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Minerals Engineering 21 (2008) 679–682

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Technical Note

The effect of heat treatment on the magnetic properties of pyrite

K.E. Waters a, N.A. Rowson a, R.W. Greenwood a,*, A.J. Williams b
a
Department of Formulation and Chemical Engineering, University of Birmingham, Edgbaston, Birmingham, B15 2TT, UK
b
Department of Metallurgy and Materials, University of Birmingham, Edgbaston, Birmingham, B15 2TT, UK

Received 28 November 2007; accepted 3 January 2008

Available online 20 February 2008

Abstract

The effect of thermal treatment on the magnetic properties of pyrite was investigated. Untreated pyrite showed evidence of both para-
magnetic and ferromagnetic components. After heat treatment, the saturation magnetisation increased considerably until 800 °C when
the magnetisation decreased, and then increased again after 900 °C. These changes are due to phase changes induced by oxidation. The
wet magnetic recovery of the untreated sample was 25%, which increased to over 90% after treatment at 500 °C. The recovery of the
magnetic fraction plateaus after treatment at higher temperatures, implying that a sample magnetisation greater than 5 kA m 1 leads
to a recovery greater than 90% for this size fraction.
Ó 2008 Elsevier Ltd. All rights reserved.

Keyword: Magnetic separation

1. Introduction Thermal treatment can increase the recovery of minerals

through magnetic separation. This work aims to categorise
Pyrite is an iron disulphide (FeS2), which is the most the mineralogical changes that occur when pyrite is heated
common of the sulphide minerals. It is most often found in a muffle furnace, and relate these changes to alterations
in association with a number of other sulphides or oxide in the magnetic properties of the sample, and the recovery
minerals, and is a major constituent of the sulphur contain- after magnetic separation.
ing minerals in some coals (Male, 1984; Rowson, 1986;
Uslu and Atalay, 2004). Pyrite has been reported to be 2. Experimental
weakly paramagnetic, with a very small and positive sus-
ceptibility (Wilson, 1921; Ramaseshan, 1947; Schneider Mineral samples of Peruvian pyrite were obtained from
et al., 2004). However, ferromagnetic tendencies have been Gregory, Bottley & Lloyd (London, UK). The mineral
noted (Male, 1980, 1984; Waters et al., 2007). sample was crushed and milled to obtain a suitable size
Roasting of hematite and siderite has been shown to fraction. Then, the sample in the less than 125 lm size frac-
produce magnetite and hence give an enhanced magnetic tion (d16 = 20 lm; d50 = 66 lm; d84 = 115 lm) were repre-
recovery (Wills, 1985). Microwave treatment of Palabora sentatively sampled into 50 g samples to be heated in a
ore (containing 1% copper sulphide) showed an increase Carbolite muffle furnace for 2 h at set temperatures, rang-
in the copper grade through magnetic separation (Sah- ing from 100 to 1100 °C.
youn, 2004), which is due to the increase in the magnetic X-ray diffraction (XRD) analysis was carried out on the
properties of chalcopyrite from the formation of new pyrite samples using a Philips X-Pert MRD (with Cu
phases such as hematite and maghemite. tubes). Scanning electron microscopy (SEM) was carried
out using a JSM-6060 LV (JEOL Ltd., UK) fitted with
*
Corresponding author. an Inca 300 EDS (energy dispersive spectrum) analysis sys-
E-mail address: [email protected] (R.W. Greenwood). tem (Oxford Instruments, UK).

0892-6875/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2008.01.008
680 K.E. Waters et al. / Minerals Engineering 21 (2008) 679–682

Magnetic properties were measured using a Lakeshore gold, which was used to coat the samples prior to analysis.
7300 Series vibrating sample magnetometer, using 0.2 g This is to be expected as the formula is FeS2. The sample
representative samples. The VSM was calibrated using a treated at 800 °C showed the atomic ratio of 57% oxygen,
nickel sphere (model 730908.) Hystersis loops were 43% iron and no sulphur present. This ratio is close to that
obtained for magnetic field strengths of up to of the 2iron:3oxygen that is found in hematite, and was con-
1600 kA m 1. sistent with the mineral phase detected with XRD analysis.
Fifty grams representative samples were used for wet The untreated pyrite showed a saturation magnetisation
magnetic separation processing, using a Boxmag Rapid of approximately 900 A m 1 (Fig. 1a). This indicates a
high intensity wet magnetic separator. Suspensions were degree of ferromagnetism probably due to impurities in
made up using 100 ml of water for every 10 g of sample. the mineral sample. Male (1980, 1984) speculated the ferro-
The suspension was passed through the separator with an magnetic impurity found in his pyrite sample was due to
applied field strength across the metal matrix of 0.7 T. surface oxidation, creating a small amount of magnetite,
After every 50 ml of suspension the magnetic field was or a low-temperature phase-transition to monoclinic pyr-
switched off and the matrix was washed out so that the rhotite. The formation of a Honda–Owen plot gives a
matrix was not overloaded. The magnetic and non-mag- magnetic susceptibility of 6  10 5 for the paramagnetic
netic fractions were then weighed and determined as a per- component, this fits with the range of 3.5  10 5 6 v 6
centage of the initial feed. 500  10 5 given by Hunt et al. (1995) for the initial volu-
metric magnetic susceptibility of pyrite.
3. Results and discussion Figs. 1a and 1b show the hysteresis loops in the first
quadrant, showing how the curves change with the treat-
The initial and final mass of all the pyrite samples were ment and the formation of new phases (Fig. 1a is for max-
measured. The change in mineral phase also brings about a imum magnetisation lower than 10 kA m 1; Fig. 1b is for
change in the mass of the sample, as the sulphur is evolved those with greater maximum magnetisations). As the tem-
as sulphur dioxide, and then oxygen bonds with the iron perature increases above 400 °C, the magnitude of the max-
atoms to form magnetite, hematite and maghemite. The imum magnetisation increases quite considerably from less
theoretical mass change from FeS2 to FeS is a decrease than 1 kA m 1 prior to treatment to a value of approxi-
of 27%. From FeS to Fe3O4 the mass change is a decrease mately 55 kA m 1 after 700 °C. The magnetisation after
in 35.7% from the original mass, and from Fe3O4 to Fe2O3 treatment at 800 °C is considerably lower than that at
the final mass would be 33.5% less than the original start- 700 °C. This is due to the formation of hematite, which is
ing mass. These theoretical mass changes correspond well considerably less magnetic than pyrrhotite, magnetite and
to the changes in mass observed. maghemite. Fig. 2 shows the magnetisation of the treated
EDS analysis of the untreated pyrite shows a ratio of samples at a set value of the field strength of 1600 kA m 1.
sulphur to iron on the surface as being 2:1 (66% sulphur, Similar results have been reported by Martinez et al.
33% iron), with no other elements observed apart from (1999) on strontium hexaferrite. This was attributed to

800 degrees Celsius

7

500 degrees Celsius

6

5
M [kA m-1]

2
400 degrees Celsius
100 degrees Celsius
1
Untreated

0
0 200 400 600 800 1000 1200 1400 1600 1800
-1
H [kA m ]
Fig. 1a. Hysteresis curves from the first quadrant for pyrite thermally heated that has a maximum magnetisation less than 10 kA m 1.
 K.E. Waters et al. / Minerals Engineering 21 (2008) 679–682 681

60

700 degrees Celsius

50
1000 degrees Celsius
900 degrees Celsius
40
M [kA m-1]

30 600 degrees Celsius

20

10

0
0 200 400 600 800 1000 1200 1400 1600 1800
-1
H [kA m ]
Fig. 1b. Hysteresis curves from the first quadrant for pyrite thermally treated that has a maximum magnetisation greater than 10 kA m 1.

70
Pyrite, FeS2
Pyrrhotite, Fe1-xS
60 Magnetite, Fe3O4
Pyrite, FeS2
Pyrrhotite, Fe1-xS
50

Pyrite, FeS2
M [kA m-1]

40

Maghemite, γ-Fe2O3
30

20
Hematite, α-Fe2O3

10

0
0 200 400 600 800 1000 1200
o
T [ C]

Fig. 2. Mineral phases detected (through XRD analysis) after thermal treatment for 1 h at temperatures up to 1000 °C, and the corresponding
magnetisation at 1600 kA m 1 of the heat treated pyrite.

the formation of antiferrimagnetic hematite (a-Fe2O3). than 5% of the bulk volume, and this may not have
Once the temperature increased above 800 °C, the magnet- occurred in this study until 700 °C. Sahyoun et al. did
isation increased once again due to the formation of ferro- notice a change in the crystalline structure of the hematite
magnetic maghemite (c-Fe2O3). As the pyrite sample has to forming maghemite at a temperature of 850 °C, which is in
go through a number of phase changes before reaching agreement with this study.
hematite, it is likely that this formation occurs at a point The results of the magnetic separation of the pyrite sam-
around 800 °C. Work by Sahyoun et al. (2003) on Norwe- ples are shown in Fig. 3. Initially the recovery in the mag-
gian chalcopyrite found that hematite formation started to netic fraction is very low, approximately 20% and remains
occur at a temperature of 450 °C. The discrepancy between so until 200 °C. Once the treatment temperature was
their results and where the hematite formation occurs in 400 °C, the magnetic recovery increased considerably to
this study can be attributed to the fact that the formation 80%. This is where the first sign of the formation of new
of new phases to be detectable by XRD needs to be greater phases was observed (Fig. 2) and a slight increase in the
682 K.E. Waters et al. / Minerals Engineering 21 (2008) 679–682

100

90

80
Magnetic recovery [%]
70

60

50

40

30

20

10

0
0 200 400 600 800 1000 1200
Temperature [°C]

Fig. 3. Magnetic recovery of the heat treated sample.

magnetisation at 1600 kA m 1. At higher temperatures, the Male, S.E., 1980. Magnetic measurements on coal. Journal of Physics D:
magnetic recovery reaches a plateau at 95%. So even Applied Physics 13 (4), L67–L70.
Male, S.E., 1984. Magnetic susceptibility and separation of inorganic
though the magnetisation has decreased, it is still sufficient material from UK coals. Journal of Physics D: Applied Physics 17 (1),
to ensure that the force acting on the particle ensures that 155–161.
the particles remain in the magnetic fraction. From Figs. 2 Martinez, N., Williams, A.J., Seyyed Ebrahimi, S.A., Harris, I.R., 1999. A
and 3, for the size fractions investigated here a magnetisa- study of the evolution of the constituent phases and magnetic
tion greater than 5 kA m 1 demonstrated a magnetic properties of hydrogen-treated Sr-hexaferrite during calcination.
Journal of Materials Science 34, 2401–2406.
recovery greater than 90%. Ramaseshan, S., 1947. The magnetic properties of iron-pyrites. Proceed-
ings of the Indian Academy of Sciences, Section A 25, 201–207.
4. Conclusions Rowson, N.A., 1986. Desulphurisation of coal by microwave energy,
Ph.D. Thesis. The University of Leeds, UK.
Thermal treatment has a considerable effect on the mag- Sahyoun, C., Kingman, S.W., Rowson, N.A., 2003. The effect of heat
treatment on chalcopyrite. Physical Separation in Science and Engi-
netic properties of pyrite increasing the saturation magnet- neering 12 (1), 23–30.
isation, due to the formation of the more magnetic phases Sahyoun, C., 2004. The effect of microwave radiation on the liberation of
of pyrrhotite and magnetite. At a temperature of 800 °C, minerals from ores. Ph.D. Thesis, The University of Birmingham, UK.
the magnetisation was considerably lower, due to the for- Schneider, J., de Wall, H., Kontny, A., Bechstadt, T., 2004. Magnetic
mation of hematite, which has much weaker magnetic susceptibility variations in carbonates of the La Vid Group (Canta-
brian Zone, NW-Spain) related to burial diagenesis. Sedimentary
properties. At treatment temperatures greater than Geology 166 (1–2), 73–88.
800 °C, the magnetisation increases due to the formation Uslu, T., Atalay, U., 2004. Microwave heating of coal for enhanced
of maghemite. Following the increase in the magnetisation magnetic removal of pyrite. Fuel Processing Technology 85 (1), 21–29.
of the thermally treated pyrite, the magnetic recovery Waters, K.E., Rowson, N.A., Greenwood, R.W., Williams, A.J., 2007.
increased. An untreated sample lead to a recovery of Characterising the effect of microwave radiation on the magnetic
properties of pyrite. Separation and Purification Technology 56 (1), 9–
23%, increasing to a maximum recovery of 94% after treat- 17.
ment at 600 °C. Wills, B.A., 1985. Mineral Processing Technology: An Introduction to the
Practical Aspects of Ore Treatment and Mineral Recovery, third ed.
References Pergamon Press, Oxford, UK.
Wilson, E., 1921. On the measurement of low magnetic susceptibility by
Hunt, C.P., Moskowitz, B.M., Banergee, S.K., 1995. Magnetic properties an instrument of new type. Proceedings of the Royal Society of
of rocks and minerals. Rock Physics and Phase Relations, A London. Series A, containing Papers of a Mathematical and Physical
Handbook of Physical Constants. A GU Reference Shelf 3, pp. 189– Character 98, 274–284.
204.