Sulfuric Acid Pressure Leaching of

Nickeliferous Limonites
E. C. CHOU, P. B. QUENEAU, AND R. S. RICKARD

This laboratory study examines the sulfuric acid pressure leaching characteristics of
nickeliferous limonite samples from South New Caledonia. The effect of temperature
(225°C to 300°C), acid-to-ore r a t i o (0.21 to 0.30), pct solids (10 to 45), particle size (--20
to -270 mesh), and agitation (50 to 600 rpm) on nickel extraction and selectivity are dis-
cussed. For overall improvement of the leach response, leaching is best conducted at
temperatures higher than 250°C and at solids less than 33 pct. Variation of goethite,
hematite, and b a s i c aluminum sulfate content of the leach residue was determined s e m i -
quantitatively as a function of leaching time. Sulfate content of the residue r i s e s sharply
during the f i r s t several minutes of leaching, then falls, and finally equilibrates at five
to six percent. This change in sulfate analysis can be explained by assuming a s e r i e s of
consecutive iron and aluminum hydrolysis reactions.

T H E world's largest known land based r e s e r v e s of ticular attention is given to the f i r s t portion of the
nickel o c c u r as nickeliferous limonites.X Limonites leaching period.
are rich in iron (40 to 50 pct), chiefly as goethite,
(FeOOH), but low in magnesia (<5 pct) and s i l i c a (<10 CHARACTERIZATION OF ORE
pct). Nickel content seldom exceeds 1.5 pct and
usually lies between 0.9 and 1.4 pct; the cobalt assay T h e weight distribution of the size fractions and as-
is typically 0.1 pct.2 Large s c a l e nickel extraction of sociated chemical analyses of the South New Caledonia
limonites utilized either reductive-roasting plus am- oxide ore used in this study are tabulated in Table I
moniacal atmospheric leaching, or sulfuric acid below.
pressure leaching. 3 This paper examines the latter, The - 3 / + 2 0 mesh fraction was removed by s c r e e n -
which has the advantage of high nickel and cobalt ex- ing because of its low nickel and cobalt content. The
traction at the expense of high pressure operation. remaining minus 20 mesh ore was designated Sample
Results presented were obtained at AMAX's Extrac- "A", and was the feed material used in this s t u d y .
tive Metallurgy Laboratory as part of their develop- The fine fractions (- 270 mesh of Sample A) are rich
ment program for recovering nickel and cobalt from in nickel and iron, whereas the c o a r s e fractions are
oxide o r e s . rich in cobalt, magnesium, manganese, chromium
Published information on sulfuric acid pressure (mostly as chromite) and aluminum. X - r a y diffraction
leaching of limonite is s c a r c e . Work performed in analysis showed the m a j o r m i n e r a l constituent of Sam-
support of a l a r g e s c a l e operation at Moa Bay in Cuba ple A was goethite. Also present were l e s s e r quanti-
was first detailed by Carlson and Simons,4 then ex- ties of quartz, kaolinite, talc, hematite, serpentine,
tended by Sobol5-7 and Chaves.8 At Moa Bay, ore was montmorillonite, chromite and lithiophorite. The in-
wet screened at 20 mesh, thickened t o 45 pct solids, f r a r e d spectra b o t h of Sample A and of a typical limoni-
and pressure leached at 240 to 250°C with sulfuric tic ore sample from Moa Bay were also obtained. F i g u r e
acid. T o attain 95 pct nickel extraction in 60 to 90 1 shows that both samples have s i m i l a r characteristic
min, 0.22 pounds of concentrated sulfuric acid per absorption bands except for Sample A's typical s i l i -
pound of ore was pumped into the f i r s t autoclave of a cate and quartz bands at wavenumber 1020 and 1100
four-autoclave train. The pregnant liquor generated cm -1, respectively. The presence of this band indicates
assayed 6 gpl Ni, 0.8 gpl Fe, 2.3 gpl AI, and 28 gpl
free acid. Carlson and Simons reported on the kinetics
and mechanism of thispressure leach, demonstrating
the importance of a c i d / o r e ratio and temperature; Table I. Size Fractions and Analyses o f New Caler;3nian Laterite Ores
kinetics of nickel extraction were explained by t h r e e Sample
nickel-bearing species, but no proof was given. The Size Fraction, -3 -20 -100 -270 "A"
remarkable feature of t h e i r work was the shape of the Mesh +20 +100 +270 +400 -400 -20
nickel extraction curves. Most of the leaching was
Wt Pct 12 8 7 4 69 88
complete in the f i r s t few minutes, with little extrac-
Assays, Pct
tion occurring during the remaining hour. The present Ni 0.67 1.08 1.77 1.84 1.80 1.73
investigation extends that of Carlson and Simons. Par- Co 0.11 0.37 0.42 0.25 0.11 0.16
Fe 45.9 30.9 29.2 35.0 44.5 41.6
Mg 1.4 3.0 2.4 2.2 1.3 1.5
Mn 0.69 1.6 1.6 1.0 0.50 0.71
E. C.CHOUand P. B. QUENEAU are Section Chiefs in AMAX's Cr 2.9 7.0 4.9 3.3 1.3 2.2
Extractive Metallurgy Laboratory, Golden,CO 80401. R. S. RICKARD AI 3.5 4.1 3.0 2.5 2.4 2.6
is Vice-President, Engineering, Earth Sciences,Inc., Golden, CO. SiO~ 8.0 16.3 26.1 21.6 10.8 13.0
Manuscript submitted December31, 1976.

METALLURGICAL TRANSACTIONS B VOLUME 8B, DECEMBER 1977-547


RELATIVE
ABSORBANCE
4oo0 3~oo z~oo tsoo ,ooo 500
WAVENUMBER, CM - I
Fig. 1 - - T h e i n f r a r e d s p e c t r a of Moa Bay Limonite and Sam-
p l e A and the r e s i d u e s obtained by leaching S a m p l e A at
250°C, 33 pct s o l i d s and 0.24 a c i d ] o r e r a t i o .
that S a m p l e A i s not a p u r e l i m o n i t e , but c o n t a i n s s o m e
s i l i c a t e m i n e r a l s , w h i c h a r e m a j o r c o n s t i t u e n t s in
s e r p e n t i n i c r o c k s . Such c o n t a m i n a t i o n is difficult to
a v o i d w h e n m i n i n g l i m o n i t e d e p o s i t s in w h i c h t h e
boundary between the limonite and underlying ser-
p e n t i n e o r e i s not w e l l d e f i n e d . F i g u r e 1 i s d i s c u s s e d
f u r t h e r i n the E x p e r i m e n t a l R e s u l t s S e c t i o n .
EXPERIMENTAL PROCEDURE
Leaching
A i r - d r i e d o r e w a s h e l d a t 4 0 ° C o v e r n i g h t u n d e r 15
m m m e r c u r y p r e s s u r e (to a s s u r e c o n s i s t e n t m o i s t u r e
content), w e i g h e d , s a m p l e d a n d m i x e d w i t h w a t e r f o r
15 m i n i n a r o l l e d b o t t l e . T h e r e s u l t i n g s l u r r y w a s
t r a n s f e r r e d into a g l a s s - l i n e d t w o - l i t e r P a r r t i t a n i u m
a u t o c l a v e a n d b r o u g h t t o t e m p e r a t u r e o v e r a 40 m i n
p e r i o d . T w o a x i a l t u r b i n e s (5.7 c m d i a m ) m o u n t e d on a
c e n t r a l s h a f t r o t a t i n g a t 600 r p m p r o v i d e d a m p l e m i x -
i n g . T o b e g i n a t e s t , s u l f u r i c a c i d (96 p c t ) w a s i n -
j e c t e d u n d e r n i t r o g e n o v e r p r e s s u r e through a tube
extending about 5 cm downward f r o m t h e autoclave
head. S a m p l e s were t a k e n through sampling b o m b s at
programmed t i m e s , filtered, and the filter c a k e s
w a s h e d w i t h pH 2 s u l f u r i c a c i d s o l u t i o n . C a k e s w e r e
d r i e d overnight at l l 0 ° C .
I n f r a - R e d S p e c t r o s c o p y (IR)
T h e i n f r a - r e d s p e c t r a of S a m p l e A and its leach
r e s i d u e w e r e o b t a i n e d u s i n g t h e Kl3r p e l l e t t e c h n i q u e
w i t h a B e c k m a n M o d e l 4250 I n f r a - R e d S p e c t r o p h o t o m e -
ter.
X - R a y Diffraction (XRD)
T h e XRD study o f S a m p l e A a n d i t s leach r e s i d u e
was c o n d u c t e d u s i n g a c o p p e r - t a r g e t X - r a y tube w i t h
a N o r e l c o 2500 X R D u n i t a n d a n A M R m o n o c h r o m a t o r .
D i f f e r e n t i a l T h e r m a l A n a l y s i s (DTA)
T h e DTA s t u d y of Sample A and its leach r e s i d u e
w a s c o n d u c t e d w i t h a D e l t a t h e r m III U n i t m a n u f a c t u r e d
by T e c h n i c a l E q u i p m e n t C o r p o r a t i o n .
548-VOLUME 8B, DECEMBER 1977
Screening Analysis
T h e w e i g h t d i s t r i b u t i o n of the s i z e f r a c t i o n s w a s d e -
t e r m i n e d by w e t - s c r e e n t e c h n i q u e u s i n g T y l e r s c r e e n s .
S u r f a c e Area Determination
T h e s u r f a c e a r e a of S a m p l e A w a s m e a s u r e d w i t h a
Q u a n t a c h r o m e s u r f a c e measurement unit manufactured
by Q u a n t a s o r b C o m p a n y .
CHEMISTRY OF LEACHING
S u l f u r i c a c i d l e a c h i n g of n i c k e l i f e r o u s l i m o n i t e i s
p e r f o r m e d at t e m p e r a t u r e s high enough to solubilize
nickel a n d cobalt as a q u e o u s sulfates w h i l e c o n v e r t -
ing most of t h e o r e ' s iron and aluminum c o n t e n t t o in-
s o l u b l e h e m a t i t e a n d a l u m i n u m sulfates: 4
2 F e O O H + 6H÷ ~ 2 F e ÷÷÷ + 4H~O [1]
2 F e ÷÷* + SO4= + 3H20 ~- F e 2 0 3 • SO3" H~O + 4H÷ [2]
F e 2 0 3 "SO3 ' H z O ~ F e z O 3 + SO4-- + 2H÷ [3]
6A1~'÷ + 4SO4= + 1 4 H 2 0 ~ 3A1203 • 4SO3 • 9H20
+ 10H+ [4]
2A1+++ + 2SO4° + 2HeO ~-~ A1203 " 2SO3 ' HzO + 2H+. [5]
R e a c t i o n [2] t a k e s p l a c e d u r i n g t h e f i r s t f e w m i n u t e s
o f l e a c h i n g w h e n a c i d i t y i s h i g h ,9 t h e n the b a s i c i r o n
s u l f a t e p r o d u c t o f R e a c t i o n [2] i s h y d r o l y z e d t o h e m a -
t i t e by R e a c t i o n [3]. A l u m i n u m h y d r o l y z e s m o r e
slowly, generating mostly 3 ' 4 •9 hydrate b e l o w 250°C
( R e a c t i o n [4]) a n d the 1 . 2 • 1 h y d r a t e a b o v e 2 8 0 ° C
( R e a c t i o n [5]).s T h e q u a n t i t y of 1 • 2 . 1 h y d r a t e a l s o i n -
c r e a s e s with acidity, even at temperatures b e l o w
250oC.lO,ll
EXPERIMENTAL RESULTS
I n f r a - r e d s p e c t r a of S a m p l e A a n d o f i t s l e a c h r e s i -
due (250°C, 0.24 a c i d / o r e , 33 p c t s o l i d s ) a p p e a r i n F i g .
1 . T h e f i v e b a n d s a t 4 4 0 , 6 0 0 , 8 0 0 , 900 a n d 3180 c m -~
are attributed t o goethite. T h e intensity of t h e s e b a n d s
d e c r e a s e s d r a m a t i c a l l y d u r i n g the f i r s t 5 m i n of l e a c h -
i n g a n d b e c o m e s i n s i g n i f i c a n t a f t e r 15 m i n . T h e b a n d s
a t 1020 c m -1 a n d 1100 c m -1 a r e a t t r i b u t e d t o s i l i c a t e
m i n e r a l s a n d q u a r t z , r e s p e c t i v e l y . T h e 1020 c m -1 b a n d
d e c r e a s e s a n d t h e 1100 c m -~ b a n d r e m a i n s u n c h a n g e d
w i t h i n c r e a s i n g l e a c h i n g t i m e , i n d i c a t i n g t h a t the s i l i -
c a t e m i n e r a l s dissolve d u r i n g leaching w h e r e a s q u a r t z
d o e s n o t . (Si a n a l y s i s o f p r e g n a n t l i q u o r i s t y p i c a l l y
1 g p l . ) T h r e e b a n d s a t 3 4 0 , 4 7 5 , a n d 550 c m -1 a r e a t -
t r i b u t e d to h e m a t i t e . T h e i n t e n s i t y o f t h e s e b a n d s
s h o w t h e i n c r e a s i n g f o r m a t i o n of h e m a t i t e w i t h i n -
c r e a s i n g l e a c h t i m e . T h e r e is a n u n i d e n t i f i e d b a n d at
a b o u t 1200 c m "~ w h i c h m a y be a t t r i b u t e d t o the a l u n i t e .
T w o b a n d s a t 1640 c m -~ a n d 3440 c m -~ p r o b a b l y o r i g i -
n a t e f r o m c o m b i n e d w a t e r ( i . e . , h y d r o x y l g r o u p ) in
v a r i o u s m i n e r a l s . T h u s , the I R d a t a do g i v e a n i n d i -
c a t i o n of t h e b e h a v i o r o f m i n e r a l s d u r i n g l e a c h i n g .
I n a d d i t i o n , g o e t h i t e a n d h e m a t i t e i d e n t i f i e d by X R D
a n d a l u n i t e i d e n t i f i e d by D T A w e r e f o u n d i n t h e s a m -
ple a n d i t s l e a c h r e s i d u e . T h e relative quantities as
c o m p a r e d to t h e c o r r e s p o n d i n g p u r e m i n e r a l s a r e il-
l u s t r a t e d i n T a b l e II a s a f u n c t i o n of l e a c h i n g t i m e .
A p o r t i o n o f t h e c h r o m i u m c o n t e n t o f t h e o r e also
METALLURGICAL TRANSACTIONS B
 HI performed in graduated cylinders on the discharge
Table Acid Leach Residues of "Sample A " Ore
I I . Phases F o u n d in slurry with no r a k e s or flocculants indicated that
(250°C, 0.24 acid/ore, 33 pct solids) ultimate compaction decreased and time to r e a c h the
compression point increased with increasing agitation
Leaching Goethite, Hematite, Alunite, Free Acid,
Time, min FeOOH Fe~O3 3A1~O3"4SO4- 9H20 gpI during the leach. In general, the rate of settling in-
c r e a s e s with increasing of particle size. Fine parti-
0 40 Trace Absent 130
cles produced under high s h e a r conditions probably in-
1 30 30 Absent 38
3 20 45 Absent 34 hibit the settling; unfortunately, the particle size dis-
5 10 60 Trace 34 tribution was not determined during the period of t e s t -
15 5 65 Minor 37 ing, which may explain why the best settling conditions
30 Nil 70 Minor 33 are in the 275°-45 pct solids-low s h e a r c a s e .
60 Nil 75 Minor 38
Low s h e a r r e f e r s to m i x i n g with a perforated pad-
dle at 50 rpm, and high s h e a r r e f e r s to m i x i n g with the
twin turbines at 600 rpm. In all of the ' n o agitation"
tests, the acid added to begin the l e a c h was m i x e d with
Table III. Effect of Agitation on Thickening Response When the ore-water slurry for 30 s at 600 rpm.
Pressure Leaching Sample " A "
(Acid/Ore = 0 . 2 4 )
Effect of Temperature
Leach F i g u r e 3 illustrates the effect of temperature on the
Type of Temperature, 24 h Compression rate and extent of nickel extraction. Temperatures a p -
Agitation °C Solids, Pct Compaction, Pct Point, h proaching 250°C are required for rapid leaching.
None 250 33 44 4.9 Comparable extraction, but at a higher initial r a t e , is
Low shear 250 33 44 6.3 attained at 275°C: leaching at 300°C lowers the nickel
High shear 250 33 42 7.3 yield. In analyzing data presented in Fig. 3, the f i r s t
None 250 45 53 2.5
Low shear 250 45 48 None o r d e r assumption fits the data fairly well in the r a n g e
High shear 250 45 46 None of 75 pct to 90 pct nickel leached, but the rate is
None 275 45 52 4.0 much higher early in the reaction. B a s e d on Arrhenius
Low shear 275 45 60 2.3 equation, a plot of log k v s lIT (K) in Fig. 4 show that
High shear 275 45 51 None
the energy of activation calculated between 225° and
275°C is approximately 30 K c a l / g mole.
Curves s i m i l a r to those shown in Fig. 3 could have
been plotted for cobalt extraction, and would have
dissolves, but is to a l a r g e extent hydrolyzed during shown that ultimate cobalt extraction lags that of
the l a t e r s t a g e of leaching (probably as Cr3(SO4)2 × nickel by 3 to 4 pct. However, the initial rate of co-
(OH)sH20 (Her. 12) and 3A1203 • 2CRO3 • 6H20.13 About balt extraction was always h i g h e r than that of nickel.
half of Sample A's magnesium and manganese content
are soluble, as is most of the t r a c e copper and zinc
content of the ore.
3.0

Effect of Particle Size 1 0 0 % - 2 7 0 Mesh ~ ~ ' ~

O
T o determine the effect of p r i o r grinding on leach-
ing, t h r e e samples of Sample A were ground t o 100 2.6
p c t - 2 0 mesh (78 p c t - 4 0 0 mesh), 100 p c t - 1 0 0 mesh
(82 p c t - 4 0 0 mesh) and 100 p c t - 2 7 0 mesh (91 pct
-400 mesh), respectively. The surface a r e a s of these
ground samples were 60.5, 65.3 and 66.8 m2/g respec-
tively. Each of these fractions was then pressure 2.2
leached at 250°C, 0.24 a c i d / o r e r a t i o (based on 96 pct Nil(Fe +AI)
H2SO4) and 33 pct solids. Neither the rate nor the ex-
tent of nickel extraction was affected by the ore grind;
however, the nickel-to-impurity ratios in the pregnant 1.8
liquor increased substantially when leaching the
gound material. See Fig. 2. Apparently the increased o

surface generated by grinding provides additional nu-

cleating sites for hydrolysis of the iron and a l u m i -
1.4
num, solubilized during the initial stages of leaching.

Effect of Agitation
After the acid had been thoroughly m i x e d with the
slurry for 30 s, no additional agitation was required. LEACHING TIME minutes
-

Thus, turning the agitator off thirty seconds after acid Fig. 2--Nickel-to-impurity ratios in Sample A leach liquor
injection hindered neither the rate nor the extent of as a function of leaching time and grind (250°C, 0.24 acid/ore
nickel extraction. Thickening tests as shown in Table and 33 pct solids).

METALLURGICAL TRANSACTIONS B VOLUME 8B, DECEMBER 1977-549

 I00 - - , i T , I

O 0.3C
275°C 250°C
90
Ni/Fe=4 . 0 / /

I
2 225°C
Ni 80
ACID / ORE
0.27
/ 275°C /
EXTN, RATIO

%
70 / 33 % Solids / 250"C
/ / / ~ Ni/AI=4.0/
60 0.21
I I i I I0
3 5 15 30 6

LEACHINGTIME- rninutes(l(R scale)

o ,~ 3'o 4'5 6'o Fig. 5--Leaching time required to attain a given nickel-to-
LEACHING TIME- minutes impurity ratio as a function of temperature and acid/ore ratio.
Fig. 3--Nickel extraction as a function of leaching time and
temperature.
The free acid in the l e a c h liquor decreased from the
initial concentration of over 100 gpl to about 25 to 50
gpl a f t e r the f i r s t s e v e r a l minutes of leaching, and
r e m a i n e d at this equilibrium concentration throughout
the rest of the leaching period. The equilibrium con-
60
centration was independent of temperature variation
50
from 250 to 275°C (Fig. 7). One might have expected
40 _ Ea the free acid l e v e l of the hotter liquors to be higher,
Log k- - 2.30"-~.3RT
30 Constant because in these solutions m e t a l hydrolysis was most
complete. However, at the h i g h e r temperature, more
20 ~ Kcal/g-mol, sulfate was tied up in the aluminum precipitate, so
hydrolysis at 275°C does not generate the quantity of
k x 102,min.-I free acid that would have been formed at 250°C.

Effect of Acid/Ore Ratio

498
52.3
548
1.8
Fig. 4--Rate of nickel extraction as a function of temperature.
It is not sufficient to consider only the nickel and
cobalt recovery; selectivity is also an important factor
for subsequent m e t a l recovery. F i g u r e 5 shows the
leaching time required to attain NiZFe and Ni/A1 ra-
tios of four in the pregnant liquor at s e v e r a l a c i d / o r e
ratios. It is c l e a r that increasing the temperature
from 250° up to 275°C substantially improves pregnant
liquor quality over the r a n g e of leaching time and
a c i d / o r e ratios investigated.
Leaching temperature also has a sharp effect on the
amount of sulfate reporting in the residue. (Sulfur
is a m a j o r operating expense, and that portion lost to
the residue is the most difficult to utilize or re-
cycle) 14 See Fig. 6. The sulfate assay of the residue
r i s e s sharply during the f i r s t s e v e r a l minutes of
leaching, then falls, and finally equilibrates at five t o
six pct. Sulfur losses are greatest at high tempera-
ture and high acid/ore, and l e a s t at low levels of tem-
perature and acid/ore. A satisfactory sulfate balance
was obtained between solid and solution in these tests.
\ One variable requiring careful control is the weight
2.73 of acid added to a given weight of ore ( i . e . , a c i d / o r e
170 ratio). Already shown was the increase in residual
51.4 Q~ sulfur content with increased acid addition. More im-
portant is the effect of a c i d / o r e ratio on the time re-
quired to attain a given l e v e l of nickel extraction.
L9
' 210 (Refer to Fig. 8). 90 pct nickel extraction is attained
t/T x 103,°K -I in 5 min at 250°C, 25 pct solids and 0.30 acid/ore;
t h r e e times longer is required if only 0.27 units of
acid are added. Unfortunately, short l e a c h t i m e s at
high a c i d / o r e also l e a v e substantial quantities of iron
and aluminum in the pregnant liquor. The same
change from 0.27 up to 0.30 acid~ore r a t i o increased
the quantity of iron and aluminum in the pregnant
liquor by 100 pct and 33 pct, respectively, at about 30
min of leaching. (See Fig. 9). The N i / F e ratio in-
c r e a s e s faster with time than does the Ni/A1 ratio,
reflecting the relative rate of hydrolysis of these im-
purities. The impurity curves generally have a posi-
tive slope, a trend which is maintained as temperature
increases. This slope reflects the increased solubility
of the iron and aluminum hydrates with the increased
acidity generated by the higher acid t o ore ratios.
Effect of Percent Solids
This variable has been saved until last, because the
l e v e l of solids which gives the best nickel extraction
decreases with increasing temperature at a given
acid addition and leach time (Tables IV and V). L i m o -
nite acid leaching literature emphasizes the d e s i r a -
bility of thickening the ore feed to at l e a s t 33 pct

550-VOLUME 8B, DECEMBER 1977 METALLURGICAL TRANSACTIONS B

 t -1
o.=L \
F i [ I I T I I - - I T
7.0

ACID;I~RE °z4 / 75%NiEXTN. 90*/= - -

SULFATE
IN
RESIDUE,
%

/ I I i ] I _ I
I 3 5 15 50 60

LEACHING TIME- minutes(log scole)

Fig. 8--Nickel extraction as a function of acid/ore ratio and
0 15 30 45 60 leaching time (250°C, 25 pct solids).
LEACHING TIME - minutes
I ! I !7 I I T I (

, 0 . 3 0 Acid/Ore
0.5(:
/
1.0
/
, ACID/ORE
RATIO
o.2t

R
E
S
ID
uE
5.0
1,/eS
U
LFA
.2
*c5A
0,0
.c
0/0
.3
.2
.!,5
T0
,''*A
E
%
0IN/O
-""~"IL~~ 0.24

0.21

3 S 15 ~K) 60

LEACHING TIME - minutes (Io9 scale)

3'OI I 530/, SolidSl I li T "l • - I --- l - -

0 15 30 45 60

LEACHING T I M E - minutes
Fig. 6--Sulfate content of Sample A's leach residue as a ACID/ORE o.27
function of leaching time, temperature, acid/ore ratio RATIO 1.5
and pct solids.

I % I *C I I 0.21
50 Solids Temp. ~ ] / I L I
O 33 250 / w I 5 5 15 30 60
• 33 275 ~ / ~
LEACHING TIME - minutes (log scele)
II
Fig. 9--Nickel-to-impurity ratio as a function of acid/ore
ratio and leaching time (250°C, 25 pct solids).
40

AVERAGE
FREE
ACID, solids and preferably to 45 pct solids.2 Such thicken-
g/I ing appears justified when operating in the 240° to
260°C temperature r a n g e utilized by p a s t practice.
30
The data shown in Table IV and Fig. 10 illustrate this
point.
Although leaching at high solids is preferred practice
at 250°C, the same is not true in the 260 t o 275°C tem-
perature r a n g e . At these higher temperatures, leach-
2C
I I i I ing should be c a r r i e d out at low solids (20 to 30 pct)
0.21 0.24 0.27 0.30
for better nickel extraction and solution quality. The
ACID/ORE RATIO r e s u l t is more nickel, but less iron and aluminum be-
Fig. 7--Average free acid in leach liquor as a function o f ing c a r r i e d into the pregnant liquor (Table V).
acid/ore ratio, temperature and pct solids. Thus, the combination of low solids and high tem-

METALLURGICAL TRANSACTIONS B VOLUME 8B, DECEMBER 1977-551

 r i a l . For the nucleation of products of hydrolysis of
Table IV. Effect o f Percent Solidson Metal Extraction When iron and aluminum, it appears that the additional sur-
Leaching Samples "'A" at 250°C for 60 Min face provided by grinding the c o a r s e fraction is more
active than the surface of the readily dissolved min-
Pregnant Liquor Pct Hi
erals.
Pct Solids Acid/Ore Ni/Fe Ni/AI Extraction
Nickel extraction was insensitive t o agitation a f t e r
25 0.21 16 6 91 the f i r s t 30 s of leaching, showing that d u r i n g most
33 0.21 14 8 93 of the reaction period the diffusion of a reacting
25 0.24 13 4 96 species through a liquid boundary l a y e r was not limit-
33 0.24 14 6 95
ing. This study of agitation d u r i n g acid pressure leach-
ing of laterite did verify one of S. I. Sobol's concepts:
to attain high leaching r a t e s and complete conversion,
rapid and perfect m i x i n g of the ore and acid is re-
Table V. Effect ofPercentSolids on Metal Extraction When quired. 5 However, Sobol also stated that "intensive
Leaching Samples"A"at 275°C for 60Min agitation is required d u r i n g the time the sludge re-
m a i n s in the reactors t o attain complete conversion". 6
Pregnant Liquor PctNi This statement is quite contrary to the results ob-
Pct Solids Acid/On Ni/Fe Ni/AI Extraction tained in the present s t u d y . Our work shows that
25 0.21 23 12 94 nickel extraction is independent of agitation after a
33 0,21 16 12 93 b r i e f initial m i x i n g period.
25 0.24 18 8 97 When sulfuric acid is m i x e d with limonite pulp, the
33 0.24 9 5 95 aluminum and iron in the feed (except that portion tied
with chromite), are readily converted to soluble sul-
fates. As this conversion progresses, the acidity of
the liquor decreases from a few hundred to about 25
IOO I I I I
to 50 gram per liter. This drop in acidity at the pre-
vailing high reaction temperature results in the hy-
drolysis of impurities as discussed e a r l i e r in the
Chemistry of Leaching Section.
90 Studies of the Fe203-SO3-H20 system performed by
Posnjak and Haigh15'16 have shown that the only stable
iron phases above 200°C are Fe203, Fe203" 2SO3" H20
and Fe203 • 3SO3. S i m i l a r studies performed by Davey

Ni
EXTN.,
%
8O / on the A1203-SO3-H20 system demonstrated that the
hydrolysis of aluminum sulfate solutions above 220°C
produces hydronium alunite (3AlzO3 •4SO3 ' 9H20) over
a wide r a n g e of operating conditions.9 The SO4:/A1
weight ratio in alunite is 2.4 t o 1. The SO4=/Al'weight
ratio found in the final l e a c h residue was 2.3 to 1.
70 Thus, the predominant f o r m s of iron and aluminum in
the f i n a l l e a c h residue were probably hematite and
alunite, respectively ( i . e . , a s s i g n all of the sulfur to
the aluminum and none to the iron). The IR spectrum
O 33 shown in Fig. 1 and the XRD data summarized in
60 • 45 Table II support this conclusion.
The temperature dependence of the nickel extraction
I" I I I0 I rate between 250 and 275°C is pronounced d u r i n g the
0 30 60 9 120
f i r s t ten min of leaching, but becomes almost tempera-
LEACHING TIME - minutes ture independent after 15 min (Fig. 3). Also, the 225°
F i g . 10--Effect of p u l p d e n s i t y o n nickel extraction b a s e d o n and 300°C reaction temperatures result in significantly
r e s i d u e analyses as a function of leaching time. S a m p l e A lower n i c k e l extraction than does the 250 to 275°C
l a t e r i t e l e a c h e d at 250°C and 0 . 2 4 acid/ore. intermediate r a n g e . Low temperature apparently does
not provide the driving f o r c e needed for rapid nickel
extraction, and very high temperature apparently re-
perature requires 10 pct less acid to attain a com- sults in coprecipitation of nickel with the s o l i d hy-
parable l e v e l of nickel extraction than does the low drolysis products.V
temperature-high solids combination. The sulfur content or the l e a c h residue i n c r e a s e s
with increasing temperature, probably because the
stable form of the aluminum hydrolysis product
DISCUSSION
changes. 8 At 250°C and 20 to 50 gpl H2SO4 concentra-
The rate of nickel extraction is not affected by p r i o r tion, alunite (3A1203 "4SO3" 9H20) is the most stable
grinding of the ore. This insensitivity is probably due aluminum hydrolysis product. At 285°C, the compound
to the insignificant amount of soluble nickel in the A1203' 2SO3 "H20 becomes the stable phase.1° The
c o a r s e fraction ( r e f e r back to Table I). However, the higher temperature aluminum product contains 50 pct
nickel-to-impurity ratio in the pregnant liquor in- more sulfur, and thus accounts for a portion of the in-
creased substantially when leaching the ground m a t e - c r e a s e d sulfur content of the leach residues generated

552-VOLUME 8B, DECEMBER 1977 METALLURGICAL TRANSACTIONS B

at the h i g h e r l e a c h temperatures. The sulfur content
of the l e a c h residue also increases with increasing
a c i d / o r e r a t i o due t o the increased stability of Fe2Oa
•SO3 "H20 and A12Oa' 2SO3" H20 in high acid media.11
The activation energy, calculated between 225° and
275°C, was approximately 30 K c a l / g mole. Such a high
activation energy is associated either with diffusion
of a reactant through a solid (such as hydrolysis pro-
ducts coated on a limonite particle) or with a chemi-
cal reaction. Agitation data indicate that the leaching
reaction is not a diffusion controlled reaction of a
liquid boundary layer.
The characteristic shape of the curves drawn in
Fig. 6 can be constructed by assuming that first a hy-
drolysis product high in sulfur, such as b a s i c alumi-
num sulfate or b a s i c iron sulfate or a mixture of both,
is formed. T h e s e compounds are sensitive to initial
a c i d / o r e r a t i o and temperature. They become unsta-
ble as leaching conditions approach equilibrium (i.e.,
a f t e r the initial c h a r g e is consumed) and transform
t o products containing less sulfur such as alunite and
hematite. F i g u r e 11 illustrates how two hydrolysis
curves additively can reproduce the r a t h e r strange
looking curves of Fig. 6. X-ray diffraction analysis
of leach residues (Table II) confirms that this is what
is taking p l a c e within the autoclave as leaching time
increases. Goethite is not fully converted to hematite
until about 10 min have elapsed (250°C, 33 pct solids,
0.24 acid/ore) and hematite and alunite are the m a j o r
crystalline products in the final l e a c h residues.
The effect of solids content on limonite leaching
can be considered an extension of the acid concentra-
tion effect. High pct solids generate high acid concen-
trations. It has already been shown that an increasing
solution acidity increases the quantity of aluminum
and iron in the pregnant liquor (Fig. 9). Thus, the
lower the pct solids, the lower the impurity l e v e l in
the product solution. What r e a l l y counts, however, is
the nickel/impurity concentration ratio in this solu-
tion. For a given a c i d / o r e ratio, t h e r e is a pct solids
that maximizes the nickel/impurity ratio. Operating
7,0 ~ i I I
~ 2 5 0 ° C, 0,30 Acid/Ore, 3:5%
I f
SULFATE
IN ~~l,Z._/~-Stobl, H~rolwis
RESIDUE, ~/ ProducRs)
"/. 3.c /~t
] ~'\.~;-Tronsient Hydrolysis
~" R'oduct(s)
/ ,
\\
/ ".,
15 :50
LEACHING T I M E - minutes
Fig. ll--Hypothetical construction of observed residual sul-
fate curve by addition of a transient hydrolysis curve to a
jarosite-alunite formation curve.
METALLURGICAL TRANSACTIONS B
4.0 ~ t95
85
3.6
75 NICKEL
EXTRACTION
Ni/(Fe*AI) 3.2
PERCENT
28
2A
,b 2b 3'o 4b so
PERCENT SOLIDS
Fig. 12--Nickel-to-impurities ratio in laterite leach liquor
and nickel extraction as a function of pct solids. Sample A,
leached for 1 h at 250°C and 0.24 acid/ore ratio.
at very low solids results in low nickel solubilization
due t o the disproportionate amount of acid lost to the
end liquor. (See F i g s . 6 and 10).
Nickel-to-impurity ratios in laterite teach liquor
as a function of percent solids are plotted in Fig. 12,
which show that the highest nickel extraction oc-
c u r r e d at about 25 pct solids in one hour, leached at
250°C and 0.24 acid)/ore ratio. Furthermore, data
generated at 275°C show that the l e v e l of solids which
gives the best nickel extraction decreases with increas-
ing temperature. Generally speaking, increasing
temperature increases the initial rate of nickel ex-
traction; increasing a c i d / o r e ratio increases total
nickel extraction and nickel extraction r a t e , and de-
c r e a s i n g the percent solids increases leaching s e l e c -
tivity and acid utilization ( i . e . , less sulfur is lost to
the l e a c h residue.)
Concerning overall improvement of the l e a c h re-
sponse, laterite leaching is best conducted at tern-
peratures h i•g h e r than 250o C and at s o h" d s less th a n 30
pct. The a c i d / o r e l e v e l should be that required t o a t -
tain reasonable nickel extraction at an acceptable
I r
rate.
Solids
ACKNOWLEDGMENTS
The authors thank C. S. Simons (AMAX Nickel Divi-
sion) for his continued support and encouragement, and
particularly for unselfishly s h a r i n g the knowledge and
experience he gained during development of the Moa
Bay operation. Special thanks are extended t o Prof.
H. J. Roorda of Delft University for his direction dur-
ing preparation of this manuscript.
REFERENCES
45 60 1.H.J. Roordaand P.E. Queneau: Institution o f Mining and Metallurgy, Sec. C,
pp. 79-87, June 1973.
2. C.S. Simons: J. o f Metals, 1971,pp.48-58.
3.J. H.Canterford: Rev. PureAppl. Chem., 1972,vol. 22, pp. 17-51.
4.E. T. Carlson and C.S. Simons: Extractive Metallurgy o f Copper, Nickeland
Cobalt, Interscience Publishers, NewYork, N.Y., 1961.
VOLUME 8B, DECEMBER 1977-553
 5. S. I. Sobol: Rev. TechnoL, 1966, vol. 4, no. 5, pp. 3-19.
6. S. I. Sobol: Rev. Technol., 1968, vol. 6, nos. 5-6, pp. 3-24.
7. S. I. Sobol: Rev. Technol., 1969,vol. 7, no. I, pp. 3-23.
8. R. A. Chaves, V. V. Karelin, and B. P. Sobolex: Tsvet.Metal., 1968, vol. 9, no.
4, pp. 66-70.
9. P. T. Davey and T. R. Scott: Aust. J. Appl. Chem., 1962, vol. 13, pp. 229-41.
10. V. I. Goryachkin and S. 1. Sobol:Sb. Nauch. Tr. Gos. Naueh.-Issled. Inst.
Tsvet. Metal, 1965,vol. 23, pp. 252-62.
554-VOLUME 8B, DECEMBER 1977
1 I. C. Nikolic: Thesis, Department of Metallurgy, The University of British
Columbia, February 1971.
12. P. Bayliss: Can. J. Chem., 1971, vol. 49, pp. 2433-41.
13. S. H. C. Briggs: Z Chem. Soc. Proc., 1929, pp. 242-46.
14. J. G. Morrow: U.S. Patent 2,872,306, February 3, 1959.
15. E. Posnjak and H. E. Merwin: J. Amer. Chem. Soc., 1922,vol. 44, pp.
1965-94.
16. C. J. Haigh: Proc. Australas. Inst. Mining Met., 1967,vol. 9, pp. 49-56.
METALLURGICAL TRANSACTIONS B