Electrochemical flow cell for mineral processing

Genny Leinenweber* & Luis Cáceres

CSIRO-Chile International Centre of Excellence in Mining and Mineral Processing, Department of Chemical
Engineering, Universidad de Antofagasta, Chile

ABSTRACT

We have designed a planar perpendicular flow cell for electrochemical measurement of a mineral
available as a fine powder. The working electrode consisting of mineral powder supported on a
carbon paste surface as a 4 mm diameter disk, was concentrically positioned inside a vertical
tubular reactor. The counter electrode was a 316L tube embedded in the body cell. The supportive
media was a 1.2:1 mixture of candle wax and graphite powder respectively, which is a good
electrical conductor. The concentrate electrode as a film attached on a carbon paste disk was
prepared rubbing the surface carbon paste against dried powdered mineral. An Ag/AgCl 1 M KCl
cell as a reference electrode was attached to the body cell by using a fast coupling fitting. A stable
flow rate was achieved using a frequency inverter to drive the pump motor. The flow through the
cell verified to be laminar due to the Reynolds number in the cell flow passage.
Cyclic voltammetry from – 1200 a 600 mVSAgE were measured using a carbon paste with and
without mineral attached to the surface.
The main findings of this work were: a).– Electrochemical measurement of mineral powder in
contact with flowing samples was easily achieved using ground mineral. This is important where
massive samples are not available. b).– The voltammetric curve features of ground mineral
coincided with reported data. c).– The working electrode could be quickly replaced while
maintaining very good reproducibility.

Keywords: Flow cell, electrode, pulp potential, floatability of sulphide mineral.

*Genny Leinenweber: CSIRO-Chile International Centre of Excellence in Mining and Mineral

Processing, Department of Chemical Engineering, Universidad de Antofagasta, Av. Angamos 601,
fono: 56-55-2637313, Chile. gennyleinenweber@gmail.com

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INTRODUCTION
The floatability of sulphide minerals is dependent of the potential difference of a mineral-solution
interface, which is referred as pulp potential (Gotepke, F., 2002; Moslemi, H., Shams, P., Habashi.,
2011; Woods, R., Gardner, J., 1979). It is well known that mineral floatability can be manipulated
just by changing the oxidizing and reducing pulp conditions in such a way that the measured
potentials determine whether or not the mineral will float. In a mineral interface in equilibrium
with a pulp solution a mixed-potential condition should prevail, which mean that the sum of all
partial oxidation currents must equal the counterpart sum of all reduction currents. Thus, the
mixed potential (Ahmad, Z., 2006) of the partial electrochemical reactions in a mineral-solution
interface is a unique value that indicates the predominance of a particular situation (Labonté, G.,
1999), which for flotation is associated to a hydrophobicity/hydrophilicity balance on a mineral
surface. Thus, the electrochemical potential is an important parameter in controlling the recovery
and selectivity of sulphide minerals during flotation (Moslemi, H., Shamsi, P., Alimohammady, M.,
2012).
A noble metal electrode is usually used as a working electrode to measure pulp potential (Woods
R., 2003). This in flotation systems seems inadequate since different electrode materials can yield
different potential values in the same solution (Rand, D., Woods, R., 1984), and from the basic
principles of flotation, the desired potential to be monitored would be the mineral potential, not the
solution. This suggests that an electrode constructed from the mineral being concentrated should be
the most appropriate for potential measurements rather than noble metal electrodes (Gotepke, F.,
2002). Unfortunately, not always is possible to find the mineral massive to make the work electrode.
When a mineral massive sample is not available for electrochemical studies, the preparation of an
electrode using an adequate support for solid particles is an essential preliminary step (Hu, Y., Wei,
W., and Wang D, 2009). This material support must be both a good electrical conductor and an
effective adhesive for particles.
In this work, a novel flow cell suitable for electrochemical flotation studies is presented.
Electrochemical measurements of mineral in seawater were made using two mineral samples as
found in mineral deposits in Northern Chile. Each sample was subdivided in a powder a
cylindrical massive subsamples to prepare two different types of working electrodes.

METODOLOGY
We have designed a planar perpendicular flow cell (CICITEM, 2013) to measure potential of the
mineral, which was available as a fine powder sieved to get a particle size of 100 um. A schematic
diagram of the experimental apparatus is shown in Fig. 1. Its main parts are, a magnetic pump
connected to a frequency inverter, a flow cell, and a solution container. The connecting tubing was
Master flex Pharmed type. All parts and accessories except for the test specimen and counter
electrode were nonmetallic.

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 6 1

ET
ER
CE

4
N2 3
5
2 6

Fig. 1 Schematic diagram of the experimental apparatus. 1.- Electrochemical Flow cell, 2.- Magnetic drive
pump connected to a frequency inverter, 3.- Potenciostat, 4.- Flow meter, 5.- Solution container, 6).-
Connecting tubing

The flow cell represented in Fig. 2 has a cylindrical electrode (left Fig. 2) that when inserted in the
cell body forms an annular passage for solution circulation (right Fig. 2). The three electrode
terminals (labeled 1, 6 and 7 in Fig. 2) allow a broad range of electrochemical tests in a potentiostat.
Its physical design considered two basic recommendations. a).- An small distance between working
and counter electrodes, and b).- A cylindrical counter electrode for the frontal WE (specimen under
study), which allows a symmetric electric field in front of the WE. Given the high cost of a
platinum hollow cylinder, a 316L SS was used instead as a material for the counter electrode. For
this case the available electrochemical windows is restricted to a range of -1200 to 600 mVSHE as is
indicated in the voltammetric curve for SS 316L (Fig. 3). This is adequate for the present case since
a working range is -600 to 600 mV.

2 7
9

5
A A'

4
WE
3 RE
CE

–3– 8
Enhanced view A - A'
Fig. 2 Flow cell components, Left side: Cylindrical electrode assembly composed by: 1.- Steel rod as
electrical connection with the working electrode (cross section), 2.- O ring seal, 3.- Plastic holder, 4).-
Mineral sample. Right side: A cross section of the complete flow cell, cylindrical electrode and body cell,
5).- Plastic cell body, 6).- Counter electrode SS 316L hollow cylinder, 7).- Reference electrode, 8).- Inlet port,
9).- Outlet port. The solution circulates through the annular passage left between the internal parts of the
cell (Dark zones)

10

5
i (A/m2)

0
-1000 -600 -200 200 600
E(mV/SHE)

-5

-10

Fig. 3 Polarization curve for SS 316L in seawater

The flow cell was initially replenished with solution through the upper part of the flow cell taking
care to avoid any air pocket formation. Once the system was filled with solution the WE was
inserted in the flow cell and the pump was activated to keep the solution under constant
circulation. After a 60-minute stabilization period exposed to an open circuit potential condition
(OCP), a linear sweep voltammetry (LSV) measurements were carried out at 5 mV/s. Some runs
were replicated to check measurement reproducibility.

Working electrode
Two types of working electrode were prepared, namely powder (PWE) and solid electrode (SWE).
The PWE electrode consists of a mineral film particles attached to a mixture of 1.0 g graphite and
1.2 g of candle wax. The graphite was from Sigma Aldrich Company.
For the construction of the PWE a Teflon cylinder with dimensions of 10 mm diameter, 80 mm
length was drilled along its axis to insert a 3 mm diameter steel rod (Fig. 2) to be used for external
electrical connection with the internal wax-graphite body. In the internal WE end, a small 6 mm
cavity was filled with molten graphite/wax mix at 80 °C, which was solidified at room temperature.
Mineral characterization was made by X-Ray diffraction apparatus Siemens model D5000. The
operating conditions were: Goniometer: Vertical Bragg-Bretano, Radiation: Cu Kα1 (λ = 1,5406 Å),
Voltage: 40 Kv, intensity: 30mA, Scintillation detector:, Secondary Graphite Monocromator, Slits: 1
mm/1mm/0,1mm, Scan range: 3 - 70° 2θ, Step Size: 0,020° 2θ, Step Time: 1,0 s, data Base: ICDD

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(International Centre for Diffraction Data). Quantifying program: TOPAS (Total Pattern Analysis
Software).
Two mineral samples obtained from a copper mineral deposit at Taltal site in the II Region of
Northern Chile were considered for this work. According to X ray characterization, (Table 1)
mineral 1 consists of a crystalline pyrite with small amount of impurities, whereas mineral 2 has a
crystalline composition of 68% composite copper minerals, and a balance of pyrite, quartz, iron
mineral and small amount of molibdenite. The mineral characterization in Table 1 indicates that
mineral 1 was pure pyrite with small amount of impurities, whereas mineral 2 (Tabl3 2) was a
mixture of copper minerals in addition to other constituents.

Table 1 Mineral characterization by X ray diffraction for mineral 1

Muestra P
Compuesto (Fase
Cristalina) Composición Química (~%)
Pyrite FeS2 98.7
Djurleita Cu31S16 0.1
Quartz SiO2 0.53
Montmorillonite-18Å Na0.3(AlMg)2Si4O10OH2*6H2O 0.32
Crednerita Cu(Mn,Fe)O2 0.2
Tridymita SiO2 0.15

Table 2 Mineral characterization by X ray diffraction for mineral 2

Muestra MD
Compuesto(Fase
Cristalina) Composición Química (~%)
Pyrite FeS2 27.11
Djurleita Cu31S16 50.95
Chalcocite Cu2S 3.29
Quartz SiO2 3.36
Westita Fe0.880O 0.68
Tenorite CuO 4.79
Bornite Cu5FeS4 9.05
Pyrrhotite Fe1-xS 0.29
Hematite Fe2O3 0.38
Molybdenite MoS2 0.1

The mineral powder was hand ground with an agate mortar and pestle. This material was sieved to
isolate a homogeneous particle size fraction of 100 um. The working electrode as a film attached on

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the supportive media was prepared rubbing the surface tip of a WE against dried powdered
mineral.
For the construction of the SWE the same Teflon cylinder with the central steel rod was used, but
the cavity was filled with a 6 mm diameter mineral cylinder which was cut from a sample stone
using a rotating hollow cylinder diamond tool. The sealing of the mineral cylinder against the
Teflon cavity was achieved using epoxy cement.
Experimental runs
Before any electrochemical measurement a stabilization period of 30 minutes were carried out at
open circuit potential. Linear sweep voltammetry (LSV) at a potential sweep of 5 mV/s and cyclic
voltammetry (CV) at 20 mV/s for both a massive and a powder sample were measured.
Surface preparation.
The surface of the mineral solid electrode was prepared using 600 SiC abrasive paper until a
uniform surface free of large scratches in particular in the circular edge plastic-mineral which is
supposed to be sealed with epoxy cement.

RESULTS AND DISCUSSION

All electrochemical measurement showed a high degree of stability with very low noise. In
considering the low Re numbers (~ 400) a laminar flow was expected. The initial open potential
measurement previously made to all runs showed a fast convergence to stable values. This
stabilization time that was lower than 30 minutes proved to be essential to achieve good
reproducibility. It is important to highlight the operating versatility of using the present flow cell
concerning to: a).- Fast WE insertion in the cell body, b).- Hydrodynamic conditions of the
electrolyte through the WE could be easily manipulated, c).- The system is prone to insert any type
of sensor to achieve on-line measurements while electrochemical measurement are taking place. For
example dissolved oxygen, ORP, etc.
Mineral 1 (pyrite) measurements.
LSV and CV for massive and powder pyrite are shown in Figs. 4 and 5 respectively. A very good
match between massive and powder pyrite samples are observed both for LSV and CV
measurements.

1.0 0.5

0.5
0.0
i (A/m2)

-400 -200 0 200 400 600

i (A/m2)

0.0
-400 -200 0 200 400 600 800 E (mV/SHE)

-0.5 -0.5

-1.0
E (mV/SHE) -1.0

Fig. 4 Replicated electrochemical measurement for massive mineral 1 electrode in seawater

(left) Replicated LSV, (right) Replicated CV

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 1.0 0.5

0.5
0.0

i (A/m2)
-400 -200 0 200 400 600
i (A/m2)

0.0
-400 -200 0 200 400 600 800 E(mV/SHE)
E(mV/SHE) -0.5
-0.5

-1.0 -1.0

Fig. 5 Replicated electrochemical measurement for powder mineral 1 electrode in seawater

(left) Replicated LSV, (right) Replicated CV

Mineral 2 measurements.
LSV and CV for massive and powder mineral 2 are shown in Figs. 6 and 7 respectively. In contrast
with pyrite mineral, there is a poor match between massive and powder mineral 2 samples for both
LSV and CV measurements. The anodic current density values are significantly larger than that of
the massive pyrite sample. This can be explained in terms of an uneven phase distribution of
different crystalline components of the sample mineral 2. In a survey across different mining sites in
Northern Chile it was found that most copper ores had irregular distribution of mineral
components and a single electro active component is a rare event.

3 4

2
2
i (A/m2)

i (A/m2)

0
0 -400 -200 0 200 400 600
-400 -200 0 200 400
E (mV/SHE)
E (mV/SHE)
-1 -2

Fig. 6 Replicated electrochemical measurement for massive mineral 2 electrode in seawater

(left) Replicated LSV, (right) Replicated CV

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 0.5 0.5

0.0 0.0
-400 -200 0 200 400 -400 -200 0 200 400 600
i (A/m2)

i (A/m2)
E (mV/SHE) E (mV/SHE)

-0.5 -0.5

-1.0 -1.0

Fig. 7 Replicated electrochemical measurement for powder mineral 2 electrode in seawater

(left) Replicated LSV, (right) Replicated CV

CONCLUSIONS
In this work, a novel planar perpendicular flow cell was used for electrochemical measurements in
seawater using both a massive and powder mineral samples. The flow cell consists of a circular
sample surface positioned in a tubular cell exposed to a constant flow solution. The electrochemical
measurements for mineral 1 sample which consist of mainly pyrite, proved to be stable and reliable
for both powder and massive samples. The lack of agreement between powder and massive
samples for mineral 2, which consist of different copper and iron minerals is attributed to its
uneven spatial distribution in the mineral mass volume. Thus, for ideal mineral samples consisting
mainly of a single crystalline form, the use of powder electrode for electrochemical measurements is
a very good alternative for massive samples where they are not available.

The operating versatility of using the present flow cell proved to be very convenient concerning to
the stability and noise-free readings, quick WE replacement, hydrodynamic adjustability to a wide
range of conditions. Additionally the system is prone to be used for on-line measurements alone or
in combination with different type of sensors, for example ORP sensors to compare potential
measurements in flotation studies.

ACKNOWLEDGMENTS
The financial support from CONYCIT project number 21120803 developed in the Chemical
Engineering Department at the Universidad de Antofagasta, Antofagasta, Chile, is greatly
appreciated.

REFERENCES
Ahmad, Z. Corrosion Engineering and Corrosion Control. USA : Elsevier, 2006.
CICITEM Caceres Luis. Anular flow electrochemical cell to measuement on line. Patent INAPI
3107978 2013-03352.. - Chile, (2013).
Gotepke, F. Effect of pH pulp Potential and Sulphide mineral Flotation. Turkish J. Eng. Env. Sci.
(2002), ps. 309-318.
Hu, Y., Wei, W., and Wang D Electrochemistry of Flotation of Sulphide Minerals. China : (2009).

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Labonté, G. Modulation of Selectivity between Copper and Zinc Minerais Using Electrochemical
Potential of the Pulp. Engineering, Department of Mining and Metallurgical. Montreal: McGill
University, (1999) p. 257. A thesis submitted to the Faculty of Graduate Studies and Research in
partial fulfilment of the requirements for the degree of Doctor of Philosophy.
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Moslemi, H., Shams, P., Habashi. Pyrite and pyrrhotite open circuit potentials study: Effects on
flotation. Minerals Engineering. (2011) Vol. 24. ps. 1038–1045.
Rand, D., Woods, R. Eh measurements in sulphide mineral slurries. International Journal of
Mineral Processing. (1984). Vol. 13. ps. 29-42.
Woods R. Electrochemical potential controlling flotation. International Journal of Mineral
Processing Vol. 72 (2003). ps. 151– 162.
Woods, R., Gardner, J. An electrochemical investigation of the natural flotability of calcopyrite. Int.
J. Miner. Process. (1979). ps. 1-18.

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