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Sulfuric acid pressure leaching of nickeliferous limonites

Article  in  Metallurgical and Materials Transactions B · January 1977

DOI: 10.1007/BF02669329

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Sulfuric Acid Pressure Leaching of
Nickeliferous Limonites
E. C. CHOU, P. B. Q U E N E A U , AND R. S. RICKARD

T h i s l a b o r a t o r y study e x a m i n e s the s u l f u r i c a c i d p r e s s u r e l e a c h i n g c h a r a c t e r i s t i c s of
n i c k e l i f e r o u s l i m o n i t e s a m p l e s f r o m South New C a l e d o n i a . T h e e f f e c t of t e m p e r a t u r e
(225~ to 300~ a c i d - t o - o r e r a t i o (0.21 to 0.30), p ct s o l i d s (10 to 45), p a r t i c l e s i z e (--20
to - 2 7 0 m e s h ) , and a g i t a t i o n (50 to 600 r p m ) on n i c k e l e x t r a c t i o n and s e l e c t i v i t y a r e d i s -
c u s s e d . F o r o v e r a l l i m p r o v e m e n t of the l e a c h r e s p o n s e , l e a c h i n g i s b e s t c o n d u c t e d at
t e m p e r a t u r e s h i g h e r than 250~ and at s o l i d s l e s s than 33 pct. V a r i a t i o n of g o e t h i t e ,
h e m a t i t e , and b a s i c a l u m i n u m s u l f a t e c on t en t of the l e a c h r e s i d u e was d e t e r m i n e d s e m i -
q u a n t i t a t i v e l y a s a function of l e a c h i n g t i m e . S u l f a t e co n t en t of the r e s i d u e r i s e s s h a r p l y
d u r i n g the f i r s t s e v e r a l m i n u t e s of l e a c h i n g , then f a l l s , and f i n a l l y e q u i l i b r a t e s at f i v e
to s i x p e r c e n t . T h i s c h a n g e in s u l f a t e a n a l y s i s can be e x p l a i n e d by a s s u m i n g a s e r i e s of
c o n s e c u t i v e i r o n and a l u m i n u m h y d r o l y s i s r e a c t i o n s .

T HE w o r l d ' s l a r g e s t known land b a s e d r e s e r v e s of t i c u l a r a t t e n t i o n is g i v e n to the f i r s t p o r t i o n of the

n i c k e l o c c u r as n i c k e l i f e r o u s l i m o n i t e s . l L i m o n i t e s leaching period.
a r e r i c h in i r o n (40 to 50 pct), c h i e f l y as g o e t h i t e ,
(FeOOH), but low in m a g n e s i a (<5 pct) and s i l i c a (<10
CHARACTERIZATION OF ORE
pct). N i c k e l content s e l d o m e x c e e d s 1.5 pct and
usual l y l i e s b e t w e e n 0.9 and 1.4 pct; the cobalt a s s a y The weight distribution of the size fractions and as-
is t y p i c a l l y 0.1 pct. 2 L a r g e s c a l e n i c k e l e x t r a c t i o n of sociated chemical analyses of the South New Caledonia
l i m o n i t e s u t i l i z e d e i t h e r r e d u c t i v e - r o a s t i n g plus a m - oxide ore used in this study are tabulated in Table I
moniacal atmospheric leaching, or sulfuric acid below.
p r e s s u r e l e a c h i n g . 3 T h i s p a p e r e x a m i n e s the l a t t e r , The - 3/+20 mesh fraction was removed by screen-
which has the a d v a n t a g e of high n i c k e l and cobalt ex - ing because of its low nickel and cobalt content. The
t r a c t i o n at the e x p e n s e of high p r e s s u r e o p e r a t i o n . remaining minus 20 mesh ore was designated Sample
R e s u l t s p r e s e n t e d w e r e obtained at A M A X ' s E x t r a c - "A", and was the feed material used in this study.
t i v e M e t a l l u r g y L a b o r a t o r y a s p a r t of t h e i r d e v e l o p - The fine fractions (-270 mesh of Sample A) are rich
m e n t p r o g r a m f o r r e c o v e r i n g n i c k e l and cobalt f r o m in nickel and iron, whereas the coarse fractions are
oxide o r e s . rich in cobalt, magnesium, manganese, chromium
P u b l i s h e d i n f o r m a t i o n on s u l f u r i c a c i d p r e s s u r e (mostly as chromite) and aluminum. X-ray diffraction
l e a c h i n g of l i m o n i t e is s c a r c e . W o r k p e r f o r m e d in analysis showed the major mineral constituent of Sam-
s u p p o r t of a l a r g e s c a l e o p e r a t i o n at Moa Bay in Cuba ple A was goethite. Also present were lesser quanti-
was f i r s t d e t a i l e d by C a r l s o n and S i m o n s , 4 then e x - ties of quartz, kaolinite, talc, hematite, serpentine,
tended by Sobol s-7 and C h a v e s 8 At Moa Bay, o r e was montmorillonite, chromite and lithiophorite. The in-
wet s c r e e n e d at 20 m e s h , t h i c k e n e d to 45 pct s o l i d s , frared spectra both of Sample A and of a typical limoni-
and p r e s s u r e l e a c h e d at 240 to 250~ with s u l f u r i c tic ore sample from Moa Bay were also obtained. Figure
a c i d. To a t t a i n 95 pct n i c k e l e x t r a c t i o n in 60 to 90 1 shows that both samples have similar characteristic
min, 0.22 pounds of c o n c e n t r a t e d s u l f u r i c a c i d p e r absorption bands except for Sample A's typical sili-
pound of o r e was pumped into the f i r s t a u t o c l a v e of a cate and quartz bands at wavenumber 1020 and II00
four-autoclave train. The pregnant liquor generated cm -I, respectively. The presence of this band indicates
a s s a y e d 6 gpl Ni, 0.8 gpl F e , 2.3 gpl A1, and 28 gpl
f r e e acid. C a r l s o n and S i m o n s r e p o r t e d on the k i n e t i c s
and m e c h a n i s m of this }oressure l e a c h , d e m o n s t r a t i n g
the i m p o r t a n c e of a c i d / o r e r a t i o and t e m p e r a t u r e ; Table I. Size Fractions and Analyses of New Cale4~nian Laterite Ores
k i n e t i c s of n i c k e l e x t r a c t i o n w e r e e x p l a i n e d by t h r e e
Sample
n i c k e l - b e a r i n g s p e c i e s , but no p r o o f was given. T h e Size Fraction, -3 -20 100 -270 "A"
r e m a r k a b l e f e a t u r e of t h e i r w o r k was the s h a p e of the Mesh +20 +100 +270 +400 400 -20
n i c k e l e x t r a c t i o n c u r v e s . Most of the l e a c h i n g was
c o m p l e t e in the f i r s t few m i n u t e s , with l i t t l e e x t r a c - Wt Pct 12 8 7 4 69 88
Assays,Pct
tion o c c u r r i n g d u r i n g the r e m a i n i n g h o u r . T h e p r e s e n t Ni 0.67 1.08 1.77 1.84 1.80 1.73
i n v e s t i g a t i o n e x t e n d s that of C a r l s o n and S i m o n s . P a r - 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. CHOU and 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 A1 3.5 4.1 3.0 2_5 2.4 2.6
is Vice-President, Engineering, Earth Sciences, Inc., Golden, CO. SiO2 8.0 16.3 26.1 21.6 10.8 13.0
Manuscript submitted December 31, 1976.

METALLURGICAL TRANSACTIONS B VOLUME 8B, DECEMBER 1977 547


RELATIVE
ABSORBANCE
,ooo 3~oo ~oo ,5'oo ,o~o ~o
WAVENUMSER, CM -I
Fig. 1--The infrared spectra of Moa Bay Limonite and Sam-
ple A and the residues obtained by leaching Sample A at
250~ 33 pct solids and 0.24 acid/ore ratio.
that Sample A is not a pure l i m o n i t e , but contains some
s i l i c a t e m i n e r a l s , which 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
avoid when m i n i n g l i m o n i t e deposits in which the
b o u n d a r y between the l i m o n i t e and u n d e r l y i n g s e r -
p e n t i n e o r e is not well defined. F i g u r e 1 is d i s c u s s e d
f u r t h e r in the E x p e r i m e n t a l R e s u l t s Section.
E X P E R I M E N T A L PROCEDURE
Leaching
A i r - d r i e d o r e was held at 40~ overnight 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), weighed, s a m p l e d and mixed with w a t e r for
15 m i n in a r o i l e d bottle. The r e s u l t i n g s l u r r y was
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
autoclave and brought to t e m p e r a t u r e over a 40 rain
p e r i o d . Two axial t u r b i n e s (5.7 cm diam) mounted on a
c e n t r a l shaft r o t a t i n g at 600 r p m provided a m p l e m i x -
ing. To begin a test, s u l f u r i c acid (96 pct) was in-
jected 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
e x t e n d i n g about 5 c m downward f r o m the autoclave
head. S a m p l e s were taken through s a m p l i n g b o m b s at
p r o g r a m m e d t i m e s , filtered, and the f i l t e r cakes
washed with pH 2 s u l f u r i c acid solution. Cakes were
d r i e d o v e r n i g h t at l l 0 ~
I n f r a - R e d S p e c t r o s c o p y (IR)
The i n f r a - r e d s p e c t r a of Sample A and its leach
r e s i d u e were obtained u s i n g the KBr p e l l e t technique
with a B e c k m a n Model 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 D i f f r a c t i o n (XRD)
The XRD study of Sample A and its leach r e s i d u e
was conducted u s i n g a c o p p e r - t a r g e t X - r a y tube with
a Norelco 2500 XRD unit and an AMR 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)
The DTA study of Sample A and its leach r e s i d u e
was conducted with a D e l t a t h e r m III Unit 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
The weight 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 was d e -
t e r m i n e d by w e t - s c r e e n technique u s i n g T y l e r s c r e e n s .
Surface A r e a D e t e r m i n a t i o n
The s u r f a c e a r e a of Sample A was m e a s u r e d with a
Q u a n t a c h r o m e s u r f a c e m e a s u r e m e n t unit m a n u f a c t u r e d
by Q u a n t a s o r b Company.
CHEMISTRY OF LEACHING
Sulfuric acid leaching of n i c k e l i f e r o u s l i m o n i t e is
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 s o l u b i l i z e
n i c k e l and cobalt as aqueous s u l f a t e s while c o n v e r t -
ing most of the o r e ' s i r o n and a l u m i n u m content to in-
solubIe h e m a t i t e and a l u m i n u m s u l f a t e s : 4
2FeOOH + 6H* ~ 2Fe §247247
+ 4H20 [1]
2Fe §247+ SO4= + 3H20 ~-~ Fe203 'SO3 'H20 + 4H § [2]
FeeO3 "SO3 "HeO ~-~ FezO3 + SO4= + 2H § [3]
6A1~§ + 4SO4= + 14H20 ~- 3A1203 94SO3 99H20
+ 10H § [4]
2AI~§ + 2SO4: + 2H20 ~ A1203 " 2SO3 "HeO + 2H*. [5]
R e a c t i o n [2] takes place d u r i n g the f i r s t few m i n u t e s
of leaching when acidity is high, 9 then the b a s i c i r o n
sulfate p r o d u c t of R e a c t i o n [2] is h y d r o l y z e d to h e m a -
tite 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, g e n e r a t i n g mostly 3 94 99 hydrate below 250~
(Reaction [4]) and the 1 . 2 91 hydrate above 280~
(Reaction [5]).s The quantity of 1 . 2 91 hydrate also in-
c r e a s e s with acidity, even at t e m p e r a t u r e s below
250~176
E X P E R I M E N T A L RESULTS
I n f r a - r e d s p e c t r a of Sample A and of its leach r e s i -
due (250~ 0.24 a c i d / o r e , 33 pct solids) a p p e a r in Fig.
1. The five b a n d s at 440, 600, 800, 900 and 3180 cm -1
a r e a t t r i b u t e d to goethite. The i n t e n s i t y of t h e s e bands
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 -
ing and 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 min. The bands
at 1020 cm -1 and 1100 cm -1 a r e a t t r i b u t e d to s i l i c a t e
m i n e r a l s and q u a r t z , r e s p e c t i v e l y . The 1020 cm -1 band
d e c r e a s e s and the 1100 cm -~ band r e m a i n s unchanged
with i n c r e a s i n g leaching t i m e , i n d i c a t i n g that the s i l i -
cate m i n e r a l s d i s s o l v e d u r i n g l e a c h i n g w h e r e a s q u a r t z
does not. (Si a n a l y s i s of p r e g n a n t liquor is typically
1 gpl.) T h r e e bands at 340, 475, and 550 cm -~ a r e at-
t r i b u t e d to h e m a t i t e . The i n t e n s i t y of these bands
show the 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 with in-
c r e a s i n g leach t i m e . T h e r e is an unidentified band at
about 1200 cm -~ which may be a t t r i b u t e d to the a l u n i t e .
Two bands at 1640 cm -1 and 3440 cm -~ probably o r i g i -
nate f r o m c o m b i n e d water (i.e., hydroxyl group) in
v a r i o u s m i n e r a l s . T h u s , the IR data do give an indi-
cation of the b e h a v i o r of m i n e r a l s d u r i n g leaching.
In addition, goethite and h e m a t i t e identified by XRD
and a l u n i t e identified by DTA w e r e found in the s a m -
pie and its leach r e s i d u e . The r e l a t i v e q u a n t i t i e s as
c o m p a r e d to the c o r r e s p o n d i n g pure m i n e r a l s a r e il-
l u s t r a t e d in T a b l e II as a function of l e a c h i n g t i m e .
A p o r t i o n of the c h r o m i u m content of the ore also
METALLURGICALTRANSACTIONS B
 III p e r f o r m e d in g r a d u a t e d c y l i n d e r s on the d i s c h a r g e
Table II. Phases Found in Acid Leach Residues of "Sample A" Ore s l u r r y with no r a k e s o r f l o c c u l a n t s i n d i c a t e d that
(250~ 0.24 acid/ore, 33 pct solids)
u l t i m a t e c o m p a c t i o n d e c r e a s e d and t i m e to r e a c h the
Leaching Goethite, Hematite, Alunite, Free Acid, c o m p r e s s i o n p o i n t i n c r e a s e d with i n c r e a s i n g a g i t a t i o n
Time, min FeOOH Fe~O3 3AI~O3-4SO4"9H20 gpl d u r i n g the l e a c h . In g e n e r a l , the r a t e of s e t t l i n g in-
c r e a s e s with i n c r e a s i n g of p a r t i c l e s i z e . F i n e p a r t i -
0 40 Trace Absent 130
1 30 30 Absent 38 c l e s p r o d u c e d u n d e r high s h e a r c o n d i t i o n s p r o b a b l y in-
3 20 45 Absent 34 hibit the s e t t l i n g ; u n f o r t u n a t e l y , the p a r t i c l e s i z e d i s -
5 10 60 Trace 34 t r i b u t i o n was not d e t e r m i n e d d u r i n g the p e r i o d of t e s t -
15 5 65 Minor 37 ing, which m a y e x p l a i n why the b e s t s e t t l i n g c o n d i t i o n s
30 Nil 70 Minor 33 a r e in the 2 7 5 ~ pct s o l i d s - l o w 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 p e r f o r a t e d pad-
dle at 50 r p m , and high s h e a r r e f e r s to m i x i n g with the
twin t u r b i n e s at 600 r p m . In a l l of the 'n o a g i t a t i o n "
t e s t s , the a c i d added to b e g i n the l e a c h was m i x e d with
Table III. Effect of Agitation on Thickening Response When the o r e - w a t e r s l u r r y f o r 30 s at 600 r p m .
Pressure Leaching Sample "'A"
(Acid/Ore = 0.24)
E f f e c t of T e m p e r a t u r e
Leach
F i g u r e 3 i l l u s t r a t e s the e f f e c t of t e m p e r a t u r e on the
Type of Temperature, 24 h Compression r a t e and e x t e n t of n i c k e l e x t r a c t i o n . T e m p e r a t u r e s a p-
Agitation ~ Solids, Pct Compaction,Pet Point, h
p r o a c h i n g 250~ a r e r e q u i r e d f o r r a p i d l e a c h i n g .
None 250 33 44 4.9 C o m p a r a b l e e x t r a c t i o n , but at a h i g h e r i n i t i a l r a t e , is
Low shear 250 33 44 6.3 a t t a i n e d at 275~ l e a c h i n g at 300~ l o w e r s the n i c k e l
Highshear 250 33 42 7.3 y i e l d . In a n a l y z i n g data p r e s e n t e d in F i g , 3, the f i r s t
None 250 45 53 2.5
Low shear 250 45 48 None o r d e r a s s u m p t i o n f i t s the d a t a f a i r l y w e l l in the r a n g e
Highshear 250 45 46 None of 75 p ct to 90 pct n i c k e l l e a c h e d , but the r a t e is
None 275 45 52 4.0 m u c h h i g h e r e a r l y in the r e a c t i o n . B a s e d on A r r h e n i u s
Low shear 275 45 60 2.3 equation, a plot of log k v s 1/T (K) in F i g . 4 show that
High shear 275 45 51 None
the e n e r g y of a c t i v a t i o n c a l c u l a t e d b e t w e e n 225 ~ and
275~ is a p p r o x i m a t e l y 30 K c a l / g m o l e .
C u r v e s s i m i l a r to t h o s e shown in F i g . 3 could have
b e e n p l o t t ed f o r c o b a l t e x t r a c t i o n , and would have
d i s s o l v e s , but is to a l a r g e extent h y d r o l y z e d d u r i n g shown that u l t i m a t e cobalt e x t r a c t i o n l a g s that of
the l a t e r s t a g e of l e a c h i n g (probably as Cr3(SO4)2 • n i c k e l by 3 to 4 pct. H o w e v e r , the i n i t i a l r a t e of c o -
(OH)sHeO (Ref. 12) and 3A12Oa 9 2CRO3 9 6HeO. 13 About b a l t e x t r a c t i o n was a l w a y s h i g h e r than that of n i c k e l .
half of S a m p l e A ' s m a g n e s i u m and m a n g a n e s e content
a r e s o l u b l e , as is m o s t of the t r a c e c o p p e r and z i n c
content of the o r e .
~.O!
E f f e c t of P a r t i c l e S i z e 100%-270 Mesh

To d e t e r m i n e the effect of p r i o r g r i n d i n g on l e a c h -
ing, t h r e e s a m p l e s of S a m p l e A w e r e ground to 100
2.6
p c t - 20 m e s h (78 p c t - 4 0 0 m e s h ) , 100 p c t - 100 m e s h
(82 p c t - 4 0 0 m es h ) and 100 p c t - 2 7 0 m e s h (91 pct
- 4 0 0 m e s h ) , r e s p e c t i v e l y . T h e s u r f a c e a r e a s of t h e s e
ground s a m p l e s w e r e 60.5, 65.3 and 66.8 m 2 / g r e s p e c -
t i v e l y . E a c h of t h e s e f r a c t i o n s was then p r e s s u r e 2.2
l e a c h e d at 250~ 0.24 a c i d / o r e r a t i o (based on 96 pct Ni/(Fe +AI)
H2SO~) and 33 pct s o l i d s . N e i t h e r the r a t e nor the ex -
tent of n i c k e l e x t r a c t i o n was a f f e c t e d by the o r e grind;
h o w e v e r , the n i c k e l - t o - i m p u r i t y r a t i o s in the p r e g n a n t 1.8
l i q u o r i n c r e a s e d s u b s t a n t i a l l y when l e a c h i n g the
gound m a t e r i a l . See F i g . 2. A p p a r e n t l y the i n c r e a s e d e

s u r f a c e g e n e r a t e d by g r i n d i n g p r o v i d e s a d d i t i o n a l nu-
c l e a t i n g s i t e s f o r h y d r o l y s i s of the i r o n and a l u m i -
num, s o l u b i l i z e d d u r i n g the i n i t i a l s t a g e s of l e a c h i n g . 1.4

E f f e c t of A g i t a t i o n
1,5 3'0 4'5 6'0
A f t e r the acid had b e e n t h o r o u g h l y m i x e d with the
s l u r r y fo r 30 s, no a d d i t i o n a l a g i t a t i o n was r e q u i r e d . LEACHING TIME minutes
T h u s , t u r n i n g the a g i t a t o r off t h i r t y s e c o n d s a f t e r a c i d Fig. 2--Nickel-to-impurity ratios in Sample A leach liquor
i n j e c t i o n h i n d e r e d n e i t h e r the r a t e n o r the e x t e n t of as a function of leaching time and grind (250~ 0.24 acid/ore
n i c k e l e x t r a c t i o n . T h i c k e n i n g t e s t s a s shown in T a b l e and 33 pct solids).

METALLURGICAL TRANSACTIONS B VOLUME SB, DECEMBER 1977-549

 I00 9 I i i I i i i

050 ~,7~oc ~0o/~c

90
2 ~ 225"C o.z'r INi/Fe: , 4 . 0 / J
Ni ACID/ ORE
80
EXTN, RATIO
%
70 / 55 % Solids
0.24 Acid/Ore
/ /// 2~o.c~
600 RPM
6C
.... I I I I I I
I 3 5 15 30 60

LEACHING TIME-minutes(l~ scale)

15 50 45 60 Fig. 5--Leaching time required to attain a given nickel-to-
LEACHING T I M E - minutes impurity ratio as a function of temperature and acid/ore ratio.
Fig. 3--Nickel extraction as a functien ofleaching time and
temperature.
T h e f r e e a c i d in the l e a c h l i q u o r d e c r e a s e d f r o m the
i n i t i a l c o n c e n t r a t i o n of o v e r 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 m i n u t e s of l e a c h i n g , and
r e m a i n e d at this e q u i l i b r i u m c o n c e n t r a t i o n throughout
the r e s t of the l e a c h i n g p e r i o d . The e q u i l i b r i u m con-
60
c e n t r a t i o n was independent of t e m p e r a t u r e v a r i a t i o n
50
f r o m 250 to 275~ (Fig. 7). One might have e x p e c t e d
40
LOg k= 2.30~'RT the f r e e a c i d l e v e l of the h o t t e r l i q u o r s to be h i g h e r ,
30 * Constant b e c a u s e in t h e s e s o l u t i o n s m e t a l h y d r o l y s i s was m o s t
c o m p l e t e . H o w e v e r , at the h i g h e r t e m p e r a t u r e , m o r e
c a I/g- molq
20 s u l f a t e was tied up in the a l u m i n u m p r e c i p i t a t e , so
h y d r o l y s i s at 275~ d o e s not g e n e r a t e the quantity of
kxlOZ,min- t f r e e a c i d that would have b e e n f o r m e d at 250~
I0
8 Effect of A c i d / O r e R a t i o
6 \ One v a r i a b l e r e q u i r i n g c a r e f u l c o n t r o l is the weight
498 2.73 of a c i d a d d e d to a given weight of o r e (i.e., a c i d / o r e
4 5?_.3 17.0 r a t i o ) . A l r e a d y shown was the i n c r e a s e in r e s i d u a l
548 51.4 s u l f u r content with i n c r e a s e d a c i d addition. M o r e i m -
3
p o r t a n t is the effect of a c i d / o r e r a t i o on the t i m e r e -
q u i r e d to a t t a i n a given l e v e l of n i c k e l e x t r a c t i o n .
,,~ ,.~ 2'.o ( R e f e r to F i g . 8). 90 p c t n i c k e l e x t r a c t i o n is a t t a i n e d
I/T• OK-I in 5 rain at 250~ 25 pct s o l i d s and 0.30 a c i d / o r e ;
t h r e e t i m e s l o n g e r is r e q u i r e d if only 0.27 units of
Fig. 4--Rate of nickel extraction as a function of temperature.
a c i d a r e a d d e d . U n f o r t u n a t e l y , s h o r t l e a c h t i m e s at
high a c i d / o r e a l s o l e a v e s u b s t a n t i a l q u a n t i t i e s of i r o n
and a l u m i n u m in the p r e g n a n t liquor. The s a m e
It is not s u f f i c i e n t to c o n s i d e r only the n i c k e l and change f r o m 0.27 up to 0.30 a c i d ~ o r e r a t i o i n c r e a s e d
c o b a l t r e c o v e r y ; s e l e c t i v i t y i s a l s o an i m p o r t a n t f a c t o r the quantity of i r o n and a l u m i n u m in the p r e g n a n t
for s u b s e q u e n t m e t a l r e c o v e r y . F i g u r e 5 shows the l i q u o r by 100 pct and 33 pct, r e s p e c t i v e l y , at about 30
l e a c h i n g t i m e r e q u i r e d to a t t a i n N i / F e and Ni/A1 r a - min of l e a c h i n g . (See F i g . 9). The N i / F e r a t i o in-
tios of four in the p r e g n a n t l i q u o r at s e v e r a l a c i d / o r e c r e a s e s f a s t e r with t i m e than does the Ni/A1 r a t i o ,
r a t i o s . It i s c l e a r that i n c r e a s i n g the t e m p e r a t u r e r e f l e c t i n g the r e l a t i v e r a t e of h y d r o l y s i s of t h e s e i m -
f r o m 250 ~ up to 275~ s u b s t a n t i a l l y i m p r o v e s p r e g n a n t p u r i t i e s . T h e i m p u r i t y c u r v e s g e n e r a l l y have a p o s i -
l i q u o r q u a l i t y o v e r the r a n g e of l e a c h i n g t i m e and tive slope, a t r e n d which is m a i n t a i n e d a s t e m p e r a t u r e
acid/ore ratios investigated. i n c r e a s e s . T h i s s l o p e r e f l e c t s the i n c r e a s e d s o l u b i l i t y
L e a c h i n g t e m p e r a t u r e a l s o has a s h a r p effect on the of the i r o n and a l u m i n u m h y d r a t e s with the i n c r e a s e d
a m o u n t of s u l f a t e r e p o r t i n g in the r e s i d u e , (Sulfur a c i d i t y g e n e r a t e d by the h i g h e r a c i d to o r e r a t i o s .
is a m a j o r o p e r a t i n g e x p e n s e , and that p o r t i o n lost to
the r e s i d u e is the m o s t difficult to u t i l i z e o r r e -
Effect of P e r c e n t Solids
cycle) .14 See F i g . 6. The sulfate a s s a y of the r e s i d u e
r i s e s s h a r p l y d u r i n g the f i r s t s e v e r a l m i n u t e s of T h i s v a r i a b l e has been s a v e d until l a s t , b e c a u s e the
leaching, then f a l l s , and f i n a l l y e q u i l i b r a t e s at five to l e v e l of s o l i d s which gives the b e s t n i c k e l e x t r a c t i o n
s i x pct. Sulfur l o s s e s a r e g r e a t e s t at high t e m p e r a - d e c r e a s e s with i n c r e a s i n g t e m p e r a t u r e at a given
t u r e and high a c i d / o r e , and l e a s t at low l e v e l s of t e m - a c i d a d d i t i o n and l e a c h t i m e ( T a b l e s IV and V). L i m o -
p e r a t u r e and a c i d / o r e . A s a t i s f a c t o r y s u l f a t e b a l a n c e nite a c i d l e a c h i n g l i t e r a t u r e e m p h a s i z e s the d e s i r a -
was obtained between s o l i d and s o l u t i o n in t h e s e t e s t s . b i l i t y of t h i c k e n i n g the o r e feed to at l e a s t 33 pct

550-VOLUME 8B, DECEMBER 1977 METALLURGICAL TRANSACTIONS B

 -- I I I I 1 I I i E I I
7.0 7
i
o,e q

AC
R
ID
oC
A
Io~
;2
E
.~
1
o
,]2
'.557~
5E
%
,N
~X
~iTN
,9l.0
,%,~.,
275~ 0.21 A / O i
5.0

SULFATE / j o~oA,o~-
IN
RESIDUE,
%

3.0

25% Solids I 3 5 15 30 60
LEACHING TIME- minutes(log scale)
Fig. 8--Nickel extraction as a function of acid/ore ratio and
I I 1
15 30 45 60 leaching time (250~ 25 pet solids).
LEACHING TIME - minutes
I ! I ! i i i i i I

9.0

1.0
o.~ /
ACID/ORE o.27 / / O'O~ff
RATIO
IN
SULFATE 7 . 0 ~
RESIDUE, : ~' 0.24
%
5.0
0.21
! ~ 250 ~ , 0.21 A / O
A~___ I _ i t __ /
3 5 15 3O 6o
LEACHING TIME- minutes (log scale)
3'~ t 33% Solids
F T- - f ..... ~ - - 9

I I L I 0.3C / ~ ~
o 15 30 45 60
1.2
LEACHING TIME - minutes
Fig. 6--Sulfate content of Sample A ' s leach residue as a
function of leaching time, temperature, acid/ore ratio RATIO .5 Ni/AI =2.O
and pct solids.
0.2~

50
I % I ~ I I 0.21
I 3 5 115
,9
30 60
Q 33 275 LEACHING TIME- minutes(log .~cale)
Fig, 9--Nickel-to-impurity ratio as a function of acid/ore
ratio and leaching time (250~ 25 pet solids).
4O
AVERAGE
FREE
ACID, s o l i d s and p r e f e r a b l y to 45 pct s o l i d s . 2 Such t h i c k e n -
g/I ing a p p e a r s j u s t i f i e d when o p e r a t i n g in the 240 ~ to
260~ t e m p e r a t u r e r a n g e u t i l i z e d by p a s t p r a c t i c e .
30 The d a t a shown in T a b l e IV and F i g . 10 i l l u s t r a t e this
point.
Although l e a c h i n g at high s o l i d s is p r e f e r r e d p r a c t i c e
at 250~ the s a m e is not t r u e in the 260 to 275~ t e m -
p e r a t u r e r a n g e . At t h e s e h i g h e r t e m p e r a t u r e s , l e a c h -
20 ing should be c a r r i e d out at low s o l i d s (20 to 30 pct)
I I I ]
0.21 0,24 0.27 0.30 f o r b e t t e r n i c k e l e x t r a c t i o n and s o l u t i o n q u a l i t y . T h e
ACID/ORE RATIO r e s u l t is m o r e n i c k e l , but l e s s i r o n and a l u m i n u m b e -
Fig. 7--Average free acid in leach liquor as a function of i n g c a r r i e d into the p r e g n a n t l i q u o r ( T a b l e V).
acid/ore ratio, temperature and pet solids. T h u s , the c o m b i n a t i o n of low s o l i d s and high t e r n -

METALLURGICAL TRANSACTIONS B VOLUME 8B, DECEMBER 1977-551

 r i a l . F o r the nucleation of products of h y d r o l y s i s of
Table IV. Effect of Percent Solids on Metal Extraction When iron and aluminum, it a p p e a r s that the additional s u r -
Leaching Samples "A" at 250~ for 60 Min face provided by grinding the c o a r s e fraction is more
active than the s u r f a c e of the r e a d i l y d i s s o l v e d min-
Pregnant Liquor Pct Ni
erals.
Pct Solids Acid/Ore Ni/Fe Ni/AI Extraction
Nickel e x t r a c t i o n was insensitive to agitation a f t e r
25 0.21 16 6 91 the f i r s t 30 s of leaching, showing that during most
33 0,21 14 8 93 of the r e a c t i o n p e r i o d the diffusion of a r e a c t i n g
25 0.24 13 4 96
s p e c i e s through a liquid boundary l a y e r was not l i m i t -
33 0.24 14 6 95
ing. This study of agitation during acid p r e s s u r e leach-
ing of l a t e r t t e did v e r i f y one of S. I. Sobol's concepts:
to attain high leaching r a t e s and complete conversion,
r a p i d and p e r f e c t mixing of the o r e and acid is r e -
Table V. Effect of Percent Solids on Metal Ext~ction When quired. 5 However, Sobol a l s o s t a t e d that " i n t e n s i v e
Leaching Samples "'A" at 275~ for 60 Min agitation is r e q u i r e d during the time the sludge r e -
mains in the r e a c t o r s to attain complete c o n v e r s i o n " . 6
Pregnant Liquor Pct Ni This s t a t e m e n t is quite c o n t r a r y to the r e s u l t s ob-
Pct Solids Acid/Ore Ni/Fe Ni/AI Extraction tained in the p r e s e n t study. Our work shows that
25 0.21 23 12 94 nickel e x t r a c t i o n is independent of agitation after a
33 0,21 16 12 93 b r i e f initial mixing p e r i o d .
25 0.24 18 8 97 When sulfuric acid is mixed with limonite pulp, the
33 0.24 9 5 95 aluminum and iron in the feed (except that portion tied
with chromite), a r e r e a d i l y converted to soluble sul-
fates. As this conversion p r o g r e s s e s , the acidity of
I00
the liquor d e c r e a s e s from a few hundred to about 25
I I I I
to 50 gram p e r l i t e r . This drop in acidity at the p r e -
vailing high r e a c t i o n t e m p e r a t u r e r e s u l t s in the hy-
d r o l y s i s of i m p u r i t i e s as d i s c u s s e d e a r l i e r in the
C h e m i s t r y of Leaching Section.
Studies of the FezO3-SO3-H~O s y s t e m p e r f o r m e d by

/
90
Posnjak and Haigh 15'16 have shown that the only stable
iron phases above 200~ a r e Fe20~, Fe203" 2SO3" H20
and Fe203 93SO3. S i m i l a r studies p e r f o r m e d by Davey
on the A1203-SO3-H20 s y s t e m d e m o n s t r a t e d that the
h y d r o l y s i s of aluminum sulfate solutions above 220~
p r o d u c e s hydronium alunite (3A1203 94SO3 ' 9H20) over
EXTN., a wide range of o p e r a t i n g conditions.9 The SO4=/A1
%
weight r a t i o in alunite is 2.4 to 1. The SO4:/A1 weight
r a t i o found in the final leach r e s i d u e was 2.3 to 1.
70
T/J E] - ~0
Thus, the predominant forms of iron and aluminum in
/~ O - 20
the final leach r e s i d u e were probably hematite and
alunite, r e s p e c t i v e l y (i.e., a s s i g n all of the sulfur to
/ & - 25
the aluminum and none to the iron). The IR s p e c t r u m
O 33 shown in Fig. 1 and the XRD data s u m m a r i z e d in
60 9 45 Table H support this conclusion.
The t e m p e r a t u r e dependence of the nickel e x t r a c t i o n
I" t ~ 70 I r a t e between 250 and 275~ is pronounced during the
0 30 60 120
f i r s t ten min of leaching, but becomes a l m o s t t e m p e r a -
LEACHING TIME - minutes ture independent after 15 min (Fig. 3). Also, the 225 ~
Fig. 1 0 - - E f f e c t of pulp d e n s i t y on nickel e x t r a c t i o n b a s e d on and 300~ r e a c t i o n t e m p e r a t u r e s r e s u l t in significantly
r e s i d u e a n a l y s e s as a function of l e a c h i n g t i m e . S a m p l e A lower nickel e x t r a c t i o n than does the 250 to 275~
l a t e r i t e leached at 250~ and 0.24 a c i d / o r e .
i n t e r m e d i a t e range. Low t e m p e r a t u r e apparently does
not provide the d r i v i n g force needed for rapid nickel
extraction, and v e r y high t e m p e r a t u r e apparently r e -
p e r a t u r e r e q u i r e s 10 pct l e s s acid to attain a com- sults in c o p r e c i p i t a t i o n of nickel with the solid hy-
p a r a b l e level of nickel extraction than does the low d r o l y s i s products. 7
temperature-high solids combination. The sulfur content or the leach r e s i d u e i n c r e a s e s
with i n c r e a s i n g t e m p e r a t u r e , probably because the
DISCUSSION stable f o r m of the aluminum h y d r o l y s i s product
changesfl At 250~ and 20 to 50 gpl H2SO4 c o n c e n t r a -
The r a t e of nickel e x t r a c t i o n is not affected by p r i o r tion, alunite (3A1203 "4SO3" 9H20) is the most stable
grinding of the ore. This i n s e n s i t i v i t y is probably due aluminum h y d r o l y s i s product. At 285~ the compound
to the insignificant amount of soluble nickel in the A1203 92SO3 "H20 becomes the stable phase.l~ The
c o a r s e fraction ( r e f e r back to Table I). However, the higher t e m p e r a t u r e aluminum product contains 50 pct
n i c k e l - t o - i m p u r i t y r a t i o in the pregnant liquor in- m o r e sulfur, and thus accounts for a portion of the in-
c r e a s e d substantially when leaching the ground m a t e - c r e a s e d sulfur content of the leach r e s i d u e s generated

552-VOLUME 8B, DECEMBER 1977 METALLURGICAL TRANSACTIONS B

 at the higher leach t e m p e r a t u r e s . T h e s u l f u r content
of the l e a c h r e s i d u e also i n c r e a s e s with i n c r e a s i n g
a c i d / o r e r a t i o due to the i n c r e a s e d s t a b i l i t y of Fe2Oa
9SOn 9H20 and A1203 92SOs 9H20 in high acid media.iX
T h e a c t i v a t i o n e n e r g y , c a l c u l a t e d b e t w e e n 225 ~ and
275~ was a p p r o x i m a t e l y 30 K c a l / g mole 9 Such a high
a c t i v a t i o n e n e r g y is a s s o c i a t e d e i t h e r with diffusion
of a r e a c t a n t through a solid (such as h y d r o l y s i s p r o -
ducts coated on a l i m o n i t e p a r t i c l e ) o r with a c h e m i -
cal r e a c t i o n . Agitation data i n d i c a t e that the l e a c h i n g
r e a c t i o n is not a diffusion c o n t r o l l e d r e a c t i o n of a
liquid b o u n d a r y layer 9
T h e c h a r a c t e r i s t i c shape of the c u r v e s d r a w n in
Fig. 6 can be c o n s t r u c t e d by a s s u m i n g that f i r s t a hy-
d r o l y s i s p r o d u c t high i n s u l f u r , such a s b a s i c a l u m i -
n u m sulfate o r b a s i c i r o n s u l f a t e o r a m i x t u r e of both,
is f o r m e d . T h e s e compounds a r e s e n s i t i v e to i n i t i a l
a c i d / o r e r a t i o and t e m p e r a t u r e . They b e c o m e u n s t a -
b l e as l e a c h i n g conditions a p p r o a c h e q u i l i b r i u m ( i . e . ,
a f t e r the i n i t i a l charge is c o n s u m e d ) and t r a n s f o r m
to p r o d u c t s c o n t a i n i n g l e s s s u l f u r s u c h a s a l u n i t e and
h e m a t i t e . F i g u r e 11 i l l u s t r a t e s how two h y d r o l y s i s
c u r v e s additively can r e p r o d u c e the r a t h e r s t r a n g e
looking c u r v e s of Fig. 6. X - r a y d i f f r a c t i o n a n a l y s i s
of leach r e s i d u e s (Table II) c o n f i r m s that this i s what
is t a k i n g p l a c e within the a u t o c l a v e a s l e a c h i n g t i m e
i n c r e a s e s . Goethite is not fully c o n v e r t e d to h e m a t i t e
u n t i l about 10 rain have e l a p s e d (250~ 33 pet s o l i d s ,
0.24 a c i d / o r e ) and h e m a t i t e and a l u n i t e a r e the m a j o r
c r y s t a l l i n e products in the f i n a l leach r e s i d u e s .
The effect of s o l i d s content on l i m o n i t e l e a c h i n g
can be c o n s i d e r e d an e x t e n s i o n of the a c i d c o n c e n t r a -
tion effect. High pet s o l i d s g e n e r a t e high a c i d c o n c e n -
t r a t i o n s . It has a l r e a d y been shown that an i n c r e a s i n g
s o l u t i o n acidity i n c r e a s e s the q u a n t i t y of a l u m i n u m
and i r o n in the p r e g n a n t liquor (Fig. 9). T h u s , the
lower the pct solids, the l o w e r the i m p u r i t y l e v e l in
the p r o d u c t s o l u t i o n . What r e a l l y c o u n t s , h o w e v e r , is
the n i c k e L / i m p u r i t y c o n c e n t r a t i o n r a t i o in this s o l u -
tion. F o r a given a c i d / o r e r a t i o , t h e r e is a pct s o l i d s
that m a x i m i z e s the n i c k e l / i m p u r i t y r a t i o , O p e r a t i n g
I -- I I
zo
r 2 5 0 * C . 0 . 3 0 Acid l o r e ,
5.0 I The a u t h o r s thank C. S. S i m o n s (AMAX N i c k e l D i v i -
f sion) for h i s c o n t i n u e d s u p p o r t and e n c o u r a g e m e n t , and
SULFATE
IN II ,~--Stable
/ Hydrolysis
RESIDUE, ~ PfOauctts)
% 3.0 /~
I .
I \ <- Tronsient Sydroly~t~
V Product(s)
\ REFERENCES
/ \,
15 30 45
LEACHING TIME - minutes
Fig. ll--Hypothetical construction of observed residual sul-
fate curve by addition of a transient hydrolysis curve to a
jarosite-alunite formation curve.
METALLURGICALTRANSACTIONSB
95
4.0
85
3.6
75 NICKEL
Ni/(Fe*AI) a.2 EXTRACTION
PERCENT
28
2.4
,b 2b 3b 4b 50
PERCENT SOLIDS
Fig. 12--Nickel-to-impurities ratio in laterlte leach liquor
and nickel extraction as a function of pet solids. Sample A ,
leached for 1 h at 250~ and 0.24 acid/ore ratio.
at v e r y low s o l i d s r e s u l t s in low n i c k e l s o l u b i l i z a t i o n
due to the d i s p r o p o r t i o n a t e a m o u n t of acid lost to the
end l i q u o r . (See F i g s . 6 and 10).
N i c k e l - t o - i m p u r i t y r a t i o s in l a t e r i t e l e a c h l i q u o r
a s a f u n c t i o n of p e r c e n t s o l i d s a r e p l o t t e d i n F i g . 12,
which show that the h i g h e s t n i c k e l e x t r a c t i o n o c -
c u r r e d at about 25 pct s o l i d s in one h o u r , l e a c h e d at
250 C and 0.24 a c i d / o r e r a t i o . F u r t h e r m o r e , data
g e n e r a t e d at 275~ show that the l e v e l of s o l i d s which
gives the b e s t n i c k e l e x t r a c t i o n d e c r e a s e s with i n c r e a s -
ing t e m p e r a t u r e 9 G e n e r a l l y s p e a k i n g , i n c r e a s i n g
t e m p e r a t u r e i n c r e a s e s the i n i t i a l r a t e of n i c k e l ex-
traction; i n c r e a s i n g a c i d / o r e ratio i n c r e a s e s total
n i c k e l e x t r a c t i o n and n i c k e l e x t r a c t i o n r a t e , and de-
c r e a s i n g the p e r c e n t s o l i d s i n c r e a s e s l e a c h i n g s e l e c -
t i v i t y and a c i d u t i l i z a t i o n ( i . e . , l e s s s u l f u r i s l o s t to
the l e a c h r e s i d u e . )
C o n c e r n i n g o v e r a l l i m p r o v e m e n t of the l e a c h r e -
s p o n s e , l a t e r i t e l e a c h i n g is b e s t conducted at t e m -
p e r a t u r e s h i g h e r than 250~ and at s o l i d s l e s s than 30
pct. The a c i d / o r e l e v e l should be that r e q u i r e d to a t -
F ~ t a i n r e a s o n a b l e n i c k e l e x t r a c t i o n at a n a c c e p t a b l e
rate.
5 3 % Solid~
ACKNOWLEDGMENTS
p a r t i c u l a r l y for u n s e l f i s h l y s h a r i n g the knowledge and
e x p e r i e n c e he gained d u r i n g d e v e l o p m e n t of the Moa
Bay o p e r a t i o n 9 S p e c i a l thanks a r e extended to P r o f .
H. J. R o o r d a of Delft U n i v e r s i t y f o r his d i r e c t i o n d u r -
ing p r e p a r a t i o n of this m a n u s c r i p t 9
60 1. H. J. Roorda and P. E. Queneau:Institution of Mining and Metallurgy, Sec.C,
pp. 79-87,June 1973.
2. C. S. Simons:J. of Metals, 1971,pp. 48-58.
3. J. H. Canterford:Rev. Pure AppL Chem., 1972,vol. 22, pp. 17-51.
4. E. T. Carlsonand C. S. Simons:Extractive Metallurgy of Copper, Nickel and
Cobalt, IntersciencePublishers,New York, N.Y., !96 I-
VOLUME 8B, DECEMBER 1977-553
 5. S. I. Sobol: Rev. Technol., 1966, vol. 4, no. 5, pp. 3-19.
6. S. 1. Sobol: Rev. Technol., 1968, vol. 6, nos. 5-6, pp. 3-24.
7. S. I. Sobol: Rev. Technol., 1969, vol. 7, no. 1, 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. I. Sobol: Sb. Nauch. Tr. Gos. Nauch.-lssled. Inst.
Tsvet. Metal, 1965, vol. 23, pp. 252-62.
5 5 4 - V O L U M E 8B, DECEMBER 1977
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11. 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: J. 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: 3". 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