ᚑくᄢቇℂᎿቇ⎇ⓥႎ๔
J. Fac. Sci. Tech., Seikei Univ.
Vol.45 No.㧞 (2008) pp.9-13㧔ᣂછ⠪⺰ᢥ㧕ᑄ࠮ࡔࡦ࠻ᓸ☳ᧃߩੇᑼ⣕⎫ᕈ⢻㘵Ⴆ ᷕ 㧘๓ ૫໑ 㧘ᾢ⼱ ৻ᷡ 㧘ጊፒ ┨ᒄ 㧞㧘ᩉᴛ ᐘ㓶 Characteristics of Waste Cement Particles as a Dry Desulphurization Sorbent
Atsushi IIZUKA 㧘Jiawei WU 㧘Kazukiyo KUMAGAI 㧘Akihiro YAMASAKI 㧘Yukio YANAGISAWA ABSTRACT 㧦 Dry desulfurization characteristics of waste cement particles were examined withlaboratory-scale experimental apparatus based on the weight change of the sample exposed to a gas flowcontaining SO2. The waste cement particles, a byproduct of recycling aggregates from waste concrete, arefine particles with diameters ranging from 10 to 200 µm, and an average diameter of 105 µm. The effects ofoperation parameters, i.e., the reaction temperature (650 ~ 950°C), SO2 concentration (61 ~ 1543 ppm), andparticle size (10 ~ 200 µm), on the desulfurization performance were investigated. The desulfurization rates
were found to depend on the 1.26-th order of the SO2 concentration, and slightly depend on the particle size.
Arrhenius type temperature dependence was observed up to 850°C with activation energy of 12 kJ/mol.
The observed dry desulfurization rates of the waste cement particle were almost equivalent to those of theconventional sorbents such as limestone and calcium hydroxide. Therefore, it is confirmed that the waste
cement particles could be applicable in dry desulfurization as an inexpensive sorbent derived from wastes.
(Received October 6, 2008)

ࠤࠗ㉄ࠞ࡞ࠪ࠙ࡓ᳓๺‛ߪ㧘㜞޿Ⴎၮᕈࠍ᦭ߒ㧘ᄢ߈ߥ㧝㧚ߪߓ߼ߦ

⴫㕙Ⓧࠍᜬߟߚ߼㜞޿⣕⎫ᕈ⢻ࠍ␜ߔ 6)‫ߚ߹ޕ‬㧘ࠤࠗ㉄
 ㉄ᕈ㔎ߩේ࿃ߣߥࠆ⎫㤛㉄ൻ‛ࠍ㒰෰ߔࠆᛛⴚߪᄢ߈ࠞ࡞ࠪ࠙ࡓ᳓๺‛ߩ⚿᥏ߪ㑆㓗᳓ࠍᄙߊ฽᦭ߒߡ߅ࠅ㧘ߊಽߌߡ㧘Ά὾એ೨ߦ⎫㤛ಽࠍ㒰෰ߔࠆ੐೨㧔Άᢱ㧕⣕㑆㓗᳓ߦṁߌㄟࠎߛ᳓㉄ൻࠞ࡞ࠪ࠙ࡓ߽⣕⎫ߦᄢ߈ߊነ⎫㧘Ά὾Ἱౝߢ㒰෰ߔࠆἹౝ⣕⎫㧘ឃࠟࠬਛ߆ࠄ㒰෰ߔਈߒߡ޿ࠆߣ⠨߃ࠄࠇߡ޿ࠆ‫ ߦ․ޕ‬CaO㨯SiO2㨯H2O ޽ࠆࠆឃᾍ⣕⎫ߦᄢ೎ߐࠇࠆ‫ߚ߹ޕ‬㧘ᓟੑ⠪ߦߟ޿ߡߪ㧘᳓ߩ૶↪ߩὐ߆ࠄḨᑼ㧘ඨੇᑼ㧘ੇᑼ⣕⎫ࡊࡠ࠮ࠬߦಽ㘃޿ߪ 4 CaO㨯Al2O3㨯13 H2O ╬ߩൻว‛ߩ⣕⎫ലᨐ߇㜞޿ߎߣ 2)㧘᳓㧘޽ࠆ޿ߪ NOx ߩ౒ሽਅߢ⣕⎫ലᨐ߇㜞ߊߥߐࠇࠆ‫ޕ‬Ḩᑼឃᾍ⣕⎫ᛛⴚߪ⎫㤛㒰෰₸߇㜞ߊ㧘ᣣᧄߦ

ࠆߎߣ 4)╬߇ႎ๔ߐࠇߡ޿ࠆ‫ࠪ࡞ࠞ㉄ࠗࠤߥ߁ࠃߩߎޕ‬߅ߌࠆ⣕⎫ᛛⴚߩዉ౉੐଀ߩᄢㇱಽࠍභ߼ࠆ‫ߒ߆ߒޕ‬㧘࠙ࡓ⣕⎫೷ࠍ↪޿ࠆߎߣߢ 57~400͠ߩૐ᷷▸࿐ߢ⣕⎫Ḩᑼ⣕⎫ᛛⴚߪᄢ㊂ߩ᳓ࠍᔅⷐߣߔࠆߎߣ㧘ឃ᳓ಣℂ߇߇น⢻ߢ޽ࠅ㧘߹ߚ⣕⎫೷ਛߩࠞ࡞ࠪ࠙ࡓ೑↪ല₸߽㜞ᔅⷐߣߥࠆߎߣ㧘⸳஻߇㜞ଔߦߥࠆ╬ߩᰳὐࠍ᦭ߔࠆ‫ޕ‬ߊߥࠆ‫ࠄ߇ߥߒ߆ߒޕ‬⣕⎫೷ߩ⺞ᢛߦᚻ㑆߇ដ߆ࠆߎߣ

৻ᣇ㧘ੇᑼ⣕⎫ᛛⴚߪ᳓ߩ૶↪㊂߇ዋߥߊⵝ⟎⾌߇቟ଔ߿ߘߩ⚿ᨐ⣕⎫ࠦࠬ࠻߇㜞ߊߥࠆߎߣ߇໧㗴ߢ޽ࠆߣߐ

ߢ޽ࠆߣ޿߁೑ὐࠍᜬߟ෻㕙㧘⣕⎫ല₸߇ૐ޿ߎߣ߇ᰳ

ࠇߡ޿ࠆ‫ޕ‬ὐߣߥߞߡ޿ࠆ‫ޕ‬ ࠊࠇࠊࠇߪࠦࡦࠢ࡝࡯࠻ᑄ᫈‛ߦ⌕⋡ߒ㧘ߎࠇࠍ⣕⎫ ੇᑼ⣕⎫ߩ⣕⎫ല₸ࠍะ਄ߐߖࠆߚ߼ߩ㜞ല₸⣕⎫೷೷ߣߒߡ೑↪ߔࠆߎߣࠍ⠨߃ߚ‫࠻࡯࡝ࠢࡦࠦޕ‬ᑄ᫈‛ਛߣߒߡ㧘ࠤࠗ㉄ࠞ࡞ࠪ࠙ࡓ᳓๺‛㧔C-S-H ࠥ࡞㧕߇ᬌ⸛ߦ฽߹ࠇࠆᑄ࠮ࡔࡦ࠻ಽߪ㧘ࠤࠗ㉄ࠞ࡞ࠪ࠙ࡓ᳓๺‛ߣ1)㨪5)‫ޕ‬⍹὇Ά὾ᣉ⸳╬߆ࠄឃ಴ߐࠇࠆࡈ࡜ࠗ᳓㉄ൻࠞ࡞ࠪ࠙ࡓࠍਥᚑಽߣߒ㧘೨ㅀߩ⣕⎫೷ߣ߶߷ห

ࠕ࠶ࠪࡘߩ๟ࠅߦ᳓㉄ൻࠞ࡞ࠪ࠙ࡓ㧔Ca(OH)2㧕ࠍⵍⷒ╬ߩ⚵ᚑࠍᜬߟ‫ߡߞ߇ߚߒޕ‬㧘ᑄ࠮ࡔࡦ࠻ߪ᦭ലߥ⣕⎫ߔࠆߎߣߢ㧘ࡈ࡜ࠗࠕ࠶ࠪࡘਛߩ⃯⚛ߣ᳓㉄ൻࠞ࡞ࠪ࠙೷ߣߒߡ೑↪ߢ߈ࠆน⢻ᕈ߇޽ࠆߣ⠨߃ߚ‫ޕ‬ᑄ࠮ࡔࡦ࠻ࡓߣࠍ෻ᔕߐߖ㧘ࠤࠗ㉄ࠞ࡞ࠪ࠙ࡓ⣕⎫೷ࠍ⺞ᢛߔࠆ‫ޕ‬ಽߪ㧘ࠦࡦࠢ࡝࡯࠻ᑄ᫈‛߆ࠄ㛽᧚ᚑಽ㧔⍾೑㧘⍾㧕ࠍ࿁෼ߔࠆࡊࡠ࠮ࠬߢᓸ☳ᧃ㧔ᑄࠦࡦࠢ࡝࡯࠻ᓸ☳ᧃ㧕ߣߐࠇߡ޿ࠆ㧦᧲੩ᄢቇ ᄢቇ㒮ᣂ㗔ၞഃᚑ⑼ቇ⎇ⓥ⑼ ⅣႺࠪࠬ࠹ࡓቇኾ᡹㧦ᚑくᄢቇℂᎿቇㇱ‛⾰↢๮ℂᎿቇ⑼ߒߡឃ಴ߐࠇࠆ߽ߩߢࠆ߇㧘⃻⁁ߢߪ᦭ലߥ೑↪ᣇᴺ߇㧙㧙ሽ࿷ߒߥ޿‫⺰ᧄޕ‬ᢥߢߪ㧘ߎߩࠃ߁ߥᑄ࠮ࡔࡦ࠻ᓸ☳ᧃ㛎ߦ↪޿ߚᑄ࠮ࡔࡦ࠻ᓸ☳ᧃߪ⴫㕙ߦዊߐ޿㗰☸⁁☸ሶߩ⣕⎫ᕈ⢻ߦߟ޿ߡ㧘ታ㛎ቶ࡟ࡌ࡞ߩⵝ⟎ࠍ↪޿ߡᬌ⸛ᓸ⚦᭴ㅧࠍᜬߟߎߣ߇ࠊ߆ࠆ‫࡯ࠩ࡯࡟ޕ‬శᢔੂ☸ᐲಽᏓࠍⴕߞߚ⚿ᨐߦߟ޿ߡႎ๔ߔࠆ‫ޕ‬⸘㧔ፉᵤ⵾૞ᚲ⵾ SALD-1100㧕ߦࠃߞߡ᷹ቯߒߚᑄ࠮ࡔ

ࡦ࠻ᓸ☳ᧃ⹜ᢱߩ☸ᓘಽᏓࠍ࿑ 2 ߦ␜ߔ‫☸ޕ‬ᓘߪ㧘߶߷
10 ~ 200 µm ߩ▸࿐ߦಽᏓߒߡ߅ࠅ㧘㕙ⓍၮḰߢߩࡇ࡯ࠢ

㧞㧚ࠦࡦࠢ࡝࡯࠻ᑄ᫈‛ߦߟ޿ߡ㩷ᓘߪ 10 ~ 30 µm ߩ▸࿐ߢ޽ߞߚ‫Ⱟޕ‬శ X ✢ಽᨆߦࠃߞߡ㩷 ࠊ߇࿖ߢߪ㧘Ფᐕᄢ㊂ߩࠦࡦࠢ࡝࡯࠻ᑄ᫈‛߇ឃ಴ߐ᷹ቯߒߚ⹜ᢱߩࠞ࡞ࠪ࠙ࡓ฽᦭₸ߪ 27.3 wt%㧘߹ߚ BETࠇߡ޿ࠆ‫ޕ‬2005 ᐕߦ߅޿ߡ㧘ᑄࠦࡦࠢ࡝࡯࠻႙ߩ⊒↢㊂ᴺ⓸⚛ๆ⌕㧔ᣣᧄࡌ࡞㧘Belsorp㧕ߦࠃࠅ᷹ቯߒߚᲧ⴫㕙ߪ 3,200 ਁ࠻ࡦߢ޽ࠅ㧘ᑪ⸳ᑄ᫈‛㊂ో૕ߩ⚂ 41%ࠍභ

Ⓧߪ 2.7410-2 cm3/g㧘⚦ሹ૕Ⓧߪ 6.15 m2/g ߢ޽ߞߚ‫ޕ‬ᑄ߼ࠆ 7) ‫࠻࡯࡝ࠢࡦࠦޕ‬ᑄ᫈‛ਛߩࠞ࡞ࠪ࠙ࡓ฽᦭₸ߪ࠮ࡔࡦ࠻⹜ᢱߩᲧ⴫㕙Ⓧ㧘⚦ሹ૕Ⓧߪ౒ߦዊߐߊ㧘Ყセ10㧑⒟ᐲߣ⸒ࠊࠇߡ߅ࠅ㧘ࠞ࡞ࠪ࠙ࡓߣߒߡ߽ᄢ㊂ߦឃ⊛✺ኒߥ᭴ㅧࠍߒߡ޿ࠆߣ⠨߃ࠄࠇࠆ‫ޕ‬಴ߐࠇߡ޿ࠆߎߣߦߥࠆ‫ ޕ‬ᐕߦቢోᣉⴕߐࠇߚᑪ⸳
࡝ࠨࠗࠢ࡞ᴺࠍฃߌߡ㧘⃻⁁ߢߪᑄࠦࡦࠢ࡝࡯࠻႙ߩ߶
߷ో㊂㧔98㧑,  ᐕታ❣㧕߇〝⋚᧚╬ߣߒߡౣ೑↪ߐࠇߡ޿ࠆ 8㧕‫ࠄ߇ߥߒ߆ߒޕ‬㧘ᑄࠦࡦࠢ࡝࡯࠻ឃ಴㊂ߪჇടߩ৻ㅜࠍߚߤߞߡ߅ࠅ㧘੹ᓟ㜞ᐲᚑ㐳ᦼߦᑪ⸳ߐࠇߚ
ᄢ㊂ߩࠦࡦࠢ࡝࡯࠻ᑪㅧ‛߇㧘⠴↪ᐕᢙࠍㄫ߃ࠆߎߣߦ
ࠃߞߡߘߩ⊒↢㊂߇ᕆỗߦჇടߔࠆ߽ߩߣ⠨߃ࠄࠇߡ޿
ࠆ 9㧕‫৻ޕ‬ᣇ㧘〝⋚᧚ߦኻߔࠆ㔛ⷐߪᷫዋ௑ะߦ޽ࠅ㧘ㄭ޿዁᧪ࠦࡦࠢ࡝࡯࠻ᑄ᫈‛ߩ㔛⛎ࡃ࡜ࡦࠬ߇፣ࠇࠆߎߣ
߇ෂᗋߐࠇߡ޿ࠆ‫ߡߞ߇ߚߒޕ‬㧘〝⋚᧚એᄖߩࠦࡦࠢ࡝

࿑㧝 ᑄ࠮ࡔࡦ࠻ᓸ☳ᧃߩ 5'/ ↹௝ᐲᢙ[%]࡯࠻ᑄ᫈‛ߩౣ೑↪ᛛⴚߩ㐿⊒߇ᦸ߹ࠇߡ޿ࠆ‫ޕ‬ ࠦࡦࠢ࡝࡯࠻ᑄ᫈‛ߪਥߣߒߡ㛽᧚ᚑಽߣ࠮ࡔࡦ࠻᳓

20

Distribution [%]๺‛ᚑಽ߆ࠄߥࠆ‫ߜ߁ߩߎޕ‬㛽᧚ߪᨗᷢ⾗Ḯߢ޽ࠅ㧘㛽25ᐲᢙ㨇㧑㨉᧚ᚑಽࠍࠦࡦࠢ࡝࡯࠻ᑄ᫈‛߆ࠄౣ↢ߔࠆᛛⴚߦߟ޿ߡߪᣢߦᄙߊߩ⎇ⓥ߇޽ࠅ㧘޿ߊߟ߆ߩડᬺߦࠃߞߡታ⸽Ბ㓏ߦ޽ࠆ 9)10)‫ߚ߹ޕ‬㧘╩⠪ࠄߩ⎇ⓥࠣ࡞࡯ࡊߢ߽㜞࿶὇㉄᳓ࠍ↪޿ߚౣ↢⚦㛽᧚ߩౣ↢ᛛⴚࠍႎ๔ߒߡ޿ࠆ 11)‫ޕ‬㛽᧚ㇱಽߩ࡝ࠨࠗࠢ࡞㐿⊒߇ㅴ߻৻ᣇ㧘ࠦࡦࠢ࡝࡯࠻ᑄ151050᫈‛ਛߩ࠮ࡔࡦ࠻᳓๺‛ㇱಽߩౣ೑↪ߪߎࠇ߹ߢ࿎㔍ߣߐࠇߡ޿ߚ‫ޕ‬ᑄࠦࡦࠢ࡝࡯࠻႙ߩ☳⎈ಣℂߦ߅޿ߡ㧘࠮

1

10100

Particle diameter?m][1000☸ሶ⋥ᓘ [µm]ࡔࡦ࠻᳓๺‛ㇱಽߪᯏ᪾⊛ߥᒝᐲ߇ഠࠆߚ߼㧘ఝవ⊛ߦ☳⎈ߐࠇ㧘ᓸ☳ᧃߣߒߡᓧࠄࠇࠆ‫ߥ߁ࠃߩߎޕ‬ᑄ࠮ࡔࡦ࠻ᓸ☳ᧃߪࠦࡦࠢ࡝࡯࠻ᑄ᫈‛߆ࠄߩ㛽᧚ౣ↢ㆊ⒟ߢ೽

࿑㧞 ᑄ࠮ࡔࡦ࠻ᓸ☳ᧃߩ☸ሶᓘಽᏓ

↥‛ߣߒߡᓧࠄࠇ㧘㊀㊂Ყߢࠦࡦࠢ࡝࡯࠻ᑄ᫈‛ߩ 1/3⒟ᐲࠍභ߼ࠆ‫ޕ‬㧠㧚⣕⎫ᕈ⢻᷹ቯታ㛎㧟㧚ᑄ࠮ࡔࡦ࠻ᓸ☳ᧃ⹜ᢱ ⣕⎫ᕈ⢻ታ㛎ߪ㧘ࠟࠬᵹㅢ♽␜Ꮕᾲᄤ⒊㧔ፉᵤ⵾૞ᚲ⵾ DTG-60H㧕ࠍ↪޿ߡⴕߞߚ‫ޕ‬࿑ 3 ߦ⣕⎫ታ㛎ⵝ⟎ߩ ታ㛎ߦ↪޿ߚᑄ࠮ࡔࡦ࠻ᓸ☳ᧃ⹜ᢱߪ㧘ࢃ┙⍹ᑪ⸳߆ᮨᑼ࿑ࠍ␜ߔ‫ޕ‬෻ᔕࠟࠬߪ␜Ꮕᾲᄤ⒊ߩ⹜ᢱบߦ⟎߆ࠇࠄឭଏࠍฃߌߚ߽ߩߢ޽ࠆ‫ߪࠇߎޕ‬㧘ታ㓙ߩࠦࡦࠢ࡝࡯

ߚᑄ࠮ࡔࡦ࠻⹜ᢱࠍㅢㆊߔࠆ‫ࠬࠟޕ‬ᵹ㊂ߪ⹜ᢱ㊂ߦᲧߴ࠻ᑄ᫈‛߆ࠄ☳⎈ߔࠅ߽ߺߦࠃߞߡ㛽᧚ࠍౣ↢ߒߚ㓙ߩߡᄢ߈޿ߚ߼㧘⣕⎫ታ㛎ਛߩࠟࠬ⚵ᚑߪ৻ቯߢ޽ࠆߣ⷗

೽↢ᚑ‛ߢ޽ࠆ‫⹜ߩߎޕ‬ᢱߩᜬߟ⣕⎫ᕈ⢻ࠍታ㛎ߦࠃࠅߥߔߎߣ߇ߢ߈ࠆ㧔ᓸಽဳ෻ᔕེ㧕‫ޕ‬᷹ቯߒߚ‫ޕ‬ ⣕⎫ታ㛎ߩ೨ಣℂߣߒߡ㧘ᑄ࠮ࡔࡦ࠻ᓸ☳ᧃ⹜ᢱࠍ৻

 ࿑ 1 ߦᑄ࠮ࡔࡦ࠻ᓸ☳ᧃ⹜ᢱߩ SEM ↹௝ࠍ␜ߔ‫ޕ‬ታቯ᷷ᐲ㧔850͠㧕ߩ⓸⚛ࠟࠬ㔓࿐᳇ਅߢ㕒⟎ߒ㧘⹜ᢱ㊀㊂㧙㧙⠨߃ࠄࠇࠆ‫ߡߞ߇ߚߒޕ‬ᑄ࠮ࡔࡦ࠻ᓸ☳ᧃ⹜ᢱߩ㊀㊂Ⴧឃ᳇䋨䊄䊤䊐䊃䈻䋩෻ᔕ䉧䉴ടߪ⣕⎫෻ᔕ߇ㅴⴕߒߡ޿ࠆߎߣࠍ␜ߔ‫ޕ‬
ᵹ㊂⸘

3 CaO·2 SiO2·4 H2O + 3 SO2 → 3 CaSO3 + 2 SiO2 + 4 H2O 㧔1㧕

ᮡḰ䉶䊦
⹜ᢱ䉶䊦

ᵹ㊂⸘
࿶ജ䉭䊷䉳

CaO + SO2 → CaSO3              㧔2㧕࿶ജ䉭䊷䉳 ᧄⓂߢߪ㧘⣕⎫ᕈ⢻ߦ෸߷ߔ࿃ሶߩ߁ߜ㧘ᑄ࠮ࡔࡦ࠻
ᄤ⒊ㇱᓸ☳ᧃ☸ᓘ㧘෻ᔕ᷷ᐲ㧘ࠟࠬ⚵ᚑߩᓇ㗀ߦߟ޿ߡㅀߴࠆ‫ޕ‬N2
䊗䊮䊔

SO2(Air)䊗䊮䊔⣕⎫ታ㛎᧦ઙߩ৻ⷩࠍ⴫ 1 ߦ␜ߔ‫ޕ‬෻ᔕ᷷ᐲߦߟ޿ߡߪ㧘Ἱౝੇᑼ⣕⎫ࠍᗐቯߒ㧘650 ~ 950͠ߩ▸࿐ߢታ㛎ࠍⴕߞ

Purge gas䊌䊷䉳䉧䉴ߚ‫ߚ߹ޕ‬㧘ࠟࠬ⚵ᚑߪታ㓙ߩឃࠟࠬࠍᗐቯߒ㧘SO2 60 ~␜Ꮕᾲᄤ⒊࿑㧟 ⣕⎫ታ㛎ⵝ⟎ߩ᭎ᔨ࿑

1543 ppm㧔⓸⚛ࡃ࡜ࡦࠬ㧕ߩ▸࿐ߢᄌൻߐߖߚ߽ߩࠍ↪

޿ߚ‫ߚ߹ޕ‬㧘ੇᑼ⣕⎫ࠍᗐቯߒ㧘ੇ῎ࠟࠬࠍ↪޿ߡታ㛎ߩ቟ቯࠍᓙߞߚ‫ޕ‬㊀㊂ߩ⚻ᤨᄌൻߩᮨᑼ࿑ࠍ࿑ 4 ߦ␜ߔ‫ޕ‬ࠍⴕߞߚ‫ޕ‬ᑄ࠮ࡔࡦ࠻ᓸ☳ᧃߦട߃㧘ኻᾖ⹜ᢱߣߒߡੇ⹜ᢱ᷷ᐲߩ਄᣹ߦ઻޿㧘߹ߕ⹜ᢱ㊀㊂ߩᷫዋ߇⷗ࠄࠇߚ‫ޕ‬ᑼἹౝ⣕⎫ߦታ㓙ߦ↪޿ࠄࠇߡ޿ࠆ⣕⎫↪⍹Ἧ⍹ࠍ↪޿ߎࠇߪ㧘⹜ᢱਛߩ᳓ߩ⣕㔌߿⹜ᢱߩᾲಽ⸃ߦࠃࠆ߽ߩߣߚታ㛎߽ⴕߞߚ‫ޕ‬⠨߃ࠄࠇࠆ‫ޕ‬ᑄ࠮ࡔࡦ࠻ᓸ☳ᧃߪ㧘㑆㓗᳓߿⚿᥏᳓ߩᒻ⴫㧝 ⣕⎫ታ㛎᧦ઙ
100 mL/minߢ᳓ಽሶࠍᄙ㊂ߦ଻ᜬߒߡ߅ࠅ㧘ߎࠇࠄߩ⣕㔌ߦࠃߞߡ

ࠟࠬᵹ㊂㊀㊂ᷫዋ߇↢ߓࠆ߽ߩߣ⠨߃ࠄࠇࠆ‫ޕ‬ࠟࠬ⚵ᚑ

SO2 60 ~ 1543 ppm, N2 ࡃ࡜ࡦࠬ ߹ߚ㧘⹜ᢱਛߩ᳓㉄ൻࠞ࡞ࠪ࠙ࡓ╬ߩൻว‛ߩᾲಽ⸃᣹᷷ࡊࡠቶ᷷Ј㧔20 ͠/min㧕Ј850 ͠Ј㧔20 ͠/min㧕ߦࠃߞߡ߽⹜ᢱߩ㊀㊂ᷫዋ߇↢ߓࠆ‫⚛⓸ޕ‬㔓࿐᳇ਅ㧘

࠮ࠬ

Ј෻ᔕ᷷ᐲ

850 ͠ߢಣℂࠍⴕ߁ߎߣߢ਄ߩࠃ߁ߥ෻ᔕ߇චಽㅴⴕߒ㧘෻ᔕ᷷ᐲ

650 ~ 950 ͠㊀㊂߇৻ቯ୯ߦߥࠆߎߣࠍ⏕⹺ߒߚ‫ߩߘޕ‬ᓟ㧘੍ቯߩ⣕⎫ታ㛎᷷ᐲ߹ߢ⹜ᢱ᷷ᐲࠍᄌൻߐߖߚ‫⹜ޕ‬ᢱ᷷ᐲ߇቟ቯ

㧡㧚⚿ᨐߣ⠨ኤߒߚᓟ㧘ଏ⛎ࠟࠬࠍಾࠅᦧ߃㧘৻ቯỚᐲߩੑ㉄ൻ⎫㤛㧔SO2㧕ࠟࠬࠍ⹜ᢱߦᦑ㔺ߐߖ㧘ߘߩ㓙ߩ㊀㊂ߩ⚻ᤨᄌൻࠍ᷹ቯߒߚ‫ޕ‬ ㊀㊂⚻ᤨᄌൻ SO2 ᦑ㔺ᓟߔߋߦᑄ࠮ࡔࡦ࠻ᓸ☳ᧃ⹜ᢱߩ㊀㊂Ⴧട߇ ࿑ 5 ߦᑄ࠮ࡔࡦ࠻ߩ㊀㊂Ⴧട₸ߩ⚻ᤨᄌൻࠍ␜ߔ‫޿ޕ‬ߕࠇߩ᷷ᐲ᧦ઙߢ߽ SO2 ᦑ㔺㐿ᆎᓟ 30 ಽ⒟ᐲ߹ߢߪᦑⷰኤߐࠇߚ‫ޕ‬
㪪㪦2 / ⓸⚛㔓࿐᳇䋩⣕⎫⹜㛎䋨㪪㪦⣕⎫⹜㛎⓸⚛㔓 ᳇೨ಣℂ䋨⓸⚛㔓࿐᳇䋩೨ಣ⓸⚛㔓 ᳇㔺ᤨ㑆ߦኻߒߡ߶߷⋥✢⊛ߦ㊀㊂߇Ⴧടߒߚ߇㧘ߘߩᓟ߿߿㗡ᛂߜ௑ะߣߥߞߚ‫ޕ‬㗡ᛂߜ௑ะߪ㧘੝⎫㉄ࠞ࡞ࠪ⣕⎫෻ᔕ᷷ᐲ T1⣕⎫෻ᔕ᷷ᐲT2೨ಣℂ᷷ᐲ㪏㪌㪇䋨㷄䋩㩷࠙ࡓ╬ߩ⣕⎫෻ᔕ↢ᚑ‛߇ᑄ࠮ࡔࡦ࠻ਛߩᵴᕈߥࠞ࡞ࠪ
࠙ࡓಽࠍⵍⷒߔࠆߎߣߦࠃࠆ㧘SO2 ߣߩធ⸅ࠍ㒖ኂലᨐ

W0t=0ߦࠃࠆ߽ߩߣ⠨߃ࠄࠇࠆ‫ޕ‬
15650 Co
750 Co850 Co950 Co⣕⎫೷ߩ㊀㊂Ⴧട₸ [%]㼺W㼺W⹜ᢱ᷷ᐲ䋨㷄䋩

⣕⎫೷㊀㊂ [mg]T3t=t⣕⎫෻ᔕᤨ㑆[㫄㫀㫅]࿑㧠 ࠮ࡔࡦ࠻⹜ᢱߩ㊀㊂ᄌൻߩ᭎ᔨ࿑ ᑄ࠮ࡔࡦ࠻ᓸ☳ᧃ⹜ᢱࠍ 850͠ߢߩಣℂߒߚᓟ㧘ᑄ࠮

1050ࡔࡦ࠻ᓸ☳ᧃਛߩࠞ࡞ࠪ࠙ࡓߪࠤࠗ㉄ࠞ࡞ࠪ࠙ࡓ᳓๺‛020406080

෻ᔕᤨ㑆 [min]㧔଀߃߫㧘3 CaO·2 SiO2·4 H2O㧕޽ࠆ޿ߪ㉄ൻࠞ࡞ࠪ࠙ࡓ

CaO ߩᒻᘒߢሽ࿷ߒߡ޿ࠆ߽ߩߣ⠨߃ࠄࠇࠆ‫ߪࠄࠇߎޕ‬㧘
SO2 ᦑ㔺ߦࠃࠅએਅߩࠃ߁ߥ⣕⎫෻ᔕ߇ㅴⴕߔࠆ߽ߩߣ࿑㧡 ᑄ࠮ࡔࡦ࠻ᓸ☳ᧃߩ㊀㊂ᄌൻᦛ✢ߩ᷷ᐲଐሽᕈ51 ỚᐲRRO㧙㧙 ⣕⎫ᕈ⢻ߩฦ⒳᧦ઙଐሽᕈ

‛⾰⒖േߦࠃࠅᡰ㈩ߐࠇߡ޿ࠆߎߣࠍ␜ໂߒߡ޿ࠆ‫ޕ‬ ᷷ᐲଐሽᕈ

 51 Ớᐲଐሽᕈ

 ࿑ 6 ߪ㊀㊂ᄌൻ߆ࠄ▚಴ߒߚᑄ࠮ࡔࡦ࠻ਛߩࠞ࡞ࠪ࠙

 ࿑ 7 ߦ㧘⣕⎫೷ਛࠞ࡞ࠪ࠙ࡓ೑↪₸ߩ⚻ᤨᄌൻߩ SO2Ớᐲଐሽᕈࠍ␜ߔ‫ޕ‬ታ㛎᷷ᐲߪ 850͠ߢ޽ࠆ‫ޕ‬SO2 Ớᐲࡓ೑↪₸ߩ⚻ᤨᄌൻࠍ␜ߔ‫ߩࡓ࠙ࠪ࡞ࠞޕ‬೑↪₸ߪ㧘SO2
ߣ Ca ߩ෻ᔕ߇ᑼ㧝޽ࠆ޿ߪᑼ 2 ߦᓥ߁╬ࡕ࡞෻ᔕߢ޽

߇㜞޿߶ߤ㧘⣕⎫෻ᔕㅦᐲ߇㜞ߊߥߞߚ‫ޕ‬SO2 Ớᐲ߇ 1543

ppm ߩ႐วߦߪ㧘ᦑ㔺㐿ᆎᓟ 60 ಽߢࠞ࡞ࠪ࠙ࡓߩ೑↪

ࠆߣ⠨߃㧘એਅߩᑼࠍ↪޿ߡ▚಴ߒߚ‫ޕ‬⣕⎫೷ਛࠞ࡞ࠪ࠙ࡓߩ೑↪₸ =M Ca
M SO2× 100
W0 × wCa∆W ×₸ߪ 19.6㧑ߦ㆐ߒߚ‫ޕ‬࿑ 7 ߩ⚿ᨐ߆ࠄ㧘⣕⎫෻ᔕߩ⷗߆

[㧑] (3)ߌߩ෻ᔕᰴᢙߪ SO2 Ớᐲߦኻߒߡ 1.26 ߣ᳞߼ࠄࠇߚ‫ߎޕ‬ࠇߪ㧘⍹Ἧ⍹⣕⎫೷ߩ႐วߦႎ๔ߐࠇߡ޿ࠆ୯㧔0.4 ~ 112㧕 ߚߛߒ㧘ߎߎߢ㧘∆W: ⹜ᢱߩ㊀㊂Ⴧട㊂㧘W0: ⣕⎫෻-14)㧕ࠃࠅ߽߿߿ᄢ߈ߥ୯ߢ޽ߞߚ‫ޕ‬ᔕ㐿ᆎᤨߩ⹜ᢱ㊀㊂ߢ޽ࠆ‫ޕ‬wCa: ⣕⎫෻ᔕ㐿ᆎᤨߩ⹜ᢱߩࠞ࡞ࠪ࠙ࡓ฽᦭₸ [%]㧘MCa: ࠞ࡞ࠪ࠙ࡓߩේሶ㊂㧘

25⣕⎫೷ࠞ࡞ࠪ࠙ࡓߩ೑↪₸ [%]Mso2:ੑ㉄ൻ⎫㤛ߩಽሶ㊂ߢ޽ࠆ‫ޕ‬ห৻෻ᔕᤨ㑆ߢᲧセߒߚ႐ว㧘᷷ᐲ߇ 650 ~ 850͠ߩ▸࿐ߢߪ㧘㜞᷷߶ߤࠞ࡞ࠪ࠙ࡓ೑↪₸߇ᄢ߈ߊߥߞߚ‫ࠄ߇ߥߒ߆ߒޕ‬㧘950͠ߢߪ㧘ࠞ࡞ࠪ࠙ࡓ೑↪₸ߪ 850͠ߩ႐วߣᱴߤᏅ߇ߥ߆ߞߚ‫ޕ‬ߎࠇߪᑄ࠮ࡔࡦ࠻⹜ᢱߩ὾⚿ߦࠃࠆ߽ߩߣ⠨߃ࠄࠇࠆ‫ޕ‬850͠ߩ႐วߢߪ㧘ࠞ࡞ࠪ࠙ࡓߩ೑↪₸ߪ 60 ಽᓟߢ 17%⒟ᐲߢ޽ߞߚ‫ޕ‬⣕⎫↪⍹Ἧ⍹ߩࠞ࡞ࠪ࠙ࡓ೑↪₸ߣᲧセߒߡ߽ߎࠇࠄߩ୯ߪᄢ߈߆ߞߚ߇㧘ᑄ࠮ࡔࡦ࠻ᓸ☳ᧃߢ೑↪₸߇ᓢ‫ߦޘ‬㗡ᛂߜߦߥࠆߩߣᲧセߒ㧘⣕ᵹ↪⍹Ἧ⍹ߢߪ෻ᔕᤨ㑆 60 ಽએ਄ߢ߽೑↪₸ߩ਄᣹ߪ㗡ᛂߜߦߥ61 ppm
508 ppm
1013 ppm
1543 ppm

20
15
10500406080෻ᔕᤨ㑆 [min]ࠄߥ߆ߞߚ‫ޕ‬⣕⎫೷ਛࠞ࡞ࠪ࠙ࡓߩ೑↪₸ [%]2025

࿑㧣 ࠞ࡞ࠪ࠙ࡓ೑↪₸ߩ 51 Ớᐲଐሽᕈ
650 Co750 Co850 Co20 ☸ᓘଐሽᕈ

950 Co850 C, ⣕ ⎫↪ ⍹Ἧo ᑄ࠮ࡔࡦ࠻ᓸ☳ᧃ⹜ᢱߩ☸⚻ߩ㆑޿ߦࠃࠆ⣕⎫ᕈ⢻ߩ

15㆑޿ࠍᬌ⸛ߔࠆߚ߼㧘ᑄ࠮ࡔࡦ࠻ᓸ☳ᧃ⹜ᢱࠍ 20 µm ߆ࠄ 150 µm ߩ◎ߢಽ⚖ߒ㧘ߘࠇߙࠇߩಽ⚖⹜ᢱࠍ⣕⎫ታ10㛎ߦ↪޿ߚ‫ߒߛߚޕ‬㧘☸ᓘߩᢙ୯ߪ◎ߢಽ⚖ߒߚ▸࿐ߩ
50ਛᄩ୯ߢ޽ࠆ‫ޕ‬ᑄ࠮ࡔࡦ࠻⹜ᢱ㊀㊂޽ߚࠅߩ⣕⎫෻ᔕㅦᐲߪ☸ᓘߩᷫዋߦ઻޿ࠊߕ߆ߦჇടߒߚ‫☸ޕ‬ᓘᷫዋߦࠃ
020

406080෻ᔕᤨ㑆 [min]ࠆ෻ᔕㅦᐲߩჇടഀวߪ㧘ᑄ࠮ࡔࡦ࠻⹜ᢱࠍ⃿⁁ߣ઒ቯߒߚ႐วߩᲧ⴫㕙ⓍߩჇടࠃࠅ߽ߕߞߣዊߐߊߥߞߚ‫ޕ‬ߎߩ⚿ᨐߪ㧘ᑄ࠮ࡔࡦ࠻ᓸ☳ᧃਛߦ฽߹ࠇࠆ⣕⎫ߦ᦭ല࿑㧢 ࠞ࡞ࠪ࠙ࡓ೑↪₸ߩᤨ㑆ᄌൻߥࠞ࡞ࠪ࠙ࡓ฽᦭㊂߇☸⚻ߦࠃࠄߕ㧘߶߷৻ቯߢ޽ࠆߚ߼ߢ޽ࠆߣ⠨߃ࠄࠇࠆ‫ޕ‬੐ታ㧘⓸⚛ๆ⌕ߦࠃࠆ⴫㕙Ⓧ᷹ ෻ᔕ㐿ᆎ 5 ಽᓟ߹ߢߩ㊀㊂ᄌൻ߆ࠄ▚಴ߒߚ⣕⎫෻ᔕቯߩ⚿ᨐߣࠞ࡞ࠪ࠙ࡓ฽᦭₸ߪ☸ᓘߦࠃࠄߕ߶߷ห╬ߢߩೋᦼㅦᐲࠍ෻ᔕ᷷ᐲߩㅒᢙߦኻߒߡࡊࡠ࠶࠻㧔ࠕ࡟࠾޽ߞߚ‫ޕ‬࠙ࠬࡊࡠ࠶࠻㧕ߒߚ⚿ᨐ߆ࠄ㧘⷗߆ߌߩᵴᕈൻࠛࡀ࡞ࠡ
࡯ߪ 11.52 kJ / mol ߣ▚಴ߐࠇߚ‫ߩߎޕ‬୯ߪ㧘⍹Ἧ⍹⣕⎫೷ߦࠃࠆ⣕⎫෻ᔕߩᵴᕈൻࠛࡀ࡞ࠡ࡯ߩ⚂ 10 ಽߩ㧝ߩ୯ߢ޽ࠆ6)‫ߪࠇߎޕ‬㧘ᧄታ㛎♽ߢߩ⣕⎫෻ᔕ߇㧘⣕⎫෻ ⣕⎫෻ᔕㅦᐲߩ⚻㛎ᑼ એ਄ߩ⚿ᨐࠃࠅ㧘ᑄ࠮ࡔࡦ࠻ᓸ☳ᧃߦࠃࠆ⣕⎫෻ᔕߩߺ߆ߌߩㅦᐲᑼߪ

ᔕߦࠃࠅ↢ᚑߒߚ⎫㉄Ⴎ߿੝⎫㉄Ⴎ╬ߩ⣕⎫↢ᚑ‛ਛߩ㧙㧙

Dryer Absorbers, Ind. Eng. Chem. Res., 34, 302-307,

r [mol-SO2 / kg-ᑄ࠮ࡔࡦ࠻/ s] = ks [Cso2]1.26        㧔5㧕ߣ߹ߣ߼ࠄࠇࠆ‫ ߒߛߚޕ‬ks ߪ⣕⎫෻ᔕߩ⷗߆ߌߩ෻ᔕㅦ3)

G.-H. Jung, H. Kim, S.-G. Kim, Preparation and4)

Y. Li, B. C. Loh, N. Matsushima, M. Nishioka, M.

ᐲቯᢙߢ޽ࠅ㧘☸ᓘߦࠃࠄߕ
ks = 5.8810-5exp ( 11520/ 8.314×T) [m1.78㧔
/ mol0.26s㧕]  㧔6㧕ߢਈ߃ࠄࠇࠆ‫ߒߛߚޕ‬㧘ߎߩᑼߩㆡ↪▸࿐ߪ㧘SO2 Ớᐲ߇ 60 ppm ~ 1543 ppm ߢ㧘ᑄ࠮ࡔࡦ࠻ᓸ☳ᧃ⹜ᢱߩ☸ᓘ

߇ 10 ~ 200 µm ߢ޽ࠆ‫ߩߎޕ‬ᑼࠃࠅ㧘850͠ߩ႐วߦߪ⣕⎫೷⴫㕙Ⓧᒰߚࠅߩ⣕⎫෻ᔕㅦᐲߪ 7.68×10-8-2 -1⋅m ⋅s ߢ޽ࠆ‫ޕ‬mol-SO25)

Characterization of Lime-Silica Solids. Ind. Eng. Chem.
Res., 39, 1264-1270, 2000.

Sadakata, Chain Reaction Mechanism by NOx in SO2Removal Process. Energy & Fuel, 16, 155-160, 2002.

M.

J.

Renedo,J.

Fernandez,

Preparation,Characterization, and Calcium Utilization of Fly Ash /Ca(OH)2 Sorbents for Dry Desulfurization at Low

Temperature, Ind. Eng. Chem. Res., 41, 2412-2417,

㧢㧚߹ߣ߼෸߮੹ᓟߩዷᦸ㩷ࠦࡦࠢ࡝࡯࠻ᑄ᫈‛߆ࠄᓧࠄࠇߚᑄ࠮ࡔࡦ࠻ᓸ☳ᧃ6)߇ੇᑼ⣕⎫೷ߣߒߡߩ௛߈ࠍ᦭ߔࠆߎߣ߇⏕⹺ߐࠇߚ‫ޕ‬ᑄ࠮ࡔࡦ࠻ᓸ☳ᧃߪ㧘૶↪↪ㅜߩߥ޿ᑄ᫈‛ߢ޽ࠆߚ߼቟ଔߢ౉ᚻน⢻ߢ޽ࠅ㧘ૐࠦࠬ࠻ߥ⣕⎫ࡊࡠ࠮ࠬߩ᭴▽ᧄᛛⴚߪ㧘ᣣᧄߛߌߢߪߥߊਛ࿖߳ߩㆡ↪߇ᦼᓙߐࠇࠆ‫ޕ‬ਛ࿖ߢߪࠦࡦࠢ࡝࡯࠻ᑄ᫈‛ߦ㑐ߔࠆ⁁ᴫߪᦝߦᷓ
230 ᐕએਅߢ⸃૕ߐࠇߡ߅ࠅ㧘ࠦࡦࠢ࡝࡯࠻ᑄ᫈‛ߩ⊒↢࿖࿯੤ㅢ⋭, ᑪ⸳ᑄ᫈‛ឃ಴㊂ߩ዁᧪੍᷹, 2002.

9)

10)
11)

150-152, 2003.

⍹ୖ, ᦨ㚂㧘ഥᷡ, ෹Ỉ, 㜞ຠ⾰ౣ↢㛽᧚⵾ㅧᛛⴚߩ㐿⊒, ࠦࡦࠢ࡝࡯࠻Ꮏቇ, 37, 16-23, 1999.
㘵Ⴆ, ጊፒ, ᩉᴛ, ࠦࡦࠢ࡝࡯࠻ᑄ᧚߆ࠄߩౣ↢⚦㛽᧚⵾ㅧᛛⴚ, ࠤࡒࠞ࡞ࠛࡦࠫ࠾ࡗ࡝ࡦࠣ, 2006 ᐕ1349-1356, 1992.

13) S. V. Krishnan, S. V. Sotirchos, Sulfation of High-purity

Limestones under Simulated PFBC Conditions, Can . J.
Chem . Eng., 71, 244-255, 1993.

Ḩᑼ⣕⎫ᛛⴚߪߘߩࠦࠬ࠻߿ਛ࿖ౝ㒽ㇱߩ᳓ਇ⿷ߩ໧㗴߇㓚ኂߣߥࠅ㧘ਛ࿖߳ߩዉ౉ߪㆡಾߢߪߥ޿‫੹ޕ‬ᓟ㧘⎇ᓴ Ⅳ ࠪ ࠬ ࠹ ࡓ ߩ ㆡ ↪ , ࠦ ࡦ ࠢ ࡝ ࡯ ࠻ Ꮏ ቇ , 41,(International) on Combustion/The Combustion Institute,ਛዊߩ⍹὇Ά὾Ἱ߳ߩㆡ↪߇ㆃࠇߡ޿ࠆߎߣ߇ේ࿃ߢ޽
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Ash/Hydrated Lime Slurries for SO2 Removal in Spray㧙㧙