Minerals Engineering, Vol. 13, No. 13, pp.

1319-1328, 2000
Pergamon © 2000 Elsevier Science Ltd
All fights reserved
0892,--6875(00)00115-1 0892-6875/00/$ - see front matter

SO2/O2 AS AN OXIDANT IN HYDROMETALLURGY*

W. ZHANG II, P. SINGH I and D.M. MUIR ~

Dept. of Chemistry and Mineral Science, Murdoch University, WA 6150, Australia
Email: wzhang @central.murdoch.edu.au;
§ CSIRO Minerals, PO Box 90, Bentley, WA 6982, Australia
(Received 4 May 2000 ; accepted 20 July 2000)

ABSTRACT

Oxygen mixed with S02 can function as a powerful oxidant in acid solution. This paper summarises
basic studies on the mechanism of $02/02 oxidation, the kinetics of oxidation in acidic media, and
potential applications in hydrometallurgy. The SOz/02 system readily oxidises Fe(lI) to Fe(IlI) and
provides a simple method of regenerating Fe(III) for leaching minerals like Cu2S or U3Os. It also
oxidises As(IIl), which in the presence of iron(Ill) enables a stable ferric arsenate compound to be
precipitated.. A method for the leaching and removal of arsenic from smelter fumes is proposed.
Oxidation of Mn(II) to Mn(III)/Mn(1V) oxides by S02 /02 allows manganese impurity to be removed
from leach liquors and electrolytes. © 2000 Elsevier Science Ltd. All rights reserved.

Keywords
Mineral processing; oxidation; leaching; reaction kinetics; hydrometallurgy

INTRODUCTION

It is well known that pure sulphur dioxide is a reducing agent used in a wide range of industries [Zhdanov
(1973), Well and Sandier (1997)]. In hydrometaUurgy, pure sulphur dioxide solutions are used for leaching
of manganese ores [Pahlman and Khalafalla (1979), Abbruzzese (1987), Kanungo and Das (1988), Tindall
(1998),] and certain metal sulphides under reducing conditions [Tiwari (1976), Thom and Waters (1978),
Sohn and Wadsworth (1980), Brual et al. (1983),]. It also oxidises at an anode and acts as a depolariser in
the electrowinning of copper from leach solutions containing iron [Pace and Stauter (1974), Subbaiah et al.
(2000)]. However when combined with oxygen over a particular range of compositions, and in the presence
of certain transition metals, sulphur dioxide acts as a stronger oxidising agent than oxygen [Tiwari et al.
(1978), Devuyst et al. (1982), Sato et al. (1984), Krause (1988), Nami (1988), Kwateng (1990)]. Some
reported applications of the SO2/O2 mixture in hydrometallurgy are summarised in Table 1.

Whilst INCO [Devuyst et al. (1982), Ettel et al. (1979)] has successfully exploited the use of SO2/O2 as an
oxidant for cyanide in alkaline media, there has been relatively little development in the use of SO2/O2 as
an oxidant for metal ions in acidic media. Initial studies on the oxidation of Fe(II) were conducted around
1915 [Du Faur (1915)] and later between 1919 and 1927 [Ralston (1927)]. Although a number of other
studies on the oxidation of Fe(II) with SO2/O2 have been carried out in recent years, there is inconsistency
in the kinetic observations and the proposed mechanisms. This study therefore focuses on gaining a
fundamental, understanding of the iron and manganese catalysed SO2/O2 oxidising systems in acidic media

* Presented at Hydromet 2000, Adelaide, Australia, April 2000

1319
1320 W. Zhang et al.

and examines three selected processes in hydrometallurgy where this system may be applied more
efficiently than oxygen. These processes involve the leaching of chalcocite, the oxidation and precipitation
of arsenic from arsenical fume leachates, and the oxidation and precipitation of manganese impurity from
nickel/cobalt solutions. These represent widely different yet potentially significant applications.

TABLE 1 Applications of SO2/O2 systems in hydrometallurgy

Working
Systems Oxidation Products Potential Applications [refs]
pH range
Leaching of metal sulphides
Fe 2+~ Fe 3+ [*]
Fe-SO2/O2 0-3
S(IV) ~ SO42-/$2062- Oxidation of As(III)
[**]
Mn 2+--> Mn(III)/Mn(IV) Oxidative Precipitation of Mn
Mn-SO2/O2 3-6
S(IV) ~ 5042-/52062- [this study]
Ni(II) ~ Ni(III) Production of Ni(OH)3
Ni-SO2/O2 7-8.5 S(IV) ~ SO42- [Ettel et al. (1979)]
CU+ ~ Cu 2+
Oxidation of CN-
Cu-SOz/O2 9-10 S(IV) --~ SO42- [Devuyst et al. (1982)]
CN- ~ CNO-
*: Tiwari et al. (1978), Devuyst et al. (1982), Sato et al. (1984), Krause (1988), Nami (1988), Kwateng
(1990), this study.
**: Nishimura et al. (1996), Wang et al. (1998), Khoe et al. (1997), this study.

KINETICS AND MECHANISM OF Fe(II) OXIDATION WITH SO2/O2

The kinetics of the S 0 2 / 0 2 oxidising system were studied under a range of conditions: 0-0.5 M Fe(II), 0-
33% SO2/O2, 25-80°C, pH 0-3. Figure 1 shows typical plots for Fe(II) oxidation versus SO2/O2 ratios.

0.1
4%so , I
0.08
2

'ii°i
~-~ 0.06
Lr~
.~ 0.04
©
'i ...........
0.02
Pure 0 2

0 30 60 90 120
Tmle, rrm

Fig. 1 Typical plots showing rate of oxidation of Fe(II) with varying % SO2. (80°C and pH 0.5).

As can be seen in Figure 1, the oxidation of Fe(II) is extremely slow with O2 alone (0% SO2). With SO2/O2
mixtures, the oxidation of Fe(II) is dramatically promoted, and the oxidation rate increases with SO2 up to
an optimum SO2/O2 ratio above which the oxidation rate decreases due to significant reduction of Fe(III)
by excess SO2. The optimum SO2/O2 ratio decreases with increasing temperature due to the significant
decrease in 02 solubility. It also varies with pH, due to variation in the fraction of reactive sulphite and
bisulphite species, and with the rate of 02 mass transfer. In this work it is found that both Fe(III) and S(IV)
 SOyO2 as an oxidant in hydrometallurgy 1321

species are involved in the initial step of oxidation and that the rate is first order with respect to [Fe(III)] up
to 0.02 M.

A comparison of the kinetic features observed in the oxidation of Fe(II) with SO2/O2 and with 02 are
summarised in Table 2.

TABLE 2 Kinetic observations in Fe(H) oxidation by SO2/Oz and comparison with 02

Kinetic Observations
Factor Fe-SO2/O2 Fe-O2 [refs#]
r = kl [Fe(III)] [S(IV)]/f([H+])
Empirical rate
up to 0.02M [Fe(III)] and optimum SO2/O2 ratio, r = k2 [Fe2+]2[Oz]
expression
f([I-I+]) is function of [I-I+]
Decrease with increasing temperature, also depends
Optimum SO2/O2 ratio
on pH and 02 mass transfer
EAet (kJ/mol) 22 at 40-80 ° 51-74 at 25-100°C
Reaction Product orS(IV)
< Optimum 502/02 ] SO4z- only, and tFe(IIX)]:tSO?-a = 2 I
> Optimum SCh/O2 [ [$2062-]/[504 z-] ratio increase with SO2/O2 I
Refs~: George (1954), Huffman and Davidson (1956), Cornelius and Woodcock (1958), McKay and
Halpern (1958), Keenan (1969), Mathews and Robins (1972), Chmielewski and Charewicz (1984),
Vraca and Cerovic (1997).

As can be seen in Table 2, the kinetics of Fe(II) oxidation with SO2/O2 is totally different from that with
02, indicating an entirely different mechanism. It is observed that the rate of oxidation of Fe(II) with
SO2/O2 is markedly inhibited by addition of small amounts of hydroquinone which has been reported to be
an effective free radical schevenger [Brandt et al. (1994), Huie and Neta (1985)]. Furthermore, the
maximum potential measured for the Fe--SO2/O2 system is about 1.4 volts at pH 2 which is well above the
standard potential of O2/H20 couple, suggesting the formation of peroxy intermediate species.

A radical chain lreaction mechanism is proposed in this study with the following steps [Zhang et al.
(2000(a))].

SO2.H20 ,~ HSO3- + H + (1)

HSO3- ~' 5032- + n + (2)
Fe 3+ + 5032- ,0~FeSO3 + (3)
FeSO3 ÷ --~ Fe2+ + SO3"- Slow (4)
SO3"- + 02 -~ SOs"- Fast (5)
Fe 2+ + SO5"- + H + ~ Fe 3+ + HSO5- Fast (6)
2Fe2÷+ HSOs- + H+ ~ 2Fe3*+ SO42-+ H20 Fast (7)
2HSO5- -~ SO42- + 02 + 2H+ (8)

It involves the slow initial formation of a ferric sulphite complex and decomposition to produce sulphite
radical SO3"-. This is followed by a fast reaction with 02 to form a peroxo-monosulphate species SOs'-,
and subsequently HSOs- which are responsible for the oxidation of Fe(II) and sulphite species.

The derived rate expression essentially agrees with the observed rate law and the kinetic observations can
be rationalised based on the proposed mechanism.

EFFECT OF COPPER ON OXIDATION OF Fe(H)

The effect of copper on the oxidation of Fe(II) by 502/02 has been investigated in the range 0.1--0.5 M
Fe(II)/Cu(II). Copper catalyses the oxidation by 02 alone and the reaction exhibits a second order rate with
respect to Fe(II) concentration. A mechanism that involves the initial formation of complex CuO2+ and
1322 W. Zhanget al.

generates H202 as the oxidant for Fe(II) has been proposed, as discussed by Zhang et al. (2000(b)). In
contrast, the presence of > O.1M Cu(II) inhibits the oxidation by SO2/O2, presumably due to its effect on
the decomposition of the peroxy intermediate species.

Figure 2 compares the effect of Cu(II) on the oxidation of Fe(II) with SOjO2 and with 02 alone in the
presence of 0.5 M CuSO4 at 80°C. The rate of oxidation by the Fe/Cu/SO2/O2 system is much higher than
the corresponding Fe/Cu/O2 system. The presence of Cu(II) catalyses the Fe/O2 system quite significantly,
however, its presence in large amount has the opposite effect on the Fe/SO2/O2 system. The effect of Cu(II)
on the Fe/Cu/SO2/O2 system is characterised by two simultaneously occurring mechanisms. As can be seen
in Figure 2, the oxidation of Fe(II) in the Fe/Cu/SO2/O2 system is initially dominated by the Cu/O2
mechanism, indicated by parabolic kinetics, but is overtaken by the Fe/SO2/O2 mechanism as the
concentration of Fe(II) falls, indicated by linear oxidation kinetics in the later stages. Thus it may be
concluded that the Cu/SO2/O2 system oxidises Fe(II) at a faster rate than the Cu/O2 system, particularly at
low concentrations of Fe(II), which should maintain higher Fe(III) levels during continuous oxidative
leaching of copper bearing minerals or concentrates.

0.I j" SO2/O2,~k/ / ~ l n i t i a l l y 0.1M Fe(ll)

0.08

0.04
~ ~ 0.06

0.02
/ / Cu-SO2/O2

o2 Only

I I I

0 20 40 60 80 100
Time, min

Fig.2 Comparison of oxygen systems on rate of Fe 2÷ oxidation. (initial 0.1 M Fe 2÷ , 0.5M CuSO4; 2%
SO2/O2; pH 1.5; 80°C).

LEACHING OF COPPER SULPHIDES WITH Fe/SO2/O2

The ferric leaching of naturally occurring chalcocite and chalcocite concentrate was compared at low Fe(II)
concentrations (<0.1 M), with Fe(III) regenerated by SO2/O2 and 02. As can be seen in Figure 3, copper
extraction after 7 hours with SO2/O2 is significantly higher than that with 02 alone.

The results shown in Figure 4 indicate that under similar conditions for the Fe/SO2/O2 system, a higher
concentration of Fe(III) is maintained in the solutions as compared to the Fe/O2 system. This confirms that
the regeneration of Fe(III) by SO2/O2 during the leaching process is much faster than by 02. It has been
reported earlier that at higher [Fe(II)], the rate of Fe(III) regeneration by both Cu/O2 and Fe/SO2/O2 is
similar (Zhang e t al. (2000 b)). Furthermore the rate of second stage leaching of predominantly covellite
(CuS) is slower and less dependent upon Fe(III) concentration. However, it is also observed that the
presence of 0.5M CI- (NaC1) enhanced the recovery of copper from leaching of Cu2S by about 5% using
either 502/02 or 02. This agrees with the observation by Cheng and Lawson (1991) with 02 as the oxidant.
 SOYO2 as an oxidant in hydrometaUurgy 1323

100

80

d~ 02 Only
60

40
7 Hours Leach, 80"C
20

I I I I

0 0.02 0.04 0.0,6 0.08 0.1

Total IronConcentration,M

Fig.3 Effect of Fe(II) concentration on Cu extraction after 7 h leaching with SO2]O 2 and with 0 2 alone.
(4% Pulp density; 80°C; pH 1).

100
4 ° ° I, iFirst stage leach / o

80

60
::'7'
20 ~ - _ |

0 m ~ ~'~P I I I I I

0 60 120 180 240 300 360 420

Tine, rain

Fig .4 Comparison of %Fe(III) present during leaching of Cu2S and continuous sparging by either
SO2/O2 or 02. ( initial 0.1 M Fe(II)).

It is found that about 2 moles of H2SO4 is consumed using 02 alone when about 0.9 mole of Cu2S is
leached in the above experiments. This measured ratio is very close to the stoichiometric requirement
according to equettions (9) and (10)

Cu2S + 4Fe 3+---}2Cu2++ 4Fe2+ + S° (9)

4Fe 2+ + 02 + 2H2SO4 --~ 4Fe 3++ 2H20 (10)

However, little H2SO 4 w a s required for the similar amount of Cu2S leached with SO2/O2, agreeing with the
following reactions for generation of Fe(III) and H2SO4:

2Fe2+ + 502/02 --~ 2Fe3+ + 5042+ (11)

502/O2 -F n20 "+ H2504 (12)
1324 W. Zhanget al.

Thus the main benefit with SO2/O2 appears to be the simultaneous production of H2SO4 needed for leaching
and oxidation, and leaching with lower iron in the circuit.

As(III) OXIDATION WITH SO2/O2 AND APPLICATION TO THE PROCESSING OF

ARSENICAL SMELTER FUME

The oxidation of As(III) is found to occur at the same time as the oxidation of Fe(II) using the SO2[O 2
system and has a similar activation energy [Zhang e t al. (2000(c))]. Khoe e t al. (1997) also found that UV
light catalysed the oxidation of Fe(II) and As(III) using 02 alone. Compared with the SO2/O2 system, the
rate of oxidation of As(III) by UV/O2 in the presence of trace Fe(III) is found to be similar at low initial
concentrations of As(III) around 0.1 mM, but much slower at initial As(III) concentrations above 6.5 mM
as shown in Figure 5.

100

with F e / S ~
80

t,¢)
60
<
~D
.o~ 40
©
20

,.

0 20 40 60
Tune, min

Fig.5 Comparison of oxygen systems for oxidation of As(III). (6.5 mM As(III), 10 mM Fe(III); 25°C;
pH=l.5).

Table 3 compares the kinetic features of As(III) oxidation by Fe/SO2/O2 and UV/Fe/O2.Fundamentally the
Fe/SO2/O2 system is more suitable for oxidising more concentrated As(III) solutions found in
hydrometallurgical processes. However, in the presence of low concentrations of Fe(III), the combination
of both SO2/O2 and UV light, offers faster kinetics for the oxidation of dilute As(III) solutions than either of
the individual systems.

TABLE 3 Comparison of kinetic features of As(HI) oxidation

Oxidising
Fe/SO2/O2 UV/Fe/02
system
[As(III)]
Rate increases over range: 0-100 mM rate increases over range: 0-2.5 mM
(initial)
rate increases over range: 0-1.5 mM
[Fe(III)] Rate increases over range: 0-10 mM
excess [Fe(III)] reduces the rate*
rate decreases with increasing
Temp. Rate increases over range: 25-50°C
temperature above 25 *C*
rate increases with decrease
pH Rate increases over range: pH 0-3
in pH from 3 to 2*
Rate law d[As(III)]oc [Fe(III)][As(llI)]°.5 _ d[As(l]/)] oc[Fe(m)]°.5[As(lII)] °.z5
(empirical) dt dt
* From ANSTO Patent [Khoe e t al. (1997)]
 so7]02 as an oxidantin hydrometallurgy 1325

In order to apply this observation, a method for removing arsenic from a typical smelter fume containing
iron and valuable niickel has also been investigated in this study [Zhang et al. (1998)]. Smelter fume often
contains arsenic as As203 as well as significant amounts of base metals and iron. Hence the general method
consists of dilute ac,id leaching, oxidation of As(III) and Fe(II) using SO2/O2, and precipitation of iron(HI)
arsenate as shown in Figure 6.

Fume

STEP 1 Dilute | I Recycle

H2SO4 LEACH 4 .............................. .-.-..
.... ' Species
llo o o m a l l l a l i i o e q l m g w i w m mloom m m mQ
i
lie i
- t ~,T.2+ ~ 2+ :

Smelter Residue _.[ i r~l+,t~o+ •

~ [..... : Fe /Fe -
~FLiquor I i...A,s!.V).!..A:s..(!I!!. j
iii iiiiii Oxidation
STEP 2 SO2/O2 d [ ..... .... i;;';:":; "Fe
. . . . . .3~"
..
CO- I ~ As(III)-~As(V) i
.PRECIPITATION u. ~......................... ~l~lemllllmm•wmmmmemoelIQliO
..

iii i T ~ ) e l e e Q m l l o l l m m w l l l ~
...I): :
Tailings "*"l Precipitate~ : FeAsO4 •
• •

F Liquor [ ".................. "

........ . . m e. . m ,. m t . • io .l• • n

Bleed and Rer~ove Nn, Co ......... "

Fig.6 Proposed flowsheet for processing arsenical smelter fume.

For this particular nickel smelter fume with a high Fe:As ratio, dilute H2SO4 extracted 25-30% of the
As(III) and sufficient Fe(II) to allow oxidation and precipitation of FeAsO4 to occur at pH 3.3 with minimal
neutralisation cost. By using SO2/O2 as the oxidant, the reaction could be carded out rapidly at 30-38°C
unlike oxidation with 02. This approach appears attractive to treat smelter fumes containing significant
levels of arsenic and excess iron phases that can be leached with SO2 or dilute sulphuric acid.
1326 W. Zhang etaL

OXIDATIVE PRECIPITATION OF MANGANESE (H) WITH SO2/O2

The kinetics of oxidation of Mn(II) with SO2/O2 and subsequent precipitation of MnO2 have been
investigated in the pH range 1-6 and temperature range 25-80°C. It is found that the mechanism of
oxidation of Mn(II) is similar to the Fe(II) oxidation, with Mn(III) acting as the catalyst which
disproportionates almost spontaneously to MnO2/Mn203 [Zhang (2000)]. The oxidation of Mn(II) is slow at
pH < 3, but at pH > 4 Mn(II) is readily oxidised. When applied to nickel laterite leach solutions containing
Co and Ni, the oxidative precipitation of Co as Co(OH)3 became significant at pH > 4 and the precipitation
of Ni as Ni(OH)3 was significant at pH > 6.5. Therefore, the selective oxidative precipitation of Mn occurs
at pH 3-4, and provides a useful means for the removal of manganese impurities from nickel/cobalt leach
liquors.

Figure 7 shows the precipitation of Mn from a synthetic Co sulphate leach liquor containing 0.1M Co(II)
and 0.01 M Mn(II)/Ni(II)/Fe(II)/Cu(II)/Zn(II). As can be seen, 10 mM manganese was selectively
precipitated from nickel and cobalt within ten minutes in the pH range 3--4 with less than 1% co-
precipitation of Ni and Co. In the presence of 0.01M Fe(II), iron was oxidatively precipitated as Fe(OH)3
before manganese.

100 ~" Mn * /I
1

80 /Cu
I0 minutes
for each run /
..~
~o 60 at 5 0 " C /
40
20
Ni, Co
m
"1= I I I I

3 3.5 4 4.5 5 5.5 6

pH

Fig.7 Effect of pH on the precipitation of Mn, Cu, Zn and Ni from a Co leach liquor. (10 minute
oxidation with 2% SO2/O2; 50°C).

SUMMARY

The results of this study demonstrate that SO2/O2 can function as a strong oxidant in acidic solution for the
oxidation of Fe(II), Mn(II) and As(III). It can also function as a means of generating H2SO4 from the
autoxidation of SO2 once Fe(II) is oxidised. The SO2/O2 system, catalysed by iron(III) or manganese(III)
should be useful for a number of other hydrometallurgical applications. For example, for generating Fe(III)
and leaching copper sulphide minerals or uranium(IV) minerals requiring both oxidant and H2SO4. It is also
useful for the oxidative precipitation of As(III) and Fe(II) from leach solutions as stable ferric arsenate, and
for the oxidative precipitation of Mn(II) as MnO2 from Co(II) and Ni(II) leach liquors at around pH 3.

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