၞߣ᳇

ᵃ↢ᚑ㊂ߣߩᲧࠃࠅ▚಴ߒߚ㧚ฦΆᢱߣ߽ߦ⿥㖸ᵄᒝ ᐲ߇Ⴧᄢߔࠆߦߒߚ߇޿ࡏࠗ࠼₸ߪ㜞޿㧚ߎࠇߪ㧘ࠠ

ࡖࡆ࠹࡯࡚ࠪࡦ᳇ᵃࠍ↢ᚑߔࠆߦߪ㘻๺⫳᳇࿶એਅ

50 40 30

10 0

Void Fraction [%]

20

10 20 30 40 50

Ultrasonic intensity I[W/cm²] X_C10=0.2

n-C₁₀H₂₂ X_C10=0.6 n-C₁₆H₃₄ 50

40 30

10 0

Void Fraction [%]

20

10 20 30 40 50

Ultrasonic intensity I[W/cm²] X_C10=0.2

n-C₁₀H₂₂ X_C10=0.6 n-C₁₆H₃₄ n-C₁₆H₃₄

Fig. 8 Relation between ultrasonic intensity and void fraction (taui=0.3[s])

30 25 20

10 5

Void Fraction [%]

15

10^-2 10^-1 10⁰ 10¹ 10² 10³ 10⁴ Vapor Pressure [Pa]

C16

C10

C7 C13

C16/C7 Pure fuel C16/C10 30

25 20

10 5

Void Fraction [%]

15

10^-2 10^-1 10⁰ 10¹ 10² 10³ 10⁴ Vapor Pressure [Pa]

C16

C10

C7 C13

C16/C7 Pure fuel C16/C10 C16/C7 C16/C7 Pure fuel Pure fuel C16/C10 C16/C10

Fig. 9 Relation between vapor pressure and void fraction (taui=0.3[s])

n-c10H22 n-c12H26n-c13H28 n-c16H34

n-c7H16

Pure Fuel

Probe

I=50 [W/cm²]

I=19 [W/cm²]

Fig. 6 Ultrasonic cavitation image of pure fuel with variable ultrasonic intensity (t_aui=0.2[s], G_probe=62, 124[Pm])

0

XC10H22= 0.2 0.4 0.6 0.8

I=19 [W/cm²]

Probe

I=50 [W/cm²]

Fig. 7 Ultrasonic cavitation image of mixed fuel with variable mole fraction (t_aui=0.2[s],G_probe=62, 124[Pm]) ߩ࿶ജ߇ᔅⷐߢ޽ࠅ㧘⿥㖸ᵄᒝᐲߩჇടߦࠃࠅ㧘ߎߩ

᧦ઙࠍḩߚߔ㖸࿶߇ᝄേሶ⴫㕙߆ࠄਅᵹၞߩᐢ▸࿐

߹ߢ෸ࠎߛߎߣߦ⿠࿃ߔࠆ㧚ߒߚ߇ߞߡ㧘⿥㖸ᵄᒝᐲ ߩჇടߦ઻ߥ޿⊒ᵃ᳇ᵃᢙߪჇടߔࠆ㧚

ᷙวΆᢱߩ․ᕈ߇᳇ᵃ↢ᚑ᜼േߦਈ߃ࠆᓇ㗀 I=19 [W/cm²]㧘t_aui=0.3[s]ߢߩฦනᚑಽΆᢱ߅ࠃ߮ฦ

ᷙวΆᢱߦ߅ߌࠆࡏࠗ࠼₸ᄌൻࠍ࿑9ߦ␜ߔ㧚නᚑಽ Άᢱ㧘ᷙวΆᢱߣ߽ߦ⫳᳇࿶߇㜞ߊߥࠆߦߟࠇ㧘ࡏࠗ

࠼₸ߪ㜞ߊߥࠆ߇㧘ߘߩჇട₸ߪ⇣ߥࠆ㧚ߎߩⷐ࿃ߣ ߒߡ㧘ᷙวΆᢱߩ⫳⊒․ᕈߔߥࠊߜ᳇ᶧੑ⋧㗔ၞߩᒻ ᚑ߇⠨߃ࠄࠇࠆ㧚ߟ߹ࠅ㧘ᷙวΆᢱߩ⫳⊒․ᕈߪ㧘㘻

๺ᶧ૕ᦛ✢߆ࠄ㘻๺⫳᳇✢߹ߢߩ࿶ജ᏷ࠍ᦭ߔࠆߎ ߣ߆ࠄ㧘หߓ⫳᳇࿶ߩනᚑಽΆᢱߣᲧセߔࠆߣ㧘ᷙว Άᢱߪ⫳⊒ߒ㔍޿㧚

ᰴߦ㧘I=19㧘50[W/cm²]㧘taui=0.3[s]ߢߩC16/C10߅ࠃ

߮C16/C7 ᷙวΆᢱߩฦૐᴣὐᚑಽߩᷙวഀวߣࡏࠗ

࠼₸ᄌൻࠍ࿑ 10 ߦ␜ߔ㧚หߓ⿥㖸ᵄᒝᐲߢหߓૐᴣ ὐΆᢱߩᷙวഀวߢᲧセߔࠆߣ㧘C16/C7ߪC16/C10ࠃ ࠅࡏࠗ࠼₸߇㜞޿㧚ߎࠇߪ㧘⫳⊒․ᕈߩᡷༀലᨐ߇⇣

ߥࠆߎߣ߇ⷐ࿃ߢ޽ࠆ㧚଀߃߫㧘৻଀ߣߒߡ㧘C16/C10 ߅ࠃ߮C16/C7ᷙวΆᢱߦ߅޿ߡ㧘ߘࠇߙࠇૐᴣὐᚑಽ ߩᷙวഀว߇0.6ߢߩ᷷ᐲ㧙࿶ജ✢࿑ࠍ࿑11ߦ␜ߔ㧚

࿑ߦ␜ߔࠃ߁ߦ㧘C16/C7ߪC16/C10ᷙวΆᢱࠃࠅ㧘⫳

᳇࿶߇㜞ߊ਌ߟ㘻๺⫳᳇ᦛ✢਄ߩ࿶ജߪ߶߷╬ߒ޿㧚 ߔߥࠊߜ㧘࠺ࠞࡦࠃࠅ⫳᳇࿶߇㜞޿ࡋࡊ࠲ࡦࠍᷙวߔ ࠆߣ㧘ᶧ૕ߦਈ߃ࠆㆊᾲᐲ߇Ⴧടߒ㧘ߘߩ⚿ᨐ㧘᳇ᵃ

↢ᚑ㊂߇ᄙߊߥࠆ㧚એ਄ࠃࠅ㧘නᚑಽΆᢱߣᷙวΆᢱ ߩ᳇ᵃ↢ᚑ㊂ࠍᲧセߔࠆߣ㧘ᷙวΆᢱߪᷙว⚵ᚑ߅ࠃ

߮ᷙวഀวߦࠃࠅ㧘᳇ᵃ↢ᚑ㊂߇ᄌൻߒ㧘છᗧߦ೙ᓮ ߔࠆߎߣ߇น⢻ߣߥࠆ㧚

⿥㖸ᵄΆᢱᡷ⾰ታ㛎

ଏ⹜Άᢱߩᶧ૕ᚑಽ߳ߩಽ⸃ഀว

ᧄ⺰ᢥߢߪ㧘ฦ᧦ઙਅߦ߅ߌࠆ⿥㖸ᵄΆᢱᡷ⾰ഀว ߩᲧセߩߚ߼㧘ࠟࠬࠢࡠࡑ࠻ࠣ࡜ࡈߩಽᨆ߆ࠄᓧࠄࠇ ߚฦಽ⸃↢ᚑ‛ߩ↢ᚑㅦᐲdM/dt[mol/(l˜min)]߆ࠄฦଏ

⹜Άᢱߩಽ⸃ഀว dS/dt[Pmol/(l˜min)]ߔߥࠊߜΆᢱᡷ

⾰ഀวࠍᰴᑼࠃࠅ▚಴ߒߚ㧚

0 0.2 0.4 0.6 0.8 1.0 Mole Fraction of Low Boiling Point Fuel 0

30 40 50 60 70

Void Fraction [%]

20 10

C16/C7 C16/C10 I=50[W/cm²]

C16/C7 C16/C10 I=19[W/cm²]

0 0.2 0.4 0.6 0.8 1.0

Mole Fraction of Low Boiling Point Fuel 0

30 40 50 60 70

Void Fraction [%]

20 10

C16/C7 C16/C10 I=50[W/cm²]

C16/C7 C16/C10 I=19[W/cm²]

C16/C7 C16/C10 I=50[W/cm²]

C16/C7 C16/C7 C16/C10 C16/C10 I=50[W/cm²]

C16/C7 C16/C10 I=19[W/cm²]

C16/C7 C16/C7 C16/C10 C16/C10 I=19[W/cm²]

Fig. 10 Relation between mole fraction of low boiling point fuel and void fraction (taui=0.3[s], I=19, 50[W/cm²])

2.0

300 400 500 600 700

0.0 1.0 0.5 1.5

Vapor Pressure Pv[MPa]

Temperature T_fuel[K]

C10H22

C7H16

C16/C10 * C16/C7 * 3.0

2.5

C₁₆H₃₄

*X_C16H34=0.4 2.0

300 400 500 600 700

0.0 1.0 0.5 1.5

Vapor Pressure Pv[MPa]

Temperature T_fuel

product fuel

dM dt C dS

dt C

¦

ߎߎߢ㧘Cproduct㧘Cfuelߪಽ⸃ᕈ↢‛߅ࠃ߮ଏ⹜Άᢱߩ὇

⚛ᢙࠍߘࠇߙࠇ␜ߔ㧚ૉߒ㧘ᷙวΆᢱߦ߅ߌࠆ὇⚛ᢙ Cfuelߪ㧘ᷙวഀว߆ࠄᰴᑼࠃࠅ᳞߼ߚ㧚

fuel i fueli

C

¦

ߎߎߢ㧘Xߪࡕ࡞ಽ₸ࠍ⴫ߒ㧘ᷝሼߩiߪฦൻቇ⒳ࠍ

⴫ߔ㧚

⿥㖸ᵄΆᢱᡷ⾰ߩᡷ⾰ല₸

ฦଏ⹜Άᢱߦ߅޿ߡ㧘ᝄേሶࠍ㚟േߐߖࠆ㓙ߦᶖ⾌

ߒߚ㔚ജ㊂ߣଏ⹜Άᢱߩಽ⸃ㅦᐲ߆ࠄΆᢱᡷ⾰ല₸K ࠍᰴᑼࠃࠅ᳞߼ߚ㧚

[K]

C10H22

C10H22

C7H16

C7H16

C16/C10 * C16/C10 * C16/C7 * C16/C7 * 3.0

2.5

C₁₆H₃₄ C₁₆H₃₄

2

4 60

product

fuel probe

dH dS dt I d V

K S

˜ ˜

˜ ˜

¦

*X_C16H34=0.4

ߎߎߢ㧘dHproduct[KJ/mol]ߪฦᚑಽࠍ↢ᚑߔࠆߩߦᔅⷐ ߥࠛࡦ࠲࡞ࡇ㧘Vfuel[cm³]ߪଏ⹜Άᢱߩ૕Ⓧ㧘dprobe[mm]

ߪᝄേሶవ┵ߩ⋥ᓘࠍߘࠇߙࠇ⴫ߔ㧚

Fig. 11 Pressure-Temperature diagram of n-decane, n-hexadecane, C16/C10, and C16/C7 (X_C16H34=0.4)

Retention Time [min]

Relative Abundance

0 2 4 6 8

C6 C5

C7 C8 C9 C10

C11 Gaseous Product(C1-C4)

n-Alkane 1-Alkene Chromatogram

Retention Time [min]

Relative Abundance

0 2 4 6 8

C6 C5

C7 C8 C9 C10

C11 Gaseous Product(C1-C4)

n-Alkane 1-Alkene Chromatogram

Fig. 12 Chromatogram of n-tridecane after12min ultrasonic irradiation (I=31[W/cm²],Tamb=278[K]) Pࠕ࡞ࠞࡦߩ⿥㖸ᵄΆᢱᡷ⾰ߦ߅ߌࠆಽ⸃↢

ᚑ‛

n-࠻࡝࠺ࠞࡦ㧘Tamb=278[K]㧘Ar㔓࿐᳇ਅ㧘I=31[W/cm²] ߩ᧦ઙߢ 12 ಽ㑆⿥㖸ᵄᾖ኿ࠍⴕߥߞߚᓟߩࠢࡠࡑ࠻

ࠣ࡜ࡓࠍ࿑12ߦ␜ߔ㧚ߎߩ࿑߆ࠄ㧘n-ࠕ࡞ࠞࡦߩ⿥㖸 ᵄΆᢱᡷ⾰ߦ߅ߌࠆਥߥಽ⸃↢ᚑ‛ߪ 1-ࠕ࡞ࠤࡦ߅ ࠃ߮n-ࠕ࡞ࠤࡦߢ޽ࠆ㧚ട߃ߡ㧘ࡍࡦ࠲ࡦ(࿑ਛC5 ᚑ ಽ)ࠃࠅ߽ᣧᦼߩࡇ࡯߽ࠢ⏕⹺ߢ߈ࠆ㧚Suslickࠄ⁽⁶⁾ߪn- ࠕ࡞ࠞࡦߩ⿥㖸ᵄಽ⸃ߦ߅ߌࠆਥߥಽ⸃↢ᚑ‛ߣߒ ߡ㧘᳓⚛㧘ࠛ࠴࡟ࡦ㧘ૐಽሶ㊂ࠕ࡞ࠤࡦ߅ࠃ߮ࠕ࡞ࠞ

ࡦࠍႎ๔ߒߡ޿ࠆ㧚ߒߚ߇ߞߡ㧘ߎࠇࠄߩᚑಽߪ὇⚛

ᢙ1߆ࠄ4ߩ᳇૕ᚑಽߢ޽ࠆ㧚

ᰴߦ㧘I=31[W/cm²]㧘Tamb=293[K]ߩ࠻࡝࠺ࠞࡦߦ߅ ߌࠆಽ⸃↢ᚑ‛C5㧘C7㧘C9㧘C11 ᚑಽߩ↢ᚑỚᐲࠍ

࿑ 13 ߦ␜ߔ㧚ߎߩ࿑߆ࠄ㧘ฦಽ⸃↢ᚑ‛ߪᤨ㑆ߩ⚻

ㆊߦ઻ߥ޿↢ᚑỚᐲߪჇടߔࠆ߇㧘ߘߩჇടഀว߇ಽ

⸃↢ᚑ‛ߏߣߦ⇣ߥࠅ㧘ૐ὇⚛ᢙᚑಽߦߥࠆߦᓥ޿↢

ᚑỚᐲ߇㜞޿㧚ߎߩⷐ࿃ߣߒߡ㧘ᾲಽ⸃෻ᔕᯏ᭴߇᜼

ߍࠄࠇࠆ㧚ᾲಽ⸃෻ᔕᯏ᭴ߪRiceࠄ⁽¹²⁾ߩᾲಽ⸃෻ᔕࡕ

࠺࡞ߦࠃࠅᢛℂߐࠇࠆ߇㧘ࡋࡦ࡝࡯ߩᴺೣߦࠃࠅΆᢱ ߦ㘻๺ṁ⸃ߒߡ޿ࠆⓨ᳇ߩᓇ㗀ࠍ⠨ᘦߒߡ޿ߥ޿㧚ߘ

ߎߢ㧘Curranࠄ⁽¹³⁾߇⊒᩺ߒߚn-ࡋࡊ࠲ࡦߩ㉄ൻ෻ᔕࡕ

࠺࡞ࠍ↪޿ߡ㧘CHMKIN Υ⁽¹⁴⁾ߦࠃࠅ෻ᔕᯏ᭴ߩ⸃ᨆ ࠍⴕߥ޿㧘ߘߩ⚿ᨐࠍ࿑ 14 ߦ␜ߔ㧚ߥ߅㧘⸘▚᧦ઙ ߪ࠰ࡁࠤࡒࠬ࠻࡝࡯ߦ߅޿ߡ㧘৻⥸⊛ߦ⸒ࠊࠇߡ޿ࠆ 㔓࿐᳇᧦ઙߩPamb=100[MPa]㧘Tamb=5000[K]ߢ޽ࠆ㧚ߎ ߩ࿑ࠃࠅ㧘ૐ⚖὇⚛ᚑಽ߶ߤ↢ᚑỚᐲ߇㜞ߊ㧘ฦ὇⚛

ᢙߢࠕ࡞ࠞࡦߣ1-ࠕ࡞ࠤࡦࠍᲧセߔࠆߣ㧘1-ࠕ࡞ࠤࡦ ߩ↢ᚑỚᐲ߇㜞ߊ㧘ታ㛎⚿ᨐߣห᭽ߩ௑ะߢ޽ࠆ㧚ߒ ߚ߇ߞߡ㧘࠰ࡁࠤࡒࠬ࠻࡝࡯ߩࠃ߁ߥ㜞᷷෻ᔕ႐ߢߪ㧘

180 120 90 60 30 150 ^C7 300

50 100 150 200 250 ^C5

100

20 40 60 80

100 80 60 40 20

C9

C11

Irradiation timet_irra[min]

0 3 6 9 12 15 3 6 9 12 15

1-alken

n-alkan ^{1-alkenn-alkan}

1-alken n-alkan 1-alken

n-alkan

Concentration of Products Cproducts[Pl/l]

180 120 90 60 30 150 ^C7 300

50 100 150 200 250 ^C5

100

20 40 60 80

100 80 60 40 20

C9

C11

Irradiation timet_irra[min]

0 3 6 9 12 15 3 6 9 12 15

1-alken n-alkan 1-alken

n-alkan ^{1-alkenn-alkan1-alkenn-alkan}

1-alken n-alkan 1-alken n-alkan 1-alken

n-alkan 1-alken n-alkan

Concentration of Products Cproducts[Pl/l]

Fig. 13 Temporal change in concentration of lower carbon number (C13H28,I=31[W/cm²])

30 20 10

0.03

-3Mole fractionM˜10 0 0 CH₄

0.02 0.01

C₂H₆C₂H₄C₃H₆ C₃H₈1-C₄C₄H₁₀1-C₅ Product

30 20 10

0.03

-3Mole fractionM˜10 0 0 CH₄

0.02 0.01

C₂H₆C₂H₄C₃H₆ C₃H₈1-C₄C₄H₁₀1-C₅ 30

20 10

0.03

-3Mole fractionM˜10 0 0 CH₄

0.02 0.01

C₂H₆C₂H₄C₃H₆ C₃H₈1-C₄C₄H₁₀1-C₅ Product

Fig. 14 Calculation results for Phyrolysis of n-heptane (C7H16,Tamb=5000[K],Pamb=100[MPa])

1-C₅ C₅1-C₆

C₆1-C₇ C₇1-C₈

C₈1-C₉ C1-C_{9 10}

C₁₀1-C₁₁ C₁₁1-C₁₂ Product

Formation Rate of Product dMt/dt[Pmol/(l·min)]

0 25 20 15 10 5

Ar^*(tbub= 30min) N2*(tbub= 30min) Air (tbub= 0min)

* Ar, N₂: Air + Ar or N₂

1-C₅ C₅1-C₆

C₆1-C₇ C₇1-C₈

C₈1-C₉ C1-C_{9 10}

C₁₀1-C₁₁ C₁₁1-C₁₂ Product

Formation Rate of Product dMt/dt[Pmol/(l·min)]

0 25 20 15 10 5

Ar^*(tbub= 30min) N2*(tbub= 30min) Air (tbub= 0min) Ar^*(tbub= 30min) Ar^*(tbub= 30min) N2*(tbub= 30min) N2*(tbub= 30min) Air (tbub= 0min) Air (tbub= 0min)

* Ar, N₂: Air + Ar or N₂

Fig. 15 Relation of dissolved gas to formation rate of product

Eಽ⸃ߦࠃࠆ὇⚛⚿วߩ㐿ⵚ߇ᡰ㈩⊛਌ߟㅪ㎮⊛ߦ⿠

ߎࠅ㧘Άᢱ⒳ߪ὇⚛ᢙߩૐ޿ਇ㘻๺὇ൻ᳓⚛߇ਥߦ↢

ᚑߒ㧘ߘߩ৻ㇱߪ᳓⚛ઃട෻ᔕ߿ࠕ࡞ࠠ࡞࡜ࠫࠞ࡞ห

჻ߩౣ⚿วߦࠃࠅ㘻๺὇ൻ᳓⚛߳ߣߥࠆ㧚 ṁሽ᳇૕߇⿥㖸ᵄΆᢱᡷ⾰ߦਈ߃ࠆᓇ㗀 ṁሽ᳇૕ߩ⒳㘃ߣಽ⸃↢ᚑ‛ߩ↢ᚑㅦᐲdM/dtߩ㑐 ଥࠍ࿑ 15 ߦ␜ߔ㧚ߥ߅㧘ଏ⹜Άᢱߪn-࠻࡝࠺ࠞࡦ㧘 I=31[W/cm²]ߢ޽ࠆ㧚ߎߎߢᧄታ㛎ߢߪ㧘⣕᳇ࠍⴕߥߞ ߡ޿ߥ޿ߚ߼ଏ⹜Άᢱߦߪ੍߼ⓨ᳇߇ṁሽߒߡ޿ࠆ㧚 ߒߚ߇ߞߡ㧘ᧄታ㛎ߦ߅ߌࠆṁሽ᳇૕ߣߪⓨ᳇߅ࠃ߮

ฦ᳇૕ߣߥࠆ߇એਅߢߪߘࠇߙࠇAr㧘N₂߽ߒߊߪⓨ᳇

(એਅ㧘Airߣ⴫⸥ߔࠆ)ߣ⸥ㅀߔࠆ㧚

ฦᚑಽߩ↢ᚑㅦᐲdM/dtߪṁሽ᳇૕ߩ⒳㘃ߦଐሽߔ ࠆߣߪ޿߃Ar㧘Air㧘N2ߩ㗅ߦ㜞޿୯ࠍߣࠆߎߣ߇ࠊ ߆ࠆ㧚ߒ߆ߒߥ߇ࠄ㧘ฦᚑಽ㑆ߩdM/dtߩ௑ะߪṁሽ᳇

૕ߩ⒳㘃ߦଐࠄߕห᭽ߢ޽ࠆߎߣ߇ࠊ߆ࠆ㧚ߔߥࠊߜ㧘

⿥㖸ᵄΆᢱᡷ⾰ߦ߅޿ߡ㧘ṁሽ᳇૕ߪߘߩ෻ᔕᯏ᭴ߦ ߪ⋥ធነਈߒߥ޿ߣ޿߃ࠆ㧚ߎࠇߪవㅀߒߚCurranࠄ ߩࡕ࠺࡞ߦࠃࠆ⸘▚⚿ᨐߣห᭽ߢ޽ࠅ㧘↢ᚑߒߚ࡜ࠫ

ࠞ࡞⒳ߪ㉄⚛ઃട෻ᔕ߇↢ߓߒ㔍޿ߎߣߦ⿠࿃ߔࠆ㧚 Ar߇N₂ߦᲧߴߡ㧘ฦᚑಽߩ↢ᚑㅦᐲ߇㜞޿ⷐ࿃ߣߒߡ㧘 ṁሽ᳇૕ߩᲧᾲᲧ߅ࠃ߮ଏ⹜Άᢱ߳ߩṁ⸃ᐲ߇㜞޿

ߎߣ߇᜼ߍࠄࠇࠆ㧚ߎࠇߪ㧘᳇ᵃౝᲧᾲᲧ߇਄᣹ߒ㧘

፣უ᷷ᐲ߇㜞ߊߥࠅ㧘߹ߚ㧘ṁሽ᳇૕㊂ߩჇടߪ⊒ᵃ

᳇ᵃᩭᢙߩჇടߦ❬߇ࠆߚ߼㧘ArࠍṁሽߒߚΆᢱߪ፣

უ᳇ᵃᢙ߇ᄙߊ਌ߟฦޘߩ᳇ᵃߩΆᢱᡷ⾰ഀว߇㜞

߹ࠆ߆ࠄߢ޽ࠆ㧚৻ᣇ㧘ṁሽ᳇૕ࠍN₂ߣߒߚ᧦ઙߪAir ߩ႐วߦᲧߴ㧘dM/dt߇ૐ޿ේ࿃ߣߒߡߪࡃࡉ࡝ࡦࠣߦ ࠃࠆᓇ㗀߇⠨߃ࠄࠇࠆ㧚ߟ߹ࠅ㧘ࡃࡉ࡝ࡦࠣࠍⴕߥߞ ߚߎߣߦࠃࠅΆᢱਛߦṁሽߔࠆṁሽ᳇૕ߩ᳇ᵃᩭᓘ ߇Ⴧᄢߒ㧘ߘߩ⚿ᨐ㧘᳇ᵃ፣უ᷷ᐲߩૐਅ߽ߒߊߪ፣

უߒߥ޿᳇ᵃߩ↢ᚑߦነਈߒߚߣ⠨߃ࠄࠇࠆ㧚ߐࠄߦ㧘

⓸⚛ߪⓨ᳇ࠃࠅଏ⹜Άᢱ߳ߩṁ⸃ᐲ߇ૐ޿ߚ߼㧘᳇ᵃ

ᩭᢙߩᷫዋߦࠃࠅ㧘෻ᔕ႐ߩᷫዋߦࠃࠆᓇ㗀߽⠨߃ࠄ ࠇࠆ㧚એ਄ࠃࠅ㧘ṁሽ᳇૕ߩᲧᾲᲧ߅ࠃ߮ṁ⸃ᐲ߇㜞

޿߶ߤ⿥㖸ᵄߦࠃࠆΆᢱᡷ⾰ߩഀว߇Ⴧടߔࠆߣ޿

߃ࠆ㧚

⿥㖸ᵄᒝᐲ߇⿥㖸ᵄΆᢱᡷ⾰ߦਈ߃ࠆᓇ㗀

n-࠻࡝࠺ࠞࡦߦ߅ߌࠆ⿥㖸ᵄᒝᐲIߣಽ⸃ㅦᐲdS/dt

ߩ㑐ଥࠍ࿑16 ߦ␜ߔ㧚ߎߩ࿑ࠃࠅ㧘⿥㖸ᵄᒝᐲߩჇ

ടߦ઻ߥ޿ಽ⸃ㅦᐲ߇㜞ߊߥࠆߎߣ߇ࠊ߆ࠆ㧚ߎࠇߪ㧘

4.1.2 ▵ߢㅀߴߚࠃ߁ߦ⿥㖸ᵄᒝᐲߩჇᄢߦࠃࠅ᳇ᵃ

↢ᚑ㊂ߟ߹ࠅ෻ᔕᢙ߇Ⴧടߒߚߎߣߦ⿠࿃ߔࠆ㧚ߐࠄ ߦ㧘⿥㖸ᵄᒝᐲߩჇᄢߦ઻ߥ߁㖸࿶ߩะ਄ߦࠃࠅ᳇ᵃ ߩ፣უ᷷ᐲ߇Ⴧടߒߚߎߣ߽ⷐ࿃ߢ޽ࠆߣផ᷹ߐࠇ ࠆ㧚৻ᣇ㧘⿥㖸ᵄᒝᐲ߇㜞ߊߥࠆߦߟࠇ㧘ಽ⸃ㅦᐲߩ Ⴧട₸ߪᰴ╙ߦᷫዋߔࠆ㧚ߎࠇߪ᳇ᵃᢙߩჇട߅ࠃ߮

ᦨᄢ᳇ᵃᓘߩ᜛ᄢߦ઻ߥ޿᳇ᵃห჻ߩว૕ߔࠆ⏕┙

߇㜞߹ࠅ㧘፣უߦ⥋ࠆ᳇ᵃߟ߹ࠅൻቇ෻ᔕࠍᒁ߈⿠ߎ