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Nickel Leaching Using Pressured Sulphuric Acid
Nickel Leaching Using Pressured Sulphuric Acid
Nickel Leaching Using Pressured Sulphuric Acid
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.
S u r f a c e Area Determination
RELATIVE
ABSORBANCE 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
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).
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
/ I I i ] I _ I
I 3 5 15 50 60
, 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
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-
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
ACKNOWLEDGMENTS
The authors thank C. S. Simons (AMAX Nickel Divi-
I f
sion) for his continued support and encouragement, and
SULFATE
IN ~~l,Z._/~-Stobl, H~rolwis particularly for unselfishly s h a r i n g the knowledge and
RESIDUE, ~/ ProducRs) experience he gained during development of the Moa
"/. 3.c /~t Bay operation. Special thanks are extended t o Prof.
H. J. Roorda of Delft University for his direction dur-
ing preparation of this manuscript.
] ~'\.~;-Tronsient Hydrolysis
~" R'oduct(s)
/ ,
\\ REFERENCES
/ ".,
15 :50 45 60 1.H.J. Roordaand P.E. Queneau: Institution o f Mining and Metallurgy, Sec. C,
pp. 79-87, June 1973.
LEACHING T I M E - minutes 2. C.S. Simons: J. o f Metals, 1971,pp.48-58.
Fig. ll--Hypothetical construction of observed residual sul- 3.J. H.Canterford: Rev. PureAppl. Chem., 1972,vol. 22, pp. 17-51.
fate curve by addition of a transient hydrolysis curve to a 4.E. T. Carlson and C.S. Simons: Extractive Metallurgy o f Copper, Nickeland
jarosite-alunite formation curve. Cobalt, Interscience Publishers, NewYork, N.Y., 1961.