Mineral Processing and Extractive Metallurgy

Transactions of the Institutions of Mining and Metallurgy

ISSN: 2572-6641 (Print) 2572-665X (Online) Journal homepage: https://www.tandfonline.com/loi/ympm21

Hydrochloric acid regeneration in

hydrometallurgical processes: a review

Caitlyn McKinley & Ahmad Ghahreman

To cite this article: Caitlyn McKinley & Ahmad Ghahreman (2018) Hydrochloric acid regeneration
in hydrometallurgical processes: a review, Mineral Processing and Extractive Metallurgy, 127:3,
157-168, DOI: 10.1080/03719553.2017.1330839

To link to this article: https://doi.org/10.1080/03719553.2017.1330839

Published online: 02 Jun 2017.

Submit your article to this journal

Article views: 593

View related articles

View Crossmark data

Citing articles: 1 View citing articles

Full Terms & Conditions of access and use can be found at

https://www.tandfonline.com/action/journalInformation?journalCode=ympm21
MINERAL PROCESSING AND EXTRACTIVE METALLURGY
2018, VOL. 127, NO. 3, 157–168
https://doi.org/10.1080/03719553.2017.1330839

Hydrochloric acid regeneration in hydrometallurgical processes: a review

Caitlyn McKinley and Ahmad Ghahreman
Robert M. Buchan Department of Mining, Queen’s University, Kingston, ON, Canada

ABSTRACT ARTICLE HISTORY

Hydrochloric acid regeneration has become a vital stage in most chloride process flowsheets. Received 4 July 2016
Pyrohydrolysis has been the traditional method of regenerating hydrochloric acid from a Accepted 9 May 2017
variety of chloride solutions, including magnesium, iron and nickel brines, however, its high
KEYWORDS
thermal requirements renders it uneconomic in most processing flowsheets. Hydrochloric Chloride; acid regeneration;
acid being an expensive acid, it is vital to the continued development of chloride processes hydrochloric acid
to develop an economically favourable and environmentally sound method to recycle the
lixiviant back to the process. This paper seeks to review the latest research in this area,
including the use of electrowinning, solvent extraction, metal sulphate salt crystallisation and
hydrolytic distillation to regenerate leaching lixiviants. Metal sulphate salt crystallisation is
the most promising method included in this review; with significant research having been
conducted to date and favourable economics having been shown. Industrial application of
this method depends on careful design and operational control due to sensitive parameter
control being needed.

Introduction hydrochloric acid or chloride anion is consumed by

Over the past several decades, increasing research
has been conducted on the use of chloride mediums
in processing flowsheets. Hydrochloric acid leaching
in particular has many benefits over conventional
sulphuric acid leach systems possibly including the
following, depending on the material leached (Haba-
shi et al. 1987; Gogia & Das 1988; Winand 1991;
Van Weert & Peek 1992; Senanayake 2007; McDonald
& Whittington 2008; Senanayake 2009; de Bakker
2011; Gibson & Rice 2015):
. the relative ease of extracting several metals;
. the reduction of pre-treatment of the ore;
. higher reaction kinetics;
. higher selectivity can be exploited to reduce impur-
ity accumulation;
. higher metal complex solubilities;
. higher electrical conductivity allowing for lower
energy consumption in EW circuit;
. complex sulphide concentrates are easily leached.
Chloride leaching flowsheets have been developed for
laterite ores, manganese nodules, low-grade tin ores,
ilmenite upgrading, copper from chalcopyrite, nickel
from pyrrhotite, lead/zinc/sulphur concentrates, nickel/
copper/sulphur concentrates, rare earth element ores
and pickling oxide scales with varying levels of commer-
cialisation having been achieved (Peek 1996; Bedrossian
& Connell 2014; Park et al. 2015; Rao et al. 2015). In
most of the above processes, a proportion of the
gangue minerals - producing stable chloride complexes.
Hydrochloric acid being an expensive reagent, vital to
the commercialisation of those processes is the regener-
ation of the chloric anion, whether it is hydrochloric acid
or a hydrochloric acid/metallic salt solution (Harris &
White 2015). Recycling the lixiviant benefits the pro-
cesses both economically by reducing the amount of
the make-up acid required, and environmentally by pro-
ducing less acidic waste. The use of make-up acid can be
very expensive, with 6 M hydrochloric acid being
approximately $300 USD per tonne in North America.
In some processes, such as those in ilmenite leaching
operations, the hydrochloric acid/calcium chloride lixi-
viant is easily regenerated by recovering the valuable
metals as insignificant impurity accumulation occurs
(Das et al. 2013). However, other processes require
more complex regeneration techniques and the econ-
omic, environmental and social impacts of these
methods must be carefully analysed.
The aim of this paper is to review the current or pre-
viously industrialised hydrochloric acid regeneration
methods, all of which are based on pyrohydrolysis
techniques, and examine the different areas of research
into novel regeneration methods.
Processes in use
Pyrohydrolysis
Pyrohydrolysis is the only true form of hydrochloric
acid regeneration that has been commercialised.

CONTACT Ahmad Ghahreman ahmad.g@queensu.ca Robert M. Buchan Department of Mining, Queen’s University, Goodwin Hall room #340, 25
Union Street, Kingston, ON K7L 3N6, Canada
© 2017 Institute of Materials, Minerals and Mining and The AusIMM Published by Taylor & Francis on behalf of the Institute and The AusIMM
158 C. MCKINLEY AND A. GHAHREMAN
Beginning from relatively simple chloride brine, pyro-
hydrolysis uses a fluidised bed or a spray roaster to
remove the water units from the solution to produce
a metal oxide and hydrochloric acid as per the follow-
ing reaction:
MeCl2(aq) + H2 O(aq)  MeO(s) + 2HCl(g)
Pyrohydrolysis is a versatile process, and depending on
the operating conditions used, in particular the temp-
erature, one can control the metal chlorides targeted
to selectively hydrolyse only certain metal chlorides
(de Bakker 2011). Theoretically, pyrohydrolysis may
be used to hydrolyse any metal chloride to its metal
oxides; however, only three metals, magnesium, ferrous
and nickel, have been implemented in an industrial
setting.
Magnesium chloride pyrohydrolysis
The Aman process was first patented in 1956, and is still
used by the Dead Sea Periclase Co. at the Mishor Rotem
plant (de Bakker 2011; ICL Industrial Products). The
‘Aman-type reactors’ use temperatures of up to 800°C to
perform complete thermal hydrolysis of the magnesium
chloride, producing HCl and high purity magnesia
(Epstein 1976). A 3–10 m tall hydrolysis chamber is
used with hot combustion gases fed from the bottom
while the magnesium chloride solution is fed from the
top; the total reaction time for this process is 5–20 seconds
(de Bakker 2011). This process produces dilute (20%) HCl
Figure 1. Nickel concentrate/ore/matte or nickel concentrate and laterite processing flowsheet (recreated from Harris et al. 2009).
and 99.3% pure magnesia (Epstein 1976). The intensive
energy requirements and the necessary use of liquid
hydrocarbon fuels make the Aman process prohibitively
expensive, thus it has never been successfully used in
large-scale magnesia production.
An HCl and magnesium chloride solution has
(1)
been shown to be an effective lixiviant for certain
ores, particularly low-Mg laterite ores (Harris et al.
2009). A flowsheet proposed by Harris et al., shown
in Figure 1, uses pyrohydrolysis to regenerate the
hydrochloric acid for the leaching stage and mag-
nesium chloride is directly returned to the leaching
stage. As only part of the lixiviant must go through
pyrohydrolysis, the energy consumption, and there-
fore cost of the regeneration phase is reduced.
While this process shows promise in regard to com-
mercialisation, any amount of magnesium present in
the ore would quickly result in a large build-up of
magnesium chloride in the lixiviant; causing valuable
metal recoveries to quickly decrease and rendering
the process ineffective.
Ferrous chloride pyrohydrolysis
The industry that has been most successful in the
regeneration of hydrochloric acid is that of the
steel pickling industry (Brown & Olsen 2006). The
used pickle liquor is usually an 18–20% ferrous
chloride solution. This solution can be fed to a
spray roaster or a fluidised bed, similar to the

Aman process; however, sufficient oxygen must be
introduced to oxidise ferrous. Owing to the exother-
mic reaction of ferrous oxidation, significantly less
energy is required for FeCl2 pyrohydrolysis when
compared with MgCl2 pyrohydrolysis. The favour-
able thermodynamics and lower solution impurity
levels both aid in the economic and technical feasi-
bility of this process. Ferrous chloride pyrohydrolysis
is extremely effective in the steel pickling industry;
however, the lack of pure FeCl2 solutions in the
mining industry makes this process unfeasible for
most or all proposed flowsheets.
Nickel chloride pyrohydrolysis
The Falconbridge matte leach process was used from
1968 to 1983 in Kristiansand, Norway to treat
nickel–copper matte from a Sudbury district smelter.
The process was designed to use a strong hydro-
chloric acid leach with hydrochloric acid regener-
ation through nickel chloride hydrate
pyrohydrolysis yielding nickel oxide and hydro-
chloric acid. The hydrolysis utilised a fluidised bed
reactor, fed by the combusting of naphtha with air
at an operating temperature of 850°C (Thornhill &
Wigstol 1971). The plant also had the capacity to
Figure 2. Simplified flowsheet for the 1968–1983 Falconbridge matte leach process (recreated from Peek 1996).
MINERAL PROCESSING AND EXTRACTIVE METALLURGY 159
produce make-up hydrochloric acid at a rate of
20 T/d through the combustion of hydrogen and
chlorine in a graphite burner. A simplified Falcon-
bridge matte leach process flowsheet is shown in
Figure 2.
The Nikkelverk A/S, Kristiansand, Norway plant
was transitioned to a chlorine leach process from
1981 to 1983 due to a combination of factors
including the need to produce a different end pro-
duct and their desire to economically optimise
their process (Stensholt et al. 2001). The new chlor-
ine leach process replaced the hydrochloric acid
leach stage with a chlorine leach stage and the
nickel chloride crystallisation, drying and pyrohy-
drolysis stages with pregnant liquor purification,
non-acidic filtration and nickel chloride electrowin-
ning (Peek 1996). Nikkelverk A/S still uses a version
of this chlorine leach at this time (Glencore Nikkel-
verk AS 2016). The transition to a chlorine leach
improved the economics of the flowsheet through
reduced regeneration costs. While Falconbridge
matte leach process was effective, the high OPEX
and CAPEX of pyrohydrolysis due to intensive
energy requirements makes this process difficult to
implement in new flowsheets.
160 C. MCKINLEY AND A. GHAHREMAN

Newest research areas for chloride, durability and operating costs (Peek
1996). No work has been published on this topic since
Owing to the high industrial demand to develop an
the 1990s, likely due to difficulties with scale up and
economically and technically viable method of hydro-
commercialisation related to a lack of current mem-
chloric acid regeneration, extensive research and devel-
brane technologies and high operating costs associated
opment work has been conducted on the topic. The
with the process. In general, membranes have relatively
techniques covered in this section include electrowin-
short life and often are replaced few times per year, and
ning, solvent extraction, metal sulphate salt crystallisa-
precipitation of solids on the membrane surfaces is det-
tion and hydrolytic distillation.
rimental to the membrane performance.
In 2014, Reed Resources Ltd was granted a patent
Hydrochloric acid and metal recovery using for a novel lithium hydroxide process in Australia.
electrowinning This process involves a hydrochloric acid leach of a
lithium oxide material followed by electrolysis to pro-
In the 1990s, Delft University of Technology explored
duce the lithium hydroxide product and regenerate
the use of an electrowinning cell to generate hydro-
the hydrochloric acid (Reed Resources Ltd. 2014).
chloric acid from a nickel chloride solution. They used
They state that a successful semi-pilot scale plant
a three compartment cell separating the catholyte and
achieved 200 hours of operation with 80% efficiency.
ampholyte by an anion exchange membrane and the
The Mt Marion lithium project in Western Australia
ampholyte and anolyte separated by a cation exchange
has recently produced their first batch of lithium
membrane (Liao et al. 1995). This separation was
using the Reed Resources Ltd. patent; however, this
necessary to prevent the formation of chlorine on the
method of hydrochloric acid regeneration is limited
anode. The cell set up is shown in Figure 3 with hydro-
to the patented lithium application due to the favour-
chloric acid formed in the ampholyte. The experiments
able ore type and desired final product.
were conducted at a current density of 200 A m−2 and a
temperature of 50°C using 1 and 0.2 M NiCl2 solutions
as catholyte and ampholyte, respectively, and 1 M
Hydrochloric acid regeneration from the
H2SO4 as anolyte (Liao et al. 1995). Cell voltages and
leaching solution of spent HDS catalysts by
cathodic current efficiencies of below 3.2 V and 95%
solvent extraction
were achieved (Liao et al. 1995). A 1 M HCl solution
could be produced via this process, however, the com- Banda et al. (2013) investigated the use of solvent
mercialisation was dependent on membrane selectivity extraction (using 2-ethylhexyl amine or TEHA) to

Figure 3. Two membrane cell being used to regenerate hydrochloric acid (recreated from Liao et al. 1995).

recover hydrochloric acid from the processing of
spent HDS catalysts. The chemical composition by
weight of the spent HDS catalysts was 8.1% Mo,
2.5% Co, 0.02% Ni, 0.03% Fe, 0.01% Si and 44.5%
Al (Banda et al. 2013). Two stage counter-current
TEHA solvent extraction at an A/O ratio of 0.5 was
used to separate the hydrochloric acid from alu-
minium in the molybdenum and cobalt barren raffi-
nate (0.1 M HCl) achieving 96.4% extraction
efficiency (Banda et al. 2013). Following extraction,
water was used to strip the HCl from the loaded
TEHA. With an O/A ratio of 0.33 a stripping effi-
ciency of 99.2% was achieved using a two stage coun-
ter-current stripping simulation (Banda et al. 2013).
Banda et al. (2013) were able to recover 99% of Mo
and Co and 90% of HCl with purities higher than
99% being obtained, and have suggested the flow-
sheet as presented in Figure 4. This process effectively
recovers already present HCl from the solution;
however, it does not regenerate the concentrated
acid, making it inapplicable in most metallurgical
flowsheets.
Figure 4. Hydrochloric acid regeneration from spent HDS catalysts (recreated from Banda et al. 2013).
MINERAL PROCESSING AND EXTRACTIVE METALLURGY 161
Metal sulphate salt crystallisation
Perhaps the most thoroughly investigated of these cur-
rent research areas is that of metal sulphate salt crystal-
lisation. In this process, sulphuric acid is added to the
metal chloride solution in order to precipitate out the
metal as a metal sulphate salt and produce hydro-
chloric acid as shown below
MeCl2(aq) + H2 SO4(aq) + nH2 O
 MeSO4 · nH2 O(s) + 2HCl(aq) (2)
Metal sulphate salt crystallisation has the significant
advantage of requiring low temperatures (below 100°C);
however, improper control of the conditions can lead
to significant operational issues as discussed further
in this section. The use of metal sulphate salt crystalli-
sation has been proposed on a number of metals,
including calcium, magnesium and iron.
Calcium chloride solutions
Habashi et al. (1987) have showed that it was possible
to regenerate HCl by reacting a calcium chloride
162 C. MCKINLEY AND A. GHAHREMAN

solution with sulphuric acid. Al-Othman and Demo-

poulos (2009) further investigated this process and
showed that a slow sulphuric acid addition followed
by a 2-hour equilibrium period can produce well-
developed gypsum crystals, while faster sulphuric
acid additions produces a gel-like substance with
finer crystals. Higher temperatures and the use of
seed material can also promote larger crystal growth.
The use of seed in particular increases the size of
the crystals and though the resulting slurry may display
a poor settling rate, high filtration rates of
≥4000 kg hm−2 can be obtained (Al-Othman & Demo-
poulos 2009). To produce azeotropic strength acid, an
initial calcium chloride concentration of 3−4 M is
needed, typically necessitating an evaporation stage in
the flowsheet. The dilution of the sulphuric acid from
96% to around 50% before addition also aids to pro-
duce well-developed crystal growth. This process is
capable of producing a regenerated acid stream con-
taining 5.5 M HCl, 0.5 M CaCl2 and 0.05 M CaSO4.
While both calcium sulphate dihydrate and calcium
sulphate alpha-hemihydrate are generally conductive
to effective solid–liquid separation, the fibrous nature
of calcium sulphate anhydrite can result in much
poorer filtration rates and its formation should be
minimised (Feldmann & Demopoulos 2012a, 2012b).
SEM images of these three forms of calcium sulphate
can be seen in Figure 5.
Gypsum crystallisation can be conducted continu-
ously in a series of CSTR reaction tanks. Cost estimates
for this method of hydrochloric acid regeneration Figure 6. Simplified flowsheet for a REE plant utilising gypsum
precipitation for hydrochloric acid regeneration (recreated
incorporated into a rare earth element plant were con-
from Girgin et al. 2013).
ducted by Girgin et al. (2013) using the simplified flow-
sheet shown in Figure 6 and the basic process design
criteria shown in Table 1. Other design inputs were solutions. At 60°C, super-azeotropic hydrochloric
electricity is $0.12/kWh and 93% H2SO4 is $150 t−1. acid (up to 30 wt-% or 9 M) was produced from a con-
It was estimated that the total operating cost for the centrated calcium chloride solution being reacted with
HCl regeneration circuit would be $110 per tonne of concentrated sulphuric acid. This process can take
6 M hydrochloric acid solution regenerated (Girgin advantage of the strongly exothermic nature of both
et al. 2013). sulphuric acid dilution and the reaction itself to signifi-
Feldmann and Demopoulos (2015) have used water cantly reduce heating needs. The concentration of cal-
activity calculations to optimise the conditions used in cium chloride in the feed was found to have a
a CSTR in order to promote metastable calcium sul- significant impact on crystal size with lower concen-
phate alpha-hemihydrate in strong hydrochloric acid trations (0.5 M) producing larger crystals and less

Figure 5. SEM images of various forms of calcium sulphate (Feldmann & Demopoulos 2012).
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY 163

Table 1. Basic process design criteria (recreated from Girgin (Feldmann & Demopoulos 2014). The addition of
et al. 2013). CTAB results in thick slab crystals forming, PAA
Criteria Units Value forms long, thin crystals and PVS detrimentally effects
Leach feed characteristics calcium sulphate crystallisation and nucleation.
Phosphate % P2O5 20
Rare earth %RO 5 Although the addition of the modifiers can be helpful
Feed throughput t/h 5 in precipitation of larger crystals of gypsum; however,
HCl strength
Fresh M 6 the cost associated with the modifier reagents can
Recycled M 6 make the economics of the process less attractive.
Sulphuric acid strength
Fresh M 9 The Outotec nickel matte chloride leaching process
Filtered calcium sulphate Percent solids % 71 announced in 2014 utilises the metal sulphate salt crys-
tallisation method to recover the hydrochloric acid
from their clean calcium chloride stream as shown in
fines. The highest hydrochloric acid concentration Figure 8 (Haavanlammi 2014). Their flowsheet also
achieved during this work was 9.5 ± 0.2 M with a includes the regeneration of ammonia through the
median calcium sulphate particle size of 61 µm; using addition of calcium hydroxide to the ammonium
5.11 M calcium chloride and 17.87 M sulphuric acid chloride solution (Haavanlammi 2014), according to
feed solutions (Feldmann & Demopoulos 2015). the following reaction
Their proposed flowsheet is shown in Figure 7. This
process is very promising due to its low energy require-
2NH4 Cl + Ca(OH)2  2NH3 + CaCl2 + 2H2 O (3)
ments and highly concentrated recovered acid; how-
ever, handling of the amorphous structure of the
gypsum precipitated can be challenging in the solid/ While metal sulphate salt crystallisation has been well
liquid separation circuit. The solid/liquid separation studied on pure calcium chloride solutions, very little
issue is expected to be more evident in processes with work has been conducted on the effects of impurities
high feed solution chloride concentration. on recovery levels and reagent use. The process of
Some crystal habit modifiers have been shown to producing a pure calcium chloride solution from
affect dihydrate calcium sulphate crystal morphology in leach solutions would vary depending on the project,
strong acidic solutions with the most effective of these but could prove to be very complex and have a large
being cetryltrimethylammonium bromide (CTAB), poly- detrimental effect on the commercialisation of these
acrylic acid (PAA) and polyvinylsulphonic acid (PVS) processes.

Figure 7. Proposed flowsheet for HCl regeneration from a CaCl2 solution using a single stage CSTR (recreated from Feldmann &
Demopoulos 2015).
164 C. MCKINLEY AND A. GHAHREMAN

Figure 8. The Outotec nickel matte chloride leaching process (recreated from Haavanlammi 2014).

Magnesium and ferrous chloride The presence of 3.8 M magnesium chloride reduces
As an extension of gypsum precipitation from cal- the solubility of magnesium sulphate from 5 M to
cium chloride solutions previously discussed, the around 1 M at 100°C; however, when concentrated
reaction of a larger variety of metal chloride solutions hydrochloric acid regeneration is the objective, this
(including calcium, magnesium and iron) with sul-
phuric acid in order to crystallise the calcium, mag-
nesium or ferrous sulphate salts was investigated
(Steyl & Smit 2006). Magnesium sulphate and fer-
rous sulphate were examined due to their applica-
bility in laterite processing and pickle liquor
treatment, respectively. Figure 9 shows magnesium
sulphate solubility as a function of temperature and
solubility can be seen to peak at approximately
100°C. Operating below 100°C produces a highly
hydrated salt which increases costs associated with
calcination further downstream; however, operating
above the boiling point of water necessitates the
use of an autoclave or significant reduction in the
activity of water by operating at very high mag- Figure 9. Magnesium sulphate solubility in water (Demopou-
nesium chloride concentrations. los et al. 2008).

process is not feasible. Through the addition of sul-
phuric acid, magnesium chloride becomes mag-
nesium sulphate, the latter of which’s solubility will
increase as the process advances and the magnesium
chloride concentration decreases. As such, full mag-
nesium removal cannot be achieved using magnesium
sulphate crystallisation. This process could be appli-
cable in processes which use a hydrochloric acid–
magnesium chloride as a lixiviant for low magnesium
content ores. In this case, partial magnesium chloride
removal is conducted using magnesium sulphate crys-
tallisation to regenerate the desired lixiviant (Steyl &
Smit 2006).
Another proposed method of regenerating hydro-
chloric acid from magnesium chloride solutions is to
first react them with lime (Ca(OH)2) to precipitate
the magnesium as magnesium hydroxide and leav-
ing a solution of calcium chloride which can then
easily undergo the previously described metal sul-
phate salt crystallisation (Bedrossian & Connell
2014).
Both proposed magnesium chloride methods
result in fairly low hydrochloric acid recoveries pri-
marily due to the higher solubility of magnesium
sulphate when compared with the previously dis-
cussed calcium sulphate. Once again, the effect of
impurities has not been studied for magnesium
sulphate salt crystallisation, nor has the effect of var-
ious additives or seed material. Increases in hydro-
chloric acid recovery would need to be made in
order to successfully commercialise a process utilis-
ing this reaction.
Hydrolytic distillation
In hydrolytic distillation, the ferrous chloride is first
oxidised to ferric chloride before it undergoes
hydrolysis by neutralisation (using magnesia or simi-
lar) or in an autoclave using hydrothermal precipi-
tation as shown in Equations (4 and 5). To produce
acid suitable for recycling to the leaching process,
the hydrolytic precipitation of hematite needs to
include hydrochloric acid volatilisation and recovery
through distillation (Demopoulos et al. 2008). An
example of a flowsheet using hydrolytic distillation
can be seen in Figure 10.
12FeCl2 (aq) + 3O2 (g)  2Fe2 O3 (s) + 8FeCl3 (aq) (4)
2FeCl3 (aq) + 3H2 O(g,aq)  Fe2 O3 (s) + 6HCl(g,aq) (5)
The first reaction proceeds well at 150°C and the
second is conducted at 175–180°C, both at atmos-
pheric pressure. Essential to the second reaction is
the volatilisation of hydrochloric acid in order to
drive the reaction to the right, with the resulting
vapour having a 30% hydrochloric acid concentration
MINERAL PROCESSING AND EXTRACTIVE METALLURGY 165
Figure 10. An example of a flowsheet using hydrolytic distilla-
tion to regenerated hydrochloric acid (recreated from Zhang
et al. 2015).
and a 99% recovery (Demopoulos et al. 2008). Facili-
tating the acid volatilisation is the observed increase
in hydrochloric acid vapour pressure in mixed HCl–
MgCl2–H2O solutions.
At a laboratory scale, the recovery of all generated
acid as 5.5 M HCl condensate was achieved at 200–
220°C over 5 hours using a 360 g L−1 magnesium
chloride and 30 g L−1 iron as ferric chloride sol-
ution. Of note in this process is that the generation
of hydrochloric acid is from the chloride units
associated with the iron and the spent solution is
primarily a magnesium chloride solution with the
same concentration as the initial magnesium chlor-
ide solution. This limits the applicability of this pro-
cess to systems where no magnesium will build up in
the circuit. It is especially effective where a mag-
nesium chloride–hydrochloric acid lixiviant is pro-
posed for leaching and is the system under
development for use at the Ferguson Lake massive
Cu–Ni sulphide ore deposit in Northern Canada
(Demopoulos et al. 2008).
A process flowsheet was developed for the Ferguson
Lake orebody based on test work conducted by SGS
Lakefield Research facility and is shown in Figure 11.
This process uses a magnesium chloride–hydrochloric
acid lixiviant for the primary leach and a magnesium
chloride–ferric chloride lixiviant for the secondary
leach and produces copper, cobalt, nickel, precious
metal and iron products. The lack of significant impu-
rities, especially magnesium, prevents the accumu-
lation of undesirable elements in the circuit and
particularly in the lixiviant regeneration circuit. In
addition, the temperature of the hydrolysis phase will
contribute significantly to the operating costs of the
project.
166 C. MCKINLEY AND A. GHAHREMAN

Figure 11. Proposed flowsheet for the processing of the Ferguson Lake orebody using hydrolytic distillation (recreated from Harris
& White 2008).

Conclusions has the ability to produce valuable or at the very least

environmentally safe by products; however, careful
With chloride hydrometallurgy increasing in popular-
design and operational control is required in order to
ity, the cost of hydrochloric acid continuing to be
prevent operation impeding issues from arising. As
high and increasing environmental and social regu-
such, further work on mitigating this complexity in
lations being passed, lixiviant regeneration is becoming
operational control is needed in order to successfully
vital in many flowsheets under development. Pyrohy-
scale up the process.
drolysis, the only form of hydrochloric acid regener-
ation currently used in industry, is very energy
intensive, resulting in its use in many flowsheets Disclosure statement
being uneconomic. Research into alternative hydro- No potential conflict of interest was reported by the authors.
chloric acid regeneration schemes is ongoing and
many promising ideas have been proposed. The most
extensively studied is the method using metal sulphate Funding
salt crystallisation from calcium chloride solutions. This work was supported by Research Initiation Grant (RIG)
This method has shown favourable economics and – Queen’s University – Queen’s University.

Notes on contributors
Caitlyn McKinley obtained her Bachelor’s degree in 2015
from Queen’s University in Mining Engineering, Mineral
Processing option. She is currently working towards
obtaining her Master’s degree in Hydrometallurgy, also
from Queen’s University in the Mining Engineering
Department. She is part of the Research Affiliate Pro-
gram with Natural Resources Canada, conducting the
research for her masters at CanmetMINING in Ottawa,
ON, Canada.
Ahmad Ghahreman has a Bachelor degree (2005) and a
Master’s degree (2007) in Materials Science and Engineering
from Sharif University of Technology, Tehran, Iran, and
earned his PhD in Materials Engineering from The Univer-
sity of British Columbia, Vancouver, BC, Canada (2012).
Upon completing his PhD, Ahmad joined the Technology
Centre of Barrick Gold Corp. in Vancouver, as an NSERC
Industrial Research & Development (IRDF) Postdoctoral
Fellow. He joined The Robert M. Buchan Department of
Mining at Queen’s University as an Assistant Professor in
January 2014.
ORCID
Ahmad Ghahreman http://orcid.org/0000-0002-3568-
7880
References
Al-Othman A, Demopoulos GP. 2009. Gypsum crystallization
and hydrochloric acid regeneration by reaction of calcium
chloride solution with sulfuric acid. Hydrometallurgy.
96:95–102.
de Bakker, S. 2011. The recovery of magnesium oxide and
hydrogen chloride from magnesium chloride brines and
molten salt hydrates [doctoral thesis]. Kingston, Canada:
Department of Mining, Faculty of Engineering and Applied
Science, Queen’s University.
Banda R, Nguyen TH, Sohn SH, Lee MS. 2013. Recovery of
valuable metals and regeneration of acid from the leaching
solution of spent HDS catalysts by solvent extraction.
Hydrometallurgy. 133:161–167.
Bedrossian S, Connell M. 2014. An overview of hydrochloric
acid regeneration in rare earth processing. COM.
Vancover, Canada.
Brown CJ, Olsen DR. 2006. Regeneration of hydrochloric acid
pickle liquors by crystallization. The Third International
Symposium on Iron Control in Hydrometallurgy.
Montreal, Canada.
Das GK, Pranolo Y, Zhu Z, Cheng CY. 2013. Leaching of ilme-
nite ores by acidic chloride solutions. Hydrometallurgy.
133:94–99.
Demopoulos GP, Li Z, Becze L, Moldoveanu G, Cheng TC,
Harris B. 2008. New technologies for HCl regeneration
in chloride hydrometallurgy. World of Metallurgy –
Erzmetall. 61:89–98.
Epstein JA. 1976. Utilization of the dead sea minerals (a
review). Hydrometallurgy. 2:1–10.
Feldmann T, Demopoulos GP. 2012a. The crystal growth
kinetics of alpha calcium sulfate hemihydrate in concen-
trated CaCl2-HCl solutions. J Cryst Growth. 351:9–18.
Feldmann T, Demopoulos GP. 2012b. Phase transformation
kinetics of calcium sulfate phases in strong Ca-Cl2-HCl
solutions. Hydrometallurgy. 129-130:126–134.
MINERAL PROCESSING AND EXTRACTIVE METALLURGY 167
Feldmann T, Demopoulos GP. 2014. Effects of crystal habit
modifiers on the morphology of calcium sulfate dihydrate
grown in strong CaCl2-HCl solutions. J Chem Technol
Biotechnol. 89:1523–1533.
Feldmann T, Demopoulos GP. 2015. Water activity-based
design of a single-stage CSTR reactive crystallization pro-
cess for producing super-azeotropic HCl and well grown
metastable α-calcium sulfate hemihydrate crystals from
CaCl2 solution. Hydrometallurgy. 155:20–28.
Gibson RW, Rice NM. 2015. A hydrochloric acid process for
nickeliferous laterites. Miner Eng. 88:247–261.
Girgin S, Feldmann T, Humphrey S, Demopoulos GP. 2013.
Low temperature (T<100C) regeneration of HCl from
chloride leaching of Ca-bearing minerals. COM.
Montreal, Canada.
Glencore Nikkelverk AS. 2016. Production. Retrieved May
10, 2016. Available from: http://www.xstratanickel.no/
EN/About-us/Pages/Production.aspx
Gogia SK, Das SC. 1988. The effects of Mg 2+, Mn 2+, Zn 2+,
and Al 3+ on the nickel deposit during electrowinning
from sulfate bath. Metall Trans B. 19:823–830.
Haavanlammi, K. 2014. Nickel matte chloride leaching.
Outotec SEAP Customer eNewsletter. 7–9. Available
from: http://www.outotec.com/ImageVaultFiles/id_1486/
cf_2/Nickel_matte_chloride_leaching.PDF
Habashi F, Awadalla FT, Yao X. 1987. The hydrochloric acid
route for phosphate rock. J Chem Technol Biotechnol.
38:115–126.
Harris B, Lakshmanan V, Sridhar R, Puvvada G. 2009.
Process for the recovery of value metals from base metal
sulfide ores. U.S. patent no. 7,968,065 B2. Washington,
DC: U.S. Patent and Trademark Office.
Harris B, White C. 2008. Recent developments in the high-
strength chloride leaching of base metal sulphide ores.
ALTA. Perth, Australia.
Harris GB, White CW. 2015. Evaluation of ion exchange as a
means of separating and recovering base metals from
concentrated chloride leach solutions. COM. Toronto,
Canada.
ICL Industrial Products (n.d.). Business unit - magnesia pro-
ducts. Available from: http://icl-ip.com/business_unit_
category/magnesia-products/
Liao L, Van Sandwijk A, Van Weert G. 1995. Ion trans-
port in a two membrane electrowinning cell for the
production of hydrochloric acid. J Appl Electrochem.
25:1009–1016.
McDonald RG, Whittington BI. 2008. Atmospheric acid
leaching of nickel laterites review. Part II. Chloride and
bio-technologies. Hydrometallurgy. 91:56–69.
Park J, Nam CW, Park K, Kim H. 2015. Leaching method of
rare earth metals using hydrochloric acid from manganese
nodule. U.S. patent no. 20,150,211,095 A1. Washington,
DC: U.S. Patent and Trademark Office.
Peek EML. 1996. Chloride pyrohydrolysis - lixiviant regener-
ation and metal separation [doctoral thesis]. Delft, the
Netherlands: Faculty of Civil Engineering and
Geosciences, Delft University of Technology.
Rao C, Pontikes Y, Binnemans K, Van Gerven T. 2015.
Leaching of rare earths from bauxite residue (red mud).
Miner Eng. 76:20–27.
Reed Resources Ltd. 2014. Australian patent granted for
lithium hydroxide process. Available from: www.
neometals.com.au/reports/574-lithium-patent.pdf
Senanayake G. 2007. Review of theory and practice of
measuring proton activity and pH in concentrated chlor-
ide solutions and application to oxide leaching. Miner
Eng. 20:634–645.
168 C. MCKINLEY AND A. GHAHREMAN
Senanayake G. 2009. A review of chloride assisted copper
sulfide leaching by oxygenated sulfuric acid and mechan-
istic considerations. Hydrometallurgy. 98:21–32.
Stensholt E, Dotterud O, Henriksen E, Ramsdal P, Stalesen F,
Thune E. 2001. Development and practice of the
Falconbridge chlorine leach process. CIM Bull. 94:101–
104.
Steyl JDT, Smit JT. 2006. Leaching process in the presence of
hydrochloric acid for the recovery of a value metal from
an ore. Patent no. EP 1,809,778 B1.
Thornhill PG, Wigstol E. 1971. The Falconbridge matte leach
process. J Met. 13:1–6.
Van Weert G, Peek, EML. 1992. Reagent recovery in chloride
hydrometallurgy - some missing links. Hydrometallurgy.
29:513–526.
Winand R. 1991. Chloride hydrometallurgy. Hydrometallurgy.
27:285–316.
Zhang P, Guo Q, Wei G, Qu J, Qi T. 2015. Precipitation of
alpha-Fe2O3 and recovery of Ni and Co from synthetic
laterite-leaching solutions. Hydrometallurgy. 153:21–29.