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Control of autoclave scaling during acid pressure leaching of nickeliferous

laterite ore

Article  in  Metallurgical and Materials Transactions B · January 1984

DOI: 10.1007/BF02657373

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Control of Autoclave Scaling during Acid
Pressure Leaching of Nickeliferous Laterite Ore
P. B. QUENEAU, R.E. DOANE, M.W. COOPERRIDER, M. H. BERGGREN, and P. REY

An operating problem encountered at the Moa Bay operation in Cuba, where nickeliferous laterite ore
is processed by sulfuric acid pressure leaching, is the formation of alunite and hematite deposits on
the autoclave walls. The AMAX Extractive Research & Development, Inc., metallurgical laboratory
(Golden, Colorado) has made substantial improvements in the Moa Bay process in the area of metal
recovery, energy consumption, and feed versatility. One of the advantages of AMAX's process is its
ability to treat substantial portions of nickel- and magnesium-rich serpentine while maintaining acid
utilization efficiency. Scale formation is minimized by combining staged acid addition with vigorous
agitation and 270 ~ operation. This paper describes how advantage can be taken of MgSO4" XH20
precipitation both to inhibit alunite scaling and to disperse hematite scale within the MgSO4" XH20
matrix. Cooling the autoclave from its 270 ~ operating temperature down to 180 ~ takes advantage
of the reverse solubility of magnesium sulfate. The magnesium dissolves, liberating entrained hema-
tite, thus providing a means for control of autoclave scale with minimum process disruption.

I. INTRODUCTION tides by atmospheric leaching of roasted high-Mg ore. The

clear liquor goes to sulfide precipitation, and the solids
THE AMAX sulfuric acid leaching process involves
residue is pumped to the high-pressure leach to complete the
countercurrent digestion of nickeliferous laterite ore at
dissolution of its metal values. 6
high pressure and at atmospheric conditions.t After solid/
One of the operating problems that must be addressed in
liquid separation, the nickel and cobalt values are pre-
design of the pressure leaching system is scaling of reactor
cipitated by hydrogen sulfide ~5 and refined into nickel and
cobalt metal. 16Research at AMAX began in the early 1970's surfaces.7 The formation of alunite and hematite deposits on
the autoclave walls has been well documented by Russian
at AMAX's Extractive Research and Development Labora-
authors describing the Moa Bay operation. 7's Less recog-
tory in Golden, Colorado, using as a model Cuba's Moa Bay
nized is the potential for formation of MgSO4" U 2 0 and
laterite acid pressure leaching operation. 2 Substantial im-
silica scale. These latter compounds can become trouble-
provements were made over the Moa Bay process, particu-
some when higher grade nickeliferous laterites containing
larly in the areas of metal recovery, energy consumption,
and feed versatility.3'4'5 greater amounts of magnesium silicate are treated.
One of the advantages of AMAX's process is its ability
A block diagram of the AMAX acid leach process is
to process substantial portions of nickel-rich serpentine
shown in Figure I. The ore is first screened into two size
(Mg3Si2OT'2H20) while maintaining acid utilization effi-
fractions. The coarse fraction, being higher in magnesium,
ciency. 91~ The focus of the present work is upon the depo-
is dried and calcined to improve its reactivity.17 It is then
sition of MgSO4"XH20 o n the interior surfaces of the
used for pH adjustment of the pregnant solution before the
pressure leach vessel. The interaction of these magnesium
resulting leach residue is added to the high-pressure leach.
sulfate deposits with the alunite and hematite scale is ex-
The fine fraction is pumped directly to high-pressure leach.
amined. Causes of the deposition are detailed, and means
Optionally, the ore may be mined as separate "L" (limonite)
to minimize the rate of deposit buildup are discussed.
and "S" (serpentine) fractions and handled in separate ore
preparation circuits.
The high-pressure leach consists of a multistage pressure II. AUTOCLAVING OF LATERITE ORES
vessel equipped with turbine agitators. Sulfuric acid is HIGH IN MAGNESIUM SILICATES
added after the slurry is preheated to operating temperature.
The heating of the slurry is carried out in several stages The first commercial operation to utilize sulfuric acid
using steam recovered from the multistage flashing, as well pressure leaching to process nickeliferous laterite ore was
as high-pressure makeup steam. The flashed slurry is sub-
jected to countercurrent decantation (CCD). Neutralized
barren solution is used to displace the pregnant liquor from
the tailings. Residual acid in the pregnant solution is re-
Acid~Leach~~ Slurry Tailings

duced to an acceptable level for precipitation of metal sul-

P. B. QUENEAU, formerly with AMAX Extractive Research and Devel-

opment, Inc., Golden, CO, is now Technical Assistant to the President,
Hazen Research, Inc., Golden, CO 80403. R.E. DOANE, Process En-
gineer, M.W. COOPERRIDER, Mineralogist, and M.H. BERGGREN,
Research Metallurgist, are with AMAX Extractive Research and Devel- CoS
opment, Inc., Golden, CO 80403. P. REY, formerly with COFREMMI,
Paris, France, is now retired, Paris, France.
Manuscript submitted October 7, 1983. Fig. 1- - F l o w pattern of the AMAX acid leach process.

METALLURGICALTRANSACTIONS B VOLUME 15B, SEPTEMBER 1984--433

Freeport Sulfur's Moa Bay plant in Cuba. The Cuban gov- Table I. Autoclave Feed Composition,
ernment expropriated this plant in 1960 shortly after startup. Feed Rate, and Product Composition
The ore contained about 48 pct Fe, 5 pet AI, 4 pct SIO2,
Campaign
1.4 pet Ni, and less than 1 pet Mg. It was wet screened at
20 mesh, thickened to 45 pct solids, and pressure leached in 1 2 3 4
pachucas at 240 to 250 ~ with sulfuric acid. To attain HPL Feed*
95 pet nickel extraction in 60 to 90 minutes, 0.22 pound
of concentrated sulfuric acid per pound of ore was pumped Mg, pct 2.6 3.2 5.0 6.9
Fe, pct 40 38 33 27
into the first autoclave of a four autoclave train. The preg-
A1, pct 4.7 4.8 3.7 3.3
nant liquor assayed approximately 6 grams per liter Ni, Solids, kg/h 400 380 350 280
0.6 grams per liter Co, 3 grams per liter Mg, 2 grams per
liter AI, and 30 grams per liter H2504. The low magnesium ALR Feed*
content of the ore gave little incentive to incorporate an Mg, pct 3.7 4.1 4.1 4.4
atmospheric leaching step, such as is shown in Figure 1. Fe, pct 21 18 17 17
A serious problem at Moa Bay was the buildup of a thick A1, pct 3.4 3.4 2.9 3.1
layer (to 20 cm) of scale within the autoclaves and inter- Solids, kg/h 100 100 95 80
connecting pipelines. A five- to seven-day shutdown was *HPL = high pressure leach; ALR = atmospheric leach residue
required monthly to remove these deposits. The crust con-
tained hydronioalunite, hydroniojarosite, hematite, boeh-
mite, basic iron sulfate, and aluminochromite, s Substantial
Inert Gas
process improvements have since been made by AMAX Bleed
engineers to minimize deposition of these compounds. The
effectiveness of the process improvements was demon- Feed
Steam ALR- Feed
strated during operation of a "prototype plant" (16 tons per
day) at AMAX's Extractive Research and Development fa- T V-301
t---t 1
cility in Golden, Colorado. AMAX's plant processed rela-
tively high-magnesium ore (3 to 6 pct Mg). Acid was added ]E]F
to the autoclave at three locations, rather than all in the first
-270* C
compartment. Turbine impellers assured vigorous agitation,
thus avoiding the steep compositional and thermal gradients
that were so conducive to scaling at Moa Bay. Leaching tem-
H2SO4
perature was also high (270 ~ minimizing the solubility
of troublesome iron and aluminum scaling components. 6 Fig. 2 - High-pressure leach vessel and level-control pot configuration in
Prototype-plant demonstration runs were completed in AMAX's prototype laterite plant.
1980, Table I summarizes typical feed compositions, feed
rates, and product compositions during four campaigns
using various blends of New Caledonian limonite and V306 located immediately upstream from the first pressure
garnierite ores. The duration of these campaigns ranged letdown choke. (Refer to Figure 2.) The deposits were red-
from 12 to 26 days. The HPL (high pressure leach) feed dish brown (no change in color on drying) and fine grained.
was pumped at 25 to 30 pct solids into the first autoclave X-ray diffraction showed that the magnesium compounds
compartment. This limonite fraction was over 90 pct minus were Mg(Ni)SO4"6H20 and Mg(Ni)SO4" H20. The Mg:Ni
325 mesh, and consisted primarily of goethite (i.e., oz- ratio ranged from about 1:1 to 3:1, roughly corresponding to
FeOOH). There was also 3 to 5 pet aluminum, mainly as the ratio of the Mg to Ni concentration in the aqueous
gibbsite (i.e., o~-AI(OH)3). Magnesium was present primar- solution from which the scale deposited. The distribution of
ily as magnesium-iron silicates, although there was also concentrated H2504fed into the first three compartments of
some chromium spinel. Roasted and atmospheric-leached the autoclave was 60 pet, 25 pet, and 15 pet. The addition
residue (ALR) pumped into the fourth or fifth autoclave point for the atmospheric leach residue (ALR) was into
compartment consumed excess acid and solubilized residual compartment E for Run 1, and into compartment D for
nickel values. The ALR solids contained magnesium-iron subsequent runs.
silicates, amorphous silica and quartz, hematite and iron Table II gives typical analyses of scale samples (dried at
hydroxide, and aluminum hydroxide. room temperature) that were collected from the walls of the
For a more detailed description of ore preparation, miner- autoclave compartments after each run. Samples were also
alogy and composition, refer to the Duyvesteyn and Kay taken from the spool piece between the autoclave (V301)
papers. 1"3 The present work is directed toward magnesium and the level-control pot (V306), as well as from the bottom
sulfate deposition phenomena and the relationships between of the level control pot. A scale sample taken from the V301
the magnesium- , aluminum- , and iron-rich deposits. to V306 spool piece following Run 1 consisted of fragments
of alunite-hematite and MgSO4" H20 wall scale (apparently
dislodged from V301) cemented by MgSO4" H20. The
III. CHARACTERIZATION OF T H E piece assayed 4.8 pet Mg, 13 pet Fe, 7.5 pet A1, and 15 pct
S. Particles collected from the bottom of the level-control
MAGNESIUM SULFATE SCALE
pot were subspherical nodules 5 to 10 mm in diameter, and
Magnesium sulfate deposits were found in autoclave were often rimmed with alunite. When a nodule was broken
compartments A through F, and in the level-control pot open, its interior readily dissolved in cold water.

434--VOLUME 15B, SEPTEMBER 1984 METALLURGICAL TRANSACTIONS B

 Table II. Composition of Scale Samples from thick piece of scale sampled from the north wall of com-
the North Wall of the High-Pressure Leach Reactor partment A following Run 4. The bottom layer (1 mm) is
Scale Analysis (Weight Percent) composed of intergrown crystals of alunite and hematite
deposited during startup of Run 4 using low-magnesium
Sample Identification Mg Fe A1 S
ore left over from Run 1. The feed was then switched
Run 1 V301A 0.3 6.9 17 14 over to high-magnesium Run 4 feedstock (Table I), during
B 0.09 24 12 10 which upper 10 mm was deposited. This upper layer con-
C 0.2 16 15 -- sists of MgSO4" H20 containing highly dispersed particles
D 0.2 17 13 20 of hematite.
E 0.6 13 16 --
F 0.2 10 17 -- Figure 5 shows a magnified secondary electron image
(5(a)) of the Run l-Run 4 scale interface photographed in
Run 2 V301A 0.05 11 15 13 Figure 4. Photo 5(b) is an iron Ks X-ray image of the same
B 0.07 36 8.7 8.3
C 0.05 55 3.1 -- field shown in 5(a). The upper layer (MgSO4" H20) has iron
D 3.4 9.5 11 15 uniformly dispersed. The lower layer (alunite + hematite)
E 0.07 6 17 -- has iron dispersed in alunite, and concentrated in hematite
F 0.02 8.8 16 -- (one crystal shown). Photo 5(c) is a magnesium K~ image
V306 11 5.6 1.3 20 of this field showing the expected concentration of Mg in
Run 3 V301A 11 6.8 1.0 21 the upper layer. Photo 5(d) is an aluminum K~ image of
B 0.04 25 11 10 the same field, illustrating the absence of alunite in the
C 0.1 34 8.2 7.3 MgSO4" XH20 layer.
D 11 5.0 1.0 21 Table Ili tabulates the thickness of the scale deposits col-
E 12 4.6 0.8 21 lected from the north wall of each autoclave compartment
F 0.2 41 2.4 2.1 following each of four campaigns. Scale thickness values
V306 14 3.9 0.8 20 have been converted to mm per 30 days to facilitate com-
Run 4 V301A 12 5 0.8 17 parisons among the four campaigns. No compensation was
B 0.3 49 <4 3.9 made in the table for redissolution of magnesium scale when
C 0.2 52 <2 1.9 flushing the autoclave with water during the shutdown per-
D 6.4 11 <6 -- iod. Autoclave flushing was particularly thorough following
E 8.9 9.9 <2 16
F 6.2 16 <4 13 Run 3.
V306 6.6 17 <2 11 Table IV summarizes magnesium and free acid concen-
trations as averaged during each campaign for each of the
six autoclave compartments. Care must be exercised in
A photograph of the scale deposits in autoclave compart- utilizing these numbers, in that only the H 2 S O 4 assays can
ment F following Run 3, and a second photo showing the be taken at face value, assuming one ignores the HSO4
interior of level-control pot V306 following Run 4, appear shift reaction. The magnesium determinations represent
in Figure 3. Figure 4 shows the cross section of an I I mm not only the aqueous Mg soluble at temperature, but also

Fig. 3 - - T h e left photograph shows the interior of autoclave compartment F following Run 3. The right photograph is a shot of the inside of level-control
pot V306 following Run 4.

METALLURGICAL TRANSACTIONS B VOLUME 15B, SEPTEMBER 1984--435

 Mg(Ni}$O 4" H20

ALUNITE +
HEMATITE

Fig. 4--Cross section of an 11 mm thick piece of scale sampled from the wall of compartment A
following Run 4.

Fig. 5 - - ( a ) is a magnified secondary electron image of the interface between scale deposited during Run 4
in compartment A using Iow-Mg feed during startup (bottom portion of each photo) and that subsequently
deposited using high-Mg feed. (b) (c), and (d) are iron K alpha, magnesium K alpha, and aluminum K alpha
X-ray images, respectively. Magnification of (a) 113 times.

436--VOLUME 15B, SEPTEMBER 1984 METALLURGICAL TRANSACTIONS B

 Table III. Millimeters Projected Scale Thickness per 30 25
Days for the North Wall of the Prototype Plant Autoclave

Campaign A B C D E F 20
1 12.5 9.6 1.2 1.1 0,2
2 11.6 2.8 0.8 8.3 1.4 1,4
3 7.4 6.2 1.5 7.3 6.4 3,6
4 4.7 4.8 4.3 7.9 -- 3,7
Io
the often large quantity of Mg that dissolved from the
residue as magnesium sulfate when the sample was cooled
below 200 ~

IV. MAGNESIUM SULFATE
SOLUBILITY RELATIONSHIPS
The solubility of magnesium sulfate decreases with in-
creasing temperature, as shown in Figure 6. Above 200 ~
addition of sulfuric acid increases magnesium solubility.H
These data, as prepared by W. Marshall, apply to a solution
free of other salts. A number of solubility experiments were
also performed by AMAX Extractive R&D personnel to
determine the effect of the nickel, iron, and aluminum in
laterite leach liquor on the high-temperature solubility of
magnesium sulfate. With 20 grams per liter free acid, the
solubility of magnesium in laterite leach liquor at 200 ~
was about 25 pct higher than that published by W. Marshall
(Figure 6). Thus, presence of about 8 grams per liter total
aqueous nickel, iron, and aluminum does not decrease the
solubility of magnesium. Which hydrate of magnesium sul-
fate is the stable phase depends on temperature. The hexa-
hydrate is stable at about 60 to 80 ~ whereas at higher
temperatures, the monohydrate becomes the stable phase.
A comparison of the concentration of aqueous magnesium
at room temperature (in slurry samples collected from the
270 ~ prototype autoclave) was made with Marshall's
solubility values. This comparison appears in Table V. Also
shown is the "Mg scale quantity number" obtained by multi-
plying the measured scale thickness in mm (Table III) by
the magnesium analysis of the scale (Table II). For Run 1,
the solution concentration in all six compartments never
exceeded the solubility of magnesium. Refer to Table V.
Therefore, there was very little magnesium sulfate scaling in
the prototype plant autoclave during this run.
During Runs 2, 3, and 4, the solubility of magnesium
sulfate was exceeded by a substantial margin. The quantity
of scale was highest in the autoclave compartments where
magnesium-containing ore was added (i.e., A and D). Mag-
nesium scaling of compartments B and C was nil because
the liquor had already been relieved of its excess magnesium
via scaling in compartment A. This relief of scaling pro-
o ~ I i h
190 230 270
tEMPER,#/'ORE {oc}
Fig. 6-- Solubilityof magnesiumas a functionof temperatureand sulfuric
acid concentration,tL
pensity was enhanced by acid added to B and C, which
increased the solubility of magnesium (Figure 6). Scaling
recommenced in D not only due to HTN (high temperature
neutralization) addition of solids, but also due to the de-
creasing liquor acidity. This decreased acidity caused a por-
tion of the magnesium soluble in C to precipitate in D.
One would have expected magnesium scaling in compart-
ment A of Run 2 based on the 2.4 grams per liter solubility
differential. Perhaps there was sufficient intermittent
backmixing from the more acidic compartment B solution
to dissolve magnesium scale buildup in compartment A.
Or perhaps the water wash prior to shutdown dissolved
away the compartment A scale. The same water, now loaded
with magnesium, would be less effective in dissolving
magnesium scale from compartment D.
One would have also expected to find more scale after
Run 4 than 3, based on apparent leach liquor magnesium
concentrations. The lower measured scale thickness follow-
ing Run 4 probably was due to the autoclave being washed
particularly thoroughly with water during the shutdown
procedure that followed this high-magnesium campaign.
Thus, residual magnesium scale was greater following
Run 3 than following Run 4 due to the difference in flush-
out procedures.
V. E F F E C T OF MAGNESIUM SULFATE
DEPOSITION ON ALUNITE AND
HEMATITE SCALE FORMATION
The photographs shown in Figures 4 and 5 are striking
evidence of the change in scale morphology that can re-
sult from the presence of MgSO4" H:O. During Run 1, the

Table IV. Apparent Concentrations of Aqueous Mg and H2804 in the High Pressure Autoclave Compartments

A B C D E F
Run Mg H2SO4 Mg HzSO4 Mg H2504 Mg H2SO~ Mg H2SO4 Mg H2SO4
1 7.0 33 7.3 42 7.3 47 7.6 46 8.2 40 8.3 40
2 10.0 34 11.7 45 11.1 51 10.8 45 11.4 45 10.4 45
3 12.0 32 12.9 48 13.6 56 13.4 46 12.4 46 12.6 44
4 15.7 33 18.3 49 17.9 58 15.4 44 15.7 42 15.2 40

METALLURGICALTRANSACTIONSB VOLUME15B,SEPTEMBER1984--437
 Table V. Comparison of Apparent Aqueous Mg with Mg Solubility and the "Mg Scale Quantity" (Dimensionless)
Autoclave Compartment
Run Parameter* A B C D E F
1 apparent Mg, grams/liter 7.0 7.3 7.3 7.6 8.2** 8.3
Mg solubility, grams/liter 7.5 9.6 10.3 10.2 9.1 9.1
Mg scale quantity 4.0 0.9 0.2 0.2 0.1 --
2 apparent Mg, grams/liter 10.0 11.7 11.1 10.8"* 11.4 10.4
Mg solubility, grams/liter 7.6 10.1 11.2 10.1 10.1 10.1
Mg scale quantity 0.6 0.2 0.04 28.0 0.1 0.3
3 apparent Mg, grams/liter 12.0 12.9 13.9 13.4"* 12.4 12.6
Mg solubility, grams/liter 7.2 10.6 12.0 10.2 10.2 9.9
Mg scale quantity 84.0 0.3 0.2 83.0 74.0 0.9
4 apparent Mg, grams/liter 15.7 18.3 17.9 15.4"* 15.7 15.2
Mg solubility, grams/liter 7.3 10.9 12.5 9.9 9.6 9.1
Mg scale quantity 38.0 1.0 0.9 50.0 -- 23.0
*ApparentMg is the analysis of the aqueous phase of the slurry sampled from each autoclave compartment. This assay is the sum of magnesium soluble
at autoclave temperature, plus magnesium solubilized from MgSO~ H20 during cooling of the sample. Mg solubility is the solubility of magnesium at 270 ~
as read from Figure 6. Mg scale quantiO, is the product of scale thickness (Table III) multiplied by the magnesium assay of the scale (Table II).
**Compartment to which the ALR feed was added.

Table VI. Effect of Magnesium on Location and Extent of Alunite and Hematite Scaling
Feed Quantity of Scale
(kg/h) Stage A Stage B Stage C
Run Mg A1 Fe Mg AI Fe Mg AI Fe Mg AI Fe
1 10 20 160 4 220 85 0.9 120 230 0.2 22 20
2 12 18 140 0.6 180 130 0.2 5 100 0.1 2 40
3 18 13 120 85 7 50 0.3 70 160 0.2 12 50
4 19 9 75 55 4 30 1.0 <20 240 0.9 <9 230

solubility of magnesium was not exceeded in autoclave
compartment A. See Table V. The scale deposited in com-
partment A was composed of refractory intergrown crys-
tals of alunite and hematite (Figure 5 and Table II). When
the autoclave feed was changed over to high-magnesium
material (Run 4; Table I), deposition of alunite essentially
ceased (Figure 5). The scale deposit became MgSO4" H20
containing a fine dispersion of iron plus traces of aluminum.
Further evidence of the effect of magnesium in changing
the quantity of aluminum and iron in the autoclave scale is
presented in Table VI. The "quantity of scale" shown in this
table is attained by multiplying the scale thickness on the
wall (mm/30 days, as shown in Table 1II) by either the
Mg, A1, or Fe analysis of the scale (Table II). Thus, in
compartment A of Run 1, the scale was primarily alunite;
magnesium sulfate content was low. The same was true for
Run 2. However, in Runs 3 and 4, the compartment A scale
was primarily magnesium sulfate. Alunite content was low.
Hematite was significant, but lower than in Runs 1 and 2.
Very little magnesium deposited in autoclave compart-
ments B and C due to the relatively high acid concentration
(Table VI). Iron deposition in compartments B and C was
generally higher, and aluminum deposition generally lower,
in the high-magnesium runs. Sulfuric acid concentration
was also higher in compartments B and C during the high-
magnesium runs (Table IV).
Both the extent of hydrolysis of aluminum and iron at a
given temperature and acid concentration are increased as
the level of magnesium sulfate is increased, x2~3At 270 ~
increasing acid concentration slows down the rate of alu-
minum hydrolysis much more than the rate of iron hy-
drolysis. ~0.~4It is therefore hypothesized that where there is
insufficient magnesium to deposit magnesium sulfate, depo-
sition of hematite and alunite on autoclave surfaces should
increase with increasing magnesium concentration. Increas-
ing acid concentration should retard aluminum hydrolysis
relative to iron hydrolysis, particularly at shorter reten-
tion times.
VI. C O N T R O L OF M A G N E S I U M
SULFATE D E P O S I T I O N
Magnesium sulfate deposition sharply inhibits the rate
of alunite scaling. For instance, the highest scaling rate
measured on the north wall of the autoclave was 12 m m / 3 0
days in compartment A following Run 1 (low magnesium).
This scale was primarily alunite assaying 17 pct A1 and
0.3 pct Mg. Doubling the magnesium content of the feed
(Run 3) resulted in the deposition of 7 m m / 3 0 days of pri-
marily magnesium sulfate scale assaying 1 pct A1 and 11 pct
Mg. This substitution of magnesium for aluminum is im-
portant for autoclave descaling. Unlike alunite and hema-
tite, magnesium sulfate hydrate dissolves rapidly in water or
dilute acid at temperatures below 200 ~ Hematite precipi-
tates on autoclave internal surfaces along with magnesium
sulfate, but the hematite is dispersed within the magnesium
sulfate matrix. Magnesium sulfate has an inverse solubility

438--VOLUME 15B, SEPTEMBER 1984 METALLURGICAL TRANSACTIONS B


9 *rE.,rE ----i I---7 *'" C*P
2 I
,1 I
'
~ l I
q while inhibiting co-deposition of amorphous silica. Mag-
# l
Fig. 7--Conceptual diagram of ore, acid, and steam sequencing for at-
taining protective magnesium deposition in each autoclave compartment.
with temperature. Cooling the autoclave from 270 ~ to
180 ~ sharply increases magnesium solubility, resulting
in magnesium dissolution and liberation of the hematite.
The dissolved MgSO4 exits from the autoclave with the
pregnant liquor. The liberated hematite follows the leach
residue to tailings disposal. Thus, magnesium sulfate pro-
vides a means not only for inhibiting alunite scaling, but
also for facilitating removal of hematite scale.
To be effective as a practical alunite-hematite scale in-
hibitor, the deposition of magnesium sulfate must be reason-
ably uniform in all autoclave compartments. Figure 7 shows
a profile of ore, acid, and steam additions to the autoclave
that is designed to achieve this uniformity. Sufficient ore is
added to compartment A to exceed the magnesium solu-
bility in this compartment by about 3 grams per liter. As
much acid as possible is also added to this compartment,
commensurate with the titanium materials of construction
constraint. High initial acid concentration should also in-
crease nickel extraction, as compared to stage addition. 9
Compartment A has the following features:
I. Sufficient magnesium, as contained in the ore, is added
to sharply inhibit alunite scaling, and to entrain the hematite
scale in the magnesium sulfate matrix; and
2. High acid concentration in compartment A allows room
for decreasing the acid concentration in compartments B,
C, and D, which distributes magnesium sulfate deposition
downstream.
In the prototype plant runs, no protective layer of mag-
nesium sulfate was deposited on compartment B and C sur-
faces due to increasing H2804 concentration (as compared to
compartment A), which maintained aqueous magnesium in
soluble form. This problem can be corrected by adding
L-ore and/or atmospheric leach residue (ALR) directly to
compartments B and C (Figure 7). Ore distribution is ad-
justed to precipitate the equivalent of 1 to 3 grams per liter
Mg in each compartment. The free-acid concentration in
compartment B is maintained lower than in A; also, acid
concentration in compartment C is lower than in B. Al-
though hematite deposits along with magnesium sulfate, it
is dispersed within the MgSO4 H20 matrix. Refer to the
photomicrographs of Figure 5.
Magnesium sulfate scaling in compartment D was quite
high during operation of the prototype plant. This deposition
occurred not only due to all the ALR being added at this
location, but also because of the sudden drop in free acid
concentration in passing from compartment C to D. This
problem can be corrected by adding only a portion of the
ALR to compartment D. Magnesium deposition is also
maintained in compartment E by injecting makeup steam
METALLURGICALTRANSACTIONS B
into this compartment rather than into the gas cap. The
increase in temperature deposits magnesium sulfate into E
nesium solubility decreases with increased temperature,
whereas that of silica increases. A small quantity of air is
added to the gas cap to oxidize the ferrous iron added with
the serpentine in the ALR feed.
VII. CONCLUDING REMARKS
1. Sulfuric acid pressure leaching of nickeliferous laterite
ore containing high levels of magnesium silicates leads to
deposition of magnesium sulfate. Precipitation of mag-
nesium sulfate is highest where the ore is fed, where acid
concentration is low or decreasing, and where tempera-
ture is high or increasing.
2. The magnesium sulfate precipitates as a fine-grained,
water-soluble Mg(Ni)SOa'H20 binary salt having a
Mg:Ni ratio corresponding to the ratio of Mg to Ni con-
centration in the leach liquor.
3. Magnesium sulfate deposition sharply inhibits the rate of
alunite scaling. Hematite precipitates on autoclave inter-
nal surfaces along with the magnesium sulfate, but is
dispersed within the magnesium sulfate matrix.
4. Where there is insufficient magnesium to deposit mag-
nesium sulfate, deposition of hematite and alunite on
autoclave surfaces appears to increase with increasing
magnesium concentration.
5. To be effective as a practical alunite-hematite scale
inhibitor, magnesium sulfate deposition must be reason-
ably uniform. This uniformity is controlled by appropri-
ate selection of the ore- , acid- , and steam-injection
locations.
ACKNOWLEDGMENTS
The authors wish to extend their thanks to Compagnie
Franqaise d'Entreprise Mini~res, Metallurgiques et d'Inves-
tissements (COFREMMI), a joint-venture company of
AMAX and the Bureau de Recherches Grologiques et Mini-
~res (BRGM), Orlrans, France, for permission to publish
this paper, and to Jean-Paul Duterque (Process Engineer,
COFREMMI) for his assistance during the investigation.
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