Professional Documents
Culture Documents
Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng
a r t i c l e i n f o a b s t r a c t
Article history: The Okiep Copper District in South Africa has produced more than 110 million tons at a grade of 1.71% Cu
Available online 25 July 2013 from several small mafic ore bodies. The ore was smelted on site and generated 5 mt of slag. During the
life of mine attempts to recover copper from the slag by flotation had limited success. After mine closure
Keywords: the challenge of environmental rehabilitation and the possible disposal of the slag, triggered a reinvesti-
Environment gation into the viability of slag as a copper resource. Characterisation of the slag as a contribution to the
Okiep potential copper recovery is the objective of this study.
Copper-slag
The slags are hard, vitreous with a matrix of Si–Fe–Al–Mg–Ca glass and laths of Mg–Fe–olivine, Fe–Mg–
Characteristics
Ore mineralogy
orthopyroxene and minor Cr-spinel. Copper grade varies between 0.11% and 0.42% with minor nickel,
cobalt, molybdenum, zinc and tungsten. All economic elements are hosted by disseminated spheroidal
prills which consist mainly of the copper sulphides bornite, chalcocite, covellite and chalcopyrite with
exsolved sulphide phases of the minor base metals as well as rhenium and silver. Prills consisting of
metallic copper and alloys are minor constituents. Prill diameter is highly variable with most in the
40–60 lm range and the historically poor copper recovery is attributed to the small prill size. Crushing
of slag to 45 lm as opposed to the previous 75 lm should significantly increase sulphide liberation
and recovery of copper and minor base metal sulphides by conventional flotation.
Provided the operation is economically viable, redistribution of the processed slag to environmentally
acceptable sites will resolve the present pollution and rehabilitation challenge related to the dumps in
the Okiep Copper District. The operation will also have a positive socio-economic impact on this pov-
erty-stricken part of South Africa.
Ó 2013 Elsevier Ltd. All rights reserved.
1. Introduction slag dust was also considered a health problem for the towns of
Nababeep and Okiep. Rehabilitation of the copper oxide ore dumps
The Okiep Copper District is located 600 km north of Cape Town and extensive slimes dams remains a challenge and as part of the
in the north-western part of the Northern Cape Province, South program, are earmarked for future reprocessing and redistribution.
Africa and includes the towns of Springbok, Okiep, Nababeep and Rehabilitation of the landscape is required and would include dis-
Concordia. It is the oldest mining district in the country and has posal of slag as backfill in old open cast mines (van der Westhuizen
been a copper producer for more than 150 years. Copper smelters pers comm.). This operation has not commenced too date.
have been in operation at several localities in the area and pro- Favourable copper prices and the expected increase in future
duced slag dumps ranging from approximately 10 000 m3 to more demand coupled with the pressure of the rehabilitation, which in-
than 1.5 million m3. Mining came to an end in 2007 and the district cluded slag disposal, initiated this orientation study to investigate
has been under slow but, systematic rehabilitation ever since the slag dumps as a potential copper resource (Candy, 2011; Hur
(Fig. 1). and Sedgman, 2013).
The Okiep Copper District with its widespread distribution of When the mine was in operation, limited attempts had been
small mines and extensive mining history has been listed as a made to recover copper from the slag by means of conventional
highly polluted area with significant environmental damage copper sulphide flotation. All these attempts failed because of the
(Hohne and Hansen, 2008). The smelter slags at Nababeep and lack of a proper resource estimate and geometallurgical study to
Okiep were indicated to be a phosphorous (PO4), lead and chro- identify the various mineral phases. This resulted in variable grade
mium risk for the aquatic ecosystem in particular. The windblown of the plant feed and recovery which never exceeded 50% of the
contained copper. This poor recovery was mainly attributed to loss
⇑ Corresponding author. of elemental copper during sulphide flotation (De Beer, pers
E-mail address: ar@sun.ac.za (A. Rozendaal). comm.). A flash flotation cell was added to the milling circuit to
0892-6875/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.mineng.2013.06.020
A. Rozendaal, R. Horn / Minerals Engineering 52 (2013) 184–190 185
Table 1
Average and standard deviation (S) of major and trace element chemistry of massive (M) and frothy (F) slags from Nababeep, Okiep and Concordia in the Okiep Copper District.
Nababeep n SiO2 TiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O K2O P2O5 Cr2O3 LOI H2O– Total
M 7 61.67 0.59 3.50 23.86 0.07 3.82 1.57 0.19 0.32 0.13 0.05 3.47 0.17 99.40
F 3 49.58 1.15 6.05 29.87 0.09 6.30 2.64 0.49 0.48 0.22 0.11 2.70 0.20 99.88
S–M 8.26 0.39 2.31 3.75 0.02 1.92 0.97 0.31 0.14 0.07 0.03 0.69 0.04 0.61
S–F 14.95 0.53 2.74 11.32 0.01 1.62 1.18 0.36 0.19 0.09 0.08 0.42 0.03 1.53
Okiep
M 4 43.76 1.12 9.42 27.78 0.22 7.84 3.64 0.94 0.82 0.63 0.28 2.43 0.08 98.94
F 1 47.78 0.90 12.16 16.88 0.22 10.28 4.22 1.54 0.82 0.56 0.34 1.28 0.10 97.08
S–M 3.97 0.45 1.34 7.59 0.02 2.06 0.32 0.32 0.20 0.31 0.02 0.90 0.02 1.94
Concordia
M 3 66.11 0.63 6.92 14.96 0.11 1.89 2.49 0.85 0.53 0.49 0.17 2.44 0.20 97.90
F 1 66.52 0.68 7.44 12.76 0.12 2.26 2.62 0.94 0.54 0.46 0.16 2.22 0.20 96.92
S–M 14.95 0.53 2.74 11.32 0.01 1.62 1.18 0.36 0.19 0.09 0.08 0.42 0.03 1.53
Nababeep n Ba Cr Co Cs Cu Hf Mo Nb Ni Pb Rb Sc Sr Sn
M 7 241.15 359.84 353.90 0.76 2373.95 1.54 56.84 6.34 140.37 148.17 16.11 31.53 197.56 21.38
F 3 228.15 710.16 369.45 0.95 2601.82 2.05 46.91 11.17 141.54 149.62 22.05 35.02 355.60 25.88
S–M 240.67 148.61 240.80 0.33 559.77 0.52 37.40 3.48 60.62 61.53 5.73 4.48 119.95 11.13
S–F 53.45 434.75 151.38 0.32 889.75 0.26 20.42 5.17 45.18 81.38 8.07 2.72 154.36 16.90
Okiep
M 4 323.64 1815.44 504.98 1.62 2633.54 8.21 7.40 11.66 469.35 339.25 41.60 41.98 293.97 12.00
F 1 315.44 2237.50 120.87 1.18 3870.71 5.39 4.17 8.45 194.52 8.90 37.42 42.31 354.63 16.53
S–M 79.38 120.56 54.21 0.41 287.38 2.57 5.21 3.92 35.41 1.96 11.55 0.58 69.03 3.52
Concordia
M 3 122.82 1045.77 96.80 0.91 2492.33 5.46 10.77 6.19 104.77 8.88 27.24 30.40 207.31 10.65
F 1 132.22 988.51 107.09 1.15 1163.20 5.19 9.54 6.44 66.32 6.81 28.56 31.09 216.04 10.45
S–M 53.45 434.75 151.38 0.32 889.75 0.26 20.42 5.17 45.18 81.38 8.07 2.72 154.36 16.90
Nababeep n Ta Th U V W Y Zn Zr
M 7 0.53 12.21 1.81 103.58 736.05 18.25 2203.81 57.95
F 3 0.83 18.57 2.80 159.16 365.97 28.60 1284.67 76.21
S–M 0.23 6.91 0.70 43.88 1274.69 8.25 3545.34 19.42
S–F 0.33 8.37 0.46 60.20 229.16 6.94 886.63 6.68
Okiep
M 4 2.03 49.14 9.40 453.79 777.18 12.15 5247.26 275.74
F 1 1.33 31.07 3.72 399.05 456.15 3.72 250.91 204.87
S–M 0.71 11.67 1.82 179.13 269.35 1.82 84.02 92.99
Concordia
M 3 1.05 38.70 5.55 338.49 236.28 51.00 156.79 191.58
F 1 0.98 37.55 5.13 363.25 433.38 49.61 146.18 189.26
S–M 0.33 8.37 0.46 60.20 229.16 6.94 886.63 6.68
Nababeep n La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
M 7 57.17 117.43 13.28 51.52 7.81 0.89 5.88 0.65 3.77 0.69 1.87 0.26 1.80 0.26
F 3 94.81 194.76 22.04 84.92 12.74 1.45 9.35 1.00 5.78 1.06 3.01 0.41 2.59 0.40
S–M 25.79 53.26 6.30 24.51 3.74 0.45 2.69 0.29 1.69 0.30 0.78 0.11 0.84 0.11
S–F 27.83 59.11 6.37 25.70 4.21 0.45 2.29 0.28 1.61 0.25 0.72 0.08 0.64 0.10
Okiep
M 4 77.06 167.21 24.68 69.61 13.00 1.30 11.53 1.54 9.29 1.75 4.84 0.70 4.45 0.64
F 1 69.91 154.70 17.62 70.74 14.01 1.57 11.41 1.49 9.24 1.74 5.14 0.72 5.11 0.67
S–M 17.53 36.38 4.86 20.38 5.13 0.13 4.35 0.52 3.60 0.57 1.69 0.21 1.04 0.13
Concordia
M 3 64.75 136.56 16.66 68.17 13.62 1.18 11.89 1.62 9.96 1.90 5.32 0.76 4.74 0.68
F 1 63.40 133.90 16.11 66.83 14.29 1.13 12.12 1.56 9.47 1.83 4.78 0.71 4.32 0.65
S–M 27.83 59.11 6.37 25.70 4.21 0.45 2.29 0.28 1.61 0.25 0.72 0.08 0.64 0.10
Trace elements: Copper content of the slags varies between 5.2. The matrix mineralogy
0.11% and 0.42% and compares well with the slag data reported
by Fairfax (1955). Concentrations of up to 1% zinc, 0.36% tungsten, Silica-rich glass generally constitutes more than 60% of the slag
0.15% cobalt and 137 ppm molybdenum have been reported from matrix and hosts large crystalline euhedral grains of magnesium–
the Nababeep slags (Table 1). Lead content is also elevated com- iron olivine ((Mg, Fe)2SiO4), iron-magnesium orthopyroxene ((Mg,
pared to Okiep and Concordia, however the former may have sig- Fe)SiO3) and minor to rare amounts of ortho-amphibole (gedrite)
nificant nickel concentrations of up to 0.14%. From an economic (Fig. 4; Table 2; www.sun.ac.za/earthsci/people/rozendaal_e.htm).
point of view the Nababeep slags are the most enticing followed The major silicate phases have been confirmed by X-ray diffraction.
by those from Okiep. None of the slag analysed showed any rare An unidentified low silica phase chemically conforms to the iron-
earth element enrichment (Table 1). The platinum group element rich olivine iddingsite but, the structure has not been confirmed.
potential of the slags has not been determined by means of whole These silicate phases display a spinifex-like texture of radiating
rock analyses. There is no significant chemical difference between grains. Small isometric grains of the spinel group conforming to
frothy and massive slag and separation based on density contrast chrome-hercynite (picotite) and hercynite are common and
will serve no purpose. disseminated magnetite is responsible for the weak magnetic
188 A. Rozendaal, R. Horn / Minerals Engineering 52 (2013) 184–190
Fig. 3. Major element chemistry of slags from the Okiep Copper District. The slags Fig. 5. A mineralogically complex prill consisting of bornite, native copper and Ni–
are silica–iron-rich with variable aluminium content. All iron presented as Fe2O3. Fe alloy hosted by a glass, orthopyroxene matrix.
Legend: solid triangle Okiep, open triangle Nababeep, open square Concordia.
Most prills consist of either bornite (Cu5FeS4), chalcocite (Cu2S)
signature of the slag (Table 2; www.sun.ac.za/earthsci/people/ro- covellite (CuS) or combinations thereof and have been confirmed
zendaal_e.htm). The anomalous whole rock zinc values also report by X-ray diffraction (Table; www.sun.ac.za/earthsci/people/rozen-
to the spinels. daal_e.htm). These may contain several exsolution phases consist-
Glass chemistry is variable and is largely a function of the lo- ing of chalcopyrite (CuFeS2), cobaltian pentlandite (Ni, Fe, Co)9 S8,
cally derived sand composition which was added during the smelt- millerite (NiS), marmatitic sphalerite ((Zn, Fe) S), pyrrhotite
ing process, as well as the gangue mineralogy of the mafic host (Fe7S8), galena (PbS) and castaingite (CuMo2 (Re) S5). A cubic
rock. Glass from the Okiep, as well as Concordia slags is aluminium Pb–Ni–Cu–Co–S phase is common in the Nababeep slag and a
enriched indicating a large feldspar component of the added sand Re–Ni–Os–Fe–S phase (Rheniite, structure ReS2?) has been
(Table 3: www.sun.ac.za/earthsci/people/rozendaal_e.htm). This observed at Concordia (Table 4; www.sun.ac.za/earthsci/people/
also explains the abundance of Al-spinel in those slags. Glass has rozendaal_e.htm). In several prills cubic metallic copper occurs in
a Si–Fe–Al–Mg–Ca composition in decreasing order of abundance the core or may crosscut the prills as small veinlets, indicating sul-
with minor amounts of sulphur, chromium and traces of copper, phur deficiency during the segregation process. Prills consisting
zinc and tungsten. entirely of copper metal are rare. Alloys with a Ni–Fe, Re–Mo and
Ru–Rh composition, as well as specs of metallic silver have been
5.3. The prill mineralogy identified. The latter also occurs in solid solution with chalcopyrite.
Molybdenum occurs in all copper, as well as copper–nickel
Prills are disseminated throughout the various slags and show no phases in solid solution, with variable concentrations of up to 6%
preference for either the massive or frothy types. In general the prills molybdenum. Of the platinum group elements rhenium has a close
all have the same spheroidal shape but, mineralogical composition spatial association with zinc and a Re–Zn–S phase may occur on
can be monomineralic or complex, consisting of several sulphide, al- the contact between native copper and chalcocite. Osmium has
loy or metallic element phases (Figs. 4 and 5). Prill size has a wide noticeable concentrations in the copper phases, in particular native
range between <5 and 1500 lm with an average of approximately copper. Although the distribution of the platinum group elements
50 lm (Fig. 6). The largest prills occur in Concordia slag. in solid solution in copper phases may be considered with some
reservation, the identification of discrete PGE-rich phases lends
support to their presence.
Distribution of the economically important elements between
the three localities shows that Nababeep prills have more copper,
nickel and Pb–Zn–Re phases and less Ni–Co phases than Okiep.
The Concordia slags are more sulphur-rich and explain the
Fig. 4. Typical back scatter SEM image of Nababeep slag showing distribution of
olivine (ol), orthopyroxene (opx) and spinel (sp) in a glass matrix. Spheroidal prills Fig. 6. Prill size distribution in slags from the Okiep Copper District. The population
consist of bornite (bn). Note the variation of prill diameter. is dominated by the 40–60 lm interval. (n = 200).
A. Rozendaal, R. Horn / Minerals Engineering 52 (2013) 184–190 189
presence of large pyrrhotite prills poikilitically enclosing magnetite South Africa have shown that the slags are significantly enriched
and silicate glass. in copper with minor concentrations of zinc, tungsten, cobalt, nick-
el and molybdenum. Effectively all metals of economic significance
are hosted by discreet spherical prills disseminated throughout the
6. Discussion
massive and vesicular iron–magnesium–silicate slag. The average
drill diameter is 50 lm but, should be statistically quantified by
Slags from all three localities studied have the same basic prop-
a representative follow-up study of this more than 5 million ton
erties with relatively minor differences in the glass and silicate
slag resource.
mineralogy. Effectively all economically important elements such
Mineralogically the prills consist predominantly of copper sulp-
as copper, nickel, molybdenum, cobalt, lead, zinc and some plati-
hides with exsolved zinc, nickel, molybdenum and lead sulphide
num group elements have been scavenged by the remaining sul-
phases, metallic copper and base metal alloys. Previous attempts
phur in the silicate-rich slag and as a result report to the discreet
to extract copper from the slag by means of conventional flotation
sulphidic prills hosted by the slag matrix. Copper is mainly present
have had limited success, however this study suggests that crush-
as sulphides with less than 10% as elemental copper. Bornite is the
ing to 45 lm as opposed to 75 lm could significantly improve
dominant copper sulphide phase and accounts for more than 80%
recovery of the sulphide phases by flotation. This should be con-
of the total copper sulphides. Chalcocite, minor covellite and traces
firmed by a follow-up study. Copper will be the main earner of rev-
of chalcopyrite constitute the remaining copper sulphides.
enue and could be supported by sweeteners from the minor base
Other minor to trace elements that may contribute to the value
metals and possibly traces of platinum group elements such as
of the slag include nickel mainly present as pentlandite, molybde-
rhenium.
nite in solid solution with copper sulphides and possibly rhenium
Provided the extraction process is economically viable, the pro-
also in solid solution with nickel–copper and sulphides and sphal-
cessed slag can be redistributed to environmentally acceptable
erite. Some of the abundant zinc in Nababeep slag also reports to
sites and resolve the present pollution and rehabilitation chal-
the glass, silicate minerals and spinel phases and is refractory
lenge. From a socio-economic perspective the copper-from-slag
and not considered for extraction.
initiative could revitalize albeit on a small scale, the economy of
Although prill size is variable, the dominant 50 lm fraction
a poverty-stricken part of South Africa. The slag contains a poten-
and essential sulphide composition of the prills lends itself to
tial resource of 15 000 tons of copper metal and processing
extraction by conventional flotation by grinding to 45 lm. The
500 000 tons slag per annum a possible life of mine of 10 years is
poor recovery reported from previous attempts could have been
envisaged.
a function of grinding to 75 lm which resulted in poor liberation
and limited surface exposure of the prills. It is therefore anticipated
that grinding to 45 lm may significantly improve recovery of the Appendix A
copper sulphide phases which account for most of the copper dis-
tribution. It is also anticipated that the minor exsolved sulphide Pyrometallurgical. route Nababeep smelter Okiep Copper District
phases such as pentlandite may be recovered, as well as molybde-
num and rhenium present in solid solution with complex copper Copper sulphide concentrate is obtained by flotation of the
sulphides. Metallic copper and the metal alloy prills will be sup- crushed primary ore and assays between 20% and 40% copper.
pressed during sulphide flotation unless finely intergrown with The concentrate is mixed with high silica sand that serves as a flux
copper sulphides. The results of this study show that the metallic and fed into the reverberatory furnace for smelting. The slag is
and alloy phases are of minor concentration (10%) and will have skimmed and matte tapped and fed to the Peirce-Smith converter.
a limited effect on the overall copper recovery. The temperature of the matte is around 1115 °C and depending on
The very fine-grained prills (<20 lm) are expected to show a the mineralogy of the concentrate it assays between 60% and 65%
poor recovery, but in terms of their contribution to the overall con- copper for bornite-rich ore and 31–40% copper if dominated by
tained weight per cent copper, this loss will also be limited. chalcopyrite. The slag is discarded to the slag dump and formed
From the mineralogy of the copper-bearing phases and prill size the focus of the present study.
distribution it can be concluded that conventional sulphide flota- Chemistry of this process can be expressed as:
tion would be the most appropriate method to beneficiate the cop- 2CuFeS2ðsÞ þ 3O2ðgÞ ! 2FeOðsÞ þ 2CuSðsÞ þ 2SO2ðgÞ
per slags. Copper losses will be related to the fine prill size fraction,
elemental copper and metal alloy distribution and are expected to FeOðsÞ þ SiO2ðsÞ ! FeO SiO2ðlÞ
be relatively limited. Theoretically it should be possible to signifi-
cantly improve upon the historic recovery of less than 50% copper 2FeSðlÞ þ 3O2ðgÞ þ 2SiO2ðlÞ ! 2FeO SiO2ðlÞ þ 2SO2ðgÞ
by grinding the slag to 45 lm. This should however be confirmed
by laboratory flotation tests. To optimise the potential revenue of Sand is added as flux to the converter matte. Converter slag pro-
the slag resource, sulphide concentrates should be regularly as- duced assays around 6% copper and is returned to the reverbera-
sayed for nickel, molybdenum and rhenium in addition to copper. tory furnace. The copper smelt is cast into blister copper bars or
Several papers have recently appeared on the hydrometallurgi- 1 ton blocks which assay more than 99% copper.
cal extraction of base metals from copper and also zinc smelter slag Chemistry of this process can be expressed as:
in particular from research done in China (Yang et al., 2010; Jiang CuSðlÞ þ O2ðgÞ ! CuðlÞ þ SO2ðgÞ
et al., 2012). Although this new technology could be considered to
improve copper extraction, the advantages will have to signifi- 2FeSðlÞ þ 3O2ðgÞ þ 2SiO2ðlÞ ! 2FeO SiO2ðlÞ þ 2SO2ðgÞ
cantly outweigh the traditional sulphide flotation route and appear
unlikely at this stage. Pulverized coal is used as fuel. (Fairfax, 1955; Kinsella and Goosen,
1996).
7. Conclusions
References
An orientation textural, mineralogical and chemical study of Candy, G., 2011. Copper Prices to Rise in Q1 2012 but Supply Concerns Remain,
smelter slag from three localities in the Okiep Copper District in December 2011. <www.Mineweb.com>.
190 A. Rozendaal, R. Horn / Minerals Engineering 52 (2013) 184–190
Cornelissen, A., 1965. A History of Copper Mining in Namaqualand. Privately Lombaard, A.F., Staff of the O’okiep Copper Company Limited, 1986. The copper
published, p. 120. deposits of the Okiep District, Namaqualand. Mineral deposits of Southern
Fairfax, E., 1955. O’okiep smelting capacity keeps pace with expanded mine output. Africa. S. Afr. J. Geol. II, 1421–1445.
Special O’okiep volume. Min. World 17 (06), 52–78. Potgieter, J.E., 1996. Exploration in the Okiep Copper District, Northern Cape
Hohne, S., Hansen, R.N., 2008. Preliminary conceptual geo-environmental model of Province, South Africa: an overview. S. Afr. J. Geol. 99 (2), 209–220.
the abandoned copper mines of the Okiep Copper District, Namaqualand, Rozendaal, A., 2011. Historic Resource Information on O’okiep Copper Company.
Northern Cape. Council for Geoscience, Report Number 2008-070, April 2008, p. Unpublished Research Report, 2011, University of Stellenbosch, p. 10.
194. Smalberger, J.M., 1975. A History Of Copper Mining in Namaqualand. Publ. C Struik,
Hur, J., Sedgman, G., 2013. Morgan Stanley says Copper Price to Rise 7.6 percent in 1975, Cape Town, p. 152.
2013 on demand, January 2013. <www.Bloomberg.com/news>. Yang, Z., Rui-lin, M., Wang-dong, N., Hui, W., 2010. Selective leaching of base metals
Isky, G., 2009. O’Okiep Copper Mine at Nababeep Northern Cape SA 3. <http:// from copper smelter slag. Hydrometallurgy 103 (1–4), 25–29.
www.iskyfoto.com/index.php?PhotoID=320&KeywordID=150>. Personal communication
Jiang, K., Guo, Z., Xiao, X., Zhang, L., 2012. Extraction of metals from a zinc smelting
slag using two-step procedure combining acid and thylene diaminetetraacetic
acid disodium. J. Cent. South Univ. 19, 1808–1812. Mr. S. van der Westhuizen. Director Siteplan Environmental Consultants. P.O.
Kinsella, B., Goosen, G.J.S., 1996. Shutdown of the Smelter at O’okiep Copper Box 241 Strand, South Africa.
Company Limited. Hidden Wealth, Johannesburg, 1996. The South African Mr. A. de Beer Manager O’okiep Copper Company 2001–2007, now retired.
Institute of Mining and Metallurgy, pp. 37–43. Hermanus, Western Cape Province, South Africa.