ࢥ࣮ࢡࢫࡢ࢞ࢫ໬㐣⛬࡟࠾ࡅࡿⅣ⣲㉁ᵓ㐀ኚ໬࠾ࡼࡧ⅊⢏Ꮚᣲືࡢゎ᫂◊✲௦⾲⪅ ྡྂᒇ኱Ꮫ ᮍ᮶ᮦᩱ࣭ࢩࢫࢸ࣒◊✲ᡤ ຓᩍ ᳜ᮌಖ᫛1㸬⥴ゝ 㕲㗰ᴗࡢ CO2 ᤼ฟ㔞ࡣ᪥ᮏ඲యࡢ⥲᤼ฟ㔞ࡢ⣙ 15㸣࡟࠶ࡓࡾࠊ〇㖧ᕤ⛬࠿ࡽࡢ CO2᤼ฟ㔞ࡀ〇㕲ᡤ඲యࡢ⣙ 70㸣ࢆ༨ࡵ࡚࠸ࡿࡓࡵࠊ≉࡟㧗⅔࡛ࡢ

ᐊຠᯝ࢞ࢫ࡛࠶ࡿ

CO2 ࡢ᤼ฟ㔞๐ῶࡀᛴົ࡜࡞ࡗ࡚࠸ࡿ 1)ࠋ㧗⅔࡟࠾࠸࡚ࠊCO2 ᤼ฟ㔞ࢆ๐ῶࡍࡿ᪉ἲ
ࡢ୍ࡘࡀపࢥ࣮ࢡࢫẚ᧯ᴗ࡛࠶ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊపࢥ࣮ࢡࢫẚ᧯ᴗࠊࡘࡲࡾࠊ㧗⅔
ෆ࡟࠾࠸࡚㏻Ẽࡢࡓࡵࡢᵓ㐀యࡢᙺ๭ࢆᯝࡓࡋ࡚࠸ࡿࢥ࣮ࢡࢫࡢ౑⏝㔞పୗࡣࠊ㧗⅔
ෆ࡛ࡢࢥ࣮ࢡࢫᒙཌࡢῶᑡࢆព࿡ࡋ࡚࠾ࡾࠊࡉࡽ࡟ࡣࠊ㧗⅔ෆ࡛ࡢࢥ࣮ࢡࢫࡢ཯ᛂ㈇Ⲵቑ኱࡟ࡼࡿᙉᗘຎ໬࠾ࡼࡧᦶ⪖ࢆࡶࡓࡽࡋࠊࡇࡢኚ໬ࡣ㧗⅔ࡢᏳᐃ᧯ᴗࡢ᭱ࡶ㔜せ࡞ᣦᶆࡢ୍ࡘ࡛࠶ࡿ㏻Ẽᛶ࡟኱ࡁ࡞ᙳ㡪ࢆ୚࠼ࡿࠋ ࢥ࣮ࢡࢫࡣ㧗⅔ෆࢆ㝆ୗࡍࡿ㐣⛬࡟࠾࠸࡚୺࡟ CO2 ࡟ࡼࡿ࢞ࢫ໬཯ᛂ࡟ࡼࡗ࡚ᾘ㈝ࡉࢀࡿࠋࡇࡢࢥ࣮ࢡࢫⅣ⣲㉁ࡢᾘ㈝࡟క࠸ࠊࢥ࣮ࢡࢫෆ࡟ᩓᅾࡋ࡚࠸ࡓ⅊⢏Ꮚࡀࢥ࣮ࢡࢫ⾲㠃࡟⌧ࢀࠊࢥ࣮ࢡࢫ⏤᮶ࡢ⢊࡜ࡋ࡚⅔ෆ࡟㞟✚ࡍࡿࡇ࡜࡛࢞ࢫ㏻Ẽᛶࢆ㜼ᐖࡍࡿࠋࡲࡓࠊࢥ࣮ࢡࢫ⾲㠃ୖࡢ⅊ศࡣࢥ࣮ࢡࢫ㛫ࢆὶࢀࡿ⼥ᾮ㸦⁐⼥㕲࠾ࡼࡧࢫࣛࢢ㸧࡜཯ᛂࡍࡿࡇ࡜࡛⼥ᾮᛶ≧㸦⢓ᛶࠊ⃿ࢀᛶ࡞࡝㸧ࢆኚ໬ࡉࡏ 2-6)ࠊᾮὶࢀ࡟ᝏᙳ㡪ࢆཬࡰࡍせᅉࡢ୍ࡘ࡛࠶ࡿࠋࡉࡽ࡟ࠊ⩚ཱྀ࠿ࡽ྿ࡁ㎸ࡲࢀࡓᚤ⢊Ⅳ⏤᮶ࡢ⅊ศ࡜཯ᛂࡍࡿ
ࡇ࡜࡛࣮ࣞࢫ࢙࢘࢖ዟ࡟ࢩ࢙ࣝᒙࡀᙧᡂࡉࢀࠊ㧗⅔ୗ㒊ࡢ㏻Ẽᛶ࡟኱ࡁ࡞ᙳ㡪ࢆ୚࠼
ࡿ 7,8)ࠋࡇࡢࡼ࠺࡟ࠊࢥ࣮ࢡࢫ୰ࡢ⅊ศࡣ㧗⅔ࡢᏳᐃ᧯ᴗ࡟ᚲせ୙ྍḞ࡛࠶ࡿ⅔ෆ㏻Ẽ
ᛶ࡟኱ࡁ࡞ᙳ㡪ࢆཬࡰࡍせᅉࡢ୍ࡘ࡛࠶ࡿ࡟ࡶ࠿࠿ࢃࡽࡎࠊࢥ࣮ࢡࢫࡢ࢞ࢫ໬཯ᛂ㐣⛬࡟࠾ࡅࡿ⅊⢏Ꮚࡢᣲື࡟ࡘ࠸࡚ࡣ୙᫂࡞Ⅼࡀከ࠸ࡇ࡜࠿ࡽࠊࡑࡢヲ⣽࡟ࡘ࠸࡚ゎ᫂ࡍࡿࡇ࡜ࡀ㔜せ࡛࠶ࡿࠋ ࡑࡇ࡛ᮏ◊✲࡛ࡣࠊࢥ࣮ࢡࢫࡢ࢞ࢫ໬཯ᛂ㐣⛬࡟࠾ࡅࡿࢥ࣮ࢡࢫⅣ⣲㉁ᵓ㐀ࡢኚ໬࠾ࡼࡧ⅊⢏Ꮚᣲືࡢゎ᫂ࢆ┠ⓗ࡜ࡋࠊࢥ࣮ࢡࢫࡢ࢞ࢫ໬ᐇ㦂ࢆ⾜ࡗࡓࠋࡲࡓࠊẚ㍑ࡢ
ࡓࡵ࡟✵Ẽ㞺ᅖẼ࡟࠾ࡅࡿ⇞↝ᐇ㦂ࡶ⾜ࡗࡓࠋ⇞↝ᐇ㦂࠾ࡼࡧ࢞ࢫ໬ᐇ㦂࡛ᚓࡽࢀࡓ཯ᛂ୰᩿ヨᩱࡢ᩿㠃⤌⧊ࢆほᐹ࠾ࡼࡧ⏬ീゎᯒࡍࡿࡇ࡜࡛ࠊࢥ࣮ࢡࢫࡢ࢞ࢫ໬ᣲືࠊࡉࡽ࡟ࠊࢥ࣮ࢡࢫࡢ࢞ࢫ໬㐣⛬࡟࠾ࡅࡿ⅊⢏Ꮚ≉ᛶ࡟ࡘ࠸࡚ᐇ㦂ⓗ࡟᳨ウࡋࡓࠋ
2㸬ᐇ㦂᪉ἲ
2㸬1㸬ᐇ㦂ヨᩱ ᮏ◊✲࡛ࡣࠊᐇ㦂ヨᩱ࡜ࡋ࡚ᐇᶵࡢࢥ࣮ࢡࢫ⅔࡛〇㐀ࡉࢀࡓࢥ࣮ࢡࢫࢆ⏝࠸ࡓࠋࢥ࣮ࢡࢫࡢ⢏ᚄࡣ 10㹼20mm ࡛࠶ࡿࠋヨᩱࡢᕤᴗศᯒ⤖ᯝ࠾ࡼࡧ⅊ศࡢ໬Ꮫ⤌ᡂࢆ
Table 1 ࠾ࡼࡧ Table 2 ࡟ࡑࢀࡒࢀ♧ࡍࠋ㸫㸫

Table 1 Properties of the coke lump samples

Proximate analysis (wt%:dry base)

Sample
Coke

VM

FC

Ash

1.7

87.0

11.3

VM : Volatile matter, FC : Fixed carbon

Table 2 Ash composition in the coke

Sample

SiO2

Al2O3

Fe2O3

CaOMgONa2OK2OSO3

Coke

49.57

27.37

11.21

2.69

0.99

0.51

1.50

1.13

2㸬2㸬ᐇ㦂⿦⨨࠾ࡼࡧᐇ㦂ᡭ㡰 ࢥ࣮ࢡࢫࡢ⇞↝ᐇ㦂࠾ࡼࡧ࢞ࢫ໬ᐇ㦂࡟⏝࠸ࡓ⦪ᆺ⟶≧㟁Ẽ⅔ࡢᴫ␎ᅗࢆ Fig. 1 ࡟♧ࡍࠋᮏ⿦⨨ࡣຍ⇕㒊ࠊ཯ᛂ⟶࠾ࡼࡧィࣜࢥࢽࢵࢺⓎ⇕య࡛⾜ࡗ࡚࠸ࡿࠋ⅔ࡢ㒊ࡼࡾᵓᡂࡉࢀ࡚࠸ࡿࠋຍ⇕ࡣࡽࡏࢇᆺࢩᗘࡣ⇕㟁ᑐ࡟ࡼࡗ࡚ᐃࡋࠊไᚚ┙࡟ࡼࡗ࡚ࣉࣟࢢ࣒ࣛ࡟ἢࡗ࡚ไᚚࡋ࡚࠸ࡿࠋ཯ᛂ⟶ࡣෆᚄ 60mm ࡢ࢔࣑ࣝࢼ〇ࡢ෇⟶࡛࠶ࡾࠊ཯ᛂ⟶ࡢୖ㒊࡜ୗ㒊࡟ࡣ෭༷⏝ࡢỈ෭ࢪࣕࢣࢵࢺࡀ⿦╔ࡉࢀ࡚࠸ࡿࠋຍ⇕㒊࡜཯ᛂ⟶ࡣ୍యᆺ࡜࡞ࡗ࡚࠾ࡾࠊᆶ┤᪉ྥ࡟ୖୗ⛣ືࡀྍ⬟࡛࠶ࡿࠋィ㒊ࡣࣃ࣮ࢯࢼࣝࢥࣥࣆ࣮ࣗࢱ࡜㟁Ꮚኳ⛗࡛ᵓᡂࡉࢀ࡚࠾ࡾࠊ㟁Ꮚኳ⛗ࡣ཯ᛂ⟶ୖ㒊࡟タ⨨ࡋ࡚࠶ࡾࠊ᭱ᑠ
⛗㔞༢఩ࡣ 0.01g ࡛࠶ࡿࠋ㟁Ꮚኳ⛗ࡢᗏ㠃࡟ࡣࠊᐃ≀ࢆྞࡿࡋ࡚⛗㔞࡛ࡁࡿࡼ࠺࡟

ࣇࢵࢡࡀࡘ࠸࡚࠾ࡾࠊࡑࡢࣇࢵࢡ࡟ⓑ㔠〇ࡢࣂࢫࢣࢵࢺ࡟ධࢀࡓヨᩱࢆྞࡿࡋ࡚࠸ࡿࠋ
࢞ࢫὶ㔞ࡣ࣐ࢫࣇ࣮ࣟࢥࣥࢺ࣮ࣟࣛ࡟ࡼࡾไᚚࡋ࡚࠸ࡿࠋ཯ᛂ⟶࡟౪⤥ࡍࡿ㞺ᅖẼ࢞ࢫࡣ཯ᛂ⟶ୗ㒊ࡢỈ෭ࢪࣕࢣࢵࢺ࡟タࡅࡽࢀࡓ࢞ࢫ౪⤥ཱྀࡼࡾὶධࡉࡏ࡚࠸ࡿࠋࡲࡓࠊ
㟁Ꮚኳ⛗ࢆ᤼࢞ࢫ࠿ࡽᏲࡿࡓࡵ࡟ࠊ㟁Ꮚኳ⛗࡟ࡶࢩ࣮ࣝ࢞ࢫ࡜ࡋ࡚୙άᛶ࢞ࢫ࡛࠶ࡿ
N2 ࢆ౪⤥ࡋ࡚࠸ࡿࠋᐇ㦂ヨᩱࢆⓑ㔠〇ࡢヨᩱ࣍ࣝࢲ࣮࡟ධࢀ࡚ࠊᡤᐃᗘ࡟᪼ࡋ࡚࠾࠸ࡓ㟁Ẽ⅔ࢆ㏿ࡸ࠿࡟ヨᩱ࣍ࣝࢲ࣮ࡢ఩⨨ࡲ࡛ୖ᪼ࡉࡏࡓࠋࡇࡢ㝿ࡢ㞺ᅖẼ࢞ࢫࡣ N2 ࢞ࢫ࡛࠶ࡿࠋヨᩱࡀ༑ศຍ⇕ࡉࢀヨᩱᗘࡀᏳᐃࡋࠊࢥ࣮ࢡࢫ୰ࡢ᥹Ⓨศࡀ༑ศᨺฟࡋࡓᚋࠊ཯ᛂࢆ㛤ጞࡉࡏࡿࡓࡵ࡟ࠊ㞺ᅖẼ࢞ࢫࢆ⇞↝ᐇ㦂ࡢሙྜࡣ✵Ẽࠊ࢞ࢫ໬ᐇ㦂ࡢሙྜࡣ CO-CO2ΰྜ࢞ࢫ࡟ษࡾ᭰࠼ࡓࠋ཯ᛂ࡟ࡼࡿ㔜㔞ῶᑡ㸦Ⅳ⣲㉁ࡢᾘ㈝㸧ࢆ㟁Ẽ⅔ୖ㒊࡟ഛ࠼௜ࡅࡓ㟁Ꮚኳ⛗࡟ࡼࡾ㐃⥆ⓗ࡟ᐃࡋࡓࠋࡇࡢ㔜㔞ῶᑡࡼࡾࢥ࣮ࢡࢫࡢ཯ᛂ⋡㸦⇞↝⋡ࠊ࢞ࢫ໬⋡㸧ࢆ⟬ฟࡋࡓࠋ཯ᛂ⋡ࡣୗグࡢᘧ࡟ࡼࡾᐃ⩏ࡋࡓࠋX'Wu 100WFC

㸦1㸧ᘧ㸫㸫 ࡇࡇ࡛ࠊX ࡣ཯ᛂ⋡[%]ࠊ∆W ࡣ⇞↝ࡲࡓࡣ࢞ࢫ໬ᐇ㦂࡛ࡢࢥ࣮ࢡࢫヨᩱࡢ㔜㔞ῶᑡ
㔞[g]ࠊWFC ࡣࢥ࣮ࢡࢫヨᩱ୰ࡢᅛᐃⅣ⣲㔞㸦FC㸧[g]࡛࠶ࡿࠋࡲࡓࠊᡤᐃࡢ㔜㔞ῶᑡ࡟฿㐩ࡋࡓࡽࠊ㞺ᅖẼ࢞ࢫࢆ N2 ࢞ࢫ࡟ษࡾ᭰࠼࡚ࠊ⇞↝཯ᛂ࠾ࡼࡧ࢞ࢫ໬཯ᛂࢆ೵Ṇࡉࡏࠊ཯ᛂ୰᩿ヨᩱࢆస〇ࡋࡓࠋComputerElectricbalance

Mass flow controller

ExhaustN2 gasPt wireCooling water

Reaction
tubeSample

Electricheater
N2O2

Cooling water
CO+CO2Fig. 1 Schematic of the electrically heated vertical tube furnace for cokecombustion and gasification experimentsᐇ㦂᮲௳ࢆ Table 3 ࡟♧ࡍࠋᐇ㦂

ᗘࡣ 1673Kࠊ㞺ᅖẼ࢞ࢫࡣ⇞↝ᐇ㦂ࡢሙྜࡣ✵Ẽࠊ࢞ࢫ໬ᐇ㦂ࡢሙྜࡣ⤌ᡂࡢ␗࡞ࡿ CO-CO2 ΰྜ࢞ࢫ࡜ࡋࡓࠋ཯ᛂ⋡ࡣ 80㸣࡛࠶ࡿࠋ
Table 3 Experimental conditions

Conditions

Combustion

Atmosphere

CO:CO2=75:25,50:50, 25:75,
N2:O2=80:20
0:100

Gas flow rate

4 LN/min

Furnace temperature

1673 KReaction conversion

80 %㸫㸫

Gasification

2㸬3㸬⅊⢏Ꮚᚄ࠾ࡼࡧẼᏍ⋡ࡢᐃ᪉ἲࢥ࣮ࢡࢫࡢ⇞↝࣭࢞ࢫ໬ᐇ㦂ᚋࠊࢹࢪࢱ࣐ࣝ࢖ࢡࣟࢫࢥ࣮ࣉ㸦ගᏛ㢧ᚤ㙾㸧࡟ࡼࡾᐇ㦂ヨᩱࡢእほࢆపಸ⋡࡟࡚ほᐹ࣭᧜ᙳࡋࡓࠋࡑࡢᚋࠊࢥ࣮ࢡࢫࡢ⇞↝࣭࢞ࢫ໬ᐇ㦂࡛ᚓࡽࢀࡓ཯ᛂ⋡ 80㸣ࡢ཯ᛂ୰᩿ヨᩱ࠾ࡼࡧᐇ㦂๓ࡢࢥ࣮ࢡࢫヨᩱࢆ࢚࣏࢟ࢩᶞ⬡࡟ࡼࡾᶞ⬡ᇙࡵࡋࠊ┿✵ྵᾐ⿦⨨࡟࡚ẼἻࢆྲྀࡾ㝖ࡃࡓࡵ࡟┿✵ᘬࡁࢆ⾜࠸ࠊᶞ⬡ࡢᅛ໬ᚋࠊษ᩿࣭◊☻ࡋࡓࠋSEM ࡟ࡼࡾࡇࢀࡽࡢ᩿㠃⤌⧊ࢆほᐹ࣭᧜ᙳࡋࡓࠋ
Fig. 2 ࡟୍౛࡜ࡋ࡚⇞↝ᐇ㦂࡟࠾ࡅࡿ཯ᛂ⋡ 80㸣ࡢ཯ᛂ୰᩿ヨᩱࡢ᩿㠃 BSE ⏬ീࢆ♧ࡍࠋࡇࢀࡣಸ⋡ 50 ಸ࡟࡚ほᐹど㔝ࢆᑡࡋࡎࡘ⛣ືࡉࡏ࡚᧜ᙳࡋࡓ BSE ⏬ീࢆ⤌ࡳྜࢃࡏࡿࡇ࡜࡟ࡼࡗ࡚ࠊࢥ࣮ࢡࢫヨᩱ඲యࡢ BSE ⏬ീ࡜࡞ࡿࡼ࠺࡟స〇ࡋࡓࡶࡢ࡛࠶ࡿࠋᅗ୰࡛ⓑⰍ㒊ศࡀ⅊ࠊ᫂ࡿ࠸⅊Ⰽ㒊ศࡀⅣ⣲㉁ࠊ㯮Ⰽ࠾ࡼࡧᬯ࠸⅊Ⰽ㒊ศࡀ✵㝽࠾ࡼࡧᶞ⬡࡛࠶ࡿࠋࡇࡢࡼ࠺࡟ᚓࡽࢀࡓほᐹ㠃ࡢ཯ᑕ㟁Ꮚ⏬ീ㸦BSE ⏬ീ㸧ࢆ⏬ീฎ⌮ࢯࣇࢺ࡟ࡼࡾ஧್໬ฎ⌮ࡍࡿࡇ࡜࡛⅊⢏Ꮚ࡜ࡑࡢ௚㸦Ⅳ⣲㉁࠾ࡼࡧẼᏍ㸧ࢆ㆑ู࡛ࡁࡿࡼ࠺࡟ࡋࡓࠋᅗ୰ࡢ஧್໬⏬ീ࡟࠾࠸࡚ࠊⓑⰍ㒊ศࡀ⅊ࢆ♧ࡋ࡚࠸ࡿࠋࡇࡢ஧್໬⏬ീࢆ⏝࠸࡚ࠊ⏬ീゎᯒ࡟ࡼࡾಶࠎࡢ⅊⢏Ꮚࡢ㠃✚ࢆᐃࡋࠊ┿⌫࡜௬ᐃࡋ࡚⅊⢏Ꮚࡢయ✚┦ᙜᚄࢆ⟬ฟࡋࡓࠋࡲࡓࠊ⅊⢏Ꮚࡢ⢏Ꮚᚄᐃࡢ᪉ἲ࡜ྠᵝ࡟ࠊࢥ࣮ࢡࢫヨᩱࡢẼᏍ⋡ࢆᐃࡋࡓࠋᚓࡽࢀࡓほᐹ㠃ࡢ཯ᑕ㟁Ꮚ⏬ീ㸦BSE ⏬ീ㸧ࢆ⏬ീฎ⌮ࢯࣇࢺ࡟ࡼࡾẼᏍ࡜ࡑࡢ௚㸦Ⅳ⣲㉁࠾ࡼࡧ⅊⢏Ꮚ㸧ࢆ㆑ู࡛ࡁࡿࡼ࠺࡟஧್໬ฎ⌮ࢆ⾜ࡗࡓࠋᚓࡽࢀࡓ஧್໬⏬ീࢆ⏝࠸࡚ࠊゎᯒ࡟ࡼࡾẼᏍࡢ㠃✚ࢆᐃࡋࠊࡇࡢẼᏍ㠃✚࡜ヨᩱ᩿㠃✚࡜ࡢ๭ྜ࠿ࡽẼᏍ⋡ࢆ⟬ฟࡋࡓࠋAshparticle

Visualizationof ash particle
BSE image of the cross-sectionof coke sample after combustion

Binarized image

Fig. 2 BSE image and binarized image of the cross-section of coke sample aftercombustion3㸬ᐇ㦂⤖ᯝ࠾ࡼࡧ⪃ᐹ3㸬1㸬ࢥ࣮ࢡࢫࡢ⇞↝࠾ࡼࡧ࢞ࢫ໬㐣⛬࡟࠾ࡅࡿヨᩱ࠾ࡼࡧ⅊⢏Ꮚᙧ≧ࡢኚ໬
Fig. 3 ࡟⇞↝࣭࢞ࢫ໬཯ᛂ㐣⛬ࡢࢥ࣮ࢡࢫࡢእほ෗┿ࢆ♧ࡍࠋ⇞↝཯ᛂ࡟࠾࠸࡚ࡣࠊ㸫㸫ࢥ࣮ࢡࢫ⾲㠃࡟⁐⼥ࡋࡓᙧ㊧ࡢ࠶ࡿ⌫≧ࡢ⅊⢏Ꮚࡀ௜╔ࡋ࡚࠸ࡿࡢࡀほᐹࡉࢀࡓࠋ୍
᪉ࠊCO:CO2=50:50 ࡛ࡢ࢞ࢫ໬཯ᛂ࡟࠾࠸࡚ࡣࠊࢥ࣮ࢡࢫ⾲㠃࡟⅊ࡀ௜╔ࡋ࡚࠸ࡿᵝᏊࡣほᐹࡉࢀ࡞࠿ࡗࡓࠋࡇࡢࡼ࠺࡟ࠊᮏᐇ㦂᮲௳࡟࠾࠸࡚ࡣࠊࢥ࣮ࢡࢫࡢ⇞↝࣭࢞ࢫ໬ࡢ཯ᛂ࠾ࡼࡧ⅊⢏Ꮚᣲືࡀ኱ࡁࡃ␗࡞ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡲࡓࠊྠࡌ཯ᛂ⋡ࠊࡘࡲࡾࠊᅛᐃⅣ⣲ࡢᾘ㈝㔞ࡀྠࡌ࡟ࡶ࠿࠿ࢃࡽࡎࠊ࢞ࢫ໬཯ᛂࡼࡾࡶ⇞↝཯ᛂࡢ᪉ࡀヨᩱࡢ኱ࡁࡉࡀᑠࡉ࠸ࡇ࡜࠿ࡽࠊ཯ᛂ࡟ࡼࡗ࡚Ⅳ⣲㉁ࡢᾘ㈝ࡢࡉࢀ᪉ࡀ␗࡞ࡿࡶࡢ࡜᥎
ᐹࡍࡿࠋ
Fig. 4 ࡟⇞↝࣭࢞ࢫ໬཯ᛂ㐣⛬࡟࠾ࡅࡿࢥ࣮ࢡࢫヨᩱ⾲㠃㏆ഐࡢ᩿㠃 BSE ⏬ീࢆ♧ࡍࠋᅗ୰࡛ⓑⰍ㒊ศࡀ⅊ࠊ᫂ࡿ࠸⅊Ⰽ㒊ศࡀⅣ⣲㉁ࠊ㯮Ⰽ࠾ࡼࡧᬯ࠸⅊Ⰽ㒊ศࡀ✵㝽࠾ࡼࡧᶞ⬡࡛࠶ࡿࠋ⇞↝཯ᛂ࡟࠾࠸࡚ࡣࠊ⁐⼥࣭จ㞟ࡋࡓ⅊⢏Ꮚࡀࢥ࣮ࢡࢫ⾲㠃࡟Ꮡᅾࡋ࡚࠸ࡿࡢࡀศ࠿ࡿࠋ୍᪉ࠊCO:CO2=50:50 ࡛ࡢ࢞ࢫ໬཯ᛂ࡟࠾࠸࡚ࡣࠊ୍㒊⁐⼥ࡋࡓ⅊⢏ᏊࡀᏑᅾࡋࡓࡀࠊ⇞↝཯ᛂࡢࡼ࠺࡞⅊⢏Ꮚࡢจ㞟ࡣほᐹࡉࢀ࡞࠿ࡗࡓࠋ
Fig. 5 ࡟⤌ᡂࡢ␗࡞ࡿ CO-CO2 ΰྜ࢞ࢫୗ࡟࠾ࡅࡿ࢞ࢫ໬཯ᛂ㐣⛬࡛ࡢࢥ࣮ࢡࢫ᩿
㠃ࡢ BSE ⏬ീࢆ♧ࡍࠋᅗ୰࡛ⓑⰍ㒊ศࡀ⅊ࠊ᫂ࡿ࠸⅊Ⰽ㒊ศࡀⅣ⣲㉁ࠊ㯮Ⰽ࠾ࡼࡧᬯ࠸⅊Ⰽ㒊ศࡀ✵㝽࠾ࡼࡧᶞ⬡࡛࠶ࡿࠋCO-CO2 ΰྜ࢞ࢫ୰ࡢ CO2 ๭ྜࡀቑຍࡍࡿ࡜࡜
ࡶ࡟ࠊヨᩱᚄࡀᑠࡉࡃ࡞ࡗ࡚࠾ࡾࠊࡲࡓࠊ኱ࡁ࡞⅊⢏ᏊࡀከࡃᏑᅾࡋ࡚࠸ࡿࠋ
3㸬2㸬ࢥ࣮ࢡࢫࡢ⇞↝࠾ࡼࡧ࢞ࢫ໬㐣⛬࡟࠾ࡅࡿ⅊⢏Ꮚ≉ᛶ
Fig. 6 ࡟ཎࢥ࣮ࢡࢫ㸦཯ᛂ⋡ 0㸣㸧࠾ࡼࡧ཯ᛂ⋡ 80%ࡢヨᩱ୰ࡢ⅊⢏Ꮚࡢ⢏ᚄูయ✚๭ྜࢆ♧ࡍࠋཎࢥ࣮ࢡࢫ࡜ẚ㍑ࡋࠊ⇞↝ᚋࡢࢥ࣮ࢡࢫ㸦཯ᛂ⋡ 80%㸧࡛ࡣ⢏ᚄࡢ኱ࡁ࡞⅊⢏Ꮚ㸦100Pm ௨ୖ㸧ࡢ๭ྜࡀቑຍࡋ࡚࠾ࡾࠊ⇞↝཯ᛂ࡟࠾࠸࡚ࢥ࣮ࢡࢫ୰ࡢ⅊⢏Ꮚࡢจ㞟ࡀ㐍⾜ࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡿࠋ୍᪉ࠊCO:CO2=50:50 ࡛ࡢ࢞ࢫ໬ᚋࡢࢥ࣮ࢡࢫ㸦཯ᛂ⋡ 80%㸧ࡣཎࢥ࣮ࢡࢫ࡜ẚ㍑ࡋ࡚⢏ᚄࡢ኱ࡁ࡞⅊⢏Ꮚ㸦100Pm ௨ୖ㸧ࡢ๭ྜࡀⱝᖸቑຍࡋ࡚࠸ࡿࡀ࡯ࡰྠࡌഴྥࢆ♧ࡋࡓࠋ
Fig. 7 ࡟ཎࢥ࣮ࢡࢫ㸦཯ᛂ⋡ 0㸣㸧࠾ࡼࡧ⤌ᡂࡢ␗࡞ࡿ CO-CO2 ΰྜ࢞ࢫୗ࡟࠾ࡅ
ࡿ࢞ࢫ໬཯ᛂ㐣⛬࡛཯ᛂ୰᩿ヨᩱ୰㸦཯ᛂ⋡ 80%㸧ࡢ⅊⢏Ꮚࡢ⢏ᚄูయ✚๭ྜࢆ♧ࡍࠋ
CO:CO2=75:25 ࡛ࡢ࢞ࢫ໬ᚋࡢࢥ࣮ࢡࢫ㸦཯ᛂ⋡ 80%㸧ࡣཎࢥ࣮ࢡࢫ࡜ྠࡌഴྥࢆ♧ࡋࡓࡀࠊCO-CO2 ΰྜ࢞ࢫ୰ࡢ CO2 ๭ྜࡀቑຍࡍࡿ࡜࡜ࡶ࡟ࠊཎࢥ࣮ࢡࢫ࡜ẚ㍑ࡋ࡚
⢏ᚄࡢ኱ࡁ࡞⅊⢏Ꮚ㸦100Pm ௨ୖ㸧ࡢ๭ྜࡀቑຍࡋ࡚࠾ࡾࠊ⇞↝ᚋࡢࢥ࣮ࢡࢫ࡜ྠᵝ࡟࢞ࢫ໬཯ᛂ࡟࠾࠸࡚ࢥ࣮ࢡࢫ୰ࡢ⅊⢏Ꮚࡢจ㞟ࡀ㐍⾜ࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡿࠋࡋ࠿
ࡋࠊ⅊⢏Ꮚจ㞟ࡢ㐍⾜⛬ᗘࡣ⇞↝཯ᛂ࡜ẚ㍑ࡋ࡚࢞ࢫ໬཯ᛂ࡛ࡣ኱ࡁࡃ࡞࠸ࠋࡇࢀࡣ
Fig. 4 ࡢ᩿㠃 BSE ⏬ീ࡟࠾࠸࡚࢞ࢫ໬཯ᛂ࡛ࡣ⇞↝཯ᛂࡢࡼ࠺࡞㠀ᖖ࡟኱ࡁ࡞⅊⢏ᏊࡀᏑᅾࡋ࡞࠸ࡇ࡜࠿ࡽࡶศ࠿ࡿࠋ

㸫㸫

Combustion

X=80%
Raw coke
15mmGasification(CO:CO2=50:50)
Fig. 3 External images of raw coke and cokes during combustion and gasification(CO:CO2=50:50)

(a)

(b)

500Pm

500Pm

(c)
(a) Raw coke (X=0%)(b) Combustion (X=80%)(c) Gasification(X=80%)

500Pm

Fig. 4 BSE images of cross-sections in the vicinity of the surface of raw cokesample and of coke samples after combustion and gasification (CO:CO2=50:50)

㸫㸫

(a)CO:CO2=75:25(b)CO:CO2=50:50(c)CO:CO2=25:75(d)CO:CO2=0:100

PP2mmFig. 5 BSE images of the cross-sections of raw coke and cokes during gasification㸫㸫

Reaction ratio : X=80%

Ash particle
diameter [Pm]22-50

Volume fraction [%]1009080706050403020
10050-100>100

Raw coke

Combustion CO2:CO=50:50
O2:N2=20:80
Gasification

CO:CO2=50:50

Fig. 6 Volume fraction of ash particles with each particle size for the raw cokesample and the coke samples after combustion and gasification (CO:CO2=50:50)

Reaction ratio : X=80%

Ash particle
diameter [Pm]22-50

Volume fraction [%]

10090
80
7060
50
4030
20
10050-100>100

Raw coke

75:25

50:50
25:75
CO:CO20:100

Fig. 7 Volume fraction of ash particles with each particle size for the raw cokesample and the coke samples after gasification experiments3㸬3㸬ࢥ࣮ࢡࢫࡢ⇞↝࠾ࡼࡧ࢞ࢫ໬㐣⛬࡟࠾ࡅࡿⅣ⣲㉁ᵓ㐀ࡢኚ໬
Fig. 8 ࡟ཎࢥ࣮ࢡࢫ㸦཯ᛂ⋡ 0㸣㸧࠾ࡼࡧ⇞↝࣭࢞ࢫୗᐇ㦂ᚋࡢࢥ࣮ࢡࢫヨᩱ㸦཯ᛂ⋡ 80%㸧ࡢẼᏍ⋡ࢆ♧ࡍࠋཎࢥ࣮ࢡࢫ࠾ࡼࡧ⇞↝ᚋࢥ࣮ࢡࢫヨᩱ㸦཯ᛂ⋡ 80%㸧ࡢẼᏍ⋡ࡣࡑࢀࡒࢀ⣙ 31㸣࠾ࡼࡧ⣙ 32㸣࡛࠶ࡾࠊ⇞↝཯ᛂ࡟ࡼࡗ࡚ẼᏍ⋡ࡣኚ໬ࡋ࡞࠿

㸫㸫

ࡗࡓࠋ୍᪉ࠊCO:CO2=50:50 ࡛ࡢ࢞ࢫ໬ᚋࡢࢥ࣮ࢡࢫヨᩱ㸦཯ᛂ⋡ 80%㸧ࡢẼᏍ⋡ࡣ⣙ 40㸣࡜ཎࢥ࣮ࢡࢫ࡜ẚ㍑ࡋ࡚ቑຍࡋࡓࠋࡲࡓࠊᐇ㦂๓ᚋࡢヨᩱᚄࢆᐃࡍࡿࡇ࡜࡛

཰⦰⋡ࢆ⟬ฟࡋࡓ࡜ࡇࢁࠊ⇞↝࡛ࡣ⣙ 46㸣࡛࠶ࡗࡓࡀࠊ࢞ࢫ໬࡛ࡣ⣙ 18㸣࡟Ṇࡲࡗࡓࠋྠࡌ཯ᛂ⋡ࠊࡘࡲࡾࠊᅛᐃⅣ⣲ࡢᾘ㈝㔞ࡀྠࡌ࡟ࡶ࠿࠿ࢃࡽࡎࠊヨᩱࡢ཰⦰⋡ࡀ␗࡞ࡿࡇ࡜࠿ࡽࠊ⇞↝࡛ࡣࢥ࣮ࢡࢫ⾲㠃࡛Ⅳ⣲㉁ࡀᾘ㈝ࡉࢀࠊ࢞ࢫ໬࡛ࡣࢥ࣮ࢡࢫ⾲㠃ࡢࡳ࡞ࡽࡎࢥ࣮ࢡࢫෆ㒊ࡢⅣ⣲㉁ࡶᾘ㈝ࡉࢀࡿࡇ࡜࡛ࠊ⇞↝ࡢ཰⦰⋡ࡀ࢞ࢫ໬ࡼࡾࡶ኱ࡁࡃ࡞ࡿࡶࡢ࡜⪃࠼ࡿࠋࡇࢀࡣ⇞↝࡜࢞ࢫ໬࡟࠾ࡅࡿẼᏍ⋡ࡢᕪ␗࠿ࡽࡶ♧၀ࡉࢀࡿࠋࡇࢀࡽࡢࡇ࡜࠿ࡽࠊ⇞↝࠾ࡼࡧ࢞ࢫ໬཯ᛂ㐣⛬࡟࠾ࡅࡿࢥ࣮ࢡࢫࡢ⅊⢏Ꮚᣲືࡀ኱ࡁࡃ␗࡞ࡾࠊ⇞↝཯ᛂࡢ᪉ࡀ࢞ࢫ໬཯ᛂ࡜ẚ㍑ࡋ࡚཯ᛂ㐣⛬࡟࠾ࡅࡿ⅊⢏Ꮚࡢจ㞟ࡀ㢧ⴭ࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡇࡢ⅊⢏Ꮚᣲືࡢᕪ␗ࡣࠊ⇞↝཯ᛂ࠾ࡼࡧ࢞ࢫ໬཯ᛂ
࡟࠾ࡅࡿⅣ⣲㉁ࡢᾘ㈝ࡢࡉࢀ᪉ࡢ┦㐪࡟㉳ᅉࡍࡿࡶࡢ࡜᥎ᐹࡍࡿࠋࡲࡓࠊ࢞ࢫ໬཯ᛂ
࡟࠾ࡅࡿ CO2 ๭ྜࡢ⅊⢏Ꮚᣲື࡬ࡢᙳ㡪࡟ࡘ࠸࡚ࡣࠊCO2 ๭ྜࡀቑຍࡍࡿ࡜Ⅳ⣲㉁ࡢ
ᾘ㈝ᣲືࡀ⇞↝཯ᛂ࡟࠾ࡅࡿⅣ⣲㉁ࡢᾘ㈝ᣲື࡟㏆࡙ࡃࡓࡵ࡜᥎ᐹࡍࡿࡀࠊ௒ᚋࠊ᭦

Porosity [%]࡞ࡿ᳨ウࡀᚲせ࡛࠶ࡿࠋ50
45403530
2520
15
10
50

Reaction ratio : X=80%

Raw cokeCombustion

Gasification
CO:CO2=50:50

Fig. 8 Porosity for the raw coke sample and the coke samples after combustionand gasification (CO:CO2=50:50)
4㸬⤖ゝࢥ࣮ࢡࢫࡢ⇞↝࠾ࡼࡧ࢞ࢫ໬཯ᛂ㐣⛬࡟࠾ࡅࡿⅣ⣲㉁ᵓ㐀࠾ࡼࡧ⅊⢏Ꮚ≉ᛶࡢኚ໬ࢆᐇ㦂ⓗ࡟᳨ウࡋࡓ⤖ᯝࠊ௨ୗࡢ▱ぢࡀᚓࡽࢀࡓࠋ

㸫㸫

㸦1㸧 ⇞↝཯ᛂ࡛ࡣࠊࢥ࣮ࢡࢫ⾲㠃࡟⁐⼥࣭จ㞟ࡋࡓ኱ࡁ࡞⅊⢏ᏊࡀᏑᅾࡋࡓࠋ
㸦2㸧 ࢞ࢫ໬཯ᛂ࡛ࡣࠊ୍㒊ࡢ⅊⢏Ꮚࡀ⁐⼥ࡋࠊ⌫≧࡟࡞ࡗ࡚࠸ࡓࡀࠊ⅊⢏Ꮚྠኈࡢจ㞟ࡣ࡯࡜ࢇ࡝ほᐹࡉࢀ࡞࠿ࡗࡓࠋ
㸦3㸧 CO2 ๭ྜࡀቑຍࡍࡿ࡜኱ࡁ࡞⅊⢏Ꮚࡢ๭ྜࡀቑຍࡋࠊ⅊⢏Ꮚࡢจ㞟ࡀ㐍⾜ࡋࡓࠋ㸦4㸧 ࢞ࢫ໬ᚋࡢࢥ࣮ࢡࢫヨᩱࡢẼᏍ⋡ࡣཎࢥ࣮ࢡࢫ࠾ࡼࡧ⇞↝ᚋࡢࡶࡢ࡜ẚ㍑ࡋ
࡚ 10㸣⛬ᗘ኱ࡁࡃࠊᮏᐇ㦂᮲௳࡟࠾࠸࡚ࡣⅣ⣲㉁ࡢᾘ㈝ᣲືࡀ࢞ࢫ໬࡜⇞↝࡜࡛␗࡞ࡿࠋㅰ㎡ ᮏ◊✲ࡣࠊබ┈㈈ᅋἲே JFE21 ୡ⣖㈈ᅋࡼࡾᢏ⾡◊✲ຓᡂ (2015 ᖺᗘ) ࡢᨭ᥼ࢆཷࡅ࡚㐙⾜ࡉࢀࡓࠋグࡋ࡚῝⏒࡞ࡿㅰពࢆ⾲ࡍࡿࠋཧ⪃ᩥ⊩1)

T. Ariyama and M. Sato, ISIJ International 46(2) (2006) 1736-1744.

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K. Ohno, S. Tsurumaru, A, Babich, T. Maeda, D. Senk, H. W. Gudenau and K.
Kunitomo, ISIJ International 55(6) (2015) 1245-1251.

3)

T. Matsui, N. Ishiwata, Y. Hara and K. Takeda, ISIJ International 44(12)(2004) 2105-2111.

4)

M. W. Chapman, B. J. Monaghan, S. A. Nightingale, J. G. Mathieson and R. J.
Nightingale, ISIJ International 47(7) (2007) 973-981.

5)

F. McCarthy, R. Khanna, V. Sahajwalla and N. Simento, ISIJ International
45(9) (2005) 1261-1268.

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F. McCarthy, V. Sahajwalla, J. Hart and N. Saha-Chaudhury, Metall. Mater.
Trans. B 34B (2003) 573-580.

7)

J.-K. Chung and N.-S. Hur, ISIJ lnternational 37(2) (1997) 119-125.

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Y. Shen, T. Shiozawa, P. Austin and A. Yu, Minerals Engineering 63 (2014)
91-99.

㸫㸫