Sulfatizing Roasting and Leaching

of Cobalt Ores at Outokumpu Oy

by Matti Palperi and Olavi Aaltonen

The Outokumpu Oy Cobalt Plant processes
nickel, copper, and zinc bearing cobaltiferrous pyrite
concentrate. Main operations: sulfatizing roasting,
leaching, soZution purification and recovery of co-
balt metal. Roasting is done in fluidized beds, most of
the material being fed' as caZcine. Green concentrate
is used onZy for the heat requirements, and for
maintaining a proper gas atmosphere for suljatizing.
Selection of the reactor design and the processing
steps was based on Zaboratory and pilot plant studies.
INTROilUCTION
The main principle of selective sulfatizing roasting
has long been used to convert the valuable metals
(like copper, nicke!, cobalt and zinc) to water or
dilute-acid-soluble sulfates. Most of the iron remains
as insoluble oxide. Developments in fl.uidized bed
techniques have made possible the accurate control of
process variables as temperature, material distribu-
tion uniformity and gas atmosphere. Industrial scale
applications of sulfatizing roasting have been re-
ported.'·"·" Since a number of detailed investigations
covering this field have been published,' only a
short survey of the main principles of sulfatizing
roasting should be adequate.
Chemical Reactions and States of Equilibrium
The bulk chemical reactions can be presented as
follows:
MeS,., + 3/20.,., ~ MeO,., + SO.,.,
so.,.,+ 1/20<(g) ~so.,.,
MeO,., + so.,.,~ MeSO""'
2Me0(0) + so.,.,~MeO·MeSO""'
where Me represents Co, Ni, Cu, Fe, Ca, Mg, and
other metals.
The thermodynamical data of these sulfides, oxides,
and sulfates are reasonably weil known,• and the
equilibria thus can be calculated.
The equilibrium decomposition total gas pressure
of different metal sulfates is given as a function of
temperature, curves such as those in Fig. 1 are ob-
tained. •·• From these, it can easily be seen that dif-
ferent metals can be separated by controlling the
reaction atmosphere and temperature.
Kinetics of the Reactions•"
The roasting reaction (1) can be quite rapid (as
with pyrite), but some minerals (for example,
pentlandites) tend to oxidize slowly at the tempera-
tures considered.0 ' 10 Oxidation of sulfur dioxide to
sulfur trioxide (2) is, as known, slow. The reaction
rate can be increased by using a suitable catalyst
which in the roasting of ferrous minerals is present
in the form of finely divided ferric oxide. Because the
sulfides change to sulfates through an intermediate
oxide phase, all phases can coexist within the same
particle. Actually, much more complex phenomena
occur during sulfate formation than are represented
by the bulk reaction formulas. The reaction can be
slowed by the formation of firm, protective shells
surrounding the minerals particles. This is observed
especially when sulfatizing nickel minerals. The for-
mation of sulfates can be improved by using alkaline
metal salts as catalysts.u.u
THE OUTOKUMPU PRACTICE
The Outokumpu Mineproduces (in addition to the
main copper concentrate) about 150,000 to 200,000
( 1)
metric tons annually pyrite-pyrrhotite ftotation con-
(2) centrate.18 The sulfur in this concentrate has for a
long time been used to supply the domestic paper and
(3) pulp industry, and for sulfuric acid production. This
(4) concentrate contains cobalt, nicke!, copper and zinc as
shown in Table 1.
Industrial scale recovery of these valuable metals
by chloridizing roasting was done by Vuoksenniska
Table 1-Composition of feed material and metals
in products

Fe 8 Co Ni Cu Zn 810•
MATTI PALPERI is plant metallurgist, Cobalt Plant, Outokumpu Oy,
Kokkola Works, Finland, and OLAVI AALTONEN is senior research Concentrate, % 48.4 40.3 0.67 0.37 0.28 0.40 6.0
metallurgist, Outokumpu Oy Metallurgical Research Center, Pori, Calclne,% 59.1 2.5 0.82 0.45 0.34 0.49 7.3
Dust in Tail Gases, % 49.9 0.77 0.42 0.39 0.58
Finland. Purpie ore, % 64.3 0.3 0.07 0.09 0.03 0.03 7.9

34-JOURNAL OF METALS, FEBRUARY 1971


700~-----4------~i
600
TEMPERATURE 'C
Fig. 1-Vapor pressure of metal sulfates as function of temperature.
Oy in Finland between 1936 and 1947. From then
until 1967, the calcines of this concentrate were ex-
ported. Then, a cobalt plant was erected and put in
operation at the Kokkola Works.
A General Review
In Fig. 2, a general review of the treatment of
pyrite-pyrrhotite concentrate is shown. Most of the
concentrate is still roasted in the chemical pulp in-
dustry, but dead roasting can also be done in a nor-
mal Lurgi roaster at the Kokkola Works.''
Calcine and green concentrate are sulfatized in
fluid bed roasters. After sulfatizing roasting, the solu-
ble metals are leached, yielding pregnant solution,
and iron oxide residue (purple ore). From the solu-
tion, copper and nicke! are precipitated and sent for
smelting and refining to Harjavalta."._18 A hydrogen
reduction process ( developed by Sherritt Gordon
Mines Ltd., Canada) is used to recover cobalt from
the purified cobalt sulfate-ammonium sulfate solu-
tion.
Fig. 3 illustrates sulfatizing roasting and leaching
at the Outokumpu Oy plant, and Fig. 4 shows a block
diagram of the main flows. Two separate sulfatizing
roasting lines are in parallel, combined with one
leaching system. Chemical compositions, distribution
of various materials, and elements of main interest
are shown in Tables I, II, and 111.
Materials Prehandling
Concentrate and calcine move to Kokkola by rail
to be stored in concrete bins. The concentrate, par-
tially dried at the concentrator at Outokumpu Mine,
has a moisture content of about 3% and is used with-
out further drying. To prevent the concentrate from
igniting and burning, waste carbon dioxide (from a
naptha reforming plant) is blown into the bins. The
calcines which are moistened after dead roasting in
Table II-Distribution of metals in products
Fe Co NI Cu
Dust in Tail Gases, % 0.3 0.3 0.3 0.4
Purpie ore, % 99.2 7.8 18.3 7.9
Solution,% 0.5 91.9 81.4 91.7
100.0 100.0 100.0 100.0
CONCENTRATE FROM OUTOKUMPU MINE
Co SO,
S0 2 -GAS
HEAT
~--....I.-_;llt___ _ _- - . . _... SO 2 -GAS
HEAT
PURPLE ORE
~---_;Jt--_ _ _~-~ ~~~~~t~M
L__ _ _ _ _ _ _ __j-~COBALT
Fig. 2-Fiowsheet for the treatment of Outokumpu pyrite-pyrrhotite
concentrate.
pulp and paper mills because of difficulties of dusting
during transportation, are dried immediately before
feeding into the sulfatizing reactor. Before drying,
sufficient sodium sulfate is added to the calcine. All
material is screened and coarse lumps crushed be-
fore being fed into the reactor.
The Fluidized Bed Roaster
The long, reetangular roaster unit, 7.5 meters high,
is divided into four compartments, each having a
grate area of 15 sqm (about 4 x 4 m) Fig. 5. Calcine
is fed to the first compartment by conveyor, its speed
being controlled beneath the bin. The calcine pro-
ceeds along the roaster through openings in the walls
between the compartments, and all of the product is
taken out from the fourth compartment of the reac-
tor. Green concentrate is added by rotating disk
feeders into each compartment at a rate that is suf-
ficient to maintain the correct gas atmosphere, and
the temperature (about 680°C) is controlled by
changing the feed rate of the concentrate and by in-
jecting water into the bed. Feed bunkers of concen-
trate are installed on a pressure gauge (Fig. 6). When
the weight of one bunker drops to a set lower Iimit,
it is automatically filled by the belt conveyor, which
has been previously loaded at the bin with a weighed
amount of concentrate. The procedure is repeated
automatically and the weights of concentrate sup-
plied to each bunker are counted. An estimated
mean value of spraying water for each compartment
is set by means of the temperature controller. lf the
change of temperature is slow, the correction is made
by changing the feed rate of concentrate. The amount
of spray water is changed only for rapid control of
temperature. The ratio of concentrate to calcine is
normally of order 1: 3 to 4. The heigh t of the fluidized
bed is about 2 to 2.5 meters. Air for reactions and
Table 111-Sulfur balance of sulfatizing roasting
Zn
In Out
0.5
5.6
93.9 Conccntrate 79.7% Raastergas 76.8%
Ca! eine 18.2 Dust ln Tal! Gases 0.3
Na.so, 2.1 Purpie ore 2.4
100.0 Solution 20 .5
FEBRUARY 1971, JOURNAL OF METALS-35
 RM..WAY WAGON AOTAAY Kll.N' 17 GAS BL.O'NER 25 TM1CKEPIIER 30 VA.CU,.,t.ol P\J>.IIP

"
SELT CONVEYOR 10 REOl.ER COI'NE~R 18 CHANGE VALVE 26 t-ORilCNlA.L ROTA.RY Fl.lER 1-EAJ EXCHANGER
VIaRATING SC RE E N
,.
I I SCRE W FEEC€R 19 lAlL G AS PIP€: 27 fl.TRATE TANK 32 SCUJ'TtCH STORAGE TAN..;

"
MO\'ING SELT CONVE 'tOR C'IIC.~E 20 FLUID BEO COOLER 28 FILTRATE RECEIVER PLATE AJoD FRAME FILTER

"
CALCINE ßiN FLUID 6EO ROASTER 2 I MAGNETIC SEI-'AA'A 0R 20 CONOENSER 34 1'1-..: ORE STOAAGE
CONCENTAAT:;: BIN 14 ROTARY PISTON COMPRESSOR 22 SC RUBBER
~
OISC
SUL.PHATE
FEEOER
81N
•
16
WAS TE HF. AT OOL.ER
EI.ECTAOStATIC PRECIPITATtJR
23
24
PNE'-"'1 ATIC CO !'NE~
P\JLPER

Fig. 3-Fiowsheet of the sulfatizing roasting and Ieeehing at the Outokumpu Oy eobalt plant.

with the gases. The gases pass from the top of the
AS reactor, through a battery of cyclones and into the
waste heat boiler. Dust from the cyclones is immedi-
ately refed, by screw feeders, into the beds of the
second, third and fourth compartments. Gases are
cooled from 650°C to 330°C in the toiler which re-
CALCINE covers about 140 Mcal per ton of initial concentrate as
steam at 70 atm. Because of the relatively low tem-
peratures of the inlet gas there is no radiation section,
but only a horizontal straight flow convection boiler
with forced water circulation.
The gases are cleaned in an electrostatic precipita-
tor operating at about 330°C. Two chambers are in
series (with two selenium rectifiers, 60 kV, 200 mA)
for each gas line. Flue dust from boiler and electro-
static precipitator is also refed into the reactor.
Taking the effect of accumulation of fines into ac-
count there is a circulating dust load of about 55 to
60% related to the total feed of the reactor. The ef-
ficiencies of dust recovery equipment are as follows:
Cyclones 85-87%
Boiler 17-19%
Electrostatic
Precipitator 95-96%
The overall efficiency of dust removal is about
WA T 1;111
99.5%.
The cleaned gasses are transferred to the neighbor-
PURP LE ORE ing sulfuric acidplant of Rikkihappo Oy. Composition
Fig. 4--Bioek diagram of sulfatizing roasting and Ieeehing at the
of the dry gas is about:
Outokumpu Oy eobalt plant.
so. 4.8%
fluidization is supplied by rotary piston compressors, so. 0.8%
one for every compartment of the reactors. o. 13.0%
Dust Handling and Heat Recovery N. 81.4%
Concentrate and calcine are relatively fine about Cooling and Magnetic Separation
50 to 60%-200 mesh. In practice, an average super- All of the sulfatized product, including the fines, is
ficial fluidizing gas velocity of 0.25 to 0.30 meters per taken out of the last compartment of the roaster. The
sec for the fluidizing gas is required. This means that sulfatized product is cooled by fluidized bed coolers,
a large fraction of the bed material is carried over two coolers with water cooled mantels are used in

36-JOURNAL OF METALS, FEBRUARY 1971


Fig. ~utokumpu fluidized bed sulfatizing roaster.
parallel. The bed in the cooler is maintained to
about ll0°C by controlling bed height and the
amount of cooling water. Dust from the coolers is
recovered by scrubbing.
After being cooled, the incompletely sulfatized
fraction of the product (which is magnetic) is sep-
arated by Laurila high intensity, dry magnetic
separators, and refed with the fine dusts into the
reactor. The operation of the magnetic separation as
weil as the progress of the sulfatization, are con-
trolled simply by a saturation magnetization analyzer
(Satmagan) marle by Outokumpu Physical Research
Laboratory.
Leaching
The counter current leaching and washing sys-
tem consist of two thickeners in series. After them
are six horizontal rotary vacuum filters connected in
parallel, Fig. 3. ·Pulp density of the underflow is
automatically controlled.
The overflow from the second thickener is used to
quench the sulfized product. The resultant slurry is
pumped into the first thickener, the overflow of which
is the pregnant solution. Underflow of the first thick-
ener is repulped with the wash solution from the
filters, and fed to the second thickener. From the
second thickener, the underflow is divided on to the
filters, where the iron oxide residue undergoes four-
step counter current washing. Total area of each filter
is 20 sqm. Precoat formed of coarse iron oxide ma-
terial is used on the filter cloth. The fresh wash water
is sprayed on the last suction section of the filters. To
keep a desired pH value during the washing,
some sulfuric acid is added. (This prevents precipita-
tion of metal hydroxides.) When removed by screws
from the filters, the cake has a moisture content of
12 to 15%. By means of belt conveyor system, the
purple ore can be stockpiled for shipping as such or,
it can be dried in aseparate rotary kiln.
The soluble fractions of all metals in the purple
ore can be kept below 0.01% each. Contents of metals
in the pregnant solution naturally vary with the
variations in the concentrate. A typical analysis con-
Fig. 6--Automatic concentrate feed and temperature control of the
roaster.
tains: Co, 20 g per 1; Ni, 9 to 10 g per I; Cu, 8 to 9 g
per 1; Zn, 11 to 13 g per 1; and Fe, 7 to 9 g per 1. Also,
metals like magnesium, aluminium, calcium, etc. are,
at least, partially sulfatized and pass into the solution.
SPECIAL FEATURES
A relatively large laboratory and pilot plant de-
velopment study for this Cobalt Plant was done at
the Metallurgical Research Center of Outokumpu Oy.
This resulted in special decisions in the process, and
in the design of the equipment.
The approximate conditions for sulfatizing roasting
were already known due to theoretical calculations
and earlier investigations. Earlier tests, run with two
fluidized bed reactors, gave promising results at about
680°C temperature and widely variable proportions
of calcine and concentrate including roasting with
only concentrate fed. To obtain more experience, a
pilot plant roaster of 5 sqm (1.25 x 4 m) grate area
was built. It also had complete equipment for dust
removal and waste heat recovery from the roaster
gases.
The Process
Roasting reactions of sulfide concentrate are, in
general, strongly exothermic. Therefore, the excess
heat generated in a roaster has to be eliminated by
direct evaporating of water, by indirect cooling, or by
feeding inert cold material. In the Outokumpu sul-
fatizing roaster, almost dry concentrate and calcine
is used. To obtain the calcine, green concentrate has
to be dead roasted separately, in normal roasters
when in the case of (for BASF type roasters) the
heat from the bed is recovered as high pressure
steam. The separate dead roasting of a major part of
the concentrate gives an advantage in flexible utiliza-
tion of the contained sulfur.
In the sulfatizing roaster, green concentrate is used
only to obtain the gas atmosphere required for sulfa-
tization and to maintain the heat balance of the reac-
tor. Even when using three to four times more
calcine than concentrate, good sulfatizing results are
achieved.
The fine particles carried along with the gases are
rapidly roasted and sulfatized yielding a good con-
version to soluble metals in dusts. But the sulfating
of iron becomes also high due to the increasing
stability of ferric sulfate with decreasing tempera-
ture in the gas handling system. Thus, the dusts can-
not be leached as such. When fed back to the reactor
FEBRUARY 1971, JOURNAL OF METALS-37
at 680°C, the iron sulfates decomposes. This adds the
sulfatizing effect, and the fine ferric meide formed
catalyses the formation of sulphur trioxide. The fine
particles also improve fluidization properties of the
bed.
Formation of iron sulfates is eliminated by rapid
cooling of the product by fluidized bed coolers,
where the fluidizing air also purges the sulfatizing
gases from the bed.
To obtain a good metal recovery, the sulfatizing as
well as leaching and washing have to be effec-
tive. The amount of water, which can be used, how-
ever, is limited, because the metal content in the
pregnant solution must be kept relatively high.
Therefore, a multistage countercurrent washing sys-
tem is used. A high-quality purple ore with low
metal content is obtained.
A New Grate
With the small reactors it was already observed
that, for a good fluidization and sulfatizing, it is es-
sential to provide even distribution of fluidizing air.
This required a grate with closely divided openings
and relatively high pressure drop. In the pilot plant
reactor, and then in full scale, grates with a pressure
drop of about 20 to 30% of the total in the grate and
bed are adequate. A special type of grate was de-
veloped,111 consisting of long boxes, pushed through
openings in the side walls of the reactor, close to each
other on a stationary bottom plate (see Fig. 4). Ad-
vantages include the easy handling of the relatively
small grate units, good sealing, and easier operation
and maintenance of the reactor and grate.
The Fluid Bed
Much published data exists concerning the mass
and heat transfer in fluidized beds. To get informa-
tion in this particular situation, tracer tests in the
pilot plant reactor (repeated for comparison later in
the full scale plant) and tests with various trans-
parent models were made. Practical use of these tests
was made tagether with other data to determine the
velocity of fluidization air, to develope the grate, and
to select the feeding and discharging points of the
reactor.
By dividing the pilot plant reactor into compart-
ments in series, the number of short circuiting par-
ticles was greatly reduced, but the use of more than
four compartments did not produce significant im-
provements. Dividing of the reactor into separate
compartment~qual to several reactors in series-
provides other advantages. Of most value are pos-
sibilities for separate control temperature and gas
composition in each.
One of the diffi.culties in the pilot plant reactor was
the build-up of materials on the reactor walls in the
bed zone. Though these accretions were friable, they
were hard enough to remain as lumps when falling
down on the grate. The roaster gradually filled with
nonfluidizing material. When the walls were built
with a slight inward inclination, this phenomenon
disappeared. This design was successfully used in
the full-scale plant."" Build up of significant accretions
on the walls of the upper part of the reactor has not
been noticed.
38-JOURNAL OF METALS, FEBRUARY 1971
Magnetic Separation
It was observed that a mean retention time of
about 25 hr for sulfatizing the material was re-
quired to give desired high recovery of metals into
soluble form. It was noticed, however, that the main
part of the metal was sulfatized relatively rapidly.
As long as a particle is not fully oxidized, sulfatiza-
tion is incomplete, and the particle is magnetic. This
incompletely sulfatized fraction should be separated
from the bulk material flow by magnetic separators,
and recirculated to the reactor. In this way, the re-
quired mean retention time and the volume of reac-
tor could be reduced about 50%.
SUMMARY
The fluidized bed sulfatizing roasting and leaching
process, described in this paper, has been in operation
for three years at the Outokumpu Oy Cobalt Plant.
The main characteristics of this practice are:
Feed consists mainly of oxide materials, while sul-
fide concentrate is used for controlling heat and sul-
fatizing gas atmosphere only.
The essentially dry feed, the recirculation of dusts,
the special grate and other design details give good
fluidization and sulfatization.
Dividing the reactor into four compartments
minimizes the amount of short circuiting.
Good sulfatizing result is also assured by the use of
magnetic separation of the product and recirculation
of the partially sulfatized, magnetic fraction.
By accurate control of the process variables, in-
cluding the fluidized bed cooling of the product, the
solubility of iron becomes low, while the degree of
sulfatization of desired metals is high.
Effective counter-current leaching and washing as-
sures a pure leaching residue, purple ore, and high
recovery of the. valuable metals in the solution.
REFERENCES
1 Theys, L. F. and Lee, L. V., Sulfate Roasting Copper-Cobalt Sul-
fide Concentrates, JouRNAL OF METALS, 1958, Vol. 10, No. 2, pp. 134-136.
• Theys, L. F., Progress Report on Roasting Copper-Cobalt Sulfide
Concentrates -JouRNAL OF METALS, 1958, Vol. 10, No. 7, p. 476.
• Queneau,'P., ExtTacttve Metallurgy of Copper, Nickel and Cobalt,
1961, pp. 55-66.
• Ingraham, T. R. and Kerby, R., Roasting in Extractive Metallurgy
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205-210.
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"" Finnlsh Patent Appllcatlon No. 3542/68.