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hydrometallurgy
Hydrometallur
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School of Chemical and Metallurgical Engineering, University of the Witwatersrand, Johannesburg, P/Bag 3, Wits 2050, South Africa b TTI,
Texas A&M University System, College Station, TX 77843, USA
a
A R T I C L E
I N F O
Article history:
Received 22 August 2009
Received in revised form 11 March 2010
Accepted 16 March 2010
Available online 25 March 2010
Keywords:
Microbial leaching
Nickel laterites
Chemoorganotrophic
Fungal
Chemolithotrophic
Microorganisms
1.
A B S T R A C
T
Nickel is an important metal in human life and in the industry. In recent years,
the world nickel demand has been driven by soaring steel production,
particularly in China. With the rapid growing demand for nickel coupled with
the depletion of high grade sulphide reserves, low-grade nickel ores, which
cannot be economically processed by conventional metallurgical processes,
become increasingly important sources of nickel. Laterite ore, which is often
considered as a low-grade nickel ore, contains several kinds of metal elements
including nickel, cobalt, iron, silicon, aluminium, and chromium; and thus,
constitutes an alternative source of nickel. The nickel present in nickel
laterites is not usually present as discrete minerals, but as cations substituted
within manganese oxides, goethite, and/or clays. Because of this, it is difficult
to upgrade the ore by beneficiation. As a result, nickel laterites are
traditionally processed using pyrometallurgical and hydrometallurgical
methods. In recent years, microbiological leaching has been found to be a
promising novel technology for recovering valuable minerals from traditionally
difficult-to- process ores. Microbial leaching of low-grade ores offers many
advantages over other conventional methods due to its relative simplicity,
requiring mild operating conditions, low capital costs, low energy input,
relatively unskilled labour requirements, and being environmentally friendly.
Because of the importance of microbial leaching, recent advances in microbial
assisted leaching of nickel laterites are discussed in this paper with emphasis
on fungal (chemoorganotrophic) and chemolithotrophic microorganisms.
2010 Elsevier B.V. All rights reserved.
Introduction
Resource
Mt
400
Pyrometallurgy
0
Hydrometallurgy
860
0
Total
12,
600
Mt = metric tonnes; Ni = nickel.
Ni content
Mt
62
99
161
Distribution
%
39
61
100
(2)
(3)
Complexation/chelation
Ni2 + +C6H8O7^Ni(C6H5O7)- + 3H+
(4)
Table 2
Smelting
Proven technology
Caron process
Proven technology
Disadvantag
es
Environmental concerns
Environmental concerns
Environmental concerns
Expensive to run
Expensive to run
Expensive to run
Microbial leaching
Low temperature
process
Runs at
atmospheri
c pressure
Low degree
of process
control
Can treat
low-grade
nickel
lateritetime
ores
Long residence
required
Only been successful
at demonstration plant
scale
Table 3
PHIEP of
Ore type
Limonite
Nontronite
6.6
2.0
Saprolite
Weathered saprolite
3.6
3.8
quantities, such as Fe, Mg, Al, Mn, Ca, etc. As a result, acid
attack (Eq. (2)) of any carbonate material in the ore also
enhances nickel liberation. However, this reaction requires
the generation of excess acid. Furthermore, the reduction of
soluble manganese (Eq. (3)) can result in the equilibrium
pHIEP is the pH value that corresponds to isoelectric point of the
ore.
Type of fungi or
strains
Aspergillus,
Penicillum
Aspergillus,
Penicillum
Penicillum
Aspergillus,
Penicillum
Aspergillus niger
Aspergillus foetidus
Aspergillus,
Penicillum
Aspergillus
Acid types
Ni recoveries (%
wt)
X
Citric, oxalic
Citric
Citric, oxalic
Up to 36
50-60
Up to 72
55-60
Citric, oxalic
X
X
Citric acid, oxalic,
gluconic
Up to 78
28
Up to 35
Up to 34
Reference
(2001a)
al. (1993)
(1986)
(1994)
al. (2000)
(2006)
(2001d)
(2007)
Fig. 2. Schematic comparison of the thiosulfate (A) and polysulfide (B) mechanisms in (bio)leaching of
metal sulfides (
).
1996
10
bactem
^ Mx+ + XSO24~
NiO
2H
^Ni2
H2O
(6)
(where M is a metal).
The use of a mixed culture of chemolithotrophic
microorganisms is also expected to promote the dissolution
of nickel laterites. This is because competition for oxygen
by iron oxidizing bacteria (Simate, 2009; Simate et
al., 2009b) could lead to reductive dissolution of ferric
iron in nickel laterites, thus destabilizing the structure of the
nickel laterites (Bridge and Johnson, 1998). As
indicated in the following equation (Bridge and
Johnson, 1998), the reduction of soluble ferric iron by
bacteria can result in the equilibrium between solid-phase
iron (III) and soluble-phase iron (III) being shifted somewhat,
accelerating the dissolution of the mineral:
2Fe
soTidphase
2"
2Fe
so"lublephase
2F
2 ^ ^
(7)
+ 'A O2 + 2H+(bybacterialreduction)
Using a mixed culture of chemolithotrophic
microorganisms (Acidithiobacillus ferrooxidans,
Acidithiobacillus caldus and Leptospirillum ferrooxidans),
Simate and Ndlovu (2007, 2008) statistically
determined the parameters that were effective in the
bacterial leaching of nickel laterites, whose mineralogy is
shown in Table 5. The
Table 5
Simate
and Ndlovu, 2008; Simate et al., 2009b).
Relative abundances of minerals in the nickel laterite ore sample (
Mineral phase
Nickeliferrous serpentine [(Mg, Fe, Ni)3Si4O5(OH)4]
Goethite, hematite [(Fe,Ni)O(OH), Fe4O3H4O]
Titaniferrous pyrite [(Feji^]
Nickeliferrous pyrite [(Fe,Ni) S2]
Talc [Mg6Si8O20(OH)4]
Saponite [Cao.45(Mg,Fe)3(Si,Al)4O'o(OH)4nH4O]
Tremolite [Ca4Mg5Si8O44(OH)4]
Quartz [SiO2]
Occurrenc
e
Minor
Major
Trace
Trace
Trace
Trace
Trace
Predomina
nt
Predominant: >50% by mass; major: 20-50% by mass; minor: 5-10% mass; trace:
<5% by mass.
5.1. Fungi
Although the amenability of nickel laterite mineral to
fungal leaching process has been successfully
demonstrated through this review, there still remains a
considerable amount of challenges before this process can
be applied commercially.
The successful growth and maintenance of the
organisms in an in-situ bioleaching environment amidst
abiotic stresses are key to the successful application of this
technology. Abiotic stresses from the immediate
environment of the organism, such as the heavy metals
which are dissolved by the organism, can initiate cellular
responses that can inhibit specific metabolic pathways
critical in maintaining bio-acid production and leaching of
minerals (Le et al., 2006). Heavy metals in small
concentrations can induce morphological changes and then
destroy the microorganism cell (Valix et al.,
2001c), while at relatively high concentrations the heavy
metals act as a general protoplasmic poison, inducing
denaturation of proteins and nucleic acid (Avakyan,
1994). However, it was observed that serial acclimatization
could lead to the organisms being tolerant to heavy metals
(Alibhai et al., 1993; Valix et al.,
11
12
permit purposes.
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