, 32, 1 (2008) 1 6J. Inst. Electrostat. Jpn.

⺰ᢥࠝ࠱ࡦ㧙⸅ᇦⶄว♽ߦ߅ߌࠆVOC ಽ⸃ߦ᦭ലߥᵴᕈ㉄⚛⒳ߩᬌ⸛
㥲⮮࿻Ꮢ*,**, የᒻ ᢕ*,1, ㊄⾫ ᄐ*, ੑ㩊᧛ ᫪*, ᦭⼱ඳᢥ**, ᳗㐳ਭኡ***㧔2007 ᐕ 10 ᦬ 9 ᣣฃઃ㧧2007 ᐕ 12 ᦬ 24 ᣣฃℂ㧕Reactivity of Oxygen Species on an Ozonolysis Catalyst
for VOC Decomposition with Ozone
Keiichi SAITO*, **, Atsushi OGATA*,1, Hyun-Ha KIM*, Shigeru FUTAMURA*,
Hirofumi ARITANI** and Hisahiro EINAGA***(Received October 9, 2007; Accepted December 24, 2007)

In the catalyzed decomposition of VOCs, it was known that reactivity was enhanced by the combination with ozone at
low temperature. We carried out the decomposition of toluene and dichloromethane on a Ba-CuO-Cr2O3/Al2O3
catalyst by ozone in a range of 100 to 400͠. In order to clarify the role of ozone and other oxygen species, weinvestigated three types of oxidation methods, i.e., by gas phase ozone alone (R1), the catalyst alone (R2), and thecatalyst with ozone (R3). The performance in the gas phase ozone was equal to or higher than that on the catalystalone. However, it was shown that the performance on the catalyst was enhanced with ozone in a range of 100 to200͠. In other words, the active oxygen species on the catalyst derived from ozone, Oads, were effective for VOCsdecomposition even at low temperature. The utilization factor of ozone for VOCs, which is defined as a ratio ofremoved VOC and consumed ozone, was investigated in R3. The lower the reaction temperature, the higher theutilization factor was. It seems that Oads was consumed for not only the removal of VOC but also the recombination
into oxygen at high temperature.
1.

ߡߔߢߦ㧘Ά὾ᴺ㧘ๆ⌕ᴺ㧘↢‛ಣℂᴺ╬ߩᛛⴚ߇㐿⊒ߐࠇ㧘ߪߓ߼ߦើ⊒ᕈ᦭ᯏൻว‛㧔VOC㧕ߪ㧘శൻቇࠝࠠࠪ࠳ࡦ࠻߿ᶋㆆታ㓙㧘ᄙߊߩዉ౉ታ❣߇޽ࠆ㧚ߎߩ߁ߜ㧘⋥ធ㧔⫾ᾲ㧕Ά὾☸ሶ‛⾰ߩේ࿃ߩ৻ߟߣ⠨߃ࠄࠇߡ߅ࠅ㧘ᣣᧄ࿖ౝߢߪᐔᚑᴺ߿⸅ᇦ㉄ൻᴺߪ㧘ⷙ೙ኻ⽎ߣߥߞߡ޿ࠆ㜞Ớᐲ VOC ኻ╷

18 ᐕ߆ࠄⷙ೙෸߮⥄ਥ⊛ขࠅ⚵ߺߦࠃࠆឃ಴ᛥ೙ኻ╷߇ផᛛⴚߣߒߡ㧘ᣢߦᄢⷙᮨ⊒↢Ḯߦዉ౉߇ㅴࠎߢ޿ࠆ㧚ߒ߆ߒ㧘1)ㅴߐࠇࠆߎߣߣߥߞߚ㧔ࡌࠬ࠻ࡒ࠶ࠢࠬ㧕 㧚VOC ኻ╷ߣߒਛዊ੐ᬺᚲߢߪ㧘⸳⟎႐ᚲ߿⸳⟎ᓟߩࠦࠬ࠻㕙ߢㆡᒰߥᛛⴚ߇ߥ޿ߎߣ߆ࠄ㧘ኻ╷߇ㆃࠇߡ޿ࠆ㧚ߎࠇࠄࠍ⢛᥊ߦ㧘ਛዊ䉨䊷䊪䊷䊄䋺䉥䉹䊮䋬⸅ᇦ䋬ᵴᕈ㉄⚛⒳䋬ើ⊒ᕈ᦭ᯏൻว‛䋬VOC* ↥ᬺᛛⴚ✚ว⎇ⓥᚲⅣႺ▤ℂᛛⴚ⎇ⓥㇱ㐷䋨305-8569⨙ၔ⋵䈧䈒䈳Ꮢዊ㊁Ꮉ 16-1䋩
National Institute of Advanced Industrial Science andTechnology (AIST), 16-1 Onogawa, Tsukuba, Ibaraki
305-8569, Japan** ၯ₹ᎿᬺᄢቇᎿቇㇱ䋨369-0293 ၯ₹⋵ᷓ⼱Ꮢ᥉ᷣኹ1690䋩
Saitama Institute of Technology, 1690 Fusaiji, Fukaya,
Saitama 369-0293, Japan*** ਻Ꮊᄢቇᄢቇ㒮✚วℂᎿቇ⎇ⓥ㒮䋨816-8580 ⑔ጟ⋵ᤐᣣᏒᤐᣣ౏࿦ 6-1䋩Kyushu University, 6-1 Kasugakoen, Kasuga, Fukuoka
816-8580, Japan1
atsushi-ogata@aist.go.jp੐ᬺᚲࠍኻ⽎ߣߒߚశ⸅ᇦ㧘ૐ᷷ࡊ࡜࠭ࡑ㧘ࠝ࠱ࡦߥߤࠍ೑
↪ߒߚᣂߚߥଦㅴ㉄ൻᛛⴚ߇ᬌ⸛ߐࠇߡ޿ࠆ 2)㧚
ૐ᷷ࡊ࡜࠭ࡑᴺߪ㧘ૐỚᐲߩើ⊒ᕈ᦭ᯏ‛⾰ߦኻߒߡ㧘ᓥ᧪ဳߩಽ⸃ᴺࠃࠅ߽ࠦࠬ࠻ࠍૐߊᛥ߃ࠄࠇ㧘ᄙߊߩൻቇ‛⾰ࠍಽ⸃ߢ߈ࠆᣇᴺߣߒߡ⍮ࠄࠇߡ޿ࠆ㧚․ߦ㧘ಽ⸃⢻ജࠍ㜞߼ࠆߚ߼ߦ⸅ᇦߣߩⶄวൻ߇ㅴ߼ࠄࠇ㧘⋧ਸ਼ലᨐߦߟ޿ߡ߽ᄙߊߩႎ๔߇ߥߐࠇߡ޿ࠆ 3)㧚
⋧ਸ਼ലᨐߪ㧘ࡊ࡜࠭ࡑߦࠃࠆ⊒శ㧘ࠝ࠱ࡦ↢ᚑ㧘⸅ᇦߩᵴᕈൻߥߤߦ⿠࿃ߔࠆߣ⠨߃ࠄࠇߡ޿ࠆ 4)㧚ߘߩਛߢ߽㧘ࠝ࠱ࡦ⸅ᇦಽ⸃ᴺߢ⍮ࠄࠇࠆࠃ߁ߦ 5)㧘౒ሽߐߖࠆ⸅ᇦߦㆡᒰߥ
ࠝ࠱ࡦಽ⸃⢻߇޽ࠅ㧘߆ߟࡊ࡜࠭ࡑ෻ᔕེౝߢలಽߥࠝ࠱ࡦ

23212008߇ᓧࠄࠇࠆ႐ว㧘ࠝ࠱ࡦ߇ VOC ಽ⸃ߦᨐߚߔᓎഀߪᭂ߼ߡౝߢ⊒↢ߐߖߚࠝ࠱ࡦ㧔O3㧕ࠍ 100͠ߩࠝ࡯ࡉࡦౝߢᷙวߐ㊀ⷐߣߥࠆ㧚ታ㓙ߦ㧘Gervasini ࠄߪ㧘ࠕࠢ࡝ࡠ࠾࠻࡝࡞㧘ࡔߖ㧘ߐࠄߦ᷷ᐲࠦࡦ࠻ࡠ࡯࡞ߐࠇߚⓨ╴ߩ⍹⧷⵾෻ᔕེߦዉ࠲ࡁ࡯࡞㧘ࠬ࠴࡟ࡦ㧘࠻࡞ࠛࡦ㧘1,2-ࠫࠢࡠࡠࠛ࠲ࡦ㧘Ⴎൻ౉ߒߚ㧔200 ppm-VOC, 1600 ppm-O3, 20 %-O2, N2 ࡃ࡜ࡦࠬ㧕㧚6,7)ࠍኻ⽎ߦࡊ࡜࠭ࡑಽ⸃ࠍ⹜ߺߡ߅ࠅ㧘ࡊ࡜࠭ࡑ෻ᔕ

R2 ߢߪ㧘VOC ߣ N2 ߩᷙวࠟࠬߦ㧘㉄⚛ࠍ 100͠ߩࠝ࡯ࡉࡦ

ེߣߘߩᓟᲑߦ Ba-CuO-Cr2O3/Al2O3 ⸅ᇦࠍ㈩ߔࠆߎߣߦࠃߞ

ౝߢᷙวߐߖ㧘⸅ᇦ෻ᔕེߦዉ౉ߒߚ㧔200 ppm-VOC, 20 %O2,ߡ㧔ੑᲑᑼ㧕㧘ߐࠄߦ㜞޿ VOC ಽ⸃ല₸߇ᓧࠄࠇࠆߎߣࠍႎ

N2 ࡃ࡜ࡦࠬ㧕
㧚R3 ߢߪ㧘VOC ߣ N2 ࠍᷙวߐߖߚࠟࠬߦ㧘㉄๔ߒߡ޿ࠆ㧚ᓐࠄߪ೨Ბߩࡊ࡜࠭ࡑಽ⸃ߦട߃ߡ㧘ᓟᲑߢߪ⚛ࠍࡊ࡜࠭ࡑ෻ᔕེౝߢ⊒↢ߐߖߚࠝ࠱ࡦࠍ 100͠ߩࠝ࡯ࡉ

ࠝ࠱ࡦߦࠃࠅᧂಽ⸃ VOC ߥࠄ߮ߦಽ⸃೽↢ᚑ‛ߩ㉄ൻ෻ᔕࡦౝߢᷙวߐߖ㧘⸅ᇦ෻ᔕེߦዉ౉ߒߚ㧚ࡆ࠾࡞߇ߐࠄߦടㅦߔࠆߣ⠨߃ߡ޿ࠆ㧚ߒ߆ߒ㧘෻ᔕਛߩࠝ࠱ࡦỚࠟࠬಽᨆߪ㧘2.4m 㐳శ〝࠮࡞㧔Infrared Analysis ␠⵾㧕ࠍ஻ᐲᄌൻߦߟ޿ߡߪᬌ⸛ߐࠇߡ߅ࠄߕ㧘VOC ಽ⸃ߦኻߔࠆታ㓙߃ߚ FT-IR (BioRad ␠⵾㧦FTS-135)ࠍ↪޿㧘ࠝࡦ࡜ࠗࡦߢቯ

ߩࠝ࠱ࡦߩ⽸₂ᐲ㧘ߔߥࠊߜ᳇⋧߿࿕૕⴫㕙ߢߩࠝ࠱ࡦߩ᦭

ᕈ࡮ቯ㊂ࠍⴕߞߚ㧚⿒ᄖࠬࡍࠢ࠻࡞ߪ㧘ಽ⸃⢻ 0.5 cm-1㧘Ⓧ▚ല೑↪₸ߥߤߪࠊ߆ߞߡ޿ߥ޿㧚࿁ᢙ 64 ࿁ߢ᷹ቯߒߚ㧚࠻࡞ࠛࡦ㧘ࠫࠢࡠࡠࡔ࠲ࡦࠍ᳇⋧ࠝ࠱੹࿁㧘ᚒ‫ ߪޘ‬VOC ಽ⸃ߦ߅ߌࠆࠝ࠱ࡦߩലᨐ㧘․ߦࠝ࠱

ࡦߦࠃߞߡ෻ᔕ᷷ᐲ 350͠ߢಽ⸃ࠍ⹜ߺߚߣ߈ߦᓧࠄࠇߚ⿒ࡦߩỚᐲᄌൻߦ⌕⋡ߒ㧘ᄙߊߩ VOC ಽ⸃ߦ᦭ലߢ޽ࠆߎߣ

ᄖࠬࡍࠢ࠻࡞ࠍ Fig.2 ߩ(a)ߣ(b)ߦߘࠇߙࠇ␜ߔ㧚࠻࡞ࠛࡦ㧘߇⍮ࠄࠇߡ޿ࠆ Ba-CuO-Cr2O3/Al2O3 ⸅ᇦࠍ↪޿ߡ㧘࠻࡞ࠛࡦࠫࠢࡠࡠࡔ࠲ࡦ㧘CO㧘CO2㧘ࠡ㉄㧔HCOOH㧕
㧘ࡎࠬࠥࡦ㧔COCl2㧕

ߣࠫࠢࡠࡠࡔ࠲ࡦߩಽ⸃෻ᔕࠍⴕߞߚ㧚หᤨߦ㧘ࠝ࠱ࡦ㧙⸅

ߩቯ㊂ಽᨆߦߪ㧘ਥߦ 729 cm-1㧘1268 cm-1㧘2103 cm-1㧘2274 cm-1㧘ᇦⶄว♽ߢ෻ᔕߦ㑐ਈߔࠆߣ⠨߃ࠄࠇࠆ᳇⋧ਛߩᵴᕈ㉄⚛⒳ߣ࿕૕⴫㕙਄ߩᵴᕈ㉄⚛⒳ࠍಽ㘃ߒ㧘100㨪400͠ߩฦ᷷ᐲ㗔ၞߦ߅ߌࠆ㧔1㧕᳇⋧ࠝ࠱ࡦ㧘
㧔2㧕ᾲ⊛ߦᵴᕈൻߒߚ࿕૕⸅ᇦ

(a)⴫㕙㧘ਗ߮ߦ㧔3㧕ࠝ࠱ࡦ߆ࠄ↢ߓߚ࿕૕⴫㕙਄ߩ㉄⚛ᵴᕈ⒳

CO22.

ታ㛎

᳇⋧ࠝ࠱ࡦߦࠃࠆᾲಽ⸃ᴺ㧔R1㧕
㧘ᓥ᧪ဳ㧔ᾲ㧕⸅ᇦಽ⸃

Absorbance߇㧘VOC ಽ⸃ߦᨐߚߔᓎഀߦߟ޿ߡᬌ⸛ࠍⴕߞߚ㧚Afterᴺ㧔R2㧕
㧘ࠝ࠱ࡦ⸅ᇦಽ⸃ᴺ㧔R3㧕ߩᵹ〝࿑ࠍ Fig.1 ߦ␜ߔ㧚
BeforeR1 ߢߪ㧘VOC ߣ N2 ࠍᷙวߐߖߚࠟࠬߦ㧘ࡊ࡜࠭ࡑ෻ᔕེ
Ozone / Oxygen

R1COH2O

4000 3500 3000 2500 2000 1500 1000
Wavenumber / cm-1
Furnace(b)VOC / N2

Furnace
Catalyst

Ozone / OxygenR3

VOC / N2

FurnaceCatalyst࿑ 1 VOC ߩ᳇⋧ࠝ࠱ࡦಽ⸃㧔R1㧕
㧘⸅ᇦಽ⸃㧔R2㧕
㧘ࠝ࠱ࡦ⸅ᇦಽ⸃㧔R3㧕ᴺߩᵹ〝࿑
Fig.1 Flow chart of VOC decomposition: (R1) ozonolysis,(R2) catalysis, and (R3) ozonolysis assisted by catalyst.

Absorbance

Oxygen

VOC / N2HCOOH

C6H5CH3

HCl

R2

H2O

AfterBefore

CO2
CO

COCl2

CH2Cl24000 3500 3000 2500 2000 1500 1000
W avenumber / cm-1
࿑ 2 ෻ᔕ᷷ᐲ 350͠ߢߩ VOC ߩ᳇⋧ࠝ࠱ࡦಽ⸃ᴺߦࠃࠆ
෻ᔕ೨ᓟߩ⿒ᄖࠬࡍࠢ࠻࡞㧦(a)࠻࡞ࠛࡦ㧘(b)ࠫࠢࡠ
ࡠࡔ࠲ࡦ
Fig.2 Infrared spectra on the decomposition of (a) toluene and(b) dichloromethane by R1 method.

3⴫ 1 ฦ⒳ᚻᴺߦࠃࠆ࠻࡞ࠛࡦ෸߮ࠫࠢࡠࡠࡔ࠲ࡦಽ⸃ᓟߩ↢ᚑ‛ಽᏓߣ὇⚛ߩ‛⾰෼ᡰ
Table 1 Selectivity of products and material balance of carbon in three reaction systems
Temp. / ͠100͠
200͠
300͠
350͠
100͠
200͠
300͠
400͠
100͠
200͠
300͠
400͠

R1R2R3Toluene
Selectivity in products / %COCO2HCOOH
078
2232561251
45449492㧙㧙
㧙
0
100
00
100
0010001683
1128801990
1990

Dichloromethane
Selectivity in products / %COCO2
COCl2
㧙㧙㧙㧙
㧙
㧙
1000<19244㧙㧙㧙㧙㧙㧙
595039605938044560188301189
0Material
Balance / %
15
48
73
79
㧙
13120
106
81
88
100
102

Material
Balance / %
㧙
㧙
8691
㧙
㧙
166
123
91
103
119
92

1103 cm-1㧘860 cm-1 ߩๆ෼ࡇ࡯ࠢࠍ↪޿ߚ㧚ߥ߅㧘COCl2 ߪࠝ࠱ࡦߪ㧘ዊ↰ࠄߦࠃߞߡឭ᩺ߐࠇߡ޿ࠆࠦࠗ࡞ဳᴪ㕙᡼ᮡḰࠟࠬߦࠃࠆᬌ㊂✢߇ᓧࠄࠇߥ޿ߚ߼㧘࠺࡯࠲ࡌ࡯ࠬ㔚ဳࡊ࡜࠭ࡑ෻ᔕེߦࠃࠅ⊒↢ߐߖߚ 8)㧚෻ᔕེߪ㧘⍹⧷▤㧔Infrared Analysis ␠⵾㧦QA-SOFT㧕ࠍ↪޿ߡቯ㊂ࠍⴕߞߚ㧚ߩᄖ๟ߦႣᏓߒߚ㌁ࡍ࡯ࠬ࠻ࠍធ࿾ᭂߦ㧘ౝოߦࠦࠗ࡞⁁ߦࠝ࠱ࡦߪ⚡ᄖ✢ๆ෼ᑼࠝ࠱ࡦỚᐲ⸘(⨶ේታᬺ␠⵾㧦ࡕ࠺࡞ኒ⌕ߐߖߚ⊕㊄ࡢࠗࡗ࡯(0.4 mm)ࠍ᡼㔚ᭂߣߒߚ᭴ㅧߦߥߞ

HARE PG640)ࠍ↪޿ߡቯ㊂ࠍⴕߞߚ㧚ࠨࡦࡊ࡝ࡦࠣߪ⸅ᇦ෻

ߡ޿ࠆ㧚⚐㉄⚛㧔㜞ජⓄൻቇ㧕100 mL/min ࠍࡊ࡜࠭ࡑ෻ᔕེ

ᔕེࠍ 100͠߆ࠄ 400͠߹ߢછᗧߩ෻ᔕ᷷ᐲߦ⸳ቯߒ㧘30 ಽߦᵹㅢߒ㧘੤ᵹ㜞㔚࿶㧔8.3 kV㧘๟ᵄᢙ 1 kHz㧕ࠍශടߔࠆߎ

⚻ㆊߒߚߩߜⴕߞߚ㧚ߒߚ߇ߞߡ㧘޿ߕࠇ߽ೋᦼᵴᕈ୯ࠍ␜

ߣߦࠃࠅ㧘8,000 ppm ߩࠝ࠱ࡦࠍᓧߚ㧚ᷙวࠟࠬߩ⚵ᚑߪ೨

ߔ㧚

಴ߩㅢࠅ㧚

࠻࡞ࠛࡦߪ 5͠ߦ଻ᜬߒߚᶧ૕⹜⮎㧔๺శ⚐⮎㧘․⚖㧕ࠍ⸅ᇦߪ㧘ࠛ࠿࡮ࠗ࡯࡮ࠤࡓࠠࡖ࠶࠻␠⵾㧘Cu-1230E(⚵ᚑᲧ:N2 ߢࡃࡉ࡝ࡦࠣߐߖ⊒↢ߐߖߚ㧚ࠫࠢࡠࡠࡔ࠲ࡦߪ N2 ߣߩ

Ba=5.4 %㧘Cu=23.2%㧘Cr=21.9%)ࠍ↪޿㧘੍߼ 150͠ߩࠝ࡯ᷙวࠟࠬ㧔㜞ජⓄൻቇᎿᬺ, CH2Cl2=1,060 ppm㧕ࠍ↪޿ߚ㧚ߎࡉࡦߢలಽੇ῎ߐߖߚᓟ㧘෻ᔕߦଏߒߚ㧚ߥ߅㧘ห⸅ᇦߩ⴫ࠇࠄࠍߐࠄߦ N2 ߣ O2㧔߅ࠃ߮ O3㧕ߢᏗ㉼ߒ㧘ోᵹ㊂߇ 500

㕙Ⓧߪ㧘ࡌ࡞࠰࡯ࡊ␠⵾ߩๆ⌕ⵝ⟎㧔BELSORP 18㧕ࠍ↪޿㧘

3BET ᴺߦࠃࠅ 125 m2/g ߣ᳞߼ࠄࠇߚ㧚

cm /min ߦߥࠆࠃ߁⺞⵾ߒߚ㧚

3.

Conversion of toluene/ %100

3.1

R380

⚿ᨐߣ⠨ኤ
࠻࡞ࠛࡦ %*%*㧦61. ߩಽ⸃

Fig.3 ߦฦ⒳ಽ⸃ᴺ㧔R1㧘R2㧘R3㧕ࠍ↪޿ߚ႐วߩ 100㨪
400͠ߦ߅ߌࠆ C6H5CH3 ߩಽ⸃᜼േࠍ␜ߔ㧚100㨪150͠ߢߪ

60
R240

R1

R1 ߣ R2 ߢಽ⸃₸ߦ߶ߣࠎߤᏅ߇⷗ࠄࠇߕ㧘175㨪300͠ߢߪ
R1 ߩᣇ߇ R2 ࠃࠅ߽߿߿㜞޿ಽ⸃₸ࠍ␜ߒߚ㧚ߒ߆ߒ㧘R2ߪ 350͠એ਄ߢ R1 ࠍ਄࿁ࠅ㧘߶߷ 100%ߩಽ⸃₸߇ᓧࠄࠇߚ㧚৻ᣇ㧘R3 ߢߪ 100͠ߦ߅޿ߡ߽ 50㧑ߩಽ⸃₸ࠍ␜ߒ㧘Ᏹߦ

20R2㧘R3 ࠃࠅ߽㜞޿ಽ⸃ᕈ⢻ࠍ␜ߔߎߣ߇ࠊ߆ߞߚ㧚

0100

200
300
400
oTemperature / C࿑ 3 ฦ᷷ᐲߦ߅ߌࠆ࠻࡞ࠛࡦߩಽ⸃᜼േ㧦(R1) ᳇⋧ࠝ࠱ࡦߦࠃࠆᾲಽ⸃ᴺ, (R2) ⸅ᇦಽ⸃ᴺ, (R3) ࠝ࠱ࡦ⸅ᇦಽ⸃ᴺ.
Fig.3 Conversion of toluene as a function of temperature: (R1)ozonolysis, (R2) catalysis, and (R3) ozonolysis assisted bycatalyst.

ਥ↢ᚑ‛ߣߘߩㆬᛯ₸ࠍ Table 1 ߦ␜ߔ㧚⴫ਛߩㆬᛯ₸ߪ㧘㨇ฦ↢ᚑ‛㊂㨉㨇ᬌ಴ߐࠇߚో↢ᚑ‛㊂㨉/ߩᲧ₸ߣߒߡ⴫ߔ㧚
R1 ߢߪ CO2 ߳ߩㆬᛯ₸߇ 350͠ߢ 50㧑⒟ᐲߥߩߦኻߒ㧘R2
ߢߪ 200͠એ਄ߩ᷷ᐲߢ߶߷ 100%ߦ㆐ߒߚ㧚R2 ߢߪ὇⚛ߩ‛⾰෼ᡰ߇ 100%ࠍ⿥߃ࠆ⚿ᨐ߽ᓧࠄࠇߡ߅ࠅ㧘ߎࠇࠄߪ⸅ᇦ਄ߦๆ⌕ߒߚ C6H5CH3 ߹ߚߪߘߩਛ㑆૕߇ಽ⸃࡮⣕㔌ߒߚ߽ߩߦ⿠࿃ߔࠆߣ⠨߃ࠄࠇࠆ㧚R3 ߢߪ㧘100͠ߦ߅޿ߡᣢߦ

43212008

CO2 ㆬᛯ₸ߪ 83㧑ߦ㆐ߒߡ߅ࠅ㧘ߐࠄߦ᷷ᐲ਄᣹ߣ౒ߦㆬᛯ߆ߦߥߞߚ㧚߹ߚ㧘޿ߕࠇߩ♽ߢ߽ 300͠એ਄ߢ HCl ߇᷹ⷰ₸ߩะ਄߇ߺࠄࠇߚ㧚ߐࠇߚ㧔 Fig.2(b) 㧕㧚৻ᣇ㧘R1 ߢ HCOOH ߩ↢ᚑ߇ߺࠄࠇߚ߇㧘R2㧘R3 ߢߪ߶ᵴᕈ㉄⚛⒳ߩᬌ⸛

એ਄ߩ෻ᔕ⚿ᨐ㧘ਗ߮ߦએਅߢ␜ߔ O3 Ớᐲᄌൻߩ⚿ᨐࠍ߽ߣࠎߤ᷹ⷰߐࠇߥ߆ߞߚ㧚
3.23.3ࠫࠢࡠࡠࡔ࠲ࡦ(CH2Cl2㧦DCM)ߩಽ⸃

ߣߦ㧘ฦ෻ᔕ♽ߦ߅ߌࠆ VOC ಽ⸃ߦኻߔࠆฦ⒳㉄⚛ᵴᕈ⒳Fig.4 ߦฦ⒳ಽ⸃ᴺ㧔R1㧘R2㧘R3㧕ࠍ↪޿ߚ႐วߩ 100㨪ߩ෻ᔕᕈߦߟ޿ߡᬌ⸛ࠍⴕߞߚ㧚400͠ߩ᷷ᐲ㗔ၞߦ߅ߌࠆ CH2Cl2 ߩಽ⸃᜼േࠍ␜ߔ㧚R1 ߢߪ

3.3.1

250͠એਅߢ CH2Cl2 ߪ߶ߣࠎߤಽ⸃ߒߥ߆ߞߚ㧚ߒ߆ߒ㧘߹ߕ㧘R1 ߣ R3 ߦ߅ߌࠆ᳇⋧ O3 ߩỚᐲߩᄌൻ߆ࠄ㧘ߎࠇ

300͠ࠍ⿥߃ࠆߣ CH2Cl2 ߪᕆỗߦಽ⸃ߒᆎ߼㧘350͠ߢಽ⸃₸ࠄߩ෻ᔕ♽ߦ߅ߌࠆᵴᕈ㉄⚛⒳ߩ෻ᔕ․ᕈࠍ⺞ߴߚ㧚Fig.5 ߣߪ 55%ߦ㆐ߒߚ㧚R2 ߢ߽ 200͠એਅߢߪ߶ߣࠎߤಽ⸃ߒߥ߆

Fig.6 ߦ R1 ߣ R3 ߦ߅ߌࠆ VOC㧔C6H5CH3㧘CH2Cl2㧕ಽ⸃ᤨ㧘ߞߚ߇㧘250͠એ਄ߢߪ᷷ᐲ਄᣹ߣߣ߽ߦಽ⸃₸߇ะ਄ߒ㧘ਗ߮ߦ VOC 㕖ሽ࿷ਅߢߩ᳇⋧ਛߩ O3 Ớᐲࠍ␜ߔ㧚᳇⋧ਛߩᵴᕈ㉄⚛⒳

400͠ߢ 55%ߩಽ⸃₸߇ᓧࠄࠇߚ㧚R3 ߢߪ㧘100͠ߦ߅޿ߡ

Fig.5 ࠃࠅ㧘౒ሽߔࠆ C6H5CH3 ߿ CH2Cl2 ߦࠃߞߡ㧘᳇⋧ O3߽ 20%⒟ᐲߩಽ⸃₸߇ᓧࠄࠇ㧘᷷ᐲ਄᣹ߣߣ߽ߦ✭߿߆ߦಽߩᷫዋ௑ะ߇⇣ߥࠆߎߣ߇ࠊ߆ࠆ㧚ᓟ⠪ߢߪߘߩ௑ะ߇᳇⋧⸃₸߇Ⴧᄢߒ㧘300͠ߢߪ 40%ߦ㆐ߒߚ㧚ߐࠄߦߘࠇએ਄ߩO3 ߩᾲಽ⸃ߣ߶߷৻⥌ߒߡ޿ࠆߩߦኻߒ㧘೨⠪ߢߪߘࠇࠃࠅ᷷ᐲߢߪ㧘ᕆỗߦಽ⸃₸߇Ⴧᄢߒ㧘400͠ߦ߅޿ߡಽ⸃₸ߪ߽ૐ޿᷷ᐲߢ O3 ߇ᶖ⾌ߐࠇߡ޿ࠆߎߣ߇ࠊ߆ࠆ㧚250͠એਅ

84%ߦ㆐ߒߚ㧚ߩ᷷ᐲ㗔ၞߦ߅޿ߡ㧘C6H5CH3 ߪಽ⸃ߒ CH2Cl2 ߪ߶ߣࠎߤಽ

ਥ↢ᚑ‛ߢ޽ࠆ CO ߣ CO2 ߩㆬᛯ₸ࠍ Table 1 ߦ␜ߔ㧚R1⸃ߒߡ޿ߥ޿ߎߣ߆ࠄ㧘᳇⋧ VOC ߦኻߔࠆ⋥ធ⊛ߥ O3 ߩ෻ߢߪ㧘↢ᚑ‛ߩ߶ߣࠎߤ߇ CO ߢ޽ߞߚ㧚ߎࠇߣኻᾖ⊛ߦ㧘ᔕᕈߩ㆑޿߇⏕⹺ߢ߈ߚ㧚C6H5CH3 ߪ㧘100͠ߦ߅޿ߡ߽ಽ⸃

R2 ߢߪ߶ߣࠎߤ߇ CO2 ߦಽ⸃࡮㉄ൻߐࠇߚ㧚‛⾰෼ᡰ߽ 100%߇⿠ߎߞߡ޿ࠆߎߣ߆ࠄ㧘᳇⋧ O3 ߣߩ⋥ធ⊛ߥ෻ᔕ߇␜ໂߐ

ࠍ⿥߃ࠆ୯ࠍ␜ߒߡ޿ࠆߎߣ߆ࠄ㧘CH2Cl2 ߩ႐ว߽ C6H5CH3ࠇࠆ㧚ߎࠇߦኻߒߡ㧘CH2Cl2 ߩ႐ว㧘᳇⋧ਛߩ O3 ಽ⸃㧔O3 ĺߣห᭽ߦ⸅ᇦߦๆ⌕ߒߡ޿ߚ CH2Cl2㧘޽ࠆ޿ߪߘߩ෻ᔕਛ㑆O2 + O㨯gas㧕߇ᕆỗߦଦㅴߐࠇࠆ 250͠એ਄ߩ᷷ᐲၞߢ෻ᔕ߇

૕߇᷷ᐲߩ਄᣹ߣ౒ߦಽ⸃࡮⣕㔌ߒߡ߈ߚ߽ߩߣ⠨߃ࠄࠇࠆ㧚ᆎ߹ߞߡ߅ࠅ㧘O࡮gas ߣߩ෻ᔕ߇ਥ෻ᔕߣ⠨߃ࠄࠇࠆ㧚੐ታ㧘

R3 ߢߪ㧘100͠ߦ߅޿ߡ CO2 ㆬᛯ₸ߪ 38%ߢ޽ߞߚ߇㧘᷷ᐲO࡮gas ߣ CH2Cl2 ߣߩ෻ᔕㅦᐲቯᢙߪ㧘ߎߩ᷷ᐲએ਄ߢᄢ߈ߊߩ਄᣹ߣ౒ߦะ਄ߒߚ㧚ߥࠆߎߣ߇⍮ࠄࠇߡ޿ࠆ 9)㧚એ਄ߩߎߣ߆ࠄ㧘C6H5CH3 ߩ႐ߥ߅㧘COCl2 ߇ R1 ߢ 300͠ߩߣ߈ߦ᷹ⷰߐࠇߚ߇㧘⸅ᇦࠍว㧘200͠એਅߩਥߥᵴᕈ㉄⚛⒳ߪ᳇⋧ O3 ߘߩ߽ߩߣ⠨߃ࠆ↪޿ࠆߎߣ㧔R2㧘R3㧕ߢ㧘ߎߩ↢ᚑࠍᛥ೙ߢ߈ࠆߎߣ߇᣿ࠄ
Outlet ozone concentration / ppm

1600

Conversion of DCM / %

100
80

R360

R140

R220
0100

200
300
Temperature / oC

R1-DCM

R1-O 3, ozone alone

1200

800

400

0100

R1-TOL

200
300
Tempe rature / oC

400400࿑ 4 ฦ᷷ᐲߦ߅ߌࠆ DCM ߩಽ⸃᜼േ㧦(R1) ᳇⋧ࠝ࠱ࡦߦࠃࠆᾲಽ⸃ᴺ, (R2) ⸅ᇦಽ⸃ᴺ, (R3) ࠝ࠱ࡦ⸅ᇦಽ⸃ᴺ.
Fig.4 Conversion of DCM as a function of temperature: (R1)ozonolysis, (R2) catalysis, and (R3) ozonolysis assisted bycatalyst.

࿑5 VOC㧙᳇⋧ࠝ࠱ࡦಽ⸃ᴺߦ߅ߌࠆ෻ᔕ᷷ᐲߣ᳇⋧ࠝ࠱ࡦỚᐲߩ㑐ଥ㧦(R1-TOL)࠻࡞ࠛࡦ㧘(R1-DCM) ࠫࠢࡠࡠࡔ࠲ࡦ㧘
㧔R1-O3㧕VOC ߥߒ
Fig.5 Ozone concentration in the downstream as a function oftemperature on pyrolysis of ozone (R1-O3), and on
ozonolysis of (R1-TOL) toluene and(R1-DCM)
dichloromethane. (R1-O3)

5ߎߣ߇ߢ߈㧘250͠એ਄ߦߥࠆߣ O3 ߩᾲಽ⸃߆ࠄ↢ߓߚේሶᶖ⾌㊂ߦኻߔࠆ VOC ಽ⸃㊂ߩ㑐ଥ㧕ߪ R1 ߣߪ᣿ࠄ߆ߦ⇣ߥ⁁㉄⚛㧔O㨯gas㧕߇ C6H5CH3 ߩߺߥࠄߕ CH2Cl2 ߩಽ⸃ࠍଦㅴ

ߞߡ߅ࠅ㧘 R3 ߦ߅޿ߡ O3 ߆ࠄᓧࠄࠇߚ⸅ᇦ਄ߩ*Oads ߩ௛ߔࠆߣ⠨߃ࠄࠇߚ㧚߈ࠍ․ᓽߠߌࠆ߽ߩߦߥߞߡ޿ࠆ㧚ߚߛߒ㧘ᰴ▵ߢ⠨ኤߔࠆ3.3.2߇㧘ᶖ⾌ߐࠇߚᄙߊߩ O3 ߪᔅߕߒ߽ VOC ಽ⸃ߦ↪޿ࠄࠇߡ࿕૕⴫㕙਄ߩᵴᕈ㉄⚛⒳޿ߕࠇߩ᷷ᐲၞߢ߽ R3 ߪ R1 ߿ R2 ࠃࠅ߽㜞޿ಽ⸃ᵴᕈࠍ

޿ߥ޿ߎߣ߽᣿ࠄ߆ߦߥߞߚ㧚␜ߒߚ㧚㜞᷷ၞ㧔250͠એ਄㧕ߢߪ O3 ߩᾲಽ⸃߇ଦㅴߐࠇࠆR2 ߩᾲ⸅ᇦ♽ߢߪ㧘ᩰሶ㉄⚛޽ࠆ޿ߪ᳇⋧ O2 ↱᧪ߩᵴᕈߚ߼㧘R3 ߦ߅޿ߡ߽೨▵ห᭽ߩ᳇⋧ਛߩᵴᕈ㉄⚛⒳߇෻ᔕߦ

㉄⚛⒳߇⸅ᇦ਄ߢ㉄ൻ෻ᔕࠍଦㅴߔࠆߣ⠨߃ࠄࠇࠆ㧚ߒ߆ߒ㧘ነਈߒߡ޿ࠆน⢻ᕈ߇޽ࠆ㧚ߘߎߢ㧘ߘߩᓇ㗀߇ዋߥߊ⸅ᇦ

Fig.3 ߣ Fig.4 ࠃࠅ㧘߶ߣࠎߤߩ᷷ᐲ㗔ၞߢ㧘R2 ߪ R1 ࠃࠅಽߩലᨐ߇ࠊ߆ࠅ߿ߔ޿ 100㨪250͠ߩૐ᷷ၞߦߟ޿ߡ㧘ߪߓ߼⸃ᵴᕈ߇ૐ޿㧚ᧄታ㛎᧦ઙߢߪ VOC ߩಽ⸃ߦ᦭ലߥᵴᕈ㉄ߦᬌ⸛ࠍⴕߞߚ㧚⚛⒳߇⸅ᇦߛߌߢߪలಽᓧࠄࠇߥ޿߆㧘ߘߩ෻ᔕᕈ߇ O3 ߿ࠝ࠱ࡦ⸅ᇦಽ⸃ᴺߩ෻ᔕᯏ᭴ߣߒߡ৻⥸⊛ߥ‫ޟ‬࿕૕⸅ᇦ਄
ߩ O3 ߆ࠄ↢ߓߚ*Oads ߇ VOC ࠍಽ⸃ߔࠆ‫ޠ‬෻ᔕᯏ᭴ߦၮߠ޿5)O࡮gas ࠃࠅ߽ૐ޿ߎߣࠍ␜ߒߡ޿ࠆ㧚ᰴߦ㧘R3 ߩ 250͠એ਄ߦ߅ߌࠆ෻ᔕᵴᕈߩะ਄ലᨐߦߟ޿

ߡ⠨ኤࠍⴕߞߚ 㧚Fig.6 ߆ࠄ߽᣿ࠄ߆ߥࠃ߁ߦ㧘O3 ಽ⸃߇ૐߡᬌ⸛ࠍⴕߞߚ㧚C6H5CH3㧘CH2Cl2 ߣ߽㧘ૐ᷷ၞߩಽ⸃ᵴᕈ

᷷ၞ߆ࠄᆎ߹ߞߡ߅ࠅ㧘*Oads ߩ↢ᚑ߇ᦼᓙߐࠇࠆ㧚ߦട߃㧘
R1 ߣ R2 ߩᓇ㗀ࠍᒝߊฃߌߡ޿ࠆࠃ߁ߦ⷗߃ࠆ㧚Fig.3
ߣ Fig.4 ߩ෻ᔕ᷷ᐲߦኻߔࠆಽ⸃ᵴᕈߪ250͠೨ᓟࠍႺߦ⊒⃻O3 + * ĺ O2 + *Oads(1)ߒߡ߅ࠅ㧘⋧ਸ਼ലᨐ߇ߤߜࠄߩᓇ㗀ߦࠃࠆ߽ߩ߆ߪන⚐ߦ್*Oads + VOC ĺ COx + H2O + *(2)ᢿߢ߈ߥ޿㧚ߒ߆ߒ㧘R1 ߪ CO ㆬᛯ₸߇㜞ߊ㧘R2 ߪ CO2 ㆬᛯ₸߇㜞޿ߣ޿߁↢ᚑ‛ಽᏓߦ․ᓽ⊛ߥ㆑޿߇޽ࠆ㧚R3 ߩ↢*㧦⸅ᇦᵴᕈὐ㧘*Oads㧦⸅ᇦ਄ߦ↢ߓߚᵴᕈ㉄⚛

ᚑ‛ਛߩㆬᛯ₸߆ࠄ್ᢿߔࠆߣ㧘R2 ߩ㑐ਈ߇ᒝߊ␜ໂߐࠇߚ㧚޿ߕࠇߦߖࠃ R3 ߩ 300͠એ਄ߩ෻ᔕߦߪ CO ㉄ൻ෻ᔕ߽฽߼㧘Fig.7 ߦ᳇⋧ O3 ߇౒ሽߔࠆ♽ߦ߅ߌࠆ㧘⸅ᇦߩ᦭࡮ήߩ㆑
޿㧘VOC ߩ㆑޿ߦࠃࠆO3 ᶖ⾌㊂ߣVOC ಽ⸃㊂ߩ㑐ଥࠍ␜ߔ㧚ᩰሶ㉄⚛޽ࠆ޿ߪ᳇⋧ O2 ↱᧪ߩᵴᕈ㉄⚛⒳ߩ㑐ਈ߇޽ࠆߎߣߪ⏕߆ߢ޽ࠆ㧚Ყセߩߚ߼㧘᳇⋧ O3 ߦࠃࠆ C6H5CH3 ߩಽ⸃ߩ⚿ᨐ߽ࡊࡠ࠶
࠻ߒߚ㧚C6H5CH3 ߩಽ⸃㊂ߪᶖ⾌ߐࠇࠆ O3 ㊂ߣ⦟޿⋧㑐߇޽

3.4ࠆߎߣ߇ࠊ߆ࠆ㧚ߚߛߒ㧘೨▵ߢㅀߴߚࠃ߁ߦ᳇⋧ O3 ߦࠃࠆR3 ߪ VOC ಽ⸃ߦ᦭ലߢ޽ࠆߎߣ߇␜ߐࠇߚ߇㧘O3 ߩ೑↪

CH2Cl2 ߩಽ⸃ߪ⿠ߎࠄߥ޿㧚৻ᣇ㧘R3 ߽ VOC ߩ⒳㘃ߦଐࠄല₸߇ૐ޿ߚ߼㧘ߐࠄߦᕈ⢻ࠍ㜞߼ࠄࠇࠆน⢻ᕈ߇޽ࠆ㧚ߎߕ⦟޿⋧㑐߇⷗ࠄࠇࠆߎߣ߇ࠊ߆ࠆ㧚ߚߛߒ㧘ߘߩ௑߈㧔O3ࠇࠄ߇ૐ޿ℂ↱ߣߒߡߪ㧘⸅ᇦߦࠃࠆ O3 ߆ࠄ O2 ߳ߩ෻ᔕ㧘

R3 ߩࠝ࠱ࡦ೑↪ല₸ะ਄ߩߚ߼ߩᜰ㊎200

oz one al one

1200

800

R3-DCM
Decomposed VOC / ppm

Outlet ozone concentration / ppm

1600

R3-TOLR3-O3400

0100

200
300
Temperature / oC400

࿑ 6 VOC㧙ࠝ࠱ࡦ⸅ᇦಽ⸃ᴺߦ߅ߌࠆ෻ᔕ᷷ᐲߣ᳇⋧ ࠝ ࠱ ࡦ Ớ ᐲ ߩ 㑐 ଥ 㧦 (R3-TOL) ࠻ ࡞ ࠛ ࡦ ,(R3-DCM) ࠫࠢࡠࡠࡔ࠲ࡦ, (R3-O3) VOC ߥߒ.
Fig. 6 Ozone concentration in the downstream as a functionof temperature on ozonolysis assisted by catalyst of(R3-TOL) toluene and (R3-DCM) dichloromethane, andon (R3-O3) the decomposition of ozone by the catalyst.

150
R3-TOL100
R1-T OL50

R3-DC M

R1-DCM

00

400

800

1200

1600

Consumed O3 / ppm

࿑ 7 R1 ߣ R3 ߦ߅ߌࠆࠝ࠱ࡦᶖ⾌㊂ߣ VOC ಽ⸃㊂ߩ㑐ଥ
㧔100㨪250͠㧕
Fig.7 Relationship between decomposed VOC and consumedozone on R1 and R3 (100 to 250oC).

63212008ࠝ࠱ࡦ㧙⸅ᇦⶄว♽ߦ߅ߌࠆ VOC ಽ⸃ߦ᦭ലߥᵴᕈ㉄⚛⒳ߩᬌ⸛㧔㥲⮮࿻Ꮢࠄ㧕ߔߥࠊߜ VOC ಽ⸃ߦነਈߒߥ޿*Oads㧔O3 ๆ⌕ࠨࠗ࠻㧕߇ሽ޿ VOC ಽ⸃ᵴᕈࠍ␜ߒߚ㧚߹ߚ㧘⸅ᇦ਄ߢᓧࠄࠇߚᵴᕈ㉄࿷ߔࠆߎߣࠍᜰ៰ߢ߈ࠆ㧚⚛⒳(*Oads)ߪ㧘᳇⋧ࠝ࠱ࡦ߿ࠝ࠱ࡦ߆ࠄߩᾲಽ⸃ߦࠃࠅ↢ߓߚේሶ⁁㉄⚛㧔O㨯gas㧕ࠃࠅ߽㧘ࠃࠅૐ޿᷷ᐲߢ VOC ಽ⸃෻2*Oads ĺ O2 + 2*(3)ᔕߦ᦭ലߢ޽ࠆߎߣ߇᣿ࠄ߆ߦߥߞߚ㧚ߐࠄߦ㧘ห⸅ᇦࠍ↪
޿ߡࠝ࠱ࡦ೑↪ല₸ࠍ਄ߍࠆߚ߼ߦߪ㧘෻ᔕ᷷ᐲࠍૐߊߔࠆታ㓙ߦ㧘Fig.6 ߩ 100͠ߩ࠺࡯࠲߆ࠄ߽ VOC ߇ሽ࿷ߔࠆᣇߎߣ߇᦭ലߢ޽ࠆߎߣࠍᜰ៰ߒߚ㧚߇㧘O3 ߩಽ⸃߇ᛥ೙ߐࠇߡ޿ࠆߎߣ߇ࠊ߆ߞߡ߅ࠅ㧘ߎࠇࠄߪ VOC ߩๆ⌕ࠨࠗ࠻ߣ O3 ߩๆ⌕ࠨࠗ࠻߇┹วߔࠆߚ߼㧘O3ෳ⠨ᢥ₂1) ⅣႺ⊕ᦠ ᐔᚑ 18 ᐕᐲ  ⅣႺ⋭ߩಽ⸃߇ᛥ߃ࠄࠇࠆߎߣࠍ␜ໂߒߡ޿ࠆ㧚2) ㊄⾫ᄐ, ᳗㐳ਭኡ, የᒻᢕ: ⅣႺ▤ℂ, 40 (2004) 1109

Fig.7 ߦ߅޿ߡ㧘O3 ᶖ⾌㊂ߩዊߐ޿ታ㛎⚿ᨐߪૐ᷷஥ߢᓧ3) C. M. Nunez, G. H. Ramsey, W.H. Ponder, J. H. Abbott, L.E.

ࠄࠇߚ߽ߩࠍ෻ᤋߒߡ޿ࠆߎߣ߆ࠄ㧘෻ᔕ᷷ᐲ߇ૐ᷷ߦߥࠆ

Hamel and P.H. Kariher: Air Waste, 43 (1993) 242

߶ߤ O3 ೑↪ല₸߇㜞޿ߎߣ߇᣿ࠄ߆ߦߥߞߚ㧚ߚߛߒ㧘Table.1 ߢ߽᣿ࠄ߆ߥࠃ߁ߦ㧘᷷ᐲ߇ૐߊߥࠆߣ෻ᔕ೨ᓟߩ὇4) የᒻᢕ: ࠛࠕࡠ࠱࡞⎇ⓥ, 21 (2006) 215⚛ߩ‛⾰෼ᡰ߿ CO2 ㆬᛯ₸߇ૐਅߔࠆน⢻ᕈ߇޽ࠆߚ߼㧘R35) ᳗㐳ਭኡ: ࠢ࡝࡯ࡦ࠹ࠢࡁࡠࠫ࡯㧘16 (2006) 6

ߢߪ VOC ߩ⒳㘃ߏߣߦ᷷ᐲ⸳ቯߩᦨㆡൻ߇ᔅⷐߦߥࠆߣ⠨6) A. Gervasini, G. C. Vezzoli and V. Ragaini: Catal. Today, 29(1996) 449

߃ࠄࠇࠆ㧚7) A. Gervasini and V. Ragaini: Catal. Today, 60 (2000) 129
4.

8) T. Oda, T. Takahashi, K. Tada: IEEE Trans. Ind. Appl., 35(1999)

߹ߣ߼373᳇⋧ࠝ࠱ࡦߪ 100㨪400͠ߩ᷷ᐲၞߢ Ba-CuO-Cr2O3/Al2O39) J. T. Herron: J. Phys. Chem. Ref., Data, 17 (1988) 967

⸅ᇦߣห╬߆ߘࠇએ਄ߩಽ⸃⢻ജࠍ␜ߒߚ㧚৻ᣇ㧘᳇⋧ࠝ࠱ࡦߣ⸅ᇦࠍ⚵ߺวࠊߖߚⶄว♽ߢߪ㧘ߘࠇࠄࠃࠅ߽ߐࠄߦ㜞- 6 -