Trans. Nonferrous Met. Soc.

China 23(2013) 3421−3427

Utilization of nickel slag using

selective reduction followed by magnetic separation

Jian PAN, Guo-lin ZHENG, De-qing ZHU, Xian-lin ZHOU

School of Minerals Processing and Bioengineering, Central South University, Changsha 410083, China
Received 8 October 2012; accepted 30 January 2013

Abstract: In order to utilize slag discarded by nickel plants, the selective recovery of nickel and copper versus iron was investigated
by selective reduction, which was achieved by controlling the reduction parameters and magnetic separation process on bench scale.
The results show that increasing the basicity (mass ratio of CaO to SiO2) of nickel slag facilitates the enrichment of nickel and copper.
The process parameters for selective reduction were optimized as follows: basicity of 0.15, reducing at 1200 °C for 20 min, 5% coal
on a dried slag mass base. The grinding−magnetic separation results of reduced briquettes show that concentrate containing 3.25%Ni,
1.20%Cu and 75.26%Fe is obtained and selective enrichment is achieved with a recovery of 82.20%, 80.00% for nickel and copper
respectively, while the recovery of iron is only 42.17%. The S and P contents are not reduced obviously and further research may be
needed to examine the behaviors of S and P in the process.
Key words: nickel slag; selective reduction; magnetic separation

which can be realized by slag modifier [13] or selective

1 Introduction reduction, but the latter does not appear to receive much
attention in the utilization of nickel slag.
Nickel can be produced from laterite ores by This study involves the selective recovery of
reduction−smelting process [1] or from sulfide ores by non-ferrous metals (nickel and copper) versus iron, from
roasting−smelting process [2], and both of these nickel slag by selective reduction−magnetic separation
processes generate slags, which will not only take up a process, with an aim to make high-grade nickel and
lot of land, bring pollution to the environment, but will copper concentrate for producing special steel, i.e.
also cause waste of resources [3]. Similar to other stainless steel or weathering steel [14,15].
non-ferrous metal slag, nickel slag without sufficient
amount of valuable metals can be used to produce 2 Experimental
ceramics [4], cement [5], etc. Hydrometallurgical,
pyrometallurgical or even physical processes can be 2.1 Raw materials
applied when non-ferrous slag contains valuable metals. The nickel slag, which was generated from a flash
These processes include acid leaching to recover smelter furnace, appears to be round, black granules. The
non-ferrous metals (nickel, cobalt, copper and zinc) [6,7], chemical composition of the slag, which was determined
smelting reduction process to recover iron [8], roasting by chemical titration, is listed in Table 1. It is easy to find
followed by electrowinning [9] or leaching with water from Table 1 that FeO and SiO2, are the main
[10], direct reduction-magnetic separation process to components which exist mainly as fayalite (FexSiO4) in
recover iron and copper [11] and flocculation-magnetic the slag. Nickel and copper constitute 0.90% and 0.34%
separation to recover iron as magnetite [12]. Since the of the slag mass, respectively. The X-ray diffraction
content of non-ferrous metals is low compared with iron pattern shown in Fig. 1 confirms that the major mineral
in the slag, the enrichment of these non-ferrous metal in the nickel slag is crystallized fayalite, which is
may be enhanced by controlling the reduction of iron, consistent with previous research [6]. By analysis of the

Foundation item: Project ([2009]606) supported by the National Development and Reform Commission of China; Project (50974135) supported by the
National Natural Science Foundation of China
Corresponding author: Guo-lin ZHENG; Tel: +86-13467506186; E-mail: [email protected]
DOI: 10.1016/S1003-6326(13)62883-6
3422 Jian PAN, et al/Trans. Nonferrous Met. Soc. China 23(2013) 3421−3427
chemical phase composition for this slag, as listed in Table 3 Proximate analysis of soft coal (mass fraction, %)
Table 2, it can be found that iron mainly exists as iron FCad Mad Vdaf S Ad
silicate or fayalite, and a large part of copper and nickel 53.08 16.06 32.21 0.43 5.44
are in the compounds of oxides or sulfides. The FCad—Fixed carbon; Mad—Moisture; Vdaf—Volatile; Ad—Ash
backscatter electron (BSE) image for a block-section slag
sample and elemental surface scanning result in Fig. 2 2.2 Relevant thermodynamics principles
show that nickel and copper are finely disseminated in The main reactions of blending coal with nickel,
the iron silicate matrix, which makes the enrichment of copper and iron oxides, and fayalite within the nickel
nickel and copper difficult. The slag was ground to slag which may occur during reduction are as follows
88.16% (mass fraction) passing 0.075 mm by wet screen [17,18]:
sizing test for making briquettes. CuO(s)+C(s)=Cu(s)+CO(g),
ΔG m=37860−171.02T (1)
Table 1 Chemical composition of nickel slag (mass fraction, NiO(s)+C(s)=Ni(s)+CO(g),
%) ΔG m=120218−171.37T (2)
Fetotal FeO Ni Cu Co SiO2 Fe3O4(s)+4C(s)=3Fe(s)+4CO(g),
37.80 44.31 0.90 0.34 0.12 33.41 ΔG m =645520−650.46T (3)
Fe2SiO4(s)+2C(s)=2Fe(s)+SiO2(s)+2CO(g),
Al2O3 CaO MgO P S LOI*
ΔG m=335400−321.81T (4)
2.64 2.60 9.67 0.02 0.43 0.50
The main reactions of nickel, copper, iron sulfides
LOI—Loss on ignition
and fayalite in the slag with reducing agent and calcium
carbonate which may occur during reduction are as
follows [17,18]:
FeS(s)+2C(s)+CaCO3(s)=Fe(s)+CaS(s)+3CO(g),
ΔGm=469677−462.54T (5)
NiS(s)+2C(s)+CaCO3(s)=Ni(s)+CaS(s)+3CO(g),
ΔGm=433160−499.61T (6)
CuS(s)+2C(s)+CaCO3(s)=Cu(s)+CaS(s)+3CO(g),
ΔGm=430602−487.49T (7)
Fe2SiO4(s)+4C(s)+2CaCO3(s)=
2Fe(s)+Ca2SiO4(s)+6CO(g),
ΔGm=909601−941.09T (8)
Ni2SiO4(s)+4C(s)+2CaCO3(s)=
2Ni(s)+Ca2SiO4(s)+6CO(g),
Fig. 1 XRD pattern of nickel slag ΔGm=642777−850.15T (9)
Under the standard state, it can be calculated from
Table 2 Chemical phase analysis of nickel slag (mass fraction, formulas (1)−(4) that the reduction temperatures of
%) CuO(s), NiO(s), Fe3O4(s), Fe2SiO4(s), which are 221.25
FeM Py FexOy FexSiO4 NixS NiM K (−51.90 °C), 701.51 K (428.36 °C), 992.41 K (719.26
0.43 0.21 2.72 34.44 0.22 0.11 °C),1042.23 K (769.08 °C) respectively, vary a lot. And
Nickel in ferrite Copper in from formulas (5) to (9) it can be found that the
CuxS CuxO CuM reduction temperatures of FeS(s), NiS(s), CuS(s),
and oxide other compounds
Fe2SiO4(s), Ni2SiO4(s) also have difference, which are
0.57 0.13 0.015 0.025 0.17
1015.53 K (742.38 °C), 867.00 K (593.85 °C), 883.30 K
FeM—Metal iron; Py—Iron in pyrite; FexOy—Iron in oxide; FexSiO4—Iron
in silicate; NixS—Nickel in sulfide; NiM—Metallic nickel; CuxS—Copper in (610.15 °C), 966.54 K (693.39 °C), 732.55 K (459.40 °C)
sulfide; CuxO—Copper in oxide; CuM—Metallic copper respectively. Therefore, the reduction of nickel and
copper is prior to the reduction of iron oxides and
Soft coal was used as reductant in this study and its fayalite to metallic iron by controlling the reduction
proximate analysis results are listed in Table 3, from parameters, such as the reduction temperature and
which it can be concluded that the coal is a good reduction duration.
reducing agent for its high fixed carbon, high volatile
and low ash content [16]. Calcium carbonate and an 2.3 Experimental procedure and equipment
additive which has a role in the promotion of grain The nickel slag, reductant, water and additive,
growth, are analytically pure reagents (AR). whose amount was fixed at 3% on the basis of nickel
 Jian PAN, et al/Trans. Nonferrous Met. Soc. China 23(2013) 3421−3427 3423

Fig. 2 BSE image (a) for slag sample and corresponding elemental surface scanning images of Ni (b), Cu (c), Fe (d), S (e) and Si (f)

slag mass according to the preliminary test, were RFe=[mcβFe/(mcβFe+mtγFe)]×100%

homogeneously mixed at a given ratio and prepared for
where mc is the mass of concentrate; mt is the mass of
briquettes. 3 g of the mixture was loaded into a cylinder tailing; βFe is the iron grade in concentrate; γFe is the iron
with d10 mm×50 mm to form a briquette, followed by grade in tailing.
being dried at 120 °C for at least 4 h in a drying oven to The calculation of nickel and copper recovery is
ensure complete drying of the briquettes. Dried similar.
briquettes with a total mass around 45 g were loaded into Respectively, SX-12-16Q type resistance furnace
a graphite crucible and reduced in a muffle furnace, then (muffle furnace) was used for selective reduction, and
were slowly cooled in a container to about 100 °C under the RK/ZQM (BM) series ball mill was applied to finely
nitrogen atmosphere. The cooled briquettes were broken grinding; XCGS−73 Davis tube was used for weak
and ground in a wet ball mill, and then were separated in magnetic separation.
a Davis tube: the grinding fineness of the reduced calcine
is 100% passing 0.075 mm and the magnetic field 3 Results and discussion
intensity is maintained at 131.34 kA/m. After grinding−
magnetic separation, the concentrate and tailing were 3.1 Effect of basicity on selective reduction−magnetic
dried, weighed, sampled and analyzed by chemical separation
titration following the Chinese standard to determine the The effects of basicity (mass ratio of CaO to SiO2 in
iron, nickel and copper grade. The iron recovery was the mixture of nickel slag, additive and calcite) on the
calculated according to the following formula: metal grade and the metal recovery from the nickel slag
3424 Jian PAN, et al/Trans. Nonferrous Met. Soc. China 23(2013) 3421−3427
were examined under the conditions of the amount of enrichment of nickel, copper and iron were examined
blending soft coal being 3% based on the dried slag mass, and the results are shown in Fig. 4.
reduction at a temperature of 1200 °C for 60 min.
As shown in Fig. 3(a), with a rise in basicity, the
grades of nickel, copper and iron in concentrate were
elevated at first, and then declined. The result indicates
that adding a certain amount of CaCO3 could promote
the reduction of minerals containing these metals.
However, higher basicity will result in the increase of
melting point of slag phase [11], retarding the
aggregation of metal grains and decreasing the metal
grade in concentrate.
From Fig. 3(b), it can be seen that the metal
recoveries do not change significantly and the iron
recovery is much lower than that of nickel or copper,
reflecting that the selective reduction is achieved. The
suitable basicity is recommended at 0.15 to obtain
relatively high nickel and copper grades in the
concentrate with a satisfactory recovery.

Fig. 4 Effect of temperature on metal grade (a) and metal

recovery (b)

It can be found from Fig. 4(a) that with the

temperature increasing, the nickel grade shows a
downward trend in the whole process; however, the
copper grade is less affected by temperature; and the iron
grade is raised continuously. This may be explained by
that the starting reduction temperature of nickel oxide is
lower than that of the iron oxide, the reduction of nickel
will be prior to iron at low temperatures, but with the
temperature increasing, more iron oxide is reduced,
leading to a drop in the nickel grade. The change in the
copper grade is not so significant as it is quite lower
compared with the nickel grade.
Figure 4(b) shows that the recoveries of nickel,
copper and iron go up as the temperature increases in the
Fig. 3 Effect of basicity on metal grade (a) and recovery (b) range of temperature examined, which clearly
demonstrates that the raising of temperature contributes
3.2 Effect of reduction temperature on selective to the reduction of nickel, copper and iron. But higher
reduction−magnetic separation temperatures mean higher energy consumption and lower
Under the conditions that the basicity, the reduction nickel grade, so the suitable reduction temperature is
time, and the dosage of coal are 0.15, 60 min and 3%, selected at 1200 °C. The temperature used in this study is
respectively. The effects of reduction temperature on the much higher than the aforementioned commence
 Jian PAN, et al/Trans. Nonferrous Met. Soc. China 23(2013) 3421−3427 3425
reduction temperature for the metal-containing minerals. nickel and copper. Comprehensively considering the
This indicates that the reduction rate and the aggregation energy consumption and the grade of nickel and copper,
of reduced metals are essential to provide a satisfactory the reduction duration is selected as 20 min.
recovery during grinding−magnetic separation as high
temperature is beneficial to reduction and the growth of 3.4 Effect of dosage of coal on selective reduction−
metallic particles [19]. magnetic separation
Under the conditions of the reduction temperature
3.3 Effect of reduction duration on selective 1200 °C, reduction time 20 min and basicity 0.15, the
reduction−magnetic separation effect of the amount of blending soft coal on the
Under the conditions of basicity 0.15, the reduction enrichment of metals from the nickel slag is shown in
temperature 1200 °C and the amount of coal 3%, a series Fig. 6.
of reduction tests were performed for various time to
determine the effect of reduction duration on the metal
concentration as shown in Fig. 5.

Fig. 6 Effect of dosage of coal on metal grade (a) and metal

recovery (b)

Fig. 5 Effect of reduction duration on metal grade (a) and metal From Fig. 6(a) it can be found that the grades of
recovery (b) nickel and copper in the concentrate decline as the ratio
of reducing agent increases, while the iron grade
As can be seen from Fig. 5(a), with the reduction increases. This indicates that sufficient reductant can
time prolonging, both the grades of nickel and copper in promote the reduction of iron oxide to metallic iron,
the concentrate show a downward trend, while the grade which is similar to the effect of long reduction duration.
of iron is ascending. Meanwhile, the recoveries of nickel, The impact of the blending soft coal on the metal
iron and copper are elevated, as shown in Fig. 5(b). It recovery is shown in Fig. 6(b), from which it can be seen
can be concluded that with the reduction time prolonging, that the recovery is elevated at first, but further increase
nickel, copper and iron can be reduced more fully but the in coal addition (higher than 5%) gives no obvious
increase in iron reduction will result in lower grades of improvement in the recovery of nickel and copper but
3426 Jian PAN, et al/Trans. Nonferrous Met. Soc. China 23(2013) 3421−3427
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 Jian PAN, et al/Trans. Nonferrous Met. Soc. China 23(2013) 3421−3427 3427

选择性还原−磁选回收镍渣中的有价金属
潘 建，郑国林，朱德庆，周仙霖

中南大学 资源加工与生物工程学院，长沙 410083

摘 要：采用选择性还原−磁选工艺富集某镍渣中的镍、铜，通过控制还原过程参数实现选择性还原。结果表明：
添加熔剂并适当提高渣料的碱度(CaO 与 SiO2 质量比)有助于镍、铜的富集；对碱度 0.15、还原温度 1200 °C、还
原时间 20 min、内配煤量 5%(质量分数)的优化条件下得到的还原样品，通过磨矿−磁选获得镍、铜、铁品位分别
为 3.25%、1.20%、75.26%的精矿，镍、铜、铁的回收率分别为 82.20%、80.00%、42.17%，实现了镍、铜相对于
铁的选择性富集；选择性还原−磁选没有显著降低 S、P 的含量，两者在工艺过程中的行为需要进一步研究。
关键词：镍渣；选择性还原；磁选
(Edited by Xiang-qun LI)