Chapter 7

Refining Molten Ferronickel

The ferronickel product from electric furnace smelting contains up to 0.06% P

and 0.4% S from the ore and coal feeds to the smelter.1 These elements lower
the strength, toughness and corrosion resistance of ferrous alloys, which means
that they must be removed before the ferronickel is used for alloying.
Typical market requirements for ferronickel are that the phosphorus content
must be less than 0.02% and the sulfur content must be less than 0.03%.
It is optimal to remove phosphorus and sulfur from ferronickel just after it
has been tapped from the smelting furnace – when it is molten and hot. All
ferronickel smelters do this. Typical flowsheets for the refining operations are
shown in Figures 4.1 and 7.1 (Marin and Vahed, 2009).
The objective of this chapter is to describe the removal of phosphorus and
sulfur from molten ferronickel. The removal of carbon, cobalt, chromium and
silicon and the casting of ferronickel are also described.

7.1. PHOSPHORUS REMOVAL

Phosphorus is removed from molten ferronickel into molten slag by reacting
the ferronickel with lime, CaO and oxygen.
The reaction can be represented as (Simeonov et al., 1997):
1550 C
2½P þ 5½O þ 4CaOðsÞ ƒƒ!
in molten added to molten mixed into molten
ferronickel ferronickel by ferronickel
injecting oxygen

ðCaOÞ4 P2 O5 ð[Þ (7.1)

molten slag that floats and is decanted
from the molten ferronickel

The reaction indicates that the removal of phosphorus from ferronickel is

favored by (i) efficient mixing of lime into the molten ferronickel and (ii) deep
injection of oxygen into the molten ferronickel.

1. Some smelters use low-phosphorus, low-sulfur fossil fuels to minimize these concentrations
(Hyuga, 2007; Kohga et al., 1997).

Extractive Metallurgy of Nickel, Cobalt and Platinum-Group Metals. DOI: 10.1016/B978-0-08-096809-4.10007-3

Copyright Ó 2011 Elsevier Ltd. All rights reserved. 85
86 PART | I Extractive Metallurgy of Nickel and Cobalt

Efficient mixing of lime into the molten ferronickel is obtained by adding it

to the ferronickel ladle before and during tapping from the smelting furnace.
Deep injection of oxygen into the molten ferronickel is obtained by blowing
the oxygen through refractory-coated stainless steel lances.
Finally, the phosphorus is removed from the ladle by carefully decanting off
the floating slag.
Lime removes phosphorus down to less than 0.03% P and occasionally
down to 0.01% P (Warner et al., 2006). This range is acceptable to virtually all
stainless steel and ferrous alloy makers.

7.2. SULFUR REMOVAL

Sulfur is removed from molten ferronickel most commonly by mixing calcium
carbide, CaC2, into the molten ferronickel. A representative reaction is given as
follows:
1550 C
½S þ CaC2 ðsÞ ƒƒ! 2½C þ CaSð[Þ
in molten mixed into molten in molten molten slag; decanted
ferronickel ferronickel ferronickel from molten ferronickel

(7.2)

This reaction shows that the removal of sulfur into slag as CaS is favored by
(i) efficient mixing of calcium carbide into the ferronickel; and, (ii) a low initial
carbon content (%C) in the ferronickel.
The calcium carbide is mixed into the molten ferronickel by induction or
mechanical stirring. It forms calcium sulfide slag that floats to the top, from
where it is decanted and discarded.
Sulfur can also be removed with CaO, CaCO3, CaSi, Na2O and Na2CO3
(Bergman, 2003; Warner et al., 2006; Young, Brosig, & Candy, 2009).

7.3. INDUSTRIAL REFINING

The removal of phosphorus and sulfur from molten ferronickel is regarded as
‘ladle metallurgy’. All removal of phosphorus and sulfur is done in a ladle of
freshly tapped ferronickel, which is physically moved through dephosphori-
zation, desulfurization and casting stations as shown in Figure 7.1.
The methods used at a variety of industrial operations are summarized in
Table 7.1.

7.4. REMOVING OTHER IMPURITIES

Ferronickel that arises from the smelting of laterites also contains the following
impurities:
cobalt 0.3%–1%
carbon trace to 2.4%
 Chapter | 7
phosphorus removal sulfur removal
1st electric arc heating 2nd electric arc
station heating station

molten crude

Refining Molten Ferronickel

ferronickel
from smelting CaO
furnace additions
1450°C casting
station

ladle movement ladle movement ladle movement

weigh station
rails
1. CaO is added to ladle.
2. Crude molten ferronickel is
tapped into ladle while
additional CaO is added.
3. Ladle + ferronickel are weighed.
4. Roof + electrodes are lowered
and ferronickel is heated to
1550°C.
5. Roof and electrodes are raised,
ferronickel is stirred, and oxygen
is injected.
6. Calcium phosphate slag is
removed by tipping ladle.
7. CaC2 is added. 12. Refined ferronickel is cast into
8. Roof + electrodes are lowered huge streams of water (granu-
and ferronickel is heated to lation) or continuously into
1550°C then stirred. small molds.
9. Calcium sulfide slag is removed
by tipping ladle.
10. More CaC2 is added and
ferronickel is re-heated.
11. Slag is removed by tipping ladle.

FIGURE 7.1 Representative ferronickel refining flowsheet. It depicts a ladle (2 m diameter, 3 m high, 40 tonnes of ferronickel) moving through four refining
stations: Crude ferronickel tapping from smelting furnace, phosphorus removal, sulfur removal and refined ferronickel casting. The phosphorus content of the
ferronickel is lowered from 0.03% to less than 0.02%. The sulfur content of the ferronickel is lowered from 0.3% to less than 0.03%. Other heating and stirring
methods include induction furnaces, induction stirring, shaking ladles, and refractory-lined stirrers. Most smelters use the same station for dephosphorization and
for desulfurization.

87
 88
TABLE 7.1 Details of the Refining of Ferronickel.* The First Step Always Begins with Crude Molten Electric Furnace Ferronickel,
1450 C
Falcondo, Dominican Le Nickel, New Loma de Niquel,
Smelter Republic Hyuga Smelting, Japan Caledonia Venezuela
Refining

First step Dephosphorization Desulfurization Desulfurization Dephosphorization

PART | I Extractive Metallurgy of Nickel and Cobalt

Equipment Two 4 MW ASEAeSKF Low frequency induction Shaking ladle Electrically heated
ladles furnace ladles

Reagents Basic oxidizing slag CaC2 CaC2 CaO þ oxygen


Process temperature, C 1500e1550 1400e1450 e 1650e1700

Start and finish 0.03%e0.01% P 0.3%e0.03% S 0.2%e0.03% S 0.06%e0.03% P

compositions

Second step Deoxidation Decarburization and Decarburization Desulfurization

Desiliconization
Equipment Same as above LD converter Shaking ladle Same as above

Reagents Ferrosilicon Oxygen Oxygen CaO, CaSi, FeSi,

CaCO3

Process temperature,  C 1500e1550 1600e1650 1600

 Chapter | 7
Third step Desulfurization,
if required
Equipment Same as above

Reagents Basic reducing slag

Refining Molten Ferronickel

Process temperature 1500e1550

Casting method Belt casting Mostly water granulation Casting and

granulation
Product 0.1 kg ferrocones Water-granulated shot Shot, 15e40 kg Water-granulated
ingots shot

Ferronickel composition, % High C & S Low C & S FN 1 FN 4

Ni 39 16 17e28 24e30 22e28 20e25

Co 0.93 < %Ni  0.05 0.5

C 0.06 3 <0.02 0.03 1.2e1.9 <0.04

S 0.04 >0.03 <0.03 0.03 0.23 <0.06

Si 0.35 <5 <0.3 0.03 1.0e3.0 <0.2

P 0.01 <0.05 <0.02 <0.03

Cr 0.02 <2.5 <0.3

* Bergman, 2003; Warner et al., 2006; Young et al., 2009

89
90 PART | I Extractive Metallurgy of Nickel and Cobalt

silicon trace to 3%
chromium trace to 1.7%
This section discusses the impact of each of these impurities.

7.4.1. Cobalt
Cobalt is never removed from ferronickel. The chemical properties of molten
cobalt and nickel are so similar that cobalt cannot be removed from ferronickel
without also removing considerable amounts of nickel.
In small quantities, cobalt is not deleterious to stainless or alloy steels.

7.4.2. Carbon
The ferronickel from some laterite smelting furnaces contains as little as
0.02% C (Bergman, 2003; Solar, Candy, & Wasmund, 2008). The ferronickel
from others contains up to 2.4% C. These concentrations are purposefully
obtained by controlling the amount of carbon in the calcine feed to the
smelting furnace.
A high-carbon product tends to be produced by smelters that smelt calcine
that is rich in nickel and low in iron (Warner et al., 2006). It is the product of
strongly reducing conditions in the smelting furnace. Strongly reducing
conditions give recoveries of nickel as high as 98% into the ferronickel.
A low-carbon product tends to be produced by smelters that smelt calcine
that is high in iron and low in nickel. Mildly reducing conditions are used in the
smelting furnace. Such conditions prevent excessive iron reduction and hence
ferronickel that is excessively dilute in nickel (Solar et al., 2008).
Carbon can be oxidized from ferronickel, which lowers the content of carbon
down to 0.02% without significant oxidation of nickel. Oxygen is injected into
ladles or into small oxygen-steelmaking furnaces to burn the carbon (Bergman,
2003; Warner et al., 2006). A representative reaction is given as follows:
1550 C
2½C þ O2 ðgÞ ƒƒ! 2COðsÞ (7.3)
in molten injected oxygen offgas
high-carbon
ferronickel

Industrially, the process is done either during dephosphorization or after

dephosphorization and desulfurization.

7.4.3. Chromium
Chromium is present in ferronickel arising from smelting furnaces that operate
with high contents of carbon in the feed. The chromium content in this type of
ferronickel can be up to 1.7% (Bergman, 2003). It is removed during carbon
oxidation with little loss of nickel.
Chapter | 7 Refining Molten Ferronickel 91

7.4.4. Silicon
The concentration of silicon in low-carbon ferronickel is low enough (<0.1%
Si) to be used directly in stainless steel manufacture. However, the concen-
trations of silicon are relatively high in ferronickel that is high in carbon. In
these types of ferronickel, the silicon content can be as high as 3%.
Silicon is readily oxidized. As a result, it is removed during the oxidation of
carbon.

7.5. CASTING OF FERRONICKEL

All ferronickel is used for making stainless steel and other ferrous alloys. It is
therefore cast into shapes that are convenient for adding it to molten metal in
furnaces and ladles.
It is usually cast in small molds on a moving conveyor belt, as shown in
Figure 4.1, or granulated in water, as shown in Figure 7.2.

FIGURE 7.2 Production of ferronickel ‘beans’ by controlled pouring of molten ferronickel into
a spinning refractory cup and on into water. The product is flat, ~0.03 m diameter  0.005 m thick
‘beans’ suitable for controlled addition into alloy-making ladles or furnaces. Source: Photograph
courtesy of Pacific Metals Co., Ltd., Hachinohe, Japan.
92 PART | I Extractive Metallurgy of Nickel and Cobalt

The products from casting vary from 0.1 kg ‘ferrocones’ through 20 kg

ingots (and occasionally 90 kg ingots). They are used for all types of melting
and alloying. The product from granulation is about 0.03 m diameter, 0.005 m
thick flat ferronickel ‘beans’. This product is particularly useful for controlled-
rate feeding to argon–oxygen and vacuum-oxygen stainless steelmaking
furnaces (Kohga, Yamagiwa, Kubo, & Akada, 1997).

7.6. APPRAISAL
Most impurities are readily removed from molten ferronickel without losing
nickel. The exception is cobalt, which behaves so much like nickel that it
cannot be preferentially removed.

7.7. SUMMARY
The ferronickel product from laterite smelting always contains phosphorus and
sulfur from ore and hydrocarbon fuels.
These elements are detrimental to the properties of ferrous alloys. As
a result, they must be removed from ferronickel before it is used to make
stainless steel and other alloys. The impurity elements are typically removed
down to less than 0.02% P and less than 0.03% S.
Phosphorus is removed by oxidation from molten ferronickel in the pres-
ence of lime, CaO. Sulfur is then removed by reaction with calcium carbide,
CaC2, and/or other calcium and sodium compounds.
Molten refined ferronickel is cast in small ingots or water granulated to
0.03 m diameter flat beans. The latter are especially useful for controlled-rate
additions to argon- and vacuum-oxygen stainless steelmaking furnaces.

REFERENCES
Bergman, R. A. (2003). Nickel production from low-iron laterite ores: Process descriptions. CIM
Bulletin, 96, 127–138.
Hyuga. (2007). Hyuga Smelting Co., Ltd. www.smm.co.jp\E\business\metal\hyuga.html. Accessed
19.05.2011.
Kohga, T., Yamagiwa, M., Kubo, N., & Akada, A. (1997). Recent ferronickel production at Hyuga
smelter. In C. Diaz, I. Holubec & C. G. Tan (Eds.), Pyrometallurgical operations, the envi-
ronment and vessel integrity in nonferrous smelting and converting. Proceedings of the Nickel/
Cobalt 97 International Symposium, Vol. III (pp. 217–228). CIM.
Marin, T., & Vahed, A. (2009). Thermodynamic model of FeNi refining, Mineracao Onca Puma. In
J. Liu, J. Peacey, M. Barati, S. Kashani-Nejad & B. Davis (Eds.), Pyrometallurgy of Nickel and
Cobalt 2009 (pp. 431–447). CIM.
Simeonov, S., Bergman, R. A., Uceda, D., et al. (1997). Study of the behavior of sulfur, phos-
phorus and oxygen during refining of ferronickel melts. In C. Diaz, I. Holubec & C. G. Tan
(Eds.), Pyrometallurgical operations, the environment and vessel integrity in nonferrous
smelting and converting processess. Proceedings of the Nickel/Cobalt 97 International
Symposium, Vol. III (pp. 229–236). CIM.
Chapter | 7 Refining Molten Ferronickel 93

Solar, M. Y., Candy, I., & Wasmund, B. (2008). Selection of optimum ferronickel grade for
smelting nickel laterites. CIM Bulletin, 101, 1–8.
Warner, A. E. M., Diaz, C. M., Dalvi, A. D., et al. (2006). JOM world nonferrous smelter survey,
part III: Laterite. JOM, 58, 11–20.
Young, J., Brosig, D., & Candy, I. (2009). Comparison of ladle refining in the ferronickel and steel
industries. In J. Liu, J. Peacey, M. Barati, S. Kashani-Nejad & B. Davis (Eds.), Pyrometallurgy
of nickel and cobalt 2009 (pp. 463–474). CIM.

SUGGESTED READING
Bergman, R. A. (2003). Nickel production from low-iron laterite ores: Process descriptions. CIM
Bulletin, 96, 127–138.
Warner, A. E. M., Diaz, C. M., Dalvi, A. D., et al. (2006). JOM world nonferrous smelter survey,
part III: laterite. JOM, 58, 11–20.