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050296B.CHM + Source: ONR Asia +
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Contributory Categories: ENG,ENV,GEO
Country: Japan
From: Proceedings of the First (1995) ISOPE
Ocean Mining Symposium
Tsukuba, Japan
21-22 November 1996
ISBN: 1-880653-21-4
233 pp.
KEYWORDS: Japan; Ocean Mining, ferro-managanese nodules,
polymetallic sulfides. ***ADDITIONAL KEYWORDS WITH EACH
ITEM***
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Item 1
REDUCTION LEACHING OF MANGANESE NODULES WITH SODIUM SULFITE
IN AMMONIUM CHLORIDE SOLUTION
K.-S. Choi and J.-W Sohn
Korea Mining Promotion Corporation
Seoul Korea
Abstract
The leaching characteristics of manganese nodules were
investigated in ammonium chloride solution by using sodium
sulfite as a reductant.
Experiments were conducted in leaching of manganese, cobalt
nickel, copper and iron using sodium sulfite in the ammonium
chloride solution. It was found that the leaching behaviour of
manganese, copper, cobalt and nickel depended on the amount of
added sodium sulfate. The ratio of liquid to solid is impotant
factor on the extraction of metals during leaching. The
dissolution of manganese, cobalt, nickel, copper, and iron
increased with the increase in ammonium solution and that in
temperature of leachant. When the leachant pH was decreased, the
leachability increased for each of the metals.
The sodium sulfate has been found to be an effective
reductant for extracting more than 95.8% of Mn, 93.5% of Ni,
98.5% of Cu, 89.1% of Co, 3.1% of Fe when leached in 5N NH4CL at
80 C for 2.5 hr. The dissolution rates of Mn, Ni and Cu are
controlled by pore diffusion, while that of Fe is controlled by
surface chemical reactions and that of Co is controlled by both
the surface-chemical reaction and pore diffusion process.
KEY WORD) : Manganese nodules sodium sulfite, leachability,
pore diffusion, surface chemical reaction.
References
1. Szabo, Lester J. (1976), 'Recovery of metal values from
manganese deep sea nodules using ammoniacal cuprous leach
solutions", US patent 3,983,l07.
2. Agarwal, J.C., Bamer, H.E.M Beecher, N. (1979), The cuprion
process for ocean nodules", Chem. Eng. Prog. Vol 75, No 1, pp 59
-63
3. Das, R., Jena, P., (1987), "A process for the extraction of
Cu, Ni and Co metal values from sea-bed nodules, Indian IN
160,536
4. Anand, S., Das S.C., Jena, P.K., (1988), 'Recovery of Cu, Ni,
Co from deep-sea manganese nodules by ammoniacal leaching",
Indian IN 162,452
5. Bhattacharya, I.N., Anand, S., Das, S.C., Das R.P. (1989),
'Ammonia leaching of manganese nodules in the nodule test plant".
'Trans. Indian Inst. Met. Vol 42, NO 4, pp 385 392
6. Okuwaki, A., Ito, H., Okabe, T. (1977), 'Study on the
hydrometallurgy of manganese nodules", Nippon Kagaku Kaishi (in
Japanese), Vol 10, pp 1462 1468
7. Rokukwa, N. (1990), 'Recovery of nickel, cobalt and copper
from ocean manganese nodules with mixed solution of ammonium
carbonate and ammonium sulfate, Shigen Lo Sozai (in Japanese),
Vol 106, NO 4, pp 205-209
8. Bare, C.B., Pasquali, J.W. (19733), "Extracation of nickel,
copper and cobalt from manganiferous ores", US. Patent 3,751,554
9. Han, K.N., Hoover, M., Fuerstenau, D.W. (1974), "Ammonia-an-
imonium leaching of deep-sea manganese nodules', Int J. Miner.
Process. Vol 1, NO 3, pp 2l5-230
10. Kanetova, D., Stofko, M., Kmet, S.(1985), 'Ammoniacal
leaching for extraction of nonferrous metals from deep sea
nodules', Int. J. Miner. Process. Vol 5, No 1, pp 145-153
11. Kawahara, M., Esaki, S., Shirane, Y. (1985), "Reduction
roasting and ammnonia leaching of low grade manganese nodules',
Nippon Kogyo Kaishi (in Japanese), Vol 101, NO 1170, pp 489-494
12. Kanungo, S. B., Jena, P.K. (1988), "Studies on the
dissolution of metal values in manganese nodules of Indian Ocean
origin in dilute hydrochloric acid.", Hydrometallurgy, Vol 21, pp
23-39
13. Sohn, H.Y., Wadswort, M.F., (1979), "Rate processes of
extractive metallurgy, pp l33-186, Plenum Press (New York)
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Item 2
BIOLEACHING OF MARINE MANGANESE NODULES
BY ACIDOPHILIC SULFUR-OXIDIZING BACTERIA
Y Konishi and S Asai
University of Osaka Prefecture
Sakai, Osaka, Japan
ABSTRACT
A unique bioprocess is proposed for extracting metals from
marine manganese nodules. In this bioleaching, sulfurous acid
and sulfuric acid are biologically produced from elemental sulfur
and simultaneously used as leaching agents to manganese nodules.
In the leachability aspect of nodules, the thermophile "Acidianus
brierleyi" growing on elemental sulfur at 65 C is more effective
than the mesophile "Thiobacillus" species at 30 C, Leaching
experiments with "A. brierleyi" were undertaken to optimize the
conditions under which valuable metals in nodules arc solubilized
during the bacterial growth on elemental sulfur.
KEY WORDS: Manganese nodules, metals recovery, bioleaching,
sulfur-oxidizing bacteria, "Acidianus brierleyi", "Thiobacillus
ferrooxidans", "Thiobacillus thiooxidans"
REFERENCES
Brierley, C.L. (1974). "Molybdenite-Lcaching: Use of a
High-Temperature Microbe." J. Less-Common Metals, Vol. 36, pp
237-247.
Fuerstenau, D.W., Herring, A.P., and Hoover, M.P. (1973).
'The Charatcrization and Extraction of Metals from Sea Floor
Manganese Nodules." Trans. Am. Inst. Min. Metall. Pet. Eng.,
Vol. 254, pp 205-211.
Fuerstenau, D.W.,and Han, K.N. (1983). "Metallurgy and
Processing of Marine manganese Nodules." Min. Proc. Tech. Rev.,
Vol. 1, pp l-83.
Konishi, Y., Takasaka, Y., and Asai, S. (1994). "Kinetics
of Growth and Elemental Sulfur Oxidation in Batch Culture of
"Thiobacillus ferrooxidans". " Biotechnol. Bioeng., Vol. 44, pp
667-673.
Nakazawa, H., Kudo, N., Chen, M., and Sato, H. (1989).
'Bactcrial Leaching of Manganese Nodules.' J. MMIJ, Vol. 105, pp
470-474.
Silverman, M.P., and Lundgren, D.G. (1959). 'Studies on the
Chcmoautrophic Iron Bacterium "Ferrobarillus ferrooxidans".' J.
Barteriol., Vol. 77, pp 642-647.
Takakuwa, S., Nishikiwa, T., Hosoda, K., Tominaga, N., and
Iwasaki, H. (1977). "Promoting Effect of Molybdate on the Growth
of a Sulfur-Oxidizing bactcrium, "Thiobacillus thiooxidans."" J.
Gen. Appl. Microbiol., Vol. 23, pp 163-173.
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Item 3
CARBON DIOXIDE FIXING-TYPE HYDROGEN REDUCTION LEACHING OF DEEP-
SEA OXIDE MINERALS USING A PT/PTFE CATALYST IN AMMONIUM CARBONATE
SOLUTION AT MODERATE TEMPERATURE AND ATMOSPHERIC PRESSURE
T Konta, T. Ohkosh4 T Yoshioka and A. Okuwaki
Tohoku University
Sendai Japan
ABSTRACT
H2 reduction leaching of cobalt crust was carried out to
study the optimum mixing conditions of NH3-(NHa4)2CO3-CuSO4,
solutions. Cobalt and Ni was extracted 90% or higher in the 2M
NH3-0.5M(NH4)2,CO3-.01M CuSO4 solution using a Pt catalyst loaded
on polytetra-fluoroethylene (PTFE) under 60 C, 0.5 atm of H2
pressure, 3.3g/l of slurry concentration for 2-3h.
KEY WORDS: cobalt crust, H2 reduction , hydrophobicity, ammonical
leaching, Pt/PTFE, catalyst
REFERENCES
Okabe,T. and Okuwaki, A. Kagaku Kogyou, 30, pp 84 (1979a).
Okabe,T and Okuwaki, A., Kagaku Kogyou, 30, pp 205 (1979b).
Agarwal, J.C., Barner, H. E., Beecher, N., Davis, D.S.,
Kust, R. N., Preprint No.78-89B, for presentational the 1978 AIME
Meeting, Denver, Colorado, Feb. 28-Mar. 2 (1978).
Rokukawa,N. Shigen Sozai Gakkaishi, 108, pp 287 (1992).
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Item 4
LEACHING OF COBALT-RICH FERROMANGANESE CRUST WITH AMMONIACAL
SOLUTIONS USING AMMONIUM SULFITE AND AMMONIUM THIOSULFATE AS
REDUCING AGENTS
M Niinae
Kyoto University,
Kyoto, Japan
C-H. Park
Inha University,
Inha, Korea
Y Nakahira and T Wakanuitsu
Kyoto University,
Kyoto, Japan
J Shibata
Kansai University,
Suita, Osaka, Japan
Abstract
Preferential ammoniacal leaching of Co, Ni and Cu from
cobalt rich ferromanganese crust under reducing conditions was
performed using ammonium sulfite and/or ammonium thiosulfate as
reducing agents. The effects of reducing agent concentration,
initial pH, leaching time, temperature and the combined
concentration of ammonium sulfitc and ammonium thiosulfaie on the
extraction of Co, Ni, Cu, Mn and Fe were investigated.
The extraction of Co, Ni and Cu with ammonium sulfite was
better than that with ammionium thiosulfate. When ammonium
sulfite was used as the reducing agent, Mn was precipitated and
appeared in the residue as (NH4)2Mn(SO3)-H20.
Key Words: Cobalt-Rich Ferromanganese Crust, Ammoniacal Leaching,
Amnionium Sulfite, Ammonium Thiosulfite
References
Acharya, S (1991). "Rcdtictivc Ammonia Leaching of
Manganese Nodules by Thiosulfate," Metal Trans B, Vol 22B, pp
259-261.
Agarwal, J.C, Barner, H. E, Beecher, N, Davies, DS, and
Kust, R N (1979). "Kennecott Process for Recovery of Copper,
Nickel, Cobalt and Molybdenum from Ocean Nodules," Min Eng., Vol
31, pp 1704-1707
Allen, J P, Abercrombie, HL, and Rice, DA (1991). "Leaching
and Recovery of Metals from Cobalt-Rich Manganese Ocean Crust,"
Miner & Metall Process, May, pp 97-104.
Anand, S, Das, SC, Das, RP, and Jena, PK (1988). "Leaching
of Manganese Nodules in Ammoniacal Medium Using Ferrous Sulfate
as the Reductant," Metall Trans B, Vol 19B, pp 331-334.
Das, RP, Anand, S, Das, SC, and Jena, PK (1986). "Leaching
of Manganese Nodules in Ammoniacal Medium Using Glucose as
Reductant, "Hydrometallurgy, Vol 16, pp 335-344.
Fujii, Y, Mizota, T, and Kono, Y (1987). "Smelting of
Marine Mineral Resources-Smelting of Cobalt Crust," Marine
Science Monthly, Vol 19, pp 245-252.
Han, KN, and Fuerstenau, DW (I 975). "Preferential Acid
Leaching of Nickel, Copper and Cobalt from Ocean Floor Manganese
Nodulrs," Trans Inst Min Metal, Vol 84C, pp 105 -110.
Hardingr, H (1960). "Dry Grinding," Handbook of mineral
Drevving Ores and Industrial Minerals, Taggart, AF, ed, John
Wilcy and Sons, New York, pp 60-01-6-54.
Kanungo, SB, and Jena, PK (1988a). "Studies on the
Dissolution of Metal Values in Manganese Nodules of Indian Ocean
Origin in Dilute Hydrochloric Acid," Hydrometallurgy, Vol 21, pp
23-39.
Kanungo, SB, and Jena, PK (1988b). "Reduction Leaching of
Manganese Nodules of Indian Ocean Origin in Dilute Hydrochloric
Acid," Hydromeltallurgy, Vol 21, pp 41-58.
Kanungo, SB, and Das, RP (1988). "Extraction of Metals from
Manganese Nodules of the Indian Ocean by Leaching in Aqueous
Solution of Sulphur Dioxide, Hdrometallurgy, Vol 20, pp 135-146,
Kumar, V, Pandey, BD, and Bagchi, D (1991)."Application of
LIX 84 for Separation of Coppcr, Nickel and Cobalt in Ammoniacal
Leaching of Occan Nodules." Material Transactions, JIM, Vol 32,
pp 157-163.
Oktiwaki. A, Noda. Y, Ito, H, and Okabe, T (1974).
"Leaching of Copper, Nickel, and Cobalt from Manganese Nodules
with Anunonium Sulfitc Solution," Nippon Kagaku Kaishi, No 11, pp
2091-2084.
Okuwaki, A, Ito, H, and Okabe, T (1977). "Extraction of
Copper, Nickel, and Cobalt from Ocean Manganese Nodules by
Aqueous Ammonia-Ammonium Salt-Carbohydrate Solution," Nippon
Kagaku Kaishi, No 10, pp 1462-1468.
Ossco-Asare, K, and Fuerstenau, DW (1979). "Adsorption
Phenomena in Hydrometallurgy, 1. The Uptake of Copper, Nickel and
Cobalt by Oxide Adsorbcnts in Aqueous Ammoniacal Solutions," Int
J. Miner. Process, Vol 6, pp 85-104.
Rokukawa, N (1992). "Extraction of Nickel, Cobalt and
Copper from Ocean Cobalt Crusts with Ammioniacal Alkaline
Solutions," Shigen-to-Sozai, Vol 108, pp 187-191.
Rokukawa, N (1993). "Separation of Cobalt, Nickel and
Copper from Ammioniacal Alkaline Leach Liquor of Cobalt Crusts by
Solvent Extraction," Sigen-to-Sozai, Vol 109, pp 373-377.
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