㧗ࡾࢇࢫࣛࢢࡢỈ⁐໬ฎ⌮࡟ࡼࡿࡾࢇ㈨※ᅇ཰௦⾲◊✲⪅ ᮾ໭኱Ꮫ ከඖ≀㉁⛉Ꮫ◊✲ᡤ ෸ᩍᤵ᳜⏣⁠ඹྠ◊✲⪅ Chosun Univ., Dept. of Mater. Sci. & Eng Assistant Professor㔠ᐉ୰     ᮾ໭኱Ꮫ ከඖ≀㉁⛉Ꮫ◊✲ᡤ ຓᩍ㧗᪫◊✲༠ຊ⪅ ᮾ໭኱Ꮫ ከඖ≀㉁⛉Ꮫ◊✲ᡤ

ᮭఏ᫂

1㸬⥴ゝ
 ୡ⏺࡟࠾ࡅࡿᖺ㛫ࡢ㕲㗰⏕⏘㔞ࡣ 16 ൨ t ࢆ㉸࠼࡚࠾ࡾࠊ
Ⰻ㉁࡞㕲㖔▼㈨※ࡢᯤῬࡸ๪⏘≀ࡢ᭷ຠ฼⏝ࡀ㔜せ࡞ㄢ㢟࡜࡞ࡗ࡚࠸ࡿࠋ㕲㖔▼ࡢຎ㉁໬࡜ࡋ࡚㕲⃰ᗘࡢపୗࠊࡾࢇࠊࢩ
ࣜ࢝ࠊ࢔࣑ࣝࢼ⃰ᗘࡢୖ᪼ࡀ࠶ࡆࡽࢀࠊ⢭⦎ᢏ⾡ࡢྥୖࡀồࡵࡽࢀࡿࠋ ࡾࢇ⃰ᗘࡢ㧗࠸㕲㖔▼ࡣ౫↛ୡ⏺୰࡟㈿Ꮡࡋ࡚࠸ࡿࠋࡇࢀࡽࡢ㖔▼ࢆ౑⏝ࡋ㖧㕲ࢆ〇㐀ࡍࡿ࡜ࠊ౛࠼ࡤࠊ0.1㸣P ࢆྵ᭷ࡍࡿ㖔▼࠿ࡽ 0.25㸣P ࢆྵ᭷ࡍࡿ㖧㕲ࡀ࡛ࡁࡿ 1)ࠋ㏻ᖖࡢ
〇㗰ࢫࣛࢢ࡛ࡣ P2O5 ࢆ⣙ 1~3㸣ྵ᭷ࡍࡿࡀࠊ㧗 P ྵ᭷㔞㖔▼࡟ࡼࡿ〇㕲ࡢ⬺ࡾࢇᕤ⛬࡟ࡼࡾᚓࡽࢀࡿ〇㗰ࢫࣛࢢࡢ P2O5 ྵ᭷㔞ࡣࠊ10㸣௨ୖ࡟㐩ࡍࡿྍ⬟ᛶࡀ࠶ࡿ 2㸧ࠋ ୍᪉ࠊࡾࢇࡣ⫧ᩱ࡜ࡋ࡚ࡢ㟂せࡀቑຍࡋ࡚࠾ࡾࠊ2060 ᖺ௦࡟ࡣ㟂せࡀ⌧ᅾࡢ⤒῭ⓗྍ᥇㔞ࢆୖᅇࡿࡇ࡜ࡀண᝿ࡉࢀ࡚࠸ࡿࠋ㧗ရ఩ࡢኳ↛ࡾࢇ㖔▼ࡢᇙⶶ㔞ࡣపୗࡋࠊపရ఩ࡢ㖔▼࡟ࡣ Cd ࡸ U ࡞࡝ࡢ㔜㔠ᒓࡀྵ᭷ࡍࡿ࡜࠸࠺ၥ㢟ࡀ࠶ࡾࠊ௦᭰㈨※ࡀᮃࡲࢀ࡚࠸ࡿࠋᅜෆࡢ㕲㗰⏕⏘࡜ࡾࢇ฼⏝ࡢつᶍࢆ⪃៖ࡍࡿ࡜ࠊP2O5 ྵ㔞ࡢ㧗࠸〇㗰ࢫࣛࢢࡣࡾࢇࡢ᭷ຊ࡞౪⤥※࡟࡞ࡿྍ⬟ᛶࡀ࠶ࡿࠋ ࡑࡇ࡛ࠊ㕲㖔▼࠿ࡽ㕲㗰ࣉࣟࢭࢫ࡟ᑟධࡉࢀࡿࡾࢇࢆ㈨※࡟㌿᥮ࡍࡿࣉࣟࢭࢫᵓ⠏࡟ࡼࡿ㧗ࡾࢇ㖔▼ࡢ฼⏝ಁ㐍࡜ࡾࢇ㓟㈨※๰ᡂᢏ⾡ࡀồࡵࡽࢀࡿࠋ㕲㗰ᴗ࠿ࡽ๪⏘≀࡜ࡋ࡚⏕ᡂࡉࢀࡿࠊ㧗⃰ᗘࡢࡾࢇ㓟ࢆྵ᭷ࡍࡿࢫࣛࢢࢆࡾࢇ⫧ᩱ࡟㌿᥮ྍ⬟࡛࠶ࢀࡤࢫࣛࢢࡢ㧗௜ຍ౯್໬ࡀྍ⬟࡟࡞ࡿࠋ 〇㗰ࢫࣛࢢ୰ࡢࡾࢇࡣ୺࡟ 2CaO·SiO2-3CaO·P2O5 (C2S-C3P)ᅛ⁐య┦࡟⃰⦰ࡍࡿࠋ㏆ᖺࡢࢫࣛࢢ࠿ࡽࡢࡾࢇᅇ཰◊✲࡛ࡣ C2S-C3P ┦ࡢ⁐ฟࡀὀ┠ࡉࢀ࡚࠸ࡿࠋ஝ᘧ⢭㘐࡟ࡼࡿ
C2S-C3P ┦࡬ࡢࡾࢇࡢ⃰⦰ࡀ᳨ウࡉࢀࠊOno ࡽ 1)ࡣจᅛ୰ࡢ C2S ࡢᾋୖ࡟ࡼࡿ LD ㌿⅔ࢫࣛࢢ࠿ࡽࡢ⬺ࡾࢇࢆ᳨ウࡋࠊMiki ࡽ 2)ࡣẟ⣽⟶⌧㇟࡟ࡼࡿ FeO ࣜࢵࢳࡢᾮ┦࠿ࡽࡢ P2O5
ྵ᭷ C2S ┦ࡢศ㞳ࢆ◊✲ࡋࡓࠋSugiyama ࡽ 3)ࡣࠊ⬺ࡾࢇࢫࣛࢢࡢ 82㸣࡯࡝ࡀ 1.0mol / Lࡢ HNO3 ⁐ᾮ࡟⁐ゎࡍࡿࡇ࡜ࡀ࡛ࡁࠊ⁐ᾮ୰ࡢ Fe ࡣ࢝ࣝࢩ࣒࢘ࣁ࢖ࢻࣟ࢟ࢩ࢔ࣃࢱ࢖ࢺࡢῧຍ࡟ࡼࡾ㝖ཤྍ⬟࡛ࠊࡾࢇ㓟ࡢ⃰⦰࠾ࡼࡧᅇ཰࡟ࡘ࡞ࡀࡿࡇ࡜ࢆ♧ࡋࡓࠋࡾࢇ㓟⫧ᩱ
࠿ࡽ 2㸣ࢡ࢚ࣥ㓟࡛⁐ฟࡋࡓ P ࡢ㔞ࡣ⫧ᩱࡢホ౯್࡜ࡋ࡚ᗈࡃ౑⏝ࡉࢀ࡚࠸ࡿࠋJ. Diaoࡽ 4)ࠊL. Lin ࡽ 5)ࡣࢡ࢚ࣥ㓟࡟ࡼࡿࠊࢫࣛࢢ࠿ࡽࡢࡾࢇ⁐ฟࢆ᳨ウࡋࡓࠋ ࡾࢇࡀ⃰⦰ࡋࡓ C2S-C3P ┦ࡀ㑅ᢥⓗ࡟Ỉ⁐ᾮ࡟⁐ゎྍ⬟࡛࠶ࢀࡤࠊࡾࢇ㓟⫧ᩱ〇㐀ࡢࡓࡵࡢ᭷ᮃ࡞ཎᩱ࡛࠶ࡾࠊ⬺ࡾࢇࡉࢀࡓ㖔≀┦ࡣ〇㗰ࣉࣟࢭࢫ࡛ࡢ෌฼⏝ࡀᮇᚅ࡛ࡁࡿࠋࡾࢇࡢ㑅ᢥⓗᾐฟᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ࠊTeratoko ࡽ 6)࠾ࡼࡧ Numata ࡽ 7)ࡣࠊHNO3㸫㸫࡟ࡼࡾ pH ࢆไᚚࡋࡓỈ⁐ᾮ୰ࡢ C2S-C3P ᅛ⁐య࠾ࡼࡧྜᡂࢫࣛࢢࡢᾐฟᣲືࢆ◊✲ࡋࡓࠋࢫࣛࢢࡢ࣐ࢺࣜࢡࢫ┦࠿ࡽ࡛ࡣ࡞ࡃࠊC2S-C3P ࠿ࡽ㑅ᢥⓗ࡟ࡾࢇࢆᾐฟࡍࡿࡇ࡜ࡀྍ⬟࡛࠶ࡗࡓࠋࡋ࠿ࡋࠊCa2+ࡢ⁐Ꮡ⃰ᗘࡀୖ᪼ࡍࡿࡇ࡜ࡀᙳ㡪ࡋࠊࡾࢇ㓟ሷࡀỿẊࡍࡿࡓࡵỈ⁐ᾮ୰ࡢࡾࢇ⃰ᗘࡣୖ᪼ࡏࡎࠊC2S-C3P ⮬యࡢỈ⁐ᛶࡣ༑ศ㧗ࡃ࡞࠸ࠋ ᮏ◊✲࡛ࡣ C2S-C3P ࡢỈ⁐ᛶࢆྥୖࡍࡿࡓࡵ࡟ࠊ
C2S-C3P ࡢ CaO ࢆỈ⁐ᛶࡢ࠶ࡿ Na2O࡛⨨᥮ࡋ⁐ゎᗘࢆᨵၿࡍࡿࡇ࡜ࢆ᳨ウࡋࡓࠋᐇ㦂࡛ࡣᨵ㉁๣࡜ࡋ࡚ࠊNa2SiO3 ࢆ⏝࠸ࠊῧຍ࡟ࡼࡿᅛ⁐యࡢỈ⁐≉ᛶࡢኚ໬ࢆᐇ ࡋࡓࠋࡲࡓࠊࡾࢇ⁐ゎ࡟ᑐࡍࡿỈ⁐ᾮ୰ࡢ⁐ゎCa2+ࢆపୗࡍࡿࡇ࡜ࢆ᳨ウࡋࡓࠋCa2+ࡣࢩࣗ࢘㓟࢖࢜ࣥ㸦C2O42-㸧8)ࡲࡓࡣࢡ࢚ࣥ㓟࢖࢜ࣥ
㸦C6H5O73-㸧9)࡜㘒యࢆᙧᡂࡍࡿࡓࡵࢩࣗ࢘㓟(H2C2O4)࠾ࡼࡧࢡ࢚ࣥ㓟㸦H3C6H5O7㸧ࢆᾐฟࡢࡓࡵࡢ㓟࡜ࡋ࡚㑅ᢥࡋࠊࡾࢇࡢ⁐ゎ≉ᛶࢆㄪ࡭ࡓࠋ2㸬ᐇ㦂᪉ἲ
2.1 C2S-C3P ᅛ⁐యࡢ⏕ᡂ࡜ Na2SiO3 ࡟ࡼࡿᨵ㉁ ヨ⸆ࡢ SiO2ࠊCa3(PO4)2 ࠾ࡼࡧ CaO ࢆ⏝࠸࡚ C2S-C3P ᅛ⁐యࢆ⏕ᡂࡋࡓࠋCaO ࡣࠊヨ⸆ࡢ CaCO3 ࢆ 1273K ࡛ 12 ᫬㛫௨ୖಖᣢࡋ⏕ᡂࡋࡓࠋCaO ࡜ SiO2 ࢆ 2㸸1 ࡢࣔࣝẚ࡛ࡼࡃΰྜࡋࠊᅽ⢊ࡋࢱࣈࣞࢵࢺࢆసࡾࠊࡇࢀࢆ✵Ẽ㞺ᅖẼୗ 1773K ࡛ 48 ᫬㛫ಖᣢࡋࡓࠋḟ࡟ࠊ↝ᡂࡋࡓࢱࣈࣞࢵࢺࢆ⅔࠿ࡽྲྀࡾฟࡋࠊ✵Ẽ୰࡛෭༷ࡋࡓࠋࢱࣈࣞࢵࢺࢆ⢊○ࡋࠊྠᵝࡢసᴗࢆ⾜࠸ C2S-C3P ᅛ⁐యࢆ⏕ᡂࡋࡓࠋNa2SiO3 ࢆῧຍヨᩱࡣ⤌ᡂࢆㄪᩚࡋࠊ෌ᗘᅽ⢊ࡋࠊ⏕ᡂࡋࡓࢱࣈࣞࢵࢺࢆⓑ㔠ࡿࡘࡰෆࠊ1773K ࡛㸰᫬㛫ಖᣢࡋࡓࠋヨᩱࡢ⤌ᡂࢆ⾲㸯࡟♧ࡍࠋ
Table 1 Compositions of the C2S-C3P samples with and without Na2SiO3 (mass%)
Sample0%Na2SiO3
10%
Na2SiO3
20%
Na2SiO330%
Na2SiO3

beforemodification
CaO SiO2 P2O5CaO

SiO2

P2O5 Na2SiO3

60.4

19.6

20.0

60.4

19.6

20.0

0

59.8

18.0

22.2

53.9

16.2

20.0

9.8

59.2

15.9

24.9

47.5

12.8

20.0

19.7

58.4

13.3

28.4

41.1

9.4

20.0

29.5

with Na2SiO3 modification

2.2 ᾐฟᐇ㦂 సᡂࡋࡓ C2S-C3P ヨᩱࢆࠊ53μm ௨ୗ࡟⢊○ࡋࡓࠋ1g ࡢ⢊ᮎヨᩱࢆỈᵴ୰ࡢ 400mL ࡢ⬺࢖࢜ࣥỈ࡟ᢞධࡋࡓࠋ࢛࣮࢘ࢱ࣮ࣂࢫ࠾ࡼࡧᅇ㌿ࢫࢱ࣮࣮ࣛࢆ⏝࠸࡚ᨩᢾࡋ࡞ࡀࡽỈ⁐ᾮࡢ ᗘࢆ 298K ࡟⥔ᣢࡋࡓࠋࡇࡢ࡜ࡁヨᩱࡢ⁐ゎ࡛ pH ࡀୖ᪼ࡍࡿࡓࡵࠊpH ィࢆỈᵴ࡟ྲྀࡾ௜ࡅࠊ㓟ࢆᑡ㔞ࡎࡘ౪⤥ࡋ࡞ࡀࡽ pH ࢆ୍ᐃ࡟ಖࡗࡓࠋHNO3ࠊH2C2O4 ࠾ࡼࡧ㸫㸫H3C6H5O7 ࢆࡑࢀࡒࢀᾐฟ⏝ࡢ㓟࡜ࡋ࡚౑⏝ࡋࡓࠋ㑅ᢥⓗ࡟ࡾࢇࢆ⁐ฟࡍࡿࡓࡵ࡟ pH ࡣ 5௨ୖ࡜ࡋࡓࠋ୍ᐃ᫬㛫ࡈ࡜࡟ 5ml ⛬ᗘࡢ⁐ᾮࢆ⃰ᗘᐃ㔞ࡢࡓࡵ࡟ࢧࣥࣉࣜࣥࢢࡋࠊ120 ศࡲ࡛ᐇ㦂ࢆࡘ࡙ࡅࡓࠋࢧࣥࣉࣜࣥࢢ࡟ࡣ-0.45μm ࡢࣇ࢕ࣝࢱ࣮ࢆྲྀࡾ௜ࡅࡓࢩࣜࣥࢪࢆ⏝࠸ࡓࠋᐇ㦂⿦⨨ࡢᴫ␎ᅗࢆᅗ 1 ࡟♧ࡍࠋ

Fig.1 Schematic of leaching apparatus
Table 2 Leaching experiments at various pH values (pH)SampleAcidHNO3H2C2O4H3C6H5O70%
10%
Na2SiO3 Na2SiO3
7777
720%
Na2SiO330%
Na2SiO35, 7, 95, 7, 95, 7, 977ᾐฟᕤ⛬ᚋࠊỈ⁐ᾮࢆࢁ㐣ࡋṧ␃ᅛయ࠾ࡼࡧࢁᾮࢆᅇ཰ࡋࡓࠋ᥇ྲྀࡋࡓỈ⁐ᾮ୰ࡢྛඖ⣲ࡢ⃰ᗘࢆࠊࣉࣛࢬ࣐Ⓨගศගἲ㸦ICP-AES㸧ࢆ⏝࠸࡚ศᯒࡋࡓࠋᐇ㦂࡛ࡣ pH ࠾ࡼࡧ Na2SiO3⃰ᗘࢆኚ໬ࡋ C2S-C3P ࢆᨵ㉁ࡋࠊࡇࢀࡽࡢᙳ㡪ࢆㄪ࡭ࡓࠋᐇ㦂᮲௳ࡢ⤌ࡳྜࢃࡏࢆ⾲ 2 ࡟♧ࡍࠋ3㸬ᐇ㦂⤖ᯝ3.1 ␗࡞ࡿᾐฟ᮲௳ୗ࡛ࡢ C2S-C3P ࡢ⁐ゎᣲື ᾐฟ᮲௳ࡢᙳ㡪ࢆᗈ⠊࡟ㄪ࡭ࡿࡓࡵ࡟ࠊᮍᨵ㉁ C2S-C3P ࢆ pH7 ࡛ HNO3ࠊH2C2O4ࠊ࠾
ࡼࡧ H3C6H5O7 ࡟ࡼࡗ࡚ᾐฟࡋࡓࠋᅗ 2 ࡣᾐฟ᫬㛫࡜ Ca ࠾ࡼࡧ P ⃰ᗘࡢ㛵ಀࢆ♧ࡍࠋึᮇ࡟ࡣ⁐ᾮ୰ࡢ࢖࢜ࣥ⃰ᗘࡀప࠸ࡓࡵ࡟ C2S-C3P ⁐ゎࡀ㏿ࡃࠊCa ࠾ࡼࡧ P ⃰ᗘࡣᛴ㏿࡟ୖ᪼ࡍࡿࠋHNO3 ࢆ⏝࠸ࡓ⁐ᾮ࡛ࡣࠊCa ⃰ᗘࡣ㧗ࡃࠊ⁐ゎ P ࡢ⃰ᗘࡣᏳᐃࡏࡎࠊ20 ศᚋ㸫㸫࡟ࡣపୗࢆ㛤ጞࡋࡓࠋᾐฟᾮࡢ㓟໬๣࡜ࡋ࡚ H2C2O4 ࢆ⏝࠸ࡓሙྜࠊ⁐ᾮ୰ࡢ Ca ⃰ᗘࡣᛴ㏿࡟ῶᑡࡋࠊP ⃰ᗘࡣୖ᪼ࡋࡓࠋH3C6H5O7 ⁐ᾮ࡛ࡣࠊCa ⃰ᗘࡣ HNO3 ⁐ᾮ࡜ྠ⛬ᗘ࡟ୖ᪼ࡋࡓࡀࠊP ⃰ᗘࡣ㐃⥆ⓗ࡟ୖ᪼ࡋࠊ120 ศᚋ࡟ࡣ 41.4mg / L ࡟㐩ࡋࡓࠋ Ỉ⁐ᾮ୰ࡢྛඖ⣲ࡢ⃰ᗘኚ໬࠿ࡽࠊᘧ㸦1㸧ࢆ⏝࠸࡚ CaࠊSi ࠾ࡼࡧ P ࡢ⁐ゎ⋡ࢆィ⟬ࡋࡓࠋࡇࡇ࡛ࠊRM ࡣඖ⣲ M ࡢ⁐ゎ⋡࡛࠶ࡾࠊCM ࡣỈ⁐ᾮ୰ࡢඖ⣲ M ࡢ⃰ᗘ㸦mg / L㸧࡛࠶ࡿࠋV ࡣỈ⁐ᾮࡢ ᐃ⤊஢᫬ࡢయ✚㸦L㸧࡛࠶ࡿࠋmM ࡣ C2S-C3P ヨᩱ 1g ୰ࡢඖ⣲ M
ࡢඖࡢ㉁㔞㸦mg㸧࡛࠶ࡿࠋ

RM =㸦CM∙V㸧/ mM

㸦1㸧

120 ศ⤒㐣ᚋࡢ C2S-C3P ࠿ࡽࡢ CaࠊSi ࠾ࡼࡧ P ࡢ⁐ฟ⋡ࢆᅗ 3 ࡟♧ࡍࠋCa ࡢ⁐ฟ⋡ࡣ㓟໬๣࡟ HNO3 ࠾ࡼࡧ H3C6H5O7 ࢆ⏝࠸ࡓሙྜ 22㸣ࢆ㉸࠼ࡿࡀࠊ
H2C2O4 ࡛ࡣ㠀ᖖ࡟ప࠸ࠋ
HNO3 ⁐ᾮ࡛ࡣࠊP ࡢࢃࡎ࠿࡞㒊ศࡋ࠿⁐ฟࡋ࡞࠿ࡗࡓࠋࡋ࠿ࡋࠊH2C2O4 ࠾ࡼࡧ H3C6H5O7⁐ᾮ୰ࡢ P ⁐ฟ⋡ࡣࠊࡑࢀࡒࢀ 14.3㸣࠾ࡼࡧ 17.8㸣࡜᭷ព࡞ቑຍࢆぢࡏࡓࠋࡋࡓࡀࡗ࡚ࠊH2C2O4 ࠾ࡼࡧ H3C6H5O7 ࡣࠊpH7 ࡢỈ⁐ᾮ୰࡛ C2S-C3P ࠿ࡽ P ࢆᾐฟࡍࡿ㝿࡟ࠊHNO3ࡼࡾࡶຠᯝⓗ࡛࠶ࡿ࡜ゝ࠼ࡿࠋ

Fig.2 Change in the Ca and P concentrations in different leaching agents at pH7㸫㸫Fig.3 Dissolution ratios of each element from the C2S-C3P in different leaching
agents at pH7
3.2 Na2SiO3 ࡟ࡼࡿ C2S-C3P ࡢᨵ㉁ ᅗ 4 ࠾ࡼࡧ⾲ 3 ࡟ࡑࢀࡒࢀ Na2SiO3 ࡢῧຍ㔞ࡢ␗࡞ࡿ C2S-C3P ヨᩱࡢ᩿㠃࠾ࡼࡧ⤌ᡂࢆ♧ࡍࠋNa2SiO3 ࡟ࡼࡿᨵ㉁ᚋࠊヨᩱ୰࡟ 2 ┦ࡀᏑᅾࡍࡿࠋ୍᪉ࡢ┦ࡣ Na2O ࡛ᨵ㉁ࡉࢀ
ࡓ C2S-C3P ᅛ⁐య࡟┦ᙜࡋࠊࡶ࠺୍᪉ࡣ᪂ࡓ࡟⏕ᡂࡋࡓ CaOSiO2 ┦࡛࠶ࡿࠋ ᨵ㉁๓ࡢ C2S-C3P ࡢ⤌ᡂ㸦⾲ 1 ཧ↷㸧࡜ẚ㍑ࡋ࡚ࠊᨵ㉁ࡋࡓ C2S-C3P ୰ࡢ SiO2 ࠾ࡼࡧP2O5 ྵ᭷㔞ࡣ࡯࡜ࢇ࡝ኚ໬ࡋ࡞࠿ࡗࡓࡀࠊCaO ྵ᭷㔞ࡣ Na2O ࡟⨨᥮ࡉࢀῶᑡࡋࡓࠋᅗ 5࡟♧ࡍࡼ࠺࡟ࠊῧຍࡉࢀࡓ Na2SiO3 ࡀቑຍࡍࡿ࡜ࠊC2S-C3P ᅛ⁐య୰ࡢ Na2O ྵ᭷㔞ࡀቑ
ຍࡋࠊCaO ྵ᭷㔞ࡀῶᑡࡍࡿࠋTable 3 Compositions of each phase in the C2S-C3P samples with different massfractions of the added Na2SiO3 (mass%)
SampleCaO

SiO2

P2O5Na2
O

0% Na2SiO3

1

59.7

18.5

21.9

-10%Na2SiO3

154.8

17.2

23.6

4.5

2

47.3

43.3

6.1

3.3

1

49.9

15.5

25.7

8.9

2

41.1

45.9

4.9

8.1

1

45.5

12.8

30.1

11.6

2

30.7

51.7

4.8

12.8

20%Na2SiO3
30%Na2SiO3

㸫㸫

Phase
C2S-C3P
C2S-C3PCS
C2S-C3PCS
C2S-C3PCS

0% Na2SiO3㻌

10% Na2SiO3
2㻌

1㻌

1㻌

20% Na2SiO3

30% Na2SiO3
2㻌
1㻌

1㻌

2㻌

Fig.4 Cross section of the C2S-C3P samples (×500) with different mass fractions of theadded Na2SiO3Fig.5 Change in CaO and Na2O contents

Fig.6 Mass ratios of each elementin the solid solution phase withdistributed in the C2S-C3PNa2SiO3 addition

solid solution ᅗ 6 ࡟┦㛫ࡢඖ⣲ࡢ࣐ࢫࣂࣛࣥࢫࢆィ⟬ࡋࠊC2S-C3P ᅛ⁐య୰࡟Ꮡᅾࡍࡿඖ⣲ࡢ㉁㔞ẚࢆồࡵࡓ⤖ᯝࢆ♧ࡍࠋࡇࡢ⤖ᯝࡣࠊῧຍࡋࡓ Na2O ࠾ࡼࡧ P2O5 ࡢ࡯࡜ࢇ࡝ࡀ C2S-C3P ᅛ⁐య୰࡟ᏑᅾࡋࠊNa2SiO3 ࡢቑຍࡣ P2O5 ࡢศ㓄࡟ᙳ㡪ࡏࡎࠊNa2O ࡢᅛ⁐య࡬ࡢศ㓄ẚࢆῶᑡࡍࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋ ᅗ 7 ࡟ᨵ㉁ࡋࡓ C2S-C3P ࡢ XRD ࢫ࣌ࢡࢺࣝ࡬ࡢ Na2SiO3 ῧຍࡢᙳ㡪ࢆ♧ࡍࠋNa2SiO3࡟ࡼࡿᨵ㉁ࢆ⾜ࢃ࡞࠸ሙྜࠊ┦ࡣ C2S-C3P ࡟┦ᙜࡍࡿࠋNa2SiO3 ࡀ 20㸣௨ୖ C2S-C3P ࡟ῧຍࡉࢀࡿ࡜ࠊCa2SiO4-Ca2Na2P2O8㸦C2S-C2NP㸧ᅛ⁐య┦࡜࡞ࡿࠋࡇࡢᙧᡂࡉࢀࡓ C2NP
໬ྜ≀ࡣࠊC3P-C2NP ⣔ 10)ࡢ┦ᅗ࡟♧ࡉࢀ࡚࠸ࡿࠋ

㸫㸫Fig.7 XRD spectra for the C2S-C3P samples with different mass fractions of theadded Na2SiO3
 EPMA ཬࡧ XRD ࡢ⤖ᯝ࠿ࡽࠊ㧗 ࡛ࡢ C2S-C3P ᅛ⁐య࡜ Na2SiO3 ࡜ࡢ཯ᛂࡣࠊᘧ㸦2㸧࡛⾲ࡍࡇ࡜ࡀ࡛ࡁࡿࠋNa2SiO3 ࡟ࡼࡿᨵ㉁ࡢ⤖ᯝࠊC2S-C2NP ᅛ⁐య࡜ CaO.SiO2 ┦ࡀᙧᡂࡉࢀࡿࠋ
Ca2SiO4-Ca3P2O8+ Na2SiO3 = Ca2SiO4-Ca2Na2P2O8 + CaO࣭SiO2

㸦2㸧

3.3 ᨵ㉁ࡋࡓ C2S-C3P ࡢ H2C2O4 ࠾ࡼࡧ H3C6H5O7 ⣔⁐ᾮ࡬ࡢ⁐ゎᣲື
 Na2SiO3 ࡟ࡼࡿᨵ㉁ࡢᙳ㡪ࢆㄪ࡭ࡿࡓࡵ࡟ࠊ␗࡞ࡿ⃰ᗘࡢ Na2SiO3 ࢆྵ᭷ࡍࡿ C2S-C3Pヨᩱࢆ pH7 ࡢ H2C2O4 ࠾ࡼࡧ H3C6H5O7 ࡛ pH ࢆㄪᩚࡋࡓ⁐ᾮ࡟ᾐฟࡉࡏࡓࠋᅗ 8 ࡣࠊ
H2C2O4 ⣔⁐ᾮ୰ࡢ Ca ࠾ࡼࡧ P ⃰ᗘࡢኚ໬ࢆ♧ࡍࠋỈ⁐ᾮ୰࡟ᾐฟࡍࡿ Ca ⃰ᗘࡣᨵ㉁๓
࠿ࡽప࠸ࡀࠊNa2SiO3 ࡢቑຍ࡜ඹ࡟ࡉࡽ࡟ῶᑡࡋࡓࠋNa2SiO3 ࡟ࡼࡿᨵ㉁ᚋࠊỈ⁐ᾮ࡟ᾐ
ฟࡋࡓ P ⃰ᗘࡣⴭࡋࡃቑຍࡋࡓࠋ20㸣ࡢ Na2SiO3P ࡢῧຍ࡟ࡼࡾ C2S-C3P ࠿ࡽࡢࡾࢇࡢ
⁐ฟ⃰ᗘࡣ⣙ 3 ಸ࡟࡞ࡾࠊᨵ㉁࡟ࡼࡾ pH7 ࡢ H2C2O4 ⣔⁐ᾮ୰࡬ࡢ C2S-C3P ࠿ࡽࡢ P ⁐ゎࢆಁ㐍࡛ࡁࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ 120 ศᚋ⤒㐣ᚋࡢ H2C2O4 ⁐ᾮ୰ࡢ C2S-C3P ࠿ࡽࡢඖ⣲ࡢ⁐ฟ⋡ࢆᅗ 9 ࡟♧ࡍࠋCa ࡢ⁐ฟ⋡ࡣ㠀ᖖ࡟ప࠸ࠋNa2SiO3 ῧຍ㔞ࡢኚ໬࡟ࡼࡿ C2S-C3P ヨᩱ࠿ࡽࡢ Si ࡜ Na ࡢ⁐ฟ⋡ࡢኚ໬ࡣᑠࡉ࠸ࠋࡋ࠿ࡋ Na2SiO3 ࡢ P ࡢ⁐ฟ⋡࡬ࡢᙳ㡪ࡣ኱ࡁࡃࠊ20㸣ࡢ Na2SiO3 ࡢῧຍ࡟ࡼࡾ⁐ฟ⋡ࡣ 43.9㸣࡟㐩ࡋࡓࠋࡋ࠿ࡋࠊNa2SiO3 ྵ᭷㔞ࢆࡉࡽ࡟ቑຍࡉࡏ࡚ࡶࠊP⁐ฟ⋡ࡣୖ᪼ࡋ࡞࠸ࠋ㸫㸫Fig.8 Change in the Ca and P concentrations in the H2C2O4 solution at pH7Fig.9 Dissolution ratios
the modifiedti off eachh elementlt ffrom thdifi d C2SS-C
C3P in the H2C2O4solution at pH7
 ᅗ 10 ࡣࠊpH7 ࡢ H3C6H5O7 ⣔⁐ᾮ࡟࠾ࡅࡿ Ca ࠾ࡼࡧ P ⃰ᗘࡢኚ໬ࢆ♧ࡍࠋࡲࡎ Ca⃰ᗘࡣᛴ㏿࡟ቑຍࡍࡿࠋH2C2O4 ⁐ᾮ࡬ࡢ⁐ฟ࡜␗࡞ࡾࠊNa2SiO3 ࡢቑຍ࡜࡜ࡶ࡟Ỉ⁐ᾮ୰ࡢ Ca ⃰ᗘࡣቑຍࡍࡿࠋH3C6H5O7 ⁐ᾮ୰ࡢ P ⃰ᗘࡶ Ca ྠᵝ࡟㧗࠸ࠋNa2SiO3 ࡢῧຍ㔞ࡢቑຍ࡟క࠸ࠊ⁐ᾮ୰ࡢ P ⃰ᗘࡶቑຍࡋࡓࠋ 120 ศ⤒㐣ᚋࡢ H3C6H5O7 ⁐ᾮ୰࡬ࡢྛඖ⣲ࡢ⁐ゎ⋡ࢆᅗ 11 ࡟♧ࡍࠋH3C6H5O7 ⁐ᾮ୰࡬ࡢᨵ㉁ࡋࡓ C2S-C3P ࠿ࡽࡢ CaࠊP ࠾ࡼࡧ Na ࡢ⁐ゎ⋡ࡣࠊNa2SiO3 ࡢῧຍ㔞ࡢቑຍ࡜࡜ࡶ࡟ቑຍࡍࡿࠋC2S-C3P ࡬ࡢ 20㸣Na2SiO3 ῧຍ࡟ࡼࡾࠊP ࡢ⁐ฟ⋡ࡣ 24.6㸣࡟ࡲ࡛ࡋ࠿ୖ᪼ࡋ࡚࠾ࡽࡎࠊNa2SiO3 ࡟ࡼࡿᨵ㉁ࡀ H3C6H5O7 ⣔⁐ᾮ୰࡬ࡢ P ⁐ฟࢆቑຍࡉࡏࡿࡀࠊ
ࡑࡢຠᯝࡣ H2C2O4 ⣔⁐ᾮ࡬ࡢ⁐ฟࡼࡾᑠࡉ࠸ࠋ㸫㸫Fig.10 Change in the Ca and P concentrations in the H3C6H5O7 solution at pH7Fig 11 Dissolution ratios of each element from the modified C2S-C3P in theH3C6H5O7 solution at pH7
3.4 ᨵ㉁ࡋࡓ C2S-C3P ࡢ⁐ゎᣲື࡬ࡢ pH ࡢᙳ㡪 ᭱㐺࡞ᾐฟ᮲௳ࢆ᥈ᰝࡍࡿࡓࡵ࡟ࠊNa2SiO3 ࢆ 20㸣ྵࡴᨵ㉁ࡋࡓ C2S-C3P ࡢ⁐ゎᣲື࡬ࡢ pH ࡢᙳ㡪ࢆㄪᰝࡋࡓࠋ㑅ᢥⓗ࡟ P ࡢᾐฟࢆ⾜࠺ࡓࡵ࡟ࠊpH ࢆ 5 ௨ୖ࡜ࡋࡓࠋᅗ 12ࡣࠊᾐฟ࡟⏝࠸ࡿ㓟ࡢ✀㢮ࢆኚ࠼ࡓ᫬ࡢ pH5 ⁐ᾮ୰ࡢ Ca ࠾ࡼࡧ P ࡢ⃰ᗘኚ໬ࢆ♧ࡍࠋ
HNO3 ࠾ࡼࡧ H3C6H5O7 ⁐ᾮ୰࡛ࡢ Ca ⃰ᗘࡣẚ㍑ⓗ㧗ࡃ㸦ࡑࢀࡒࢀ 508.3mg / L ࠾ࡼࡧ
729.9mg / L㸧ࠊ
H2C2O4 ⁐ᾮ୰࡛ࡣ Ca ⃰ᗘࡣῶᑡࡍࡿࠋ
HNO3 ⣔⁐ᾮ୰ࡢ P ⃰ᗘࡣࠊ
H2C2O4⣔⁐ᾮ୰ࡢ⃰ᗘ㸦100mg / L ௨ୖ㸧࡜࡯ࡰྠ➼࡛࠶ࡗࡓࠋH3C6H5O7 ⣔⁐ᾮ࡛ࡣࠊᐇ㦂᮲௳ࡢ୰࡛ࡣ P ⃰ᗘࡀ᭱ࡶ㧗ࡃࠊ178.2mg / L ࡟㐩ࡋࡓࠋ pH ㄪᩚ࡟⏝࠸ࡓ㓟ࡢ✀㢮࠾ࡼࡧ pH ࡢ P ࡢ⁐ฟ⋡࡬ࡢᙳ㡪ࢆᅗ 13 ࡟♧ࡍࠋP ࡢ⁐ゎ⋡ࡣ㓟ࡢ✀㢮࡟࠿࠿ࢃࡽࡎ pH ࡢపୗ࡜ඹ࡟ቑຍࡍࡿࡀࠊࡑࡢഴྥࡣ pH ⠊ᅖ࡟ࡼࡗ࡚␗࡞
ࡿࠋHNO3 ⁐ᾮ࡛ࡣࠊᨵ㉁ࡋࡓ C2S-C3P ࠿ࡽࡢ P ࡢ⁐ฟ⋡ࡣࠊpH7 ௨ୖ࡛ࡣ㠀ᖖ࡟ప࠿ࡗࡓࡀࠊpH ࡀ 5 ࡟పୗࡍࡿ࡜⁐ฟ⋡ࡣ 51.5㸣ࡲ࡛ቑຍࡋࡓࠋ㧗 pH ᮲௳࡛ࡣࠊH2C2O4⁐ᾮ୰࡬ࡢ P ࡢ⁐ฟ⋡ࡀ᭱ࡶ㧗࠸ࠋࡋ࠿ࡋࠊpH ࢆపୗࡋ࡚ࡶ⁐ฟ⋡ࡣୖ᪼ࡋ࡞࠸ࠋ㧗 pH㸫㸫᮲௳࡛ࡣࠊH3C6H5O7 ⣔⁐ᾮ୰࡬ࡢ P ࡢ⁐ฟ⋡ࡣ H2C2O4 ⣔⁐ᾮࡼࡾࡶప࠸ࠋpH ࢆ 5 ࡟పୗࡍࡿ࡜ࠊP ࡢ⁐ฟ⋡ࡀ㢧ⴭ࡟ୖ᪼ࡋࠊH3C6H5O7 ⣔⁐ᾮ࡬ C2S-C3P ୰ࡢ P ࡢ 85.7㸣ࢆ⁐ฟࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋࡋࡓࡀࡗ࡚ࠊH2C2O4 ࡣࠊ㧗 pH ᮲௳࡛ C2S-C3P ࠿ࡽࡢ P ⁐ฟ࡟᭷ຠ࡛࠶ࡾࠊH3C6H5O7 ࡣࠊẚ㍑ⓗప࠸ pH㸦5ӌpH<7㸧࡛ P ࢆ⁐ฟࡍࡿࡓࡵࡢ᭷ຠ࡞㓟࡛࠶ࡿࠋFig.12 Change in the Ca and P concentrations in different leaching agents at pH5Fig.13 Relationship between the P dissolution ratio from the modified C2S-C3P andpH in different leaching agents4㸬ࡲ࡜ࡵ 㧗ࡾࢇ㓟ࢫࣛࢢ࠿ࡽ㑅ᢥⓗ࡟ P ࢆ⁐ฟࡍࡿࡓࡵ࡟ࠊC2S-C3P ᅛ⁐యࡢỈ⁐ᾮ࡬ࡢ⁐ฟᣲືࢆ᳨ウࡋࡓࠋNa2SiO3 ࡟ࡼࡿᨵ㉁ࠊᾐฟ࡟⏝࠸ࡿ㓟ࡢ✀㢮ࠊpH ࡢᙳ㡪ࢆㄪ࡭௨ୗࡢ▱ぢࢆᚓࡓࠋ(1) H2C2O4 ࡸ H3C6H5O7 ࢆᾐฟ๣࡜ࡋ࡚⏝࠸ࡿ࡜ࠊCaC2O4 ࡢỿẊ࠿ CaC6H5O7-㘒యࡢᙧᡂ࡟ࡼࡾỈ⁐ᾮ୰ࡢ Ca2+⃰ᗘࡀపୗࡍࡿࠋࡇࡢ⤖ᯝࡾࢇ㓟ࡢỿẊࡀᢚไࡉࢀࠊ⁐ฟ⋡ࡀ㸫㸫ቑຍࡍࡿࠋ(2) C2S-C3P ᅛ⁐యࡀNa2SiO3 ࡢῧຍ࡟ࡼࡾᨵ㉁ࡉࢀࡿ࡜ࠊ
ᅛ⁐యࡢCaO ࡢ୍㒊ࡀNa2O
࡟⨨᥮ࡉࢀࠊCaO·SiO2 ࡜ 2CaO·SiO2-2CaO·Na2O·P2O5 ┦ࢆ⏕ᡂࡍࡿࠋࡾࢇࡢᐩ໬┦ࡢ୍㒊ࡣ 2CaO·Na2O·P2O5 ࡜࡞ࡾỈ⁐ᛶࡀྥୖࡍࡿࠋ
(3) Na2SiO3 ࡢῧຍ࡟ࡼࡾᨵ㉁ࡋࡓ C2S-C3P ࡣ H2C2O4 ࡸ H3C6HO7 ࢆᾐฟ๣࡟⏝࠸ࡿࡇ࡜࡛ࡾࢇࡢ⁐ฟᛶࡀࡼࡾྥୖࡍࡿࠋ
(4) H2C2O4 ࡣ㧗 pH ᇦ(pH≥7)࡛ࡢࡾࢇࡢ⁐ゎ࡟ຠᯝⓗ࡛࠶ࡿࠋࡋ࠿ࡋࠊ5≤pH<7 ᇦ࡛ࡣH3C6H5O7 ࡢ᪉ࡀࡾࢇࡢ⁐ฟ࡟᭷ຠ࡛ࠊᮏᐇ㦂᮲௳ୗ࡛ Na2SiO3 ࡟ࡼࡾᨵ㉁ࡋࡓ C2S-C3P࠿ࡽࡢ P ࡢ⁐ฟࡣ 85.7%࡟㐩ࡋࡓࠋㅰ㎡ ᮏ◊✲ࡣබ┈㈈ᅋἲே JFE21 ୡ⣖㈈ᅋࡢຓᡂࢆཷࡅ࡚㐙⾜ࡉࢀࡓࠋⴭ⪅ࡽࡣྠ㈈ᅋ࡟
ᑐࡋ࡚ឤㅰࡢពࢆ⾲᫂ࡍࡿࠋ
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