Chapter 10

Technology of Ferronickel
Oleg Polyakov
National Metallurgical Academy of Ukraine, Dnipropetrovsk, Ukraine

Chapter Outline
10.1 Properties of Nickel and Its 10.3.1 Ferronickel and Its
Compounds 367 Smelting 371
10.2 Nickel Raw Materials 371 10.3.2 Refining and Casting
10.3 Ferronickel Smelting and of Ferronickel 373
Refining 371 References 374

10.1 PROPERTIES OF NICKEL AND ITS COMPOUNDS

Nickel (atomic number, 28; atomic weight, 58.6934) belongs to group VIII of
the periodic table and together with iron and cobalt is commonly referred to as
the “iron triad.” Indeed properties of these three elements are rather close. The
outer electron shell configuration of the nickel atom is 3d84s2, so its common
valence is þ2, and less often þ3. Nickel’s melting temperature is 1455 C, and
its boiling temperature is ~2915 C. The density of nickel is 8.92 g/cm3
(i.e., slightly higher than that of iron).
Nickel is an important and widely used constituent of many alloy steels. It is
a well-known solid solution strengthener and a promoter of high toughness,
especially at low temperatures. Nickel has only one stable solid phase (FCC) in
the whole practical temperature range, and its addition usually stabilizes the
austenitic (FCC) structure in steels and alloys. This is an important application
in stainless steelmaking (austenitic, martensitic, and duplex grade stainless
steel compositions). Besides stainless, nickel is also widely used in low-alloys
steels, and it is a major component of nonferrous, high-temperature-resistant
superalloys and heat-, oxidation-, and corrosion-resistant materials.
With iron, nickel forms continuous solid solutions with austenitic (FCC)
compositions (Fig. 10.1). In the liquid state, both elements have unlimited

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Copyright Ó 2013 Elsevier Ltd. All rights reserved. 367
368 SECTION j III Minor Ferroalloys

FIGURE 10.1 The equilibrium diagram of the Ni-Fe system. Magnetic transformations and
possible intermetallics are now shown.

solubility. Earlier it was assumed that the Ni-Fe system’s behavior is close to
ideal solution, but then it was determined that the activity coefficient
of nickel is lower than unity in alloys <40% Ni. There are also indications
of the formation of an ordered FeNi3 structure below 500 C, although
this process seems to be kinetically limited and possibly of a metastable
nature.
Like iron, nickel and carbon form carbide Ni3C of a cementite type, but it is
more metastable than Fe3C and does not usually form easily. The stable phase
diagram of the Ni-C system has a simple eutectic form with Ni-C eutectics at
1326 C (Fig. 10.2). Dashed lines in this diagram indicate approximate phase
positions for metastable Ni-Ni3C equilibria.
With silicon, nickel forms several stable silicides, some of which have
a noticeable homogeneity range (Fig. 10.3). Silicon also dissolves in consid-
erable amounts of liquid and solid nickel (Sudavtseva and Zinevich, 2004).
A number of intermetallic compounds are formed between nickel and
aluminum (Fig. 10.4). The solubility of aluminum in the solid nickel is much
higher than nickel solubility in solid aluminum.
With sulfur, nickel forms four sulfides: Ni3S2, NiS, Ni3S4, and Ni2S. The
most stable nickel phosphides are Ni5P2, NiP, NiP2, Ni2P, and Ni3P (Gasik
et al., 2009). Phosphide Ni3P is isomorphic to Fe3P and Mn3P.
Nickel dissolves a significant amount of oxygen (Fig. 10.5) and forms
nickel oxides NiO and Ni2O3. The latter completely decomposes to NiO above
Chapter j 10 Technology of Ferronickel 369

FIGURE 10.2 Stable and metastable equilibria in the Ni-C system.

FIGURE 10.3 The equilibria in the Ni-Si system.

1100 C and thus is not normally observed in the materials present during the
smelting of ferronickel. Nickel oxide also forms binary compounds with silica
(Ni2SiO4) and ternary compounds with silica and calcia (CaNiSi2O6).
370 SECTION j III Minor Ferroalloys

FIGURE 10.4 The equilibrium phase diagram of the Ni-Al system.

FIGURE 10.5 The equilibrium

diagram of the Ni-O system.
Dashed lines represent equilib-
rium oxygen pressure, atm.
Chapter j 10 Technology of Ferronickel 371

10.2 NICKEL RAW MATERIALS

Nickel appears in two different mineral categories, namely the sulfide type and
the laterite type (oxide–silicate). Among known sulfide minerals of commercial
interest are violarite Ni2FeS4, siegenite (Co,Ni)3S4, polidimite Ni3S4, fletch-
erite Cu(Ni,Co)2S4, and others. These ores might contain up to 4% Ni, but their
availability is about 14% of the total known nickel reserves. Thus, recovery of
nickel from laterite ores is getting more attention, as laterite might have up to
1% to 2% Ni. Depending on the composition of the gangue, laterite ores are
classified into magnesia-, silicate-, and alumina-type varieties. There are also
known reserves of iron ore (50% to 60% Fe and 1% to 1.5% Ni), which might
be classified into limonite and saprolite ores. Limonite ore has 1.2% to 1.3% Ni,
<0.1% Co, <0.1% MgO, and 45% to 50% Fe. Saprolite ores have 2% to 2.3%
Ni, 0.01% to 0.05% Co, 15% to 20% MgO, and 15% to 20% Fe. In ferronickel
production, both lean ores (<1% Ni) and relatively nickel-rich ores (2% to 3%
Ni) might used. The lean laterite ore (Ukraine) has (wt. %) 0.9 to 1 Ni, ~20 Fe,
0.05 to 0.10 Co, 32 to 44 SiO2, 5 to 7 Al2O3, 4 to 6 MgO, <2 CaO, and 1 to 2
Cr2O3. The chemical composition of nickel ores varies widely from plant to
plantd(% wt.): 1 to 3 Ni, 0.03 to 0.1 Co, 10 to 32 Fe, <28 MgO (Weisegar
et al., 2005)dand thus different ores are blended.
Oxidized nickel ores are composed of many complex minerals, such as
nontronite (Fe[(OH)2Al0.33Si3.67O10]Na$(H2O)4), as a group of smectites. Their
general formula might be represented as X0.33Y2Si4O10(OH)2$4H2O, where
X is Ca or Na, Y is Fe3þ, Al, Cr, Mg, Ni, Zn, Li. These mineral formations are
usually composed of ~14% Al2O3, ~8% MgO, and small amounts of CaO, K2O,
and Na2O, and in some cases also NiO and Cr2O3. Some of the clay-forming
minerals are based on serpentine (Mg,Fe,Ni8-xAlx)Si4-yAlyO10(OH)8.
Potential future sources of nickel, cobalt, and manganese minerals are
manganese nodules in the ocean. It is estimated that stocks of nodule in the
Pacific Ocean have more than 1010 tons, containing up to 2.5% Ni, 0.1% to
2.6% Co, <1.9% Cu, and so on. However, all of these deposits are confined to
the central regions of the deep ocean, so their exploration requires substantial
investment and the development of new underwater mining technologies.

10.3 FERRONICKEL SMELTING AND REFINING

10.3.1 Ferronickel and Its Smelting
The standard ferronickel for steelmaking has a wide range of compositions,
from 5% to 25% Ni, Table 10.1. Solar et al. (2008) noted two trends in nickel
laterites processing, one favoring high-grade ferronickel (35% to 40% Ni) and
the other favoring lower grades (20% to 25% Ni). Because the ores processed
vary widely in terms of nickel content and other components, it is natural that
both lower and higher reduction degrees are used. Low reductions imply higher
372 SECTION j III Minor Ferroalloys

TABLE 10.1 Typical Composition of Ferronickel Alloys

Grade Ni Co Si C Cr S P
FeNi10 5e15 0.3e0.6 <0.3 <0.1 <0.3 <0.08 <0.03

FeNi15 12e18 0.5e0.8 <0.4 1e2.5 <2 <0.1 <0.03

FeNi20 15e25 * <0.4 1e2.5 <2 <0.4 <0.03

*Recommended value Ni/Co ¼ 20-40.

slag losses and lower nickel recoveries but also lower power and reductant
requirements, whereas higher reductions imply the reverse (Solar et al., 2008).
In some cases, nickel scrap and remelts are added to low-grade FeNi to increase
nickel content.
The technological scheme for ferronickel smelting in electric includes the
following steps (Fig. 10.6): preparation and averaging of nickel ore; prepara-
tion, dispensing charge materials, and calcining the charge (ore, limestone,
coal, and recirculated dust) in the rotating drum furnaces; FeNi smelting with
a hot charge supply from rotary kilns, FeNi refining (sulfur removal) in the
ladle, followed by purging with oxygen (first in a converter with an acid lining,
then with the basic lining); and finally casting of refined ferronickel.
An example of the modern large-scale FeNi smelter was given by Rodd
et al. (2010). The sources of sulfur in the charge are carbon reductant and heavy
fuel oil (1.8% S) and phosphorus, mainly carbon reductant and nickel ore. The
smelting of ferronickel using lean nickel ores usually starts with roasting
(calcining) of the ore mixture with limestone (~one third of the ore), anthracite

FIGURE 10.6 Flow sheet of ferronickel production: 1, submerged electric arc furnace; 2, slag
ladle; 3, ladle for crude FeNi; 4, converter with acid lining (removal of excess Si and Cr); 5,
converter with basic (MgO) lining for phosphorus removal; 6, ladle for refined ferronickel; 7,
filling/casting machine; 8, storage.
Chapter j 10 Technology of Ferronickel 373

(~1/10 of the ore amount), and recycled dust. Roasting is carried out in rotary
kilns (~3 m in diameter, ~75 m in length, with a hot zone length of 9 to 12 m in
the case of lean ore processing). The treatment temperature should not exceed
850 C to avoid stacking of the charge in the kiln. The hot roasted charge is fed
into the submerged arc furnace of 50 MVA with six 1200 mm electrodes
(Fig. 10.7) operating at a 30 to 40 kA current.
This furnace hearth has dimensions ~25  10  5 m, and it is lined with
carbon blocks (see Fig. 10.7). The furnace has three tap holes for slag and three
tap holes for FeNi. Other furnace types (e.g., the round type of 24 to 94 MVA)
and novel developed DC furnaces (Jones et al., 1996) are also used for FeNi
smelting (Walker et al., 2010). From 1 ton of roasted charge the yield of crude
ferronickel is 120 to 140 kg and for slag it is 650 to 700 kg. The slag has
<0.02% to 0.06% Ni, <0.02% Co and low basicity (50% to 52% SiO2 versus
25% to 30% [CaO þ MgO]), and its main utilization is as a construction
material. Slag behavior and reactions during laterite smelting have been
analyzed (e.g., by Utigard, 1994).

10.3.2 Refining and Casting of Ferronickel

Because crude ferronickel has a high sulfur content, it undergoes desulfuriza-
tion in the ladle by sodium carbonate (soda): [S]FeNi þ 2 Na2CO3 þ [C] þ
[Si] ¼ (Na2S) þ (Na2SiO3) þ 3 CO. The consumption of soda is ~4% to 5% by
weight of FeNi metal, and a practically achievable degree of desulfurization is
50% to 60%.

FIGURE 10.7 Ferronickel smelting furnace: 1, shell; 2, lining; 3, cover; 4, gaskets; 5, current bus
bars; 6, electrode moving mechanism; 7, electrode shifting mechanism. Numbers indicate the
height levels in meters.
374 SECTION j III Minor Ferroalloys

Treated ferronickel is poured into the converter with acid lining and sub-
jected to oxygen purge to remove excess chromium and silicon. An increase of
silica in the slag facilitates the transition of chromium into the slag from fer-
ronickel. This dump slag from refining ferronickel in an acid converter has the
following composition (% wt.): 52 to 55 SiO2, 15 to 25 Fe, ~1.7 CaO, 2 to 6
MgO, 1 to 8 Cr2O3, ~3 Al2O3, and <0.09 Ni. After this refining stage, ferro-
nickel is poured into the next converter with a basic lining and subjected to
conversion with oxygen purge to remove phosphorus. The oxidation of phos-
phorus in the main converter in the presence of highly basic slag is similar for
phosphorus removal in conventional steelmaking. The converted basic slag has
the following composition (%): 15 to 20 CaO, 5 to 10 SiO2, 35 to 50 FeO,
<0.05 Ni, <0.005 Co, and 1 to 10 Cr2O3. Acidic and basic slags are subjected
to conversion of magnetic separation to remove trapped particles of ferronickel.
Ferronickel is usually cast on conveyor machines in ingots of 25 to 35 kg
weight. The specific energy consumption for processing 1 ton of dry lean nickel
ore (1% Ni) is 810 kWh or 78 200 kWh per 1 ton of nickel. The use of richer
ores (2.5% to 3.0% Ni) allows the decrease of specific energy consumption at
least twofold (Novikov et al., 2005). The combined nickel yield into ferronickel
is 88% to 93%.
Among alternative technologies of ferronickel smelting and refining,
blowing molten iron and nickel ore mixture with reducing gas (Krasheninnikov
and Leontiev, 2001) might be mentioned. The addition of 20% limestone
allowed an increase of nickel content in the metal to 70%, in slag <0.1%, to
achieve a nickel yield of 93%.
In the electric furnace development for ferronickel smelting, the trend is to
go to higher-power furnaces (90 to 120 MVA), as the capital investment might
decrease almost twice when compared to the cost of using low-power furnaces
(Walker et al., 2010), but the operation of these furnaces also requires a proper
turnover of materials and lower costs of electric energy.

REFERENCES
Gasik, M.I., Lyakishev, N.P., Gasik, M.M., 2009. Physical chemistry and technology of ferroalloys
[in Ukrainian]. Dnipropetrovsk: Sistemnye Tehnologii, 494 pp.
Jones, R.T., Hayman, D.A., Denton, G.M., 1996. Recovery of cobalt, nickel and copper from slags,
using DC-arc furnace technology. Proceedings of the International Symposium on Challenges
of Process Intensification. 35th Annual Conference of Metallurgists, CIM, Montreal, Canada,
451–466.
Krasheninnikov, M.V., Leontiev, L.I., 2001. Mathematical model of ferronickel processing by
using gas blowing of oxide melt. Rasplavy (Melts) 2, 37–41.
Novikov, N.V., Kapran, I.I., Sokolov, K.A., Ovcharuk, A.N., 2005. Material balance of ferronickel
smelting using New Caldonian ore. Metallurgical and Mining Industry 3, 32–36.
Rodd, L., Voermann, N., Stober, F., Wasmund, B., Lee, S.H., Lim, K.Y., Yoo, J.-H., Roh, S.-J.,
Park, J.-H., 2010. SNNC: a new ferronickel smelter in Korea. Proceedings of the Conference
INFACON-XII. Helsinki, Finland, 697–708.
Chapter j 10 Technology of Ferronickel 375

Solar, M.Y., Candy, I., Wasmund, B., 2008. Selection of optimum ferronickel grade for smelting
nickel laterites. CIM Bulletin 11, 1107.
Sudavtseva, V.S., Zinevich, T.N., 2004. Thermodynamic properties of the Ni-Si melts. Izv. Ros.
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to composition and temperature gradients. Metallurgical and Materials Transactions 25B,
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Walker, C., Koehler, T., Voermann, N., Wasmund, B., 2010. High power, shielded-arc FeNi
furnace operation – challenges and solutions. Proceedings of the Conference INFACON-XII.
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Weisegar, M.L., Onischin, B.P., Tsemehman, Sh, L., 2005. Pyrometallurgical treatment of oxide
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