A Study on the Bioleaching of Cobalt and Copper from Cobalt Concentrate by Aspergillus niger strains

ଫ 㮩㌙㑌㜇 ପ

Aspergillus niger ܆∢ኢ 㶩㲭⺂ ⡺ᕂ⯞ 㼎㋍⁢ᆂᚦ⩖

⡺ᕂ⯞ ᔵ ڒዒ⁾ 㜗㤣㜑 䆈䅄 㮩㌙

㫟䏛䀏Á 㫟㹣 Á㝵㓁㎬*Á㎘㚮㳟*

㒳䀏㒳䊓㋧ 㪛㧁㹦㊐䊓㊠

*

㒳䀏㒳䊓㋧ 䎞㈔㊐䊓㊠

A Study on the Bioleaching of Cobalt and Copper from Cobalt Concentrate by Aspergillus niger strains.

Hyo-Jin Ahn, Jae-Woo Ahn, Duk-ki Bang* and Meong-Woon Kim*

Dept. of Advanced materials & Science. Daejin University, Korea

*Dept. of Enviromental Eng., Daejin University, Korea

Ὰ ả

⡺ᕂ⯞ ℻ط⁢ᆂᚦ⩖ ⡺ᕂ⯞ὦ ڒዒ⁾ ⾲ᬾኢ ‪⹾ἒ 3↫⁾ Aspergillus niger ܆ ₚ῏⹾ἒ ԧ ܮ᪳⁾ ➎⛂

֖೿ ↖᧒⹾ἦఊ. ∢Ὰ ᰊ⻾ ᗦᬾᆂ஺ ܆∢ ↫ቾỶ ๖ኞ ⁆ݖ᧖ ᨃᩗჯ, pH ᔵ ؆ẇળ೪ᝪ ท ₚỮఊ. ᰊ⻾ז آ ⁆ݖ᧖(ڒ἖᧖ ᔵ Ὃ᧚᧖) ᨃᩗặ⁾ ףῖ A. niger KCTC 6144Ԧ Malt Extract Broth ᕖ⋦Ỷᩂ ☮ݖ pH 3.5Ỷ ᩂ Ԧ⃋ ↱Ṿఊ. ⺂Ⳟ ⡺ᕂ⯞ ᔵ ڒዒ ➎⛂ᰊ⻾זآᆂ஺ A. niger KCTC 6985ኢ ᧒῏⺂ ףῖԦ ⿎آ℧ₚỮ஺ಖ, ؆ ẇળ೪ 10 g/L₞ ףῖ, pH 3.5, 24^oCỶᩂ ả 15₢ ףآ ⿪ ⡺ᕂ⯞⁾ ףῖ஺ 82%, ڒዒ஺ 98%⁾ ➎⛂⁎ া

⧦৚Ữఊ.

∢⅂Ớ  ؖⱇₚ, ⡺ᕂ⯞, ڒዒ, ⁆ݖ᧖, ᔞᨃᑢ ➎⛂

ABSTRACT

Bioleaching behavior of metal ions for recovery of cobalt and copper from cobalt concentrate was investigated by employing three Aspergillus niger strains. Various factors, such as organic acid generation with fungi type, pH of the culture and pulp den- sity were studied. The results showed that the best fungi for organic acid(citric acid and oxalic acid) generation was A. niger KCTC 6144 using Malt Extract Broth culture at initial pH 3.5. But A. niger KCTC 6985 was more effective for the leaching of cobalt and copper from cobalt concentrate. Our results showed that 82% cobalt and 98% copper was dissolved by A. niger KCTC 6985 at 10g/L pulp density, at pH 3.5 and 24

C after 15 days incubation.

Key words : Aspergillus niger, cobalt, copper, organic acid, bioleaching

* January 21, 2013 ÁRevised : February 21, 2013ÁAccepted : March 6, 2013 Corresponding Author : Jae woo Ahn (E-mail: [email protected])

Advanced Materials Science & Engineering, Daejin University, Hoguk-ro 1007, Pocheon-si, Gyeonggi-do, 487-711, Korea Tel : +82-31-539-1982 / Fax : +82-31-539-1980

;The Korean Institute of Resources Recycling. All rights reserved. This is an open-access article distributed under the terms

of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licenses/by-nc/3.0/), which permits

unrestricted non-commercial use, distribution and reproduction in any medium, provided the original work is properly cited.

1. ᩂ ᆆ

ᔞᨃᑢ ➎⛂ᖻ⁦ ᔻ⩲ዒṪ(Bacteria)া ؖⱇₚ(Fungi) ท ᔞᨃᑢ⁾ ⋧ÁԪℷ ᔾ⁷ݖڒỶ ⁾⺚ ܮ᪳طᩃ⁾ ᑢ ዒÁ⽺⹿℧ ᩗ⋮ ᗦ⽺ᰂ⡂ ܮ᪳ ₚ὎᧧⨂ᆂ ➎⛂

ᰂ⧊஺ ؛℻⁢ᆂ, ܮ᪳⺎ჯₚ ৔Ṫ ݖ↚⁾ ֚ᰃ ᔵ ᯛ ᰃ؛℻⁢ᆂ ▾ዒ⹾ݖỶ ᚦ℧⺏⺂ Ωⶮ‪ طᩃₚা ᪲ ჯ⁾ ܮ᪳ₚ ᚪ᧖ാỚ ₮஺ ⳶ݖᑢᆂᚦ⩖ ⁆Ԧܮ᪳

⾲ᬾ⺆ ᬾ ₮஺ ᕏᖻₚఊ. ⼪⃒ ڒዒ⁾ ףῖ K◚ ᨃ ᧖ჯ⁾ 25% ₚ᧧ₚ ᔞᨃᑢ ➎⛂ᖻ⁢ᆂ ⾲ᬾാ؆ ₮⁢

᎖ ఊኞ ⾏⽺ᑢ ༶஺ ᧖⽺ᑢᆂᚦ⩖ Ṫ἖, ௮⠮, ⡺ᕂ

⯞, ܞዒ؆ Ꮦዒᜲಚ ⾲ᬾὦ Ωⶮ‪ طᑢ₶ῶ⁾ ⶮ‪

⻋᧧ ᔵ ᚮᭂᑢ ⅂֖ኢ ‪⹾ἒ ᔞᨃᑢ ₚ῏⺂ ݖᭆ Ղᕂₚ ⋪⺯ ∷Ỷ ₮ఊ^1,2). ܞ೿Ṯ⁦ ∢ᆂ ᔻ⩲ዒṪ⁾

₢↫₞ Thiobacillus܆ ᧒῏⹾ἒ ⾏೿طỶᩂ ڒዒኢ

➎⛂⹾஺ ݖᭆₚ ዴₚ ᘚ؆ാỚ ὺ⁢া ₚ ףῖ஺ ⾏

⽺طỶዲ ℧῏ₚ Ԧோ⹾ݖ ๲ᑞỶ ℧῏ ῶᇲỶ ⺂תԦ

₮ఊ. ܞᄒা ᔞᨃᑢᆂ ؖⱇₚኢ ₚ῏⺆ ףῖỶ஺ ؖ ⱇₚ܆⁾ ᰆ⋪ద᧒ ₷῏Ỷ ⁾⺚ ᨃᩗാ஺ ڒ἖᧖(citric acid), Ὃ᧚᧖(oxalic acid), ዶዓ᧖(malic acid)ท⁾ ⁆ ݖ᧖ ᧒῏⺎⁢ᆂ᲎ ⯟℻ ܮ᪳ᩗᚪ⁾ ᩆ⨃℧ ➎⛂ₚ Ԧோ⹾ఊ. ๖Ⴂᩂ ᝪ⾏⽺ط₞ Ωⶮ‪ Ⴂ⩲Ⴂₚ⯞طₚ

া^3-5)ₚὦ ⁆᧒⺂ طᑢ⹿℧ ⼻⨂ኢ া⧦৚஺ Ωⶮ‪

⡺ᕂ⯞ ᧖⽺طₚা ᘛ⺏ط ܞዒ؆ ؛℻⳶ݖᑢ ᔵ ೪ᰂ ط᧖ ท⁢ᆂ ℧῏ ‪⺚ ἖ڒԦ ⾂ᕂギ ⋪⺯ ∷Ỷ

₮ఊ.^6-11)

ݖ↚⁾ ⺎⡺ᕂ⯞ طᩃₚা ⳶ݖᑢỶᩂ ⡺ᕂ⯞ኢ ➎⛂

⹾஺ ףῖ దᚦᚪ ᑚݖ᧖ (H2SO₄, HCl, HNO₃) ➎

⛂⅂ᆂ ᧒῏⹾؆ ₮⁢᎖, ₚ ףῖ Cl2, SO_X ܞዒ؆

NOx gasা ⁆೫ᩗ ➎⛂₺᧒Ԧ ᕂᨃാݖ ๲ᑞỶ ⽾ףỶ ṫἧ⻋ ᔞ❾؆ ₮ఊ. ๖Ⴂᩂ ⽾ף➂⽺℧₞ ⁆ݖ᧖

ₚ῏⹾ἒ ⡺ᕂ⯞ ᔵ ڒዒ⁾ ➎⛂Ỷ ئ⺂ ἖ڒኢ ᰊᰂ⹾

؆₶ ⹾ἦఊ.

ₚᔞ K ἖ڒ זآỶᩂ ڒ἖᧖ ₚা ዶዓ᧖ ท⁾ ⁆ ݖ᧖Ỷ ⁾⺚ ᘛ⺏طᑢ₞ ⡺ᕂ⯞ ℻طỶᩂ ⡺ᕂ⯞ὦ ڒ ዒ⁾ ➎⛂⁎ₚ ῖᬾ⹾ఊ஺ ֩ ⽻₞ ⹾ἦఊ.¹²⁾๖Ⴂᩂ ᘞ ἖ڒỶᩂ஺ ₚᄒ⺂ ⁆ݖ᧖ ᨃᩗ⺆ ᬾ ₮஺ ܆∢ᆂ

ؖⱇₚቾ₞ Aspergillus niger(ₚ⹾ A. niger)܆∢ኢ ᧒

῏⹾ἒ ⁆ݖ᧖ ᨃᩗỶ ئ⺂ ⚂℧ ↖֚ ⽻ዣ⹾؆, ⡺ ᕂ⯞ ℻طỶ ℧῏ᰂ⡂ ڒዒ ᔵ ⡺ᕂ⯞⁾ ➎⛂֖೿ ؆

╖⹾؆, ⻋⿪ ᔞᨃᑢ ➎⛂ݖᭆ⁾ ݖ☮ ₶ᇲኢ ỡ؆₶ ⹾ ἦఊ.

2. ᰊ⻾ ⃒ᇲ ᔵ ᕏᖻ

ᘞ ᰊ⻾Ỷᩂ ᧒῏⺂ ؖⱇₚ ܆⁢ᆂ஺ A. niger KCTC 6985, A. niger KCTC 6144, A. niger KCTC 6906 ท 3↫ቾኢ ڒ₫⹾ἒ ᧒῏⹾ἦఊ. ܆⁾ ᕖặ ‪

⺚ ᧒῏⺂ ᕖ⋦ᆂ஺ Malt Extract Broth(Difco᧒)ኢ ᧒

῏⹾ἒ 15 g/Lᆂ ↖℮⺂ ⿪ ᕖ⋦ẇ⁢ᆂ ᧒῏⹾ἦఊ.

Table 1Ỷ ᕖ⋦⁾ ↖ᩗ া⧦৚Ữఊ.

2.2. ܆∢ ᕖặ

250 ml Erlenmeyer flaskỶ 100 ml⁾ ᕖặẇኢ ੉⁦

ఊ⁲ ܆∢ኢ ℷ↫ ⹾ἒ Shaking incubatorỶᩂ 24^oC, 180 rpm⁢ᆂ 3₢Ԫ ᕖặᰂ⧊؆, ₚỚᩂ ᧮ᆂῚ ᕖ⋦ẇ

 ᧒῏⹾ἒ 2╎ תద ᕖặ ⹾؆ 30₢Ԫ ᕖặᰂ⧊᎚

ᩂ ₢℻ᰂԪ ዮఊ ᧾⸲ ╪✎⹾ἦఊ. ╪✎⺂ ᧾⸲

micro syringe filter(cellulose acetate, 0.45µm)ኢ ₚ

῏⹾ἒ ἒآ⺂ ⿪ HPLC(MetaCarb 87H Column, Waster)ኢ ₚ῏⹾ἒ ᨃᩗൂ ⁆ݖ᧖(ڒ἖᧖, Ὃ᧚᧖ ท)

⁾ ળ೪ኢ ❇℻⹾؆, pHᔞ⩖(Horiba, Model:D-51)ኢ ₚ῏⹾ἒ pHኢ ❇℻⹾ἦఊ.

2.3. ➎⛂ ᰊ⻾

ᰊ⻾ᕏᖻ⁢ᆂ஺ 500 ml ᧢ԧ⸲Ⴂᯊ⦒Ỷ ᕖ⋦ẇ

300 ml ◎Ԧ⹾؆ ☮ݖ pHኢ 3.5ᆂ ↖℮ ⺂ ఊ⁲ 24^oC Ỷᩂ 180 rpm⁢ᆂ 3₢Ԫ ᕖặᰂ⧎ ᕖ⋦ ẇỶ ⡺ᕂ⯞

℻ط ԧԧ 5 g/L, 10 g/L, 20 g/L, 50 g/Lᆂ ◎Ԧ⹾ἒ

؆ẇળ೪(pulp density) ᗦ⽺Ỷ ๖ኞ ➎⛂ᰊ⻾ ᰊᰂ⹾

ἦఊ. ➎⛂ᰊ⻾⁦ shaking incubatorỶᩂ 24^oC, 180 rpm

⁢ᆂ Կ⁦ ↖֚⁢ᆂ ᔾ⁷ᰂ⡖ఊ. ₢℻ᰂԪ ᔾ⁷ ᰂ⧎ ⿪

᧾⸲ ╪✎⹾ἒ ἒآ ⿪Ỷ ➎⛂ẇ⁾ pHኢ ❇℻⹾؆, micro syringe filter(cellulose acetate, 0.45µm)ኢ ₚ

῏⹾ἒ 2╎ ἒآ ⿪ ➎⛂ẇ∷⁾ ܮ᪳ₚ὎⁾ ળ೪ኢ

Table 1. Composion of culture medium

Component wt%

Malt Extract Broth

Malt Extract 40.0 Maltose,Technical 12.0

Dextrose 40.0

Yeast Extract 8.0

ICP-OES(Perkin Elmer / Optima 2000DV)ኢ ₚ῏⹾

ἒ ᚪᩃ⺂ ⿪ ᰃ(1) ₚ῏⹾ἒ ԧ ܮ᪳⁾ ➎⛂⁎

ڒ⹾ἦఊ. ⺂Ⳟ ᘞ ➎⛂ᰊ⻾Ỷ ᧒῏⺂ ⡺ᕂ⯞ ℻ط⁾

ףῖ ᾞړ(⢏؆)Ỷᩂ ₫ᬾ⺂ ֩⁢ᆂ ⽺⹿↖ᩗ⁦ Table 2 ὦ Կ؆ ∢ᆂ ᧖⽺ᑢآ ⧪᧖ἢ⁾ ᘛ⺏⼻⨂ኢ া⧦৚

Ữఊ.

(1)

3. ᰊ⻾ זآ ᔵ ؆╖

3.1. ܆∢ ᕖặ זآ

ؖⱇₚ(Fungi)܆⁢ᆂ A. niger KCTC 6985, A. niger KCTC 6144, A. niger KCTC 6906 ⁾ 3↫ቾỶ ద⺚

Malt Extract Broth ᕖ⋦ኢ ₚ῏⹾ἒ ԧ ܆∢ᗪ ⚂℧

ᕖặ↖֚ ᔵ ₚ๲ ᨃᩗൂ ⁆ݖ᧖⁾ ળ೪ኢ Table 3Ỷ

া⧦৚Ữఊ. ☮ݖ pH஺ 3.5, ὎೪஺ 24^oC, ٶᔾ᪳೪஺

180 rpm ⁆⋦⹾ἦఊ. ᕖặൂ ܆∢஺ ዮ❾ ⴒ೪᫇ₚ▾

ᄢ ڒ⼻⁾ ⼻⨂ኢ া⧦৚Ữ⁢᎖, ܆∢ኢ 3₢Ԫ ᕖặ ⿪ HPLC ❇℻ זآ ᕖặẇ ∷Ỷ஺ ⁆ݖ᧖(ڒ἖᧖, Ὃ᧚᧖, ዶዓ᧖ ท)ₚ ᨃᩗൎ ⽻₞⹾ἦఊ. ₚ๲ ᨃᩗൂ ⁆ݖ᧖

⁾ ףῖ ܆∢Ỷ ๖Ⴂ ⁆ݖ᧖⁾ ↫ቾ ᔵ ળ೪Ԧ ఊኚֲ

ئ╖ാỮఊ. ⁆ݖ᧖ ᨃᩗₚ Ԧ⃋ ዴ⁦ ܆∢஺ A.niger KCTC 6144ὦ A. niger KCTC 6985ₚỮఊ. ܞᄒা ₚ

൶ ܆∢⁾ ףῖ ڒ἖᧖ ᘚఊ஺ Ὃ᧚᧖⁾ ᨃᩗₚ ዴṾ

؆, A. niger KCTC 6906⁾ ףῖỶ஺ ڒ἖᧖ ᨃᩗₚ ዴṾ؆, ዶዓ᧖⁦ ℧⁦ ặₚ ᨃᩗൎ ⽻₞⹾ἦఊ.

3.2. ⁆ݖ᧖ ᨃᩗ⁎ ↖᧒

ᩞ↫ቾ⁾ ؖⱇₚ(Fungi)܆Ỷ ద⺚ Malt Extract Broth ᕖ⋦ኢ ₚ῏⹾ἒ 24^oC, 180 rpm⁢ᆂ ⃋ᰂԪ ᕖặ⹾᎚ᩂ ᨃᩗൂ ڒ἖᧖, Ὃ᧚᧖, ዶዓ᧖ ท⁾ ⁆ݖ᧖ ળ೪ኢ ❇

℻⹾ἒ ܞ זآኢ Fig. 1 ᔵ Fig. 2Ỷ া⧦৚Ữఊ.

Fig. 1⁦ pHኢ ↖℮⹾⋦ Ṱ⁦ ₶἖(natural) pHₚ؆

Fig. 2஺ ☮ݖ pHኢ 3.5ᆂ ↖℮⹾ἒ ᕖặ⺂ זآₚఊ.

A. niger KCTC 6985⁾ ףῖ Ὃ᧚᧖ > ڒ἖᧖ > ዶዓ᧖

ᭂ⁢ᆂ ᨃᩗặₚ ዴṾ؆, Ὃ᧚᧖⁾ ףῖ 15₢ ₚ⿪ ܯ

׏⺂ ᨃᩗ ᘚἒ ả 12 g/L ᨃᩗ⺂ ⿪ ⋦᪳℧⁢ᆂ ᧖ ળ೪ኢ ⁆⋦⹾ἦఊ. ڒ἖᧖⁾ ףῖ 12₢ ףآ ⿪ ળ೪ Ԧ ả 5.5 g/L ݲ⋦ ⋃Ԧ⺂ ⿪ ఊᰂ Զ᪲⹾ἦ؆, ዶዓ ᧖⁾ ᨃᩗჯ⁦ ⚂ద 1 g/L℻೪⁾ ᨃᩗዲ ᘚἒ Ω↖⺂

ᨃᩗ⁎ ᘚἦఊ. A. niger KCTC 6144⁾ ףῖ ڒ἖᧖ ₚ 15₢ ףآ ⿪ ả 7.0 g/L ᨃᩗാỚ 3↫⁾ ܆∢ ∷

Leaching(%) =

Amount of metal in the leaching solution

×100 Amount of metal in the concentrate Table 2. Concentration of elements in sample

Mg Fe Al Co Cu

Wt % 13.74 4.02 11.16 9.68 17.05

Table 3. Fungal strains and culture conditions (24

C / 180 rpm / 72 hr)

Aspergillus niger (KCTC 6144) Aspergillus niger (KCTC 6906) Aspergillus niger (KCTC 6985) Culture medium Malt Extract Broth Malt Extract Broth Malt Extract Broth

Initial pH 3.5 3.5 3.5

Final pH 2.84 3.28 3.01

Citric acid (ppm) 332.63 247.69 227.06

Oxalic acid (ppm) 906.63 30.48 1017.32

Malic acid (ppm) 41.32 38.56 38.82

Ỷᩂ Ԧ⃋ ዴₚ ᨃᩗാỮ؆, Ὃ᧚᧖⁾ ףῖ஺ 15₢ ⿪ ܯ׏⺂ ᨃᩗ ᘚἒ ả 5 g/Lኢ ᨃᩗ⺂ ⿪ ⋦᪳℧⁢ᆂ ᧖ળ೪ኢ ⁆⋦⹾஺ ֩ ⽻₞⺆ ᬾ ₮Ữఊ. ዶዓ᧖⁾ ף ῖ೪ 15₢ ףآ ⿪ 3 g/L℻೪⁾ ᨃᩗ ᘚἦఊ. A.

niger KCTC 6906⁾ ףῖ஺ ڒ἖᧖ዲ ả 5.5 g/L ݲ⋦

⋃Ԧ⺂ ⿪ ܯ׏ギ Զ᪲ ⹾ἦ؆, Ὃ᧚᧖آ ዶዓ᧖⁾ ᨃ

ᩗჯ⁦ ᔞᔞ⹾ἦఊ.

Fig. 2஺ ᕖ⋦⁾ ☮ݖ pHኢ 3.5ᆂ ↖℮⹾ἒ ᕖặ⺂

זآᆂ A. niger KCTC 6985⁾ ףῖ ڒ἖᧖⁾ ףῖ 7.0 g/Lᆂ ảԪ ⋃Ԧ⹾ἦ⁢া, Ὃ᧚᧖⁾ ףῖ஺ ảԪ Զ

᪲⹾ἒ 10 g/Lኢ া⧦৚Ữ؆, ዶዓ᧖⁦ ֖⁾ ᨃᩗാ⋦

ṰṾఊ. A. niger KCTC 6144⁾ ףῖ஺ ڒ἖᧖ ળ೪Ԧ

⋃Ԧ⹾ἒ ⚂ద ả 10.0 g/L ℻೪ኢ া⧦৚Ữఊ. ⺂Ⳟ, A. niger KCTC 6906⁾ ףῖ஺ ⦖ ╎ₚԦ ỬỮఊ.

๖Ⴂᩂ ᧧ݖ זآᆂᚦ⩖ ڒ἖᧖ ᨃᩗ᎚Ỷᩂ஺ A.

niger KCTC 6144Ԧ ảԪ ῖᬾ⹾᎖, ☮ݖ pHኢ 3.5ᆂ

↖℮⺆ ףῖ ⿎آԦ ₮ఊ஺ ֩ Ṳ ᬾ ₮Ữఊ. ༶⺂

ᕖặ ⿪ 12-13₢ ףỶ ڒ἖᧖⁾ ⚂ద ᨃᩗ⁎ া⧦৚

Ữ؆, Ὃ᧚᧖⁾ ףῖỶ஺ 15₢ ₚ⿪Ỷ ܯ׏ギ ᨃᩗₚ

⋃Ԧ⹾஺ ף⻋ ᘚἦఊ.

3.3. ᔞᨃᑢ ➎⛂ ᰊ⻾

3.3.1. ܆∢ᗪ ➎⛂ኆ ᝪٶ

₢ᔾ℧⁢ᆂ ⁆ݖ᧖ ᨃᩗ ᔞᨃᑢỶ ⁾⺂ ܮ᪳ ➎⛂ ᔾ

⁷ݖڒᆂ஺ ⁆ݖ᧖⁾ ᨃᩗ/ᚪᝪኢ ⫛⺂ ᧖ Ԧᬾᚪ⺚

(acidolysis) آ℻آ ῏ẇ ∷Ỷᩂ citrate ╏ᑢ ⼻ᩗ⹾

஺ ╏⽺ ₷῏(complexolysis)⁢ᆂ ڒᚪ⺆ ᬾ ₮⁢᎖ ₚỶ ద⺂ ᔾ⁷ᰃ⁦ ఊ⁲آ Կₚ া⧦ৢ ᬾ ₮ఊ³⁾.

i) Proton attack

MO + 2H⁺ă M²⁺+ H₂O (᧖⽺ط₞ ףῖ) MCO₃+ 2H⁺ ă M²⁺+ H₂O + CO₂ (⧪᧖ἢ₞ ףῖ)

Fig. 1. Organic acid production by different Aspergillus. niger strains at natural pH (Malt Extract Broth/ 24

C / 180 rpm).

ii) Complexation / Chelation M²⁺+ C₆H₈O₇ă M(C6H₈O₇)⁻+ 3H⁺ (M : Co, Cu, Fe, Ni ท)

๖Ⴂᩂ ᔾ⁷ₚ ⋪⺯ൎỶ ๖Ⴂ ➎⛂ẇ⁾ pH ᗦ⽺Ԧ Ἦ᧧ാݖ ๲ᑞỶ ԧ ܮ᪳⁾ ➎⛂⁎ ᔵ ➎⛂ẇ⁾ pH ᗦ

⽺ኢ ❇℻⹾ἒ ᧧ئئתኢ ᚪᩃ⹾؆₶ ⹾ἦఊ.

Fig. 3⁦ 3↫ቾ⁾ ܆∢ኢ ᧒῏⹾ἒ Malt Extract Broth ᕖ⋦Ỷᩂ ؆ẇળ೪ኢ 10 g/Lᆂ ⁆⋦⹾ἒ ➎⛂ᰊ

⻾ ᰊᰂ⺂ זآₚఊ. Fig. 3(a)஺ A. niger KCTC 6985⁾ ➎⛂ᰊ⻾ זآᆂ ڒዒ⁾ ➎⛂⁎ₚ ⡺ᕂ⯞⁾ ➎

⛂⁎ ᘚఊ સֲ া⧦৒ఊ. ⡺ᕂ⯞⁾ ףῖ ☮ݖ 38% ℻ ೪⁾ ➎⛂⁎ ᘚₚఊԦ ࣞ∦ギ ➎⛂⁎ₚ ⋃Ԧ⹾ἒ 20

₢ ףآ ⿪ 80% ৚ᾞݲ⋦ ⋃Ԧ⹾஺ ף⻋ ᘚₚఊ ₚ

⿪ ảԪ Զ᪲⹾஺ ף⻋ ᘚἦఊ. ڒዒ⁾ ףῖỶ஺ ᔾ

⁷☮ݖ 21% ℻೪⁾ ➎⛂⁎ ᘚₚఊԦ ₚ⿪ ܯ׏ギ ⋃

Ԧ⹾ἒ 20₢ K⿪Ỷ஺ 98% ₚ᧧⁾ સ⁦ ➎⛂⁎ ᘚἦ

؆, ₚ⿪ ảԪ Զ᪲⹾஺ ף⻋ ᘚἦఊ. ⺂Ⳟ, ◆, ዮܞ

੊ᮾ ᔵ Ṳሎᔞப⁾ ףῖ஺ ➎⛂ኆ⁦ ጊῖ ৔Ṫ ڒዒὦ

⡺ᕂ⯞⁾ ᩆ⨃℧ ➎⛂ₚ Ԧோ⹾ఊ஺ ֩ Ṳ ᬾ ₮Ữఊ.

Fig. 3(b)஺ A. niger KCTC 6144⁾ ➎⛂ᰊ⻾ זآᆂ

⡺ᕂ⯞⁾ ➎⛂ኆₚ Ԧ⃋ સֲ াὺ⁢া ⚂ద ➎⛂ኆₚ 60%ᔞዲ⁢ᆂ Kᔾ℧⁢ᆂ ৔⁦ ➎⛂ זآኢ া⧦৚Ữ؆, ڒዒ⁾ ףῖ஺ 20% ৚ᾞ⁾ ౺ῗ ৔⁦ ➎⛂⁎ া⧦৚Ữ

؆, ݖ⧦ ܮ᪳⁾ ףῖ஺ ➎⛂⁎ₚ ጊῖ ৔Ṿఊ. Fig. 3(c)

஺ A. niger KCTC 6906 ᧒῏⺂ ᰊ⻾ זآᆂ A.

niger KCTC 6144⁾ ➎⛂ᰊ⻾ זآὦ ⁆᧒⺂ זآኢ ᘚἦ஺ಖ ⡺ᕂ⯞⁾ ➎⛂⁎ₚ 50% ৚ᾞₚ؆ ڒዒ஺

20% ৚ᾞ⁾ ➎⛂ኆ ᘚἦఊ. ๖Ⴂᩂ ᘞ ᰊ⻾זآ A.

niger KCTC 6985Ԧ Ԧ⃋ ⿎آԦ ↱ఊ஺ ֩ Ṳ ᬾ

₮Ữఊ. ₚᄒ⺂ ף⻋⁦ Ẅᩆ ᰊ⻾Ỷᩂ ⁆ݖ᧖ ᨃᩗ᎚Ỷ ᩂ஺ A. niger KCTC 6144Ԧ A. niger KCTC 6985

Fig. 2. Organic acid production with different Aspergillus niger strains at pH 3.5 (Malt Extract Broth/ 24

C / 180 rpm).

ᘚఊ સֲ াὺ஺ಖ ᰊ⅂ ➎⛂ זآ஺ A. niger KCTC 6985Ԧ ఊ᪲ સṾఊ. ₚᄒ⺂ ⼪᧧⁦ ℻ط ⭒₫⹾ἒ ᕖ ặᰂ ԧ ܮ᪳ ᩗᚪชỶ ⁾⺂ ೫ᩗ ท ἒᄒ Ԧ⋦ Ὰ₞Ỷ

⁾⺚ ᰊ⅂ ᕖặ ⿎آԦ ఒႢ⋮ ᬾ ₮ݖ ๲ᑞₚ᎖ ₚỶ ద⺂ ৚῏⁦ ⚺Ԧ ᰊ⻾ ⫛⹾ἒ ֦⫆⺆ Ἦ℻ₚఊ.

3.3.2. Pulp density ἧ⻋

ԧ ܆∢ᗪᆂ ᕖặẇآ ⡺ᕂ⯞ ℻ط⁾ ؆ẇળ೪ᝪ(Pulp density)ኢ 5 g/L, 10 g/L, 20 g/L, 50 g/Lᆂ ᗦ⽺ᰂ⡂Ԧ

᎚ᩂ ⡺ᕂ⯞ ᔵ ڒዒ⁾ ➎⛂ ֖೿ ↖᧒⹾ἦఊ. Fig. 4஺

A. niger KCTC 6985⁾ ➎⛂ ᰊ⻾ זآኢ া⧦৚Ữఊ.

Fig. 4(a)஺ ⡺ᕂ⯞ ➎⛂ זآᆂ ᔾ⁷ ☮ݖỶ஺ ؆ẇળ ೪ 5 g/Lὦ 10 g/L₞ ףῖ ➎⛂⁎ₚ 40% ৚ᾞᆂ ᝪᯝ

⺂ זآኢ ᘚἦ⁢া 5 g/L Ỷᩂ஺ ⦒ֲ ⋃Ԧ⹾⋦ Ꮱ⹾

؆ 50% ℻೪⁾ ➎⛂⁎ ⁆⋦⺂ ᔾ᎚Ỷ 10 g/L⁾ ףῖ Ỷ஺ ⋦᪳℧⁢ᆂ ⋃Ԧ⹾᎚ᩂ 20₢ ףآ ⿪ 80% ℻೪

⁾ ➎⛂⁎ ᘚἦఊ. ⺂Ⳟ, ؆ẇળ೪ 20 g/L ὦ 50 g/L

₞ ףῖỶ஺ ➎⛂⁎ₚ ԧԧ ả 35% ᔵ 25%⁾ ➎⛂⁎

 ᘚἦ؆ ⁆᧒⺂ ➎⛂ ֖೿ া⧦৚Ữఊ. Fig. 4(b)஺

ڒዒ⁾ ➎⛂ זآኢ া⧦৞ ֩⁢ᆂ ؆ẇળ೪ 5 g/L₞

ףῖỶ ☮ݖ ➎⛂⁎ₚ સֲ া⧦৒⁢া 5₢ ףآ ₚ⿪

Ỷ 75% ৚ᾞ⁾ ➎⛂⁎ া⧦৞ ᔾ᎚Ỷ 10 g/L ףῖỶ

஺ ᔾ⁷ ☮ݖ 20% ℻೪⁾ ৔⁦ ➎⛂⁎ ᘚἦ⁢া ₚ

⿪ ܯ׏⺂ ⋃Ԧኢ ᘚₚ᎚ᩂ 20₢ ףآ ⿪Ỷ஺ 95% ₚ

᧧⁾ સ⁦ ➎⛂⁎ ᘚἦఊ. ⹾⋦ዲ 20g/Lὦ 50g/L⁾

ףῖỶ஺ ➎⛂ኆₚ ܯ׏ギ Զ᪲⹾᎚ᩂ ԧԧ 10%ὦ 5%

৚ᾞ⁾ ➎⛂⁎ ᘚἦఊ. Fig. 4(c)஺ ԧ ؆ẇળ೪ ᰊ⻾

ᰂ⁾ ➎⛂ẇ⁾ pHᗦ⽺ኢ া⧦৞ ܞዢ⁢ᆂ ؆ẇળ೪Ԧ

⋃Ԧ⺆ᬾᆃ pHԦ ⋃Ԧ⹾ἒ ᧧ద℧⁢ᆂ ⚺⛂⁎ₚ ৔⁦

֩⁢ᆂ ⰶఎൂఊ.

Fig. 5஺ A. niger KCTC 6144 ܆∢ኢ ᧒῏⺂ ➎⛂

ᰊ⻾ זآኢ া⧦৞ ֩ₚఊ. Fig. 5(a)஺ ⡺ᕂ⯞⁾ ળ೪ ᗪ ➎⛂⁎ া⧦৞ ֩⁢ᆂ ᔾ⁷ ☮ݖ 3₢৚Ỷ ➎⛂⁎

ₚ ܯ׏ギ ⋃Ԧ⹾؆ ₚ⿪Ỷ஺ ⦖ ᗦ⽺Ửₚ ⚺⛂⁎ₚ ảԪ⁾ ทႣ া⧦৚؆ ₮ఊ. ؆ẇળ೪Ԧ ⋃Ԧ⺆ᬾᆃ

⚺⛂⁎ₚ Զ᪲⹾஺ ף⻋ ᘚₚ؆ ₮؆, 5 g/L Ỷᩂ 3

Fig. 3. Leaching behavior of metal ions at different Aspergillus niger (Malt Extract Broth, 24

C, 180 rpm, pulp density 10 g/L).

Fig. 4. Leaching percentage of cobalt and copper at different pulp density (A. nigerKCTC 6985 / Malt Extract Broth /pH 3.5 /

24

C / 180 rpm).

₢ ⿪ 57%ᆂ Ԧ⃋ સ⁦ ➎⛂⁎ ᘚἦఊ. 10 g/L⁾ ף ῖỶ஺ ᔾ⁷ ⿪ݖ₞ 19₢ ףآ ⿪ સ⁦ ➎⛂⁎ া⧦

৚Ữ⁢া ₚ ⿪ ఊᰂ Զ᪲⹾஺ ף⻋ ᘚἦఊ. ؆ẇળ ೪ 20 g/L ὦ 50 g/L⁾ ףῖỶ஺ ➎⛂⁎ₚ 35%ὦ 25% ℻೪ᆂ ৔⁦ ➎⛂⁎ ᘚἦఊ. Fig. 5(b)஺ ڒዒ⁾

➎⛂ זآኢ া⧦৞ ֩⁢ᆂ 5g/L Ỷᩂ Ԧ⃋ સ⁦ ➎⛂

⁎ ᘚἒ 3₢ ףآ ⿪ 75%⁾ ➎⛂⁎ া⧦৚Ữఊ. ᔾ

᎚ 10 g/L ₚ᧧⁾ ળ೪Ỷᩂ஺ ➎✲⁎ₚ ܯ׏⹾ֲ Զ᪲

⹾ἒ ԧԧ 10 g/LỶᩂ 25%, 20 g/L Ỷᩂ 20%, 50 g/L Ỷᩂ ả 5%⁾ ➎⛂⁎ া⧦৚Ữఊ. Fig. 5(c)஺ ؆ẇ ળ೪ ᗦ⽺Ỷ ๖Ⴂ ᕖ⋦ ῏ẇ⁾ pH ᗦ⽺ ⚺ₚኢ ؆╖⺂

ܞዢₚఊ. ؆ẇળ೪Ԧ 0 g/L₞ Control ῏ẇ⁾ ףῖ pH Ԧ Զ᪲⹾ఊԦ 5₢ ₚ⿪ᚦ⩖ ᩂᩂギ ⋃Ԧ⹾ఊԦ 13₢

ₚ⿪ ܯ׏ギ ⋃Ԧ⹾஺ ף⻋ ᘚₚ؆ ₮⁢া ؆ẇળ೪ ᝪԦ 5 g/L Ỷᩂ 50 g/Lᆂ ⋃Ԧ⺎Ỷ ๖Ⴂ ☮ݖ pHԦ ܯ׏ギ ⋃Ԧ⹾஺ ף⻋ ᘚₚ؆ ₮؆ ₚ⿪Ỷ஺ Ὢዲ⺂

⋃Ԧ⚺ₚኢ ᘚₚ؆ ₮⁢া ؆ẇળ೪Ԧ સᬾᆃ ⦖ ᗦ

⽺Ԧ Ử஺ ף⻋ ᘚἦఊ.

Fig. 6⁦ A. niger KCTC 6906 ᕖặᰂ⧊᎚ᩂ ➎

⛂ ᰊ⻾ ᰊᰂ⺂ זآኢ া⧦৚Ữఊ. Fig. 6(a)஺ ⡺ᕂ

⯞ ➎⛂ זآᆂ ᔾ⁷ ☮ݖỶ஺ ؆ẇળ೪ 5 g/L Ỷᩂ 50% ৚ᾞᆂ Ԧ⃋ સ⁦ ➎⛂⁎ ᘚἦ؆ ₚỚᩂ 10 g/L Ỷᩂ 40%, 20 g/L஺ 35%, 50 g/LỶᩂ஺ 25% ৚ᾞ⁾

➎⛂⁎ ᘚἦఊ. Fig. 6(b)஺ ڒዒ⁾ ➎⛂ זآኢ া⧦

৞ ֩⁢ᆂ 5g/L⁾ ףῖ ☮ݖ 40%⁾ ➎⛂⁎ₚ 9₢ ף آ ⿪ 67%ᆂ ⋃Ԧ⹾ఊԦ ఊᰂ Զ᪲⹾஺ ף⻋ ᘚἦ ఊ. ؆ẇળ೪ 10 g/L, 20 g/L, 50 g/L⁾ ףῖỶ஺ Kᔾ

℧⁢ᆂ ➎⛂⁎ₚ ܯ׏ギ Զ᪲⹾᎚ᩂ 20% ᔞዲ⁾ ➎⛂⁎

 া⧦৚Ữఊ. ๖Ⴂᩂ ₚ ףῖ஺ ⡺ᕂ⯞ ᘚఊ ڒዒ⁾ ➎

⛂⁎ₚ ảԪ ৔⁦ ף⻋ ᘚἦఊ. Fig. 6(c)஺ ؆ẇળ೪ ᗦ⽺Ỷ ๖Ⴂ ᕖ⋦ ῏ẇ⁾ pH ᗦ⽺ ⚺ₚኢ ؆╖⺂ ܞዢ

⁢ᆂ Fig. 4(c)ὦ ⁆᧒⺂ זآኢ া⧦৚؆ ₮ఊ. ؆ẇળ ೪Ԧ 0 g/L₞ control ῏ẇ⁾ ףῖ pHԦ ₢℻⹾ఊԦ 13₢ ₚ⿪ ܯ׏ギ ⋃Ԧ⹾஺ ף⻋ ᘚἦ؆, ؆ẇળ೪ᝪ

Fig. 5. Leaching percent(%) of Cobalt and Copper at different pulp density (A. niger KCTC 6144 / Malt Extract Broth / pH 3.5 /

24

C / 180 rpm).

Fig. 6. Leaching percent(%) of Cobalt and Copper at different pulp density (A. niger KCTC 6906/ Malt Extract Broth /pH 3.5 /

24

C / 180 rpm).

Ԧ 5 g/LỶᩂ 50 g/Lᆂ ⋃Ԧ⺎Ỷ ๖Ⴂ ☮ݖ pHԦ ܯ׏

ギ ⋃Ԧ⹾஺ ף⻋ ᘚₚఊԦ ₚ⿪Ỷ஺ Ὢዲ⺂ ⋃Ԧ⚺

ₚኢ ᘚₚ؆ ₮Ớ ؆ẇળ೪ᝪԦ સᬾᆃ pH⁾ ᗦ⽺ Ԧ

℧Ữఊ.

4. ז ᆆ

1) ؖⱇₚ(Fungi)܆⁢ᆂ A. niger KCTC 6985, A.

niger KCTC 6144, A. niger KCTC 6906 ท 3↫ቾኢ Malt Extract Broth ᕖ⋦ኢ ᧒῏⹾ἒ ԧ ܆∢ᗪᆂ ڒ἖

᧖, Ὃ᧚᧖ ᔵ ዶዓ᧖ ท⁾ ⁆ݖ᧖ ᨃᩗ ᝪٶ⺂ זآ A. niger KCTC 6144Ԧ ῖᬾ⹾ἦ؆, ☮ݖ pHኢ 3.5ᆂ

↖℮⺆ ףῖỶ ⁆ݖ᧖ ᨃᩗ ☯⋪⹾஺ ⿎آԦ ₮Ữఊ.

⺂Ⳟ, ڒ἖᧖⁾ ףῖ஺ ᕖặ ⿪ 12-13₢ ףỶ ⚂దԸ

ᘚἦ؆, Ὃ᧚᧖⁾ ףῖỶ஺ 15₢ ₚ⿪Ỷ ܯ׏ギ ᨃᩗₚ

⋃Ԧ⹾஺ ף⻋ া⧦৮ఊ.

2) 3↫ቾ⁾ Aspergillus niger܆∢ኢ ᕖặ⹾᎚ᩂ ⡺ᕂ

⯞ ℻ط ᧒῏⹾ἒ ➎⛂ ᰊ⻾ ᰊᰂ⺂ זآ, A.

niger KCTC 6985ኢ ᧒῏⺆ ףῖ ؆ẇળ೪ 10 g/LỶᩂ pH 3.5, 24, 180 rpm⁢ᆂ 15₢Ԫ ᕖặ ⿪ ⡺ᕂ⯞஺

⚂؆ 80%, ڒዒ஺ ⚂؆ 98%⁾ ➎⛂ኆ ᘚἦఊ. ܞዒ

؆ ◆, Ṳሎᔞப ᔵ ዮܞ੊ᮾ⁾ ➎⛂⁎⁦ 3↫ቾ⁾ ܆∢

ኢ ᧒῏⺆ ףῖ Ꮞ൶ 5%ₚ⹾⁾ ৔⁦ ➎⛂⁎ া⧦৚

Ữఊ.

3) ؆ẇળ೪(Pulp density) ᗦ⽺Ỷ ๖Ⴂ ➎⛂ ᰊ⻾

؆╖ ⺂ זآ Kᔾ℧⁢ᆂ ؆ẇળ೪Ԧ ⋃Ԧ⺎Ỷ ๖Ⴂ ڒ ዒ ᔵ ⡺ᕂ⯞⁾ ➎⛂⁎⁦ Զ᪲⹾஺ ף⻋ ᘚἦఊ.

Զ᧒⁾ ܦ

ᘞ ἖ڒ஺ ⋦ᰃף⅂ᚦ ⃒᪲ῶ◂ݖᭆՂᕂ᧒ừ₞ “➂⽾

ף ⅂ᅎ؛℻ ⾂῏⺂ طᩃ৚ ⡺ᕂ⯞ ݖ☮ ⃒᪲⽺ݖᭆ”

⋦ῶ᧒ừ⁢ᆂ ᬾ⺯ാỮᯛ௮ఊ. ₚỶ Զ᧒ขዣ௮ఊ.

╞؆ᑞ⻲

1. D.E. Rawlings, 1998 : Industrial practice and the biology of

leaching of metals from ores, J. Ind. Microbiol. Bio- technol. 20, pp. 168-274.

2. Brierley, J.A. and Brierley, C.L. 2001 : Present and future commercial applications of biohydrometallurgy, Hydro- metallurgy, 59, pp. 233-239.

3. Geoffrey S. Simate, Sehliselo Ndlovu, Lubinda F. Walubita, 2010 : The fungal and chemolithotrophic leaching of nickel laterites - Challenges and opportunities, Hydro- metallurgy, 10, pp. 1-8.

4. J.A. Tang, M. Valix, 2006 : Leaching of low grade limonite and nontronite ores by fungi metabloic acids, Minerals engineering, 19, pp. 1274-1279.

5. S. Mohapatra, N. Pradhan, S. Mohanty, L.B. Sukla, 2009 : Recovery of nickel from laterite nickel ore using Aspergillus niger and optimization of parameters, Minerals engineering, 22, pp. 311-313.

6. Catherine N. Mulligan, Mahtab Kamali, Bernard F. Gibbs, 2004 : Bioleaching of heavy metals from a low-grade mining ore using Aspergillus niger, J. of Hazardous Materials, 110, pp. 77-84.

7. F. Anjum, H. Nawaz B.M. Asgher, M. Shahid, 2010 : Leaching of metal ions from black shale by organic acids produced by Aspergillus niger, Applied Clay Science, 47, pp. 356-361.

8. Orquidea Coto, Fedrico Galizia, Ianeya Hernandez, et al., 2008 : Cobalt and nickel recoveries from laterite tailings by organic and inorganic bio-acids, Hydrometallurgy, 94, pp. 18-22.

9. Khin Moh Moh Aung, Yen-Peng Ting, 2005 : Bioleaching of spent fluid catalytic cracking catalyst using Aspergillus niger, Journal of Biotechmology, 116, pp. 159-170.

10. I.M. Castro, J.L.R. Fietto, R.X. Vieira, et al., 2000 : Bioleaching of zinc and nickel from silicates using Aspergillus niger cultures, 57, pp. 39-49.

11. Jae-Woo Ahn, Jin-Ki Jeong, Jae-Chun Lee, Dong-Gin Kim, 2005 : Bioleaching of valuable metals from electronic scrap using fungi(Aspergillus niger) as a microorganism, J.

of Korean Inst. of Resources Recycling, 14(5), pp. 24-31.

12. Jae-woo Ahn, Hyo-Jin Ahn, Meong-Woon Kim, 2011

“Chemical Leaching of Co, Cu, Ni, Al, Fe by Organic acid

from Cobalt Concentrate” J. of Korean inst. of Resources

Recycling, 20(6), pp. 63-70.

㫟 䏛 䀏

• ద⋪ద⹿ٶ ᰆ⃒᪲؛⹿آ ⹿᧒

• ⼪⃒ ద⋪ద⹿ٶ ᰆ⃒᪲؛⹿آ ద⹿ῶ

㝵 㓁 ㎬

• ద⋪ద⹿ٶ ⽾ף؛⹿آ ⹿᧒

• ద⋪ద⹿ٶ ⽾ף؛⹿آ ᩃ᧒

• ⼪⃒ (∢)‮⩳ܦᆂᖪᯊ

㫟 㹣

• ⼪⃒ ద⋪ద⹿ٶ ᰆ⃒᪲؛⹿آ ٶᬾ

• ట ⹿⾲⋦ ⅂11ڲ 6⽞ ╞↖

㎘ 㚮 㳟

• ⼪⃒ ద⋪ద⹿ٶ ⽾ף؛⹿آ ٶᬾ

• ట ⹿⾲⋦ ⅂14ڲ 1⽞ ╞↖

Óط ؆Ô

* EARTH ’93 Proceeding(1993) 457⏣, ㄫ㇮ : 20,000ῶ

(The 2th International Symposium on East Asian Resources Recycling Technology)

* ₶ῶዒᰞₚ⦚ዧ⁾ ᰊ⅂(1994) 400⏣, ㄫ㇮ : 15,000ῶ

* ⹿⾲⋦ ⺏ᘞ⋷ I~VIII ㄫ㇮ : 40,000ῶ, 50,000ῶ(ᝪ⾲ῶ)

(I : ⫛ڲ ⅂1⽞~⅂10⽞, II : ⫛ڲ ⅂11⽞~⅂20⽞, III : ⫛ڲ ⅂21⽞~⅂30⽞, IV : ⫛ڲ ⅂31~⅂40⽞, V: ⫛ڲ ⅂41⽞~⅂50⽞, Ɋ: ⫛ڲ ⅂51⽞~⅂62⽞, ɋ: ⫛ڲ ⅂63⽞~⅂74⽞, Ɍ: ⫛ڲ ⅂75⽞~⅂86⽞)

* ⺂Á₢₶ῶዒᰞₚ⦚ዧ؛೿ῲ⦒ᨛ ઢᑞ⋷(1996) 483⏣, ㄫ㇮ : 30,000ῶ

* ⺂Áᔞ₶ῶዒᰞₚ⦚ዧ؛೿ῲ⦒ᨛ ઢᑞ⋷(1996) 174⏣, ㄫ㇮ : 15,000ῶ

* ₶ῶዒᰞₚ⦚ዧ ♃ᩂI(1997੪ 1Ὼ) 311⏣, ㄫ㇮ : 18,000ῶ

* '97 ᔞ∢ ₶ῶ⃒⾂῏ݖᭆᰊ⨂↖᧒(1997੪) 107⏣, ㄫ㇮ : 15,000ῶ

* 㷰㠅⁾ ዒᰞₚ⦚ዧ 㣤㭧(1998੪ 1Ὼ) 395⏣, ㄫ㇮ : 22,000ῶ, ᕂ⺯▾-㜇㿨㣃

* EARTH 2001 Proceeding (2001) 788 ⏣, ㄫ㇮ : 100,000ῶ

(The 6th International Symposium on East Asian Resources Recycling Technology)

* Ὂ⃒⼪⁾ ₶೿╎ ዒᰞₚ⦚ዧݖ⺯(2003੪ 2Ὼ) 312⏣, ㄫ㇮ : 20,000ῶ, ᕂ⺯▾-MJᔞฺỚ

* ዒᰞₚ⦚ዧᕗᩂ(₶ῶ⃒⾂῏ᕗᩂ, 1999੪) 440⏣, ㄫ㇮ : 15,000ῶ, ᕂ⺯▾-㜇㿨㣃

* ዒᰞₚ⦚ዧᕗᩂ(₶ῶ⃒⾂῏ᕗᩂ, 2004੪) 578⏣, ㄫ㇮ : 27,000ῶ, ᕂ⺯▾-䃛㜇ㅏ

* ዒᰞₚ⦚ዧᕗᩂ(₶ῶ⃒⾂῏ᕗᩂ, 2009੪) 592⏣, ㄫ㇮ : 30,000ῶ, ᕂ⺯▾-䃛㜇ㅏ

* EARTH 2009 Proceeding (2009) 911⏣, ㄫ㇮ : 100,000ῶ

(The 10th International Symposium on East Asian Resources Recycling Technology)