⺰
ᢥ
ࠝ࠱ࡦ㧙⸅ᇦⶄว♽ߦ߅ߌࠆ
VOC ಽ⸃ߦലߥᵴᕈ㉄⚛⒳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-Cr
2O
3/Al
2O
3catalyst by ozone in a range of 100 to 400͠. In order to clarify the role of ozone and other oxygen species, we
investigated three types of oxidation methods, i.e., by gas phase ozone alone (R1), the catalyst alone (R2), and the
catalyst with ozone (R3). The performance in the gas phase ozone was equal to or higher than that on the catalyst
alone. However, it was shown that the performance on the catalyst was enhanced with ozone in a range of 100 to
200͠. In other words, the active oxygen species on the catalyst derived from ozone, O
ads, were effective for VOCs
decomposition even at low temperature. The utilization factor of ozone for VOCs, which is defined as a ratio of
removed VOC and consumed ozone, was investigated in R3. The lower the reaction temperature, the higher the
utilization factor was. It seems that O
adswas consumed for not only the removal of VOC but also the recombination
into oxygen at high temperature.
1. ߪߓߦ ើ⊒ᕈᯏൻว‛㧔VOC㧕ߪ㧘శൻቇࠝࠠࠪ࠳ࡦ࠻߿ᶋㆆ ☸ሶ‛⾰ߩේ࿃ߩ৻ߟߣ⠨߃ࠄࠇߡ߅ࠅ㧘ᣣᧄ࿖ౝߢߪᐔᚑ 18 ᐕ߆ࠄⷙ߮⥄ਥ⊛ขࠅ⚵ߺߦࠃࠆឃᛥኻ╷߇ផ ㅴߐࠇࠆߎߣߣߥߞߚ㧔ࡌࠬ࠻ࡒ࠶ࠢࠬ㧕1)㧚VOC ኻ╷ߣߒ ߡߔߢߦ㧘Άᴺ㧘ๆ⌕ᴺ㧘↢‛ಣℂᴺ╬ߩᛛⴚ߇㐿⊒ߐࠇ㧘 ታ㓙㧘ᄙߊߩዉታ❣߇ࠆ㧚ߎߩ߁ߜ㧘⋥ធ㧔⫾ᾲ㧕Ά ᴺ߿⸅ᇦ㉄ൻᴺߪ㧘ⷙኻ⽎ߣߥߞߡࠆ㜞Ớᐲ VOC ኻ╷ ᛛⴚߣߒߡ㧘ᣢߦᄢⷙᮨ⊒↢Ḯߦዉ߇ㅴࠎߢࠆ㧚ߒ߆ߒ㧘 ਛዊᬺᚲߢߪ㧘⸳⟎႐ᚲ߿⸳⟎ᓟߩࠦࠬ࠻㕙ߢㆡᒰߥᛛⴚ ߇ߥߎߣ߆ࠄ㧘ኻ╷߇ㆃࠇߡࠆ㧚ߎࠇࠄࠍ⢛᥊ߦ㧘ਛዊ ᬺᚲࠍኻ⽎ߣߒߚశ⸅ᇦ㧘ૐ᷷ࡊ࠭ࡑ㧘ࠝ࠱ࡦߥߤࠍ ↪ߒߚᣂߚߥଦㅴ㉄ൻᛛⴚ߇ᬌ⸛ߐࠇߡࠆ2)㧚 ૐ᷷ࡊ࠭ࡑᴺߪ㧘ૐỚᐲߩើ⊒ᕈᯏ‛⾰ߦኻߒߡ㧘ᓥ ᧪ဳߩಽ⸃ᴺࠃࠅ߽ࠦࠬ࠻ࠍૐߊᛥ߃ࠄࠇ㧘ᄙߊߩൻቇ‛⾰ ࠍಽ⸃ߢ߈ࠆᣇᴺߣߒߡ⍮ࠄࠇߡࠆ㧚․ߦ㧘ಽ⸃⢻ജࠍ㜞 ࠆߚߦ⸅ᇦߣߩⶄวൻ߇ㅴࠄࠇ㧘⋧ਸ਼ലᨐߦߟߡ߽ ᄙߊߩႎ๔߇ߥߐࠇߡࠆ3)㧚 ⋧ਸ਼ലᨐߪ㧘ࡊ࠭ࡑߦࠃࠆ⊒శ㧘ࠝ࠱ࡦ↢ᚑ㧘⸅ᇦߩᵴ ᕈൻߥߤߦ࿃ߔࠆߣ⠨߃ࠄࠇߡࠆ4)㧚ߘߩਛߢ߽㧘ࠝ࠱ ࡦ⸅ᇦಽ⸃ᴺߢ⍮ࠄࠇࠆࠃ߁ߦ 5)㧘ሽߐߖࠆ⸅ᇦߦㆡᒰߥ ࠝ࠱ࡦಽ⸃⢻߇ࠅ㧘߆ߟࡊ࠭ࡑᔕེౝߢలಽߥࠝ࠱ࡦ 䉨䊷䊪䊷䊄䋺䉥䉹䊮䋬⸅ᇦ䋬ᵴᕈ㉄⚛⒳䋬ើ⊒ᕈᯏൻว‛䋬 VOC * ↥ᬺᛛⴚ✚ว⎇ⓥᚲⅣႺ▤ℂᛛⴚ⎇ⓥㇱ㐷䋨305-8569 ⨙ၔ⋵䈧䈒䈳Ꮢዊ㊁Ꮉ16-1䋩National Institute of Advanced Industrial Science and Technology (AIST), 16-1 Onogawa, Tsukuba, Ibaraki
305-8569, Japan
** ၯ₹ᎿᬺᄢቇᎿቇㇱ䋨369-0293 ၯ₹⋵ᷓ⼱Ꮢ᥉ᷣኹ 1690䋩
Saitama Institute of Technology, 1690 Fusaiji, Fukaya, Saitama 369-0293, Japan
*** Ꮊᄢቇᄢቇ㒮✚วℂᎿቇ⎇ⓥ㒮䋨816-8580 ጟ⋵ᤐ ᣣᏒᤐᣣ6-1䋩
Kyushu University, 6-1 Kasugakoen, Kasuga, Fukuoka 816-8580, Japan
߇ᓧࠄࠇࠆ႐ว㧘ࠝ࠱ࡦ߇VOC ಽ⸃ߦᨐߚߔᓎഀߪᭂߡ ㊀ⷐߣߥࠆ㧚ታ㓙ߦ㧘Gervasini ࠄߪ㧘ࠕࠢࡠ࠾࠻࡞㧘ࡔ ࠲ࡁ࡞㧘ࠬ࠴ࡦ㧘࠻࡞ࠛࡦ㧘1,2-ࠫࠢࡠࡠࠛ࠲ࡦ㧘Ⴎൻ ࡆ࠾࡞6,7)ࠍኻ⽎ߦࡊ࠭ࡑಽ⸃ࠍ⹜ߺߡ߅ࠅ㧘ࡊ࠭ࡑᔕ ེߣߘߩᓟᲑߦBa-CuO-Cr2O3/Al2O3⸅ᇦࠍ㈩ߔࠆߎߣߦࠃߞ ߡ㧔ੑᲑᑼ㧕㧘ߐࠄߦ㜞VOC ಽ⸃ല₸߇ᓧࠄࠇࠆߎߣࠍႎ ๔ߒߡࠆ㧚ᓐࠄߪ೨Ბߩࡊ࠭ࡑಽ⸃ߦട߃ߡ㧘ᓟᲑߢߪ ࠝ࠱ࡦߦࠃࠅᧂಽ⸃VOC ߥࠄ߮ߦಽ⸃↢ᚑ‛ߩ㉄ൻᔕ ߇ߐࠄߦടㅦߔࠆߣ⠨߃ߡࠆ㧚ߒ߆ߒ㧘ᔕਛߩࠝ࠱ࡦỚ ᐲᄌൻߦߟߡߪᬌ⸛ߐࠇߡ߅ࠄߕ㧘VOC ಽ⸃ߦኻߔࠆታ㓙 ߩࠝ࠱ࡦߩ⽸₂ᐲ㧘ߔߥࠊߜ᳇⋧߿࿕㕙ߢߩࠝ࠱ࡦߩ ല↪₸ߥߤߪࠊ߆ߞߡߥ㧚 ࿁㧘ᚒޘߪVOC ಽ⸃ߦ߅ߌࠆࠝ࠱ࡦߩലᨐ㧘․ߦࠝ࠱ ࡦߩỚᐲᄌൻߦ⌕⋡ߒ㧘ᄙߊߩ VOC ಽ⸃ߦലߢࠆߎߣ ߇⍮ࠄࠇߡࠆBa-CuO-Cr2O3/Al2O3⸅ᇦࠍ↪ߡ㧘࠻࡞ࠛࡦ ߣࠫࠢࡠࡠࡔ࠲ࡦߩಽ⸃ᔕࠍⴕߞߚ㧚หᤨߦ㧘ࠝ࠱ࡦ㧙⸅ ᇦⶄว♽ߢᔕߦ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 㕙㧘ਗ߮ߦ㧔3㧕ࠝ࠱ࡦ߆ࠄ↢ߓߚ࿕㕙ߩ㉄⚛ᵴᕈ⒳ ߇㧘VOC ಽ⸃ߦᨐߚߔᓎഀߦߟߡᬌ⸛ࠍⴕߞߚ㧚 2. ታ㛎 ᳇⋧ࠝ࠱ࡦߦࠃࠆᾲಽ⸃ᴺ㧔R1㧕㧘ᓥ᧪ဳ㧔ᾲ㧕⸅ᇦಽ⸃ ᴺ㧔R2㧕㧘ࠝ࠱ࡦ⸅ᇦಽ⸃ᴺ㧔R3㧕ߩᵹ〝࿑ࠍ Fig.1 ߦ␜ߔ㧚 R1 ߢߪ㧘VOC ߣ N2ࠍᷙวߐߖߚࠟࠬߦ㧘ࡊ࠭ࡑᔕེ ౝߢ⊒↢ߐߖߚࠝ࠱ࡦ㧔O3㧕ࠍ100͠ߩࠝࡉࡦౝߢᷙวߐ ߖ㧘ߐࠄߦ᷷ᐲࠦࡦ࠻ࡠ࡞ߐࠇߚⓨ╴ߩ⍹⧷ᔕེߦዉ ߒߚ㧔200 ppm-VOC, 1600 ppm-O3, 20 %-O2, N2ࡃࡦࠬ㧕㧚
R2 ߢߪ㧘VOC ߣ N2ߩᷙวࠟࠬߦ㧘㉄⚛ࠍ100͠ߩࠝࡉࡦ ౝߢᷙวߐߖ㧘⸅ᇦᔕེߦዉߒߚ㧔200 ppm-VOC, 20 %O2, N2ࡃࡦࠬ㧕㧚R3 ߢߪ㧘VOC ߣ N2ࠍᷙวߐߖߚࠟࠬߦ㧘㉄ ⚛ࠍࡊ࠭ࡑᔕེౝߢ⊒↢ߐߖߚࠝ࠱ࡦࠍ 100͠ߩࠝࡉ ࡦౝߢᷙวߐߖ㧘⸅ᇦᔕེߦዉߒߚ㧚 ࠟࠬಽᨆߪ㧘2.4m 㐳శ〝࡞㧔Infrared Analysis ␠㧕ࠍ ߃ߚFT-IR (BioRad ␠㧦FTS-135)ࠍ↪㧘ࠝࡦࠗࡦߢቯ ᕈቯ㊂ࠍⴕߞߚ㧚⿒ᄖࠬࡍࠢ࠻࡞ߪ㧘ಽ⸃⢻0.5 cm-1㧘Ⓧ▚ ࿁ᢙ64 ࿁ߢ᷹ቯߒߚ㧚࠻࡞ࠛࡦ㧘ࠫࠢࡠࡠࡔ࠲ࡦࠍ᳇⋧ࠝ࠱ ࡦߦࠃߞߡᔕ᷷ᐲ 350͠ߢಽ⸃ࠍ⹜ߺߚߣ߈ߦᓧࠄࠇߚ⿒ ᄖࠬࡍࠢ࠻࡞ࠍFig.2 ߩ(a)ߣ(b)ߦߘࠇߙࠇ␜ߔ㧚࠻࡞ࠛࡦ㧘 ࠫࠢࡠࡠࡔ࠲ࡦ㧘CO㧘CO2㧘ࠡ㉄㧔HCOOH㧕㧘ࡎࠬࠥࡦ㧔COCl2㧕 ߩቯ㊂ಽᨆߦߪ㧘ਥߦ729 cm-1㧘1268 cm-1㧘2103 cm-1㧘2274 cm-1㧘 ࿑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. R1 Ozone / Oxygen Furnace VOC / N2 Ozone / Oxygen Catalyst Furnace VOC / N2 Oxygen VOC / N2 Catalyst Furnace R3 R2 ࿑2 ᔕ᷷ᐲ350͠ߢߩVOCߩ᳇⋧ࠝ࠱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. 1000 1500 2000 2500 3000 3500 4000 A bs or ba nc e Wavenumber / cm-1 HCl CO CO2 COCl2 CH2Cl2
(b)
Before After 1000 1500 2000 2500 3000 3500 4000 A bs or ba nc e Wavenumber / cm-1 CO CO2 C6H5CH3 HCOOH H2O H2O(a)
Before After1103 cm-1㧘860 cm-1ߩๆࡇࠢࠍ↪ߚ㧚ߥ߅㧘COCl 2ߪ
ᮡḰࠟࠬߦࠃࠆᬌ㊂✢߇ᓧࠄࠇߥߚ㧘࠺࠲ࡌࠬ 㧔Infrared Analysis ␠㧦QA-SOFT㧕ࠍ↪ߡቯ㊂ࠍⴕߞߚ㧚
ࠝ࠱ࡦߪ⚡ᄖ✢ๆᑼࠝ࠱ࡦỚᐲ⸘(⨶ේታᬺ␠㧦ࡕ࠺࡞ HARE PG640)ࠍ↪ߡቯ㊂ࠍⴕߞߚ㧚ࠨࡦࡊࡦࠣߪ⸅ᇦ ᔕེࠍ100͠߆ࠄ 400͠߹ߢછᗧߩᔕ᷷ᐲߦ⸳ቯߒ㧘30 ಽ ⚻ㆊߒߚߩߜⴕߞߚ㧚ߒߚ߇ߞߡ㧘ߕࠇ߽ೋᦼᵴᕈ୯ࠍ␜ ߔ㧚 ࠻࡞ࠛࡦߪ 5͠ߦᜬߒߚᶧ⹜⮎㧔శ⚐⮎㧘․⚖㧕ࠍ N2ߢࡃࡉࡦࠣߐߖ⊒↢ߐߖߚ㧚ࠫࠢࡠࡠࡔ࠲ࡦߪN2ߣߩ ᷙวࠟࠬ㧔㜞ජⓄൻቇᎿᬺ, CH2Cl2=1,060 ppm㧕ࠍ↪ߚ㧚ߎ ࠇࠄࠍߐࠄߦN2ߣO2㧔߅ࠃ߮O3㧕ߢᏗ㉼ߒ㧘ోᵹ㊂߇500 cm3/min ߦߥࠆࠃ߁⺞ߒߚ㧚 ࠝ࠱ࡦߪ㧘ዊ↰ࠄߦࠃߞߡឭ᩺ߐࠇߡࠆࠦࠗ࡞ဳᴪ㕙 㔚ဳࡊ࠭ࡑᔕེߦࠃࠅ⊒↢ߐߖߚ8)㧚ᔕེߪ㧘⍹⧷▤ ߩᄖߦႣᏓߒߚ㌁ࡍࠬ࠻ࠍធᭂߦ㧘ౝოߦࠦࠗ࡞⁁ߦ ኒ⌕ߐߖߚ⊕㊄ࡢࠗࡗ(0.4 mm)ࠍ㔚ᭂߣߒߚ᭴ㅧߦߥߞ ߡࠆ㧚⚐㉄⚛㧔㜞ජⓄൻቇ㧕100 mL/min ࠍࡊ࠭ࡑᔕེ ߦᵹㅢߒ㧘ᵹ㜞㔚㧔8.3 kV㧘ᵄᢙ 1 kHz㧕ࠍශടߔࠆߎ ߣߦࠃࠅ㧘8,000 ppm ߩࠝ࠱ࡦࠍᓧߚ㧚ᷙวࠟࠬߩ⚵ᚑߪ೨ ߩㅢࠅ㧚 ⸅ᇦߪ㧘ࠛࠗࠤࡓࠠࡖ࠶࠻␠㧘Cu-1230E(⚵ᚑᲧ: Ba=5.4 %㧘Cu=23.2%㧘Cr=21.9%)ࠍ↪㧘੍ 150͠ߩࠝ ࡉࡦߢలಽੇ῎ߐߖߚᓟ㧘ᔕߦଏߒߚ㧚ߥ߅㧘ห⸅ᇦߩ 㕙Ⓧߪ㧘ࡌ࡞࠰ࡊ␠ߩๆ⌕ⵝ⟎㧔BELSORP 18㧕ࠍ↪㧘 BET ᴺߦࠃࠅ 125 m2/g ߣ᳞ࠄࠇߚ㧚 3. ⚿ᨐߣ⠨ኤ 3.1 ࠻࡞ࠛࡦ%*%*㧦61. ߩಽ⸃ Fig.3 ߦฦ⒳ಽ⸃ᴺ㧔R1㧘R2㧘R3㧕ࠍ↪ߚ႐วߩ 100㨪 400͠ߦ߅ߌࠆ C6H5CH3ߩಽ⸃േࠍ␜ߔ㧚100㨪150͠ߢߪ R1 ߣ R2 ߢಽ⸃₸ߦ߶ߣࠎߤᏅ߇ࠄࠇߕ㧘175㨪300͠ߢߪ R1 ߩᣇ߇ R2 ࠃࠅ߽߿߿㜞ಽ⸃₸ࠍ␜ߒߚ㧚ߒ߆ߒ㧘R2 ߪ350͠એߢ R1 ࠍ࿁ࠅ㧘߶߷ 100%ߩಽ⸃₸߇ᓧࠄࠇߚ㧚 ৻ᣇ㧘R3 ߢߪ 100͠ߦ߅ߡ߽ 50㧑ߩಽ⸃₸ࠍ␜ߒ㧘Ᏹߦ R2㧘R3 ࠃࠅ߽㜞ಽ⸃ᕈ⢻ࠍ␜ߔߎߣ߇ࠊ߆ߞߚ㧚 ਥ↢ᚑ‛ߣߘߩㆬᛯ₸ࠍTable 1 ߦ␜ߔ㧚ਛߩㆬᛯ₸ߪ㧘 㨇ฦ↢ᚑ‛㊂㨉/㨇ᬌߐࠇߚో↢ᚑ‛㊂㨉ߩᲧ₸ߣߒߡߔ㧚 R1 ߢߪ CO2߳ߩㆬᛯ₸߇350͠ߢ 50㧑⒟ᐲߥߩߦኻߒ㧘R2 ߢߪ200͠એߩ᷷ᐲߢ߶߷ 100%ߦ㆐ߒߚ㧚R2 ߢߪ⚛ߩ ‛⾰ᡰ߇ 100%ࠍ߃ࠆ⚿ᨐ߽ᓧࠄࠇߡ߅ࠅ㧘ߎࠇࠄߪ⸅ ᇦߦๆ⌕ߒߚC6H5CH3߹ߚߪߘߩਛ㑆߇ಽ⸃⣕㔌ߒߚ ߽ߩߦ࿃ߔࠆߣ⠨߃ࠄࠇࠆ㧚R3 ߢߪ㧘100͠ߦ߅ߡᣢߦ 1 ฦ⒳ᚻᴺߦࠃࠆ࠻࡞ࠛࡦ߮ࠫࠢࡠࡠࡔ࠲ࡦಽ⸃ᓟߩ↢ᚑ‛ಽᏓߣ⚛ߩ‛⾰ᡰ
Table 1 Selectivity of products and material balance of carbon in three reaction systems
Toluene Dichloromethane Selectivity in products / % Selectivity in products / % Temp. / ͠ CO CO2 HCOOH Material Balance / % CO CO2 COCl2 Material Balance / % 100͠ 0 78 22 15 㧙 㧙 㧙 㧙 200͠ 32 56 12 48 㧙 㧙 㧙 㧙 300͠ 51 45 4 73 100 0 <1 86 R1 350͠ 49 49 2 79 92 4 4 91 100͠ 㧙 㧙 㧙 㧙 㧙 㧙 㧙 㧙 200͠ 0 100 0 13 㧙 㧙 㧙 㧙 300͠ 0 100 0 120 5 95 0 166 R2 400͠ 0 100 0 106 3 96 0 123 100͠ 16 83 1 81 59 38 0 91 200͠ 12 88 0 88 44 56 0 103 300͠ 1 99 0 100 18 83 0 119 R3 400͠ 1 99 0 102 11 89 0 92 ࿑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 by catalyst. 0 20 40 60 80 100 100 200 300 400 C on ve rs io n of to lu en e/ % Temperature /oC R1 R2 R3
CO2ㆬᛯ₸ߪ83㧑ߦ㆐ߒߡ߅ࠅ㧘ߐࠄߦ᷷ᐲߣߦㆬᛯ ₸ߩะ߇ߺࠄࠇߚ㧚 ৻ᣇ㧘R1 ߢ HCOOH ߩ↢ᚑ߇ߺࠄࠇߚ߇㧘R2㧘R3 ߢߪ߶ ߣࠎߤ᷹ⷰߐࠇߥ߆ߞߚ㧚 3.2 ࠫࠢࡠࡠࡔ࠲ࡦ(CH2Cl2㧦DCM)ߩಽ⸃ Fig.4 ߦฦ⒳ಽ⸃ᴺ㧔R1㧘R2㧘R3㧕ࠍ↪ߚ႐วߩ 100㨪 400͠ߩ᷷ᐲ㗔ၞߦ߅ߌࠆ CH2Cl2ߩಽ⸃േࠍ␜ߔ㧚R1 ߢߪ 250͠એਅߢ CH2Cl2ߪ߶ߣࠎߤಽ⸃ߒߥ߆ߞߚ㧚ߒ߆ߒ㧘 300͠ࠍ߃ࠆߣ CH2Cl2ߪᕆỗߦಽ⸃ߒᆎ㧘350͠ߢಽ⸃₸ ߪ55%ߦ㆐ߒߚ㧚R2 ߢ߽ 200͠એਅߢߪ߶ߣࠎߤಽ⸃ߒߥ߆ ߞߚ߇㧘250͠એߢߪ᷷ᐲߣߣ߽ߦಽ⸃₸߇ะߒ㧘 400͠ߢ 55%ߩಽ⸃₸߇ᓧࠄࠇߚ㧚R3 ߢߪ㧘100͠ߦ߅ߡ ߽20%⒟ᐲߩಽ⸃₸߇ᓧࠄࠇ㧘᷷ᐲߣߣ߽ߦ✭߿߆ߦಽ ⸃₸߇Ⴧᄢߒ㧘300͠ߢߪ 40%ߦ㆐ߒߚ㧚ߐࠄߦߘࠇએߩ ᷷ᐲߢߪ㧘ᕆỗߦಽ⸃₸߇Ⴧᄢߒ㧘400͠ߦ߅ߡಽ⸃₸ߪ 84%ߦ㆐ߒߚ㧚 ਥ↢ᚑ‛ߢࠆCO ߣ CO2ߩㆬᛯ₸ࠍTable 1 ߦ␜ߔ㧚R1 ߢߪ㧘↢ᚑ‛ߩ߶ߣࠎߤ߇CO ߢߞߚ㧚ߎࠇߣኻᾖ⊛ߦ㧘 R2 ߢߪ߶ߣࠎߤ߇ CO2ߦಽ⸃㉄ൻߐࠇߚ㧚‛⾰ᡰ߽100% ࠍ߃ࠆ୯ࠍ␜ߒߡࠆߎߣ߆ࠄ㧘CH2Cl2ߩ႐ว߽C6H5CH3 ߣห᭽ߦ⸅ᇦߦๆ⌕ߒߡߚCH2Cl2㧘ࠆߪߘߩᔕਛ㑆 ߇᷷ᐲߩߣߦಽ⸃⣕㔌ߒߡ߈ߚ߽ߩߣ⠨߃ࠄࠇࠆ㧚 R3 ߢߪ㧘100͠ߦ߅ߡ CO2ㆬᛯ₸ߪ38%ߢߞߚ߇㧘᷷ᐲ ߩߣߦะߒߚ㧚 ߥ߅㧘COCl2߇R1 ߢ 300͠ߩߣ߈ߦ᷹ⷰߐࠇߚ߇㧘⸅ᇦࠍ ↪ࠆߎߣ㧔R2㧘R3㧕ߢ㧘ߎߩ↢ᚑࠍᛥߢ߈ࠆߎߣ߇ࠄ ߆ߦߥߞߚ㧚߹ߚ㧘ߕࠇߩ♽ߢ߽300͠એߢ HCl ߇᷹ⷰ ߐࠇߚ㧔 Fig.2(b) 㧕㧚 3.3 ᵴᕈ㉄⚛⒳ߩᬌ⸛ એߩᔕ⚿ᨐ㧘ਗ߮ߦએਅߢ␜ߔO3Ớᐲᄌൻߩ⚿ᨐࠍ߽ ߣߦ㧘ฦᔕ♽ߦ߅ߌࠆVOC ಽ⸃ߦኻߔࠆฦ⒳㉄⚛ᵴᕈ⒳ ߩᔕᕈߦߟߡᬌ⸛ࠍⴕߞߚ㧚 3.3.1 ᳇⋧ਛߩᵴᕈ㉄⚛⒳ ߹ߕ㧘R1 ߣ R3 ߦ߅ߌࠆ᳇⋧ O3ߩỚᐲߩᄌൻ߆ࠄ㧘ߎࠇ ࠄߩᔕ♽ߦ߅ߌࠆᵴᕈ㉄⚛⒳ߩᔕ․ᕈࠍ⺞ߴߚ㧚Fig.5 ߣ Fig.6 ߦ R1 ߣ R3 ߦ߅ߌࠆ VOC㧔C6H5CH3㧘CH2Cl2㧕ಽ⸃ᤨ㧘 ਗ߮ߦVOC 㕖ሽਅߢߩ᳇⋧ਛߩ O3Ớᐲࠍ␜ߔ㧚 Fig.5 ࠃࠅ㧘ሽߔࠆ C6H5CH3߿CH2Cl2ߦࠃߞߡ㧘᳇⋧O3 ߩᷫዋะ߇⇣ߥࠆߎߣ߇ࠊ߆ࠆ㧚ᓟ⠪ߢߪߘߩะ߇᳇⋧ O3ߩᾲಽ⸃ߣ߶߷৻⥌ߒߡࠆߩߦኻߒ㧘೨⠪ߢߪߘࠇࠃࠅ ߽ૐ᷷ᐲߢO3߇ᶖ⾌ߐࠇߡࠆߎߣ߇ࠊ߆ࠆ㧚250͠એਅ ߩ᷷ᐲ㗔ၞߦ߅ߡ㧘C6H5CH3ߪಽ⸃ߒCH2Cl2ߪ߶ߣࠎߤಽ ⸃ߒߡߥߎߣ߆ࠄ㧘᳇⋧VOC ߦኻߔࠆ⋥ធ⊛ߥ O3ߩ ᔕᕈߩ㆑߇⏕ߢ߈ߚ㧚C6H5CH3ߪ㧘100͠ߦ߅ߡ߽ಽ⸃ ߇ߎߞߡࠆߎߣ߆ࠄ㧘᳇⋧O3ߣߩ⋥ធ⊛ߥᔕ߇␜ໂߐ ࠇࠆ㧚ߎࠇߦኻߒߡ㧘CH2Cl2ߩ႐ว㧘᳇⋧ਛߩO3ಽ⸃㧔O3ĺ O2+ O㨯gas㧕߇ᕆỗߦଦㅴߐࠇࠆ250͠એߩ᷷ᐲၞߢᔕ߇ ᆎ߹ߞߡ߅ࠅ㧘Ogasߣߩᔕ߇ਥᔕߣ⠨߃ࠄࠇࠆ㧚ታ㧘 OgasߣCH2Cl2ߣߩᔕㅦᐲቯᢙߪ㧘ߎߩ᷷ᐲએߢᄢ߈ߊ ߥࠆߎߣ߇⍮ࠄࠇߡࠆ9)㧚એߩߎߣ߆ࠄ㧘C6H5CH3ߩ႐ ว㧘200͠એਅߩਥߥᵴᕈ㉄⚛⒳ߪ᳇⋧ O3ߘߩ߽ߩߣ⠨߃ࠆ ࿑4 ฦ᷷ᐲߦ߅ߌࠆ DCM ߩಽ⸃േ㧦(R1) ᳇⋧ࠝ࠱ࡦ ߦࠃࠆᾲಽ⸃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 by catalyst. 0 20 40 60 80 100 100 200 300 400 C on ve rs io n of D C M /% Temperature / oC R1 R2 R3 ࿑5 VOC㧙᳇⋧ࠝ࠱ࡦಽ⸃ᴺߦ߅ߌࠆᔕ᷷ᐲߣ᳇⋧ࠝ ࠱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 of temperature on pyrolysis of ozone (R1-O3), and on ozonolysis of (R1-TOL) toluene and (R1-DCM) dichloromethane. (R1-O3) 0 400 800 1200 1600 100 200 300 400 O ut le to zo ne co nc en tra tio n /p pm Temperature /oC
R1-O3, ozone alone R1-DCM
ߎߣ߇ߢ߈㧘250͠એߦߥࠆߣ O3ߩᾲಽ⸃߆ࠄ↢ߓߚේሶ ⁁㉄⚛㧔O㨯gas㧕߇C6H5CH3ߩߺߥࠄߕCH2Cl2ߩಽ⸃ࠍଦㅴ ߔࠆߣ⠨߃ࠄࠇߚ㧚 3.3.2 ࿕㕙ߩᵴᕈ㉄⚛⒳ ߕࠇߩ᷷ᐲၞߢ߽R3 ߪ R1 ߿ R2 ࠃࠅ߽㜞ಽ⸃ᵴᕈࠍ ␜ߒߚ㧚㜞᷷ၞ㧔250͠એ㧕ߢߪ O3ߩᾲಽ⸃߇ଦㅴߐࠇࠆ ߚ㧘R3 ߦ߅ߡ߽೨▵ห᭽ߩ᳇⋧ਛߩᵴᕈ㉄⚛⒳߇ᔕߦ ነਈߒߡࠆน⢻ᕈ߇ࠆ㧚ߘߎߢ㧘ߘߩᓇ㗀߇ዋߥߊ⸅ᇦ ߩലᨐ߇ࠊ߆ࠅ߿ߔ100㨪250͠ߩૐ᷷ၞߦߟߡ㧘ߪߓ ߦᬌ⸛ࠍⴕߞߚ㧚 ࠝ࠱ࡦ⸅ᇦಽ⸃ᴺߩᔕᯏ᭴ߣߒߡ৻⥸⊛ߥޟ࿕⸅ᇦ ߩO3߆ࠄ↢ߓߚ*Oads߇VOC ࠍಽ⸃ߔࠆޠᔕᯏ᭴ߦၮߠ ߡ⠨ኤࠍⴕߞߚ5)㧚Fig.6 ߆ࠄ߽ࠄ߆ߥࠃ߁ߦ㧘O3ಽ⸃߇ૐ ᷷ၞ߆ࠄᆎ߹ߞߡ߅ࠅ㧘*Oadsߩ↢ᚑ߇ᦼᓙߐࠇࠆ㧚 O3 + * ĺ O2+ *Oads (1)
*Oads + VOC ĺ COx + H2O + * (2)
*㧦⸅ᇦᵴᕈὐ㧘*Oads㧦⸅ᇦߦ↢ߓߚᵴᕈ㉄⚛ Fig.7 ߦ᳇⋧ O3߇ሽߔࠆ♽ߦ߅ߌࠆ㧘⸅ᇦߩήߩ㆑ 㧘VOCߩ㆑ߦࠃࠆO3ᶖ⾌㊂ߣVOCಽ⸃㊂ߩ㑐ଥࠍ␜ߔ㧚 Ყセߩߚ㧘᳇⋧O3ߦࠃࠆC6H5CH3ߩಽ⸃ߩ⚿ᨐ߽ࡊࡠ࠶ ࠻ߒߚ㧚C6H5CH3ߩಽ⸃㊂ߪᶖ⾌ߐࠇࠆO3㊂ߣ⦟⋧㑐߇ ࠆߎߣ߇ࠊ߆ࠆ㧚ߚߛߒ㧘೨▵ߢㅀߴߚࠃ߁ߦ᳇⋧O3ߦࠃࠆ CH2Cl2ߩಽ⸃ߪߎࠄߥ㧚৻ᣇ㧘R3 ߽ VOC ߩ⒳㘃ߦଐࠄ ߕ⦟⋧㑐߇ࠄࠇࠆߎߣ߇ࠊ߆ࠆ㧚ߚߛߒ㧘ߘߩ߈㧔O3 ᶖ⾌㊂ߦኻߔࠆVOC ಽ⸃㊂ߩ㑐ଥ㧕ߪ R1 ߣߪࠄ߆ߦ⇣ߥ ߞߡ߅ࠅ㧘 R3 ߦ߅ߡ O3߆ࠄᓧࠄࠇߚ⸅ᇦߩ*Oadsߩ ߈ࠍ․ᓽߠߌࠆ߽ߩߦߥߞߡࠆ㧚ߚߛߒ㧘ᰴ▵ߢ⠨ኤߔࠆ ߇㧘ᶖ⾌ߐࠇߚᄙߊߩO3ߪᔅߕߒ߽VOC ಽ⸃ߦ↪ࠄࠇߡ ߥߎߣ߽ࠄ߆ߦߥߞߚ㧚 R2 ߩᾲ⸅ᇦ♽ߢߪ㧘ᩰሶ㉄⚛ࠆߪ᳇⋧ O2↱᧪ߩᵴᕈ ㉄⚛⒳߇⸅ᇦߢ㉄ൻᔕࠍଦㅴߔࠆߣ⠨߃ࠄࠇࠆ㧚ߒ߆ߒ㧘 Fig.3 ߣ Fig.4 ࠃࠅ㧘߶ߣࠎߤߩ᷷ᐲ㗔ၞߢ㧘R2 ߪ R1 ࠃࠅಽ ⸃ᵴᕈ߇ૐ㧚ᧄታ㛎᧦ઙߢߪVOC ߩಽ⸃ߦലߥᵴᕈ㉄ ⚛⒳߇⸅ᇦߛߌߢߪలಽᓧࠄࠇߥ߆㧘ߘߩᔕᕈ߇ O3߿ Ogasࠃࠅ߽ૐߎߣࠍ␜ߒߡࠆ㧚 ᰴߦ㧘R3 ߩ 250͠એߦ߅ߌࠆᔕᵴᕈߩะലᨐߦߟ ߡᬌ⸛ࠍⴕߞߚ㧚C6H5CH3㧘CH2Cl2ߣ߽㧘ૐ᷷ၞߩಽ⸃ᵴᕈ ߦട߃㧘R1 ߣ R2 ߩᓇ㗀ࠍᒝߊฃߌߡࠆࠃ߁ߦ߃ࠆ㧚Fig.3 ߣFig.4ߩᔕ᷷ᐲߦኻߔࠆಽ⸃ᵴᕈߪ250͠೨ᓟࠍႺߦ⊒ ߒߡ߅ࠅ㧘⋧ਸ਼ലᨐ߇ߤߜࠄߩᓇ㗀ߦࠃࠆ߽ߩ߆ߪන⚐ߦ್ ᢿߢ߈ߥ㧚ߒ߆ߒ㧘R1 ߪ CO ㆬᛯ₸߇㜞ߊ㧘R2 ߪ CO2ㆬ ᛯ₸߇㜞ߣ߁↢ᚑ‛ಽᏓߦ․ᓽ⊛ߥ㆑߇ࠆ㧚R3 ߩ↢ ᚑ‛ਛߩㆬᛯ₸߆ࠄ್ᢿߔࠆߣ㧘R2 ߩ㑐ਈ߇ᒝߊ␜ໂߐࠇߚ㧚 ߕࠇߦߖࠃR3 ߩ300͠એߩᔕߦߪCO ㉄ൻᔕ߽㧘 ᩰሶ㉄⚛ࠆߪ᳇⋧ O2↱᧪ߩᵴᕈ㉄⚛⒳ߩ㑐ਈ߇ࠆߎ ߣߪ⏕߆ߢࠆ㧚 3.4 R3 ߩࠝ࠱ࡦ↪ല₸ะߩߚߩᜰ㊎ R3 ߪ VOC ಽ⸃ߦലߢࠆߎߣ߇␜ߐࠇߚ߇㧘O3ߩ↪ ല₸߇ૐߚ㧘ߐࠄߦᕈ⢻ࠍ㜞ࠄࠇࠆน⢻ᕈ߇ࠆ㧚ߎ ࠇࠄ߇ૐℂ↱ߣߒߡߪ㧘⸅ᇦߦࠃࠆO3߆ࠄO2߳ߩᔕ㧘 0 400 800 1200 1600 100 200 300 400 O ut le t o zo ne c on ce nt ra tio n / p pm Temperature / oC ozone alone R3-DCM R3-TOL R3-O3 ࿑ 6 VOC㧙ࠝ࠱ࡦ⸅ᇦಽ⸃ᴺߦ߅ߌࠆᔕ᷷ᐲߣ᳇ ⋧ ࠝ ࠱ 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 function
of temperature on ozonolysis assisted by catalyst of (R3-TOL) toluene and (R3-DCM) dichloromethane, and on (R3-O3) the decomposition of ozone by the catalyst.
࿑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 consumed ozone on R1 and R3 (100 to 250oC). 0 50 100 150 200 0 400 800 1200 1600 D ec om po se d VO C / p pm Consumed O3 / ppm R1-TOL R1-DCM R3-DCM R3-TOL
- 6 - ߔߥࠊߜVOC ಽ⸃ߦነਈߒߥ*Oads㧔O3ๆ⌕ࠨࠗ࠻㧕߇ሽ
ߔࠆߎߣࠍᜰ៰ߢ߈ࠆ㧚 2*Oads ĺ O2 + 2* (3) ታ㓙ߦ㧘Fig.6 ߩ 100͠ߩ࠺࠲߆ࠄ߽ VOC ߇ሽߔࠆᣇ ߇㧘O3ߩಽ⸃߇ᛥߐࠇߡࠆߎߣ߇ࠊ߆ߞߡ߅ࠅ㧘ߎࠇࠄ ߪVOC ߩๆ⌕ࠨࠗ࠻ߣ O3ߩๆ⌕ࠨࠗ࠻߇┹วߔࠆߚ㧘O3 ߩಽ⸃߇ᛥ߃ࠄࠇࠆߎߣࠍ␜ໂߒߡࠆ㧚 Fig.7 ߦ߅ߡ㧘O3ᶖ⾌㊂ߩዊߐታ㛎⚿ᨐߪૐ᷷ߢᓧ ࠄࠇߚ߽ߩࠍᤋߒߡࠆߎߣ߆ࠄ㧘ᔕ᷷ᐲ߇ૐ᷷ߦߥࠆ ߶ߤ O3↪ല₸߇㜞ߎߣ߇ࠄ߆ߦߥߞߚ㧚ߚߛߒ㧘 Table.1 ߢ߽ࠄ߆ߥࠃ߁ߦ㧘᷷ᐲ߇ૐߊߥࠆߣᔕ೨ᓟߩ ⚛ߩ‛⾰ᡰ߿CO2ㆬᛯ₸߇ૐਅߔࠆน⢻ᕈ߇ࠆߚ㧘R3 ߢߪVOC ߩ⒳㘃ߏߣߦ᷷ᐲ⸳ቯߩᦨㆡൻ߇ᔅⷐߦߥࠆߣ⠨ ߃ࠄࠇࠆ㧚 4. ߹ߣ ᳇⋧ࠝ࠱ࡦߪ 100㨪400͠ߩ᷷ᐲၞߢ Ba-CuO-Cr2O3/Al2O3 ⸅ᇦߣห╬߆ߘࠇએߩಽ⸃⢻ജࠍ␜ߒߚ㧚৻ᣇ㧘᳇⋧ࠝ࠱ ࡦߣ⸅ᇦࠍ⚵ߺวࠊߖߚⶄว♽ߢߪ㧘ߘࠇࠄࠃࠅ߽ߐࠄߦ㜞 VOC ಽ⸃ᵴᕈࠍ␜ߒߚ㧚߹ߚ㧘⸅ᇦߢᓧࠄࠇߚᵴᕈ㉄ ⚛⒳(*Oads)ߪ㧘᳇⋧ࠝ࠱ࡦ߿ࠝ࠱ࡦ߆ࠄߩᾲಽ⸃ߦࠃࠅ↢ߓ
ߚේሶ⁁㉄⚛㧔O㨯gas㧕ࠃࠅ߽㧘ࠃࠅૐ᷷ᐲߢVOC ಽ⸃
ᔕߦലߢࠆߎߣ߇ࠄ߆ߦߥߞߚ㧚ߐࠄߦ㧘ห⸅ᇦࠍ↪ ߡࠝ࠱ࡦ↪ല₸ࠍߍࠆߚߦߪ㧘ᔕ᷷ᐲࠍૐߊߔࠆ ߎߣ߇ലߢࠆߎߣࠍᜰ៰ߒߚ㧚 ෳ⠨ᢥ₂ 1) ⅣႺ⊕ᦠ ᐔᚑ 18 ᐕᐲ ⅣႺ⋭ 2) ㊄⾫ᄐ, ᳗㐳ਭኡ, የᒻᢕ: ⅣႺ▤ℂ, 40 (2004) 1109 3) C. M. Nunez, G. H. Ramsey, W.H. Ponder, J. H. Abbott, L.E.
Hamel and P.H. Kariher: Air Waste, 43 (1993) 242 4) የᒻᢕ: ࠛࠕࡠ࠱࡞⎇ⓥ, 21 (2006) 215 5) ᳗㐳ਭኡ: ࠢࡦ࠹ࠢࡁࡠࠫ㧘16 (2006) 6
6) A. Gervasini, G. C. Vezzoli and V. Ragaini: Catal. Today, 29 (1996) 449
7) A. Gervasini and V. Ragaini: Catal. Today, 60 (2000) 129 8) T. Oda, T. Takahashi, K. Tada: IEEE Trans. Ind. Appl., 35(1999)
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