資 源 と素 材 (Shigen-to-Sozai)

Vol.112 p.117-121 (1996)

論文 Reduction Leaching of Manganese Nodules with

Sodium Sulfite in Ammonium Chloride Solution*

by Kyung-Soo CHOI 1, Oh-Hyung HAN 2 and Bang-Sup SHIN3

The leaching characteristics of manganese nodules were investigated by using ammonium chloride
solution with sodium sulfite as a reductant for leaching manganese, cobalt, nickel, copper and iron.
Leaching behaviors of manganese, copper, cobalt and nickel depend on the amount of added sodium sul-
fite. The ratio of liquid and solid is an important factor in the extraction of metals during leaching. The
dissolution of manganese, cobalt, nickel, copper and iron is increased with the increase in the NH4C1 con-
centration and in the temperature of the leachant. When the leachant pH was kept constant, the
leachability increased for each of the metals. The sodium sulfite 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 5 M NH4C1 at 80 t for 2.5 h. The dissolution rates of Mn, Ni and Cu are controlled by pore dif-
fusion, while Fe is controlled by surface chemical reactions and Co is limited by both the surface chemi-
cal reaction and pore diffusion process.
KEY WORDS: Manganese Nodule, Sodium Sulfite, Leachability, Pore Diffusion, Surface Chemical Re-
action

ammonia leach system, Co, Ni and Cu can be recovered.

1. lntroduction
Sometimes Mn recovery is needed because of the demand
The leaching behaviour of manganese nodules in am- for Mn resources and the tailing problem after leaching.
monia solution have been investigated by many research- But, it is not easy to find research papers dealing with the
ers1)-11) In 1974, Lester, J.1) studied how the leaching of 4 metal recovery process in ammonia solution. The pre-
deep sea manganese nodules with an ammoniacal-Cu+ so- sent work reports the reduction leaching behaviors of
lution allows the selective recovery of the Ni, Co and Mo manganese nodules from the Pacific Ocean with sodium
from the nodules. The reducting-ammoniacal leaching sulfite as a reductant in ammoniacal solution.

process was also carried out by some investigators3)-5). In

2. Experiments
this process, NH4Cl,(NH4) 2SO4,(NH4) 2CO3 or NaCl solu-
tion were used as leachant. Okuwaki et a1.6) studied the 2・1 Materials

leaching behaviors of ocean nodules in ammoniacal am- The manganese nodule sample was obtained from Pa-

monium salt solution with reductants, such as D-glucose cific Ocean at 12•‹ 03' north latitute and 139•‹26' east

and starch. Jena3) reported manganese nodules can be longtitute. The chemical composition of the sample is

leached with an ammoniacal solution at an amibent tem- shown in Table 1.

perature for 1•`4 h in the presence of glucose as a Before the leaching experiments, the manganese nod-

reductant, to recover 100 % of Cu, 70 % of Ni and 80.4 % of ule was ground by a jaw crusher and a mortar grinder

Co. Anand4) developed a process for extracting 100 % of mill and sized to obtain -100 mesh fraction. Analytical

Cu, Ni and Co when leached in 5.85 M NH4OH- (NH4) 2SO4,

grade of Na2SO3, NH4C1 and HC1 were used in this experi-

65•Ž using FeSO4 as reductant in dilute NH4OH solution. ment. Distilled water was also used.

Rokukawan also carried out the reduction leaching in am- 2・2 Experimental

monia solution. From their result, the leaching recovery The leaching experiments were conducted in 300 ml
was 93.2 % of Ni, 98.7 % of Co, 97.2 % of Co, 0.65 % of Mn three-necked glass flask to which an agitator and a ther-
and 1.2 % of Fe when leached in the mixed solution of 120 mostat were attached. The 100 ml of NH4C1 solution was
g/l (NH4)2CO3 and 50 g/l (NH4)2S03, 80 t for 2 h. In this put into the reactor and heated. When the leachant was
heated to the experimental temperature, 5 g of the nodule
sample and a relative amount of Na2S03 were put into the
* ReceivedJune 9, 1995: accepted for publication December 19, 1995
reactor. The solution pH was adjusted using HC1 solution.
1. Membership of MMIJ, Ph. D, Senior Researcher, Korea Mining Promotion
Corporation, Seoul, Korea
2. Professor, Dr., Chosun University, KwangJu, Korea Table 1 The chemical composition of the nodule (%).
3. Membership of MMIJ, Professor, Dr., Chonnam National University,
KwangJu, Korea
(For correspondence) FAX 82-2-840-5604 (Korea Mining Promotion Corp.)

資 源 と 素 材112 (1996) No.2 117 <49>

Kyung-Soo CHOI, Oh-Hyung HAN and Bang-Sup SHIN

The effect of the initial pH on the reduction leaching of

3. Results and Discussion
manganese nodules in the presence of 5 g Na2S03 without

In the NH4Cl solution, the reaction between MnO2 and controlling pH-values is shown in Fig. 2. Extractions of
Na2SO3 can be described as follows; Ni, Mn and Co showed constant from pH 1 to 5. Cu exhibits
MnO2+ 4NH4+ +2e =Mn2+ +4NH3 +2H2O (1) slight increase in extraction from the pH-value 1 to 8. Fe
SO32- +H2O =SO42- +2H+ +2e (2) extraction amount shows, however, constant values from
3・1 Effect of the amount of Na2SO3 the pH-values 1 to 10.5. The extraction of metal values
Fig. 1 shows the effect of addition of sodium sulphite show a sharp decrease from pH 9 to 10.5 due to
during the leaching of the nodule sample in 5M NH4Cl at reprecipitation of metal hydroxides. The initial pH is
80•Ž with initial pH of 5 for 2h. The solution pH was not therefore an important factor for the metal extractions.
controlled. The terms, N/R, means the ratio of the weight 3・3 Effect of NH4Cl concentration

of the nodule sample (g) and the weight of sodium sulphite Fig. 3 shows that the maximum extraction for each of
(g). The results showed that without Na2SO3, extractions Ni, Cu and Mn is attained at 5 M NH4Cl to be 91.1 %, 80.4 %
of metal values were very low. With the increase in the ad- and 35.2 %, respectively. The leaching of iron is much less
dition of Na2SO3, extraction of Cu, Ni and Co sharply in- due to the formation and precipitation of jarosite as
crease. When the N/R ratio is 0.63, the extraction of Cu, Co increase of NH4Cl-concentration. At higher NH4Cl-
and Ni are reached to 81.3 %, 51.8 % and 89.8 %, respec- concentration, the extraction of Co and Ni decrease with
tively. On the other hand, the extraction of Mn and Fe are precipitation of their metal dioxides.
9.5 % and 3.99 % for the addition of the same amount of 3・4 Effect of leachingtime

Na2SO3. This reveals that the extraction of metal values Fig. 4 shows the leaching rate of manganese nodules
decreases with high a ratio of N/R due to the precipitation in NH4Cl solution. The extraction of metal values reach
of metal ions with the pH increase in the leaching reaction: the equilibrium state in about 60 minutes when leached in
SO32-+ 2H+ →SO2 +H2O (3) 5 M NH4C1 and 5 % of Na2S03 solution. This suggests that

Fig. 1 shows that the condition of 5g Na2SO3 and 5g Cu occurs on the surface of ferro-manganese phase in a
nodule gives good results in the metal extraction. loosely adsorbed state, Ni in the lattice replacement and
3・2 Effect of the initial pH Co primarily in the replacement of Mn4+ from the disor-

Fig. 3 Effect of the concentration on the extraction of met-

Fig. 1 Effect of the ratio of nodule to reductant on the ex-
als from nodule (N/R 1: 1, temp. 80•Ž, initial pH5,
traction of metals from nodule (NH4Cl conc. 5M,
time 2 h).
temp. 80 •Ž, initial pH 5, time 2h).

Fig. 2 Effect of the initial pH on the extraction of metals Fig. 4 Rate of extraction of different metals from nodule

from nodule (N/R 1:1, temp. 80•Ž, NH4Cl conc. 5 (N/R 1:1, temp. 80•Ž, NH4Cl conc. 5 M, initial pH
5).
M, time 2h).

118 <50> 資 源 と 素 材112 (1996) No.2

 Reduction Leaching of Manganese Nodules with Sodium Sulfite in Ammonium Chloride Solution

Fig. 5 A plot for the dissolution kinetics of Fe in the leach- Fig. 8 Effect of liquid/solid ratio on the extraction metals
ing of nodule (N/R =1). from nodule (NH4C1 conc. 5 M, temp. 80 •Ž, time 2 h,
inital pH 5, N/R= 1)).

Fig. 6 A plot for the dissolution kinetics of Mn, Ni and Cu

in the leaching of nodule (N/R =1).

Fig. 9 Effect of temperature on the extraction of metal val-

ues from nodule (NH4Cl conc. 5 M, temp. 80 •Ž, time

2 h, initial pH 5, N/R= 1).

following well-known rate equation should be applicable.

2 2/3 =k2t
1- α- (1 -α) (5)
/3
The leaching curves for Ni, Mn and Cu have a good lin-
ear behaviour as shown in Fig. 6, which fit the eq. (5). The
rates on Ni, Mn and Cu extractions are all controlled by
pore diffusion.
Some processes follow the mixed control of the diffu-
sion and chemical reaction. Fig. 7 suggests an example of
Fig. 7 A plot for the dissolution kinetics of Co in the leach- the mixed control for Co dissolution for {1-(1-a)1/3 }
ing of nodule (N/R = 1).
2
/t versus { 1- α- (1 -α )2/3 }/t plot.
/3
dered layer of 6 -Mn0212) 3・5 Effect of liquid/solid ratio

An attempt to fit the kinetic curves to the shrink core The effect of liquid/solid ratio on the extraction of
model13) reveals that extraction behavior of metals follow metal values is shown in Fig. 8. The leaching curves
different equations. For Fe, which exhibits low extraction showed that the extraction of metal values sharply in-
values, it is observed that the following rate equation can creases with an increase in the ratio of liquid/solid ratio
he applicable. from 10 to 40 at which the extraction of Ni, Cu, Co, Mn and
(1 -α )1/3=klt
1- (4) Fe are 99.3 %, 83.1 %, 78.2 %, 34.9 %, and 2.1 %, respec-
Where a is the fraction leached in duration t (min- tively.
utes). Fig. 5 demonstrates the applicability of eq.(4) for 3・6 Temperature effect

the extraction of Fe in 5 M NH4C1 solution . This shows Fig. 9 shows the results of leaching experiments at

that the rate of Fe extraction is controlled by the surface various temperature from 25 •Ž to 90 t with 5 M NH4C1 at

chemical process. If the rate is controlled by diffusion, the initial pH 5 for 2 h. Extractions of Ni, Cu
, Co and Mn

資 源 と 素 材112 (1996) No.2 119 <51>

Kyung-Soo CHOI, Oh-Hyung HAN and Bang-Sup SHIN

NH4Cl-Na2SO3 reduction leaching.

3•E7 Effect of the finial pH

The pH-value of a solution is increased on consump-

tion of H+ ions in leaching process without pH-control.

The leached metal ions may therefore reprecipitate in the

form of hydroxide. Figs. 10•`12 show the effect of final pH

on the extraction of metal values. The pH of solution was

kept constant during the experiment by adding of acid so-

lution. These figures show that metal values reach their

equilibrium extractions in 30 minutes. When the pH is con-

trolled, the extraction of Mn and Co had high values in

comparison with the case of free pH. From these figures,

Fig. 10 Rate of extraction of different metals from nodule, the extraction behaviors of Mn, Co, Ni and Cu are similar
when the pH value of solution was kept at 4 (N/R 1
: 1 , temp. except that of Fe. The extraction of Fe increases with an
80•Ž, NH4Cl 5 M).
increase in H+ concentration, due to the dissolution of fer-

ric ion. At final pH value of 6, the extraction of Mn, Co, Ni

and Cu are 97.8%, 89.1%, 93.5%, 98.5%, and 3.1%, re-

spectively.

4. Conclusions

The manganese nodules can be leached effectively with

Na2SO3 as a reductant in NH4Cl solution. The experimen-

tal results are summarized as follows;

(1) In NH4Cl solution, Cu, Ni and Co can be easily

extracted in the presence of sodium sulfite. The extent of

extraction depends upon the amount of sodium sulfite.

(2) Selective extractions of Mn, Co, Cu and Ni, and

Fig. 11 Rate of extraction of different metals from nodule, dissolution of Fe can be achieved by controlling final pH
when the pH value of solution was kept at 5 (N/R 1
in the leach solution.
: 1, temp. 80•Ž, NH4Cl 5 M).

(3) The extraction rate was not so fast that the maxi-

mum extractions of metal values were achieved in 60 min-

utes.

(4) The ratios of N/R and L/S are both important

factors in the extraction of metal values.

(5) A temperature around 80•Ž is suitable for the pre-

sent reduction leaching by the presence of NH4Cl.

References
1) Szabo, L. J.: US pat. 3,983, 107,(1976)
2) Agarwal, J. C., Bamer, H. E. m and Beecher, N.: Chem. Eng. Prog.,
Vol.75, No.1, p.59-63,(1979)
3) Das, R. and Jena, P.: Indian IN 160,536,(1987)
4) Anand, S., Das, S. C. and Jena, P. K.:. Indian IN 162,452,(1988)
5) Bhattacharya, I. N., Anand, S., Das, S. C. and Das, R. P.: Trans. In-
dian Inst. Met. Vol.42, No.4, p,385-392,(1989)
Fig. 12 Rate of extraction of different metals from nodule,
when the pH value of solution was kept at 6 (N/R 1 6) Okuwaki, A., Ito. H. and Okabe, T.: Nippon Kagaku Kaishi, Vol.10, p.
: 1, temp. 80•Ž, NH4Cl 5 M). 1462-1468,(1977)
7) Rokukawa, N.: J. of MMIJ Shigen-to-Sozai, Vol.106, p.205-209,
(1990)
8) Bare, C. B. and Pasquali, J. W.: US. Pa. 3,751, 554,(1973)
except that of Fe reach to almost their maximum values at
9) Han, K. N., Hoover, M. and Fuerstenau, D. W.: Int. J. Miner. Process.
80•Ž. Below 50•Ž the extraction of Mn is low and insensi-
1(3), p.215-230,(1974)
tive in temperature change. The extraction of Fe is low due 10) Kanetova, D., Stofko, M. and Kmet, S.: Int. J. Miner. Process. Vol.5,
No.1, p.145-153,(1985)
to the precipitation of ferric hydroxide and increases
11) Kawahara, M., Esaki, S. and Shirane, Y.: Nippon Kagaku Kaishi, Vol.
slightly with the temperature elevation. Over 80•Ž, no sig-
101, p.489-494,(1985)
nificant rise in the extractions of all the metals. The 12) Kanungo, S. B. and Jena, P. K.: Hydrometallurgy, Vol.21, p.23-39,
maximum extraction amounts obtained in the present ex- (1988)
13) Sohn, H. Y. and Wadswort, M. E.: Rate processes of extractive
periment are Ni 99%, Cu 83.1%, Co 78.2% and Mn 35.2%.
metallurgy, p.133-186,(1979), Plenum Press, New York
Therefore, a temperature around 80•Ž is suitable for

(和文要 旨:次 ペ ー ジ)

資 源 と素 材 112(1996) No.2
120 <52>
 Reduction Leaching of Manganese Nodules with Sodium Sulfite in Ammonium Chloride Solution

亜 硫 酸 ナ トリウ ム ー塩 化 ア ン モ ニ ウ ム溶 液 に よ るマ ンガ ン ノ ジ ュー ル の還 元浸 出

崔 京 守1韓 五 炯2申 芳 燮3

還 元 剤 と して 亜 硫 酸 ナ トリ ウ ム を利 用 し,塩 化 ア ンモ ニ ウム 溶 とFe:3.1%の 浸 出率 を得 た 。浸 出 の 時 間 依 存 式 に フ ィ ッ トす

液 を用 い た マ ン ガ ン ノ ジ ュ ー ルの 浸 で 特 性 を明 らか にす る実 験 を る こ とに よ りMn, Ni, Cuの 浸 出 速 度 は粒 界 拡 散 に よ り,Fe

行 った 。Mn, Co, CuとNiの 浸 出 は亜 硫 酸 ナ ト リ ウ ム の 量 に は 表 面化 学 反応 律 速,そ してCoは 拡 散 と表 面 反 応 が 同時 に作 用
よっ て 変 わ り,液 体 と固 体 の 混 合 比 も重 要 な フ ァ ク タで あ った 。 す る と推 定 で きる 。
溶 液 の 温 度 の 上 昇 お よ び ア ンモ ニ ウ ム溶 液 の 濃 度 増 加 に よ って 浸 1. 正会員Ph, D大 韓鉱業振興公社技術研 究所先任研 究員
2. 工博 朝鮮大学校工科大学教授
出 率 が 増 加 した 。 溶 液 のpHを 調 節 す る と,各 金 属 元 素 の 浸 出 率
3. 正会員 工博 全南大学校工科大学教授
を増 加 させ る こ とが で きた 。 亜 硫 酸 ナ トリ ウ ム を還 元 剤 と して 使 キーワー ド:マ ンガンノジュール,亜 硫酸ナ トリウム,浸 出剤,粒 界拡 散,
表面化学反応
用 して,Mn: 95.8%, Ni: 93.5%, Cu: 98.5%, Co: 89.1%

資 源 と素 材 112(1996) No.2 121 <53>