A CASE OF IMPLEMENTING ON-LINE ANALYSIS OF IRON ORE SLURRIES

Daniel Michaud1, Guy Chevalier2

1
COREM, 1180, rue de la Minéralogie,
Québec (Québec) G1N 1X7, CANADA
2
Québec Cartier Mining Company, 24, boul. des Îles,
Port-Cartier (Québec) G5B 2H3, CANADA

Abstract: An account is presented of the development and implementation of an on-line

analyzer in an iron ore pelletizing plant. The analyzer uses Laser-Induced Breakdown
Spectroscopy (LIBS) technology to interrogate the target material and determine the
concentration of key elements. Following primary slurry sampling, prior conditioning is
necessary to ensure reliable determinations. The instrument has proved to be a very
sensitive detector of process perturbations of either chemical or physical origin and has
enabled plant operators to exert tighter control over the chemistry of the final product.
Copyright © 2007 IFAC

Keywords: Process control, Control applications, Technology transfer, Spectroscopy,

Calibration

1. INTRODUCTION large acceptance in the industry due to reasons

For cost and quality control purposes, the ore
dressing industry needs practicable means of
monitoring the chemistry of the ore as it is being
processed. At an early step in the process, the ore is
ground to some minute size and from then on is
transported as solids in slurry flows. The next steps
aim to concentrate the ore by pulling out the valuable
mineral and discarding the gangue material.
Knowledge of the composition of the ore at some
given time or location along the process line enables
plant operators to maintain specified chemical
targets. This control becomes especially beneficial
and timely when performed in real time. The most
widely used method to accomplish this task is X-ray
fluorescence but when applied to the measurement of
slurries most light elements fall out of reach because
water absorbs their characteristic emission (Braden
et al., 2002). Among these elements are carbon and
silicon, which are of paramount importance to iron
ore pelletizing plant operators. Other methods to
measure these elements exist but have not gained
related to prohibitive costs, lack of robustness,
demanding installations and security issues. Laser-
Induced Breakdown Spectroscopy (LIBS) is a
relatively recent technology that has demonstrated
good potential for real-time applications (Sabsabi et
al., 2004).
The paper reports on the development of a LIBS-
based on-line analyzer and on its implementation in
an iron ore pelletizing plant. The work stemmed from
an initial and intensive endeavour encompassing both
laboratory and field tests (Turmel et al., 1999;
Barrette et al., 1999; Michaud et al., 2003; Barrette et
al., 2004). The objective was to monitor the
concentrations of carbon (occurring essentially as
added coke), silicon (occurring as native silica and as
added silicates), magnesium, calcium and manganese
in order to gain higher control over the chemistry of
the iron ore pellets. Substantial savings were foreseen
from the use of such an on-line analyzer, the benefits
spawning from a stabilized process, an increased
product quality, and a better fuel partitioning
(between coke and oil) in the induration step, etc.
2. EXPERIMENTAL
LIBS is a growing technology offering the notable
advantages of speed (analyses produced in a matter
of seconds), sensitivity (in the 10-100 ppm range),
and the capacity for multi-elemental analyses of
virtually all elements (Radziemski and Cremers,
1989). LIBS uses energetic laser pulses to excite the
sample and promote characteristic optical emission.
This emission is collected with suitable optics and
analyzed with an optical emission spectrometer. A
spectrum is acquired from which an interpretation in
terms of elemental species and their intensities can
be completed. A calibration curve can then be
established to determine the concentration of each
component in the sample.
A LIBS instrument was thus designed and
assembled. The system is made up of three modules
as shown in Figure 1. The first module is a slurry
conditioner; it receives the primary sample from the
main process (about 150 litres of slurry per minute),
homogenizes the material and controls the density of
the slurry (solids content) prior to extracting a final
sample (about 30 L/min) for the LIBS analyzer. The
second module is the measurement “head” – an
enclosure holding the laser and the optical
components. The module is divided into three
compartments, one of which is the sample chamber
through which the slurry column falls; this chamber
is kept under positive pressure with flowing air and
periodically water-cleaned with automatic sprinklers.
The last module is the command module, which
contains the analytical instrumentation and all
control and communications means. The command
module is Nema4 compliant and includes a cooling
unit.
Fig. 1. Schematic of the application including the
components of the on-line analyzer.
The discrete components of the analyzer include an
industrial Nd-YAG laser (model CFR200 from Big
Sky Laser Technologies) set to emit pulses of 150 mJ
at the fundamental wavelength of 1064 nm. The laser
beam is focussed on a free-falling section of slurry
using a lens of 40 cm nominal wavelength. The firing
repetition rate is set at 2 Hz. The emission of the
plasma formed on the target is collected with a pair
of lenses and transported to the spectrometer via a
cable of optical fibres. The spectrometer is of the
Czerny-Turner type (model Triax 550 from Jobin-
Yvon) and the detector is an ICCD camera (model
iStar from Andor Technologies) with a grating of
2400 lines per mm. Using this combination, spectral
windows of 12 nm in wavelength span can be
recorded. To cover all elements of interest in this
application, three windows are necessary.
Following common practice, the intensities are
averaged over many consecutive laser shots (120
here) to reduce standard deviation of signals. In
addition, intensities are ratioed over a reference
element (here an iron peak) in order to further
stabilize the measurements. Calibration curves and
precision are calculated using these element ratios.
All control and data software for the LIBS instrument
was developed in-house.
Particular efforts were invested to build in the
instrument the properties of robustness, reliability
and security. Robustness was required on account of
using scientific instrumentation in a tough industrial
environment. The spectrometer in particular is a
sensitive tool and was consequently seated on a
vibration-damping stage. Reliability refers to the
quality of the data acquired, in terms of precision and
accuracy. Security measures were needed to confine
the laser radiation inside its enclosure and to halt the
analyses in response to different external failures.
The absence of flowing slurry in front of the laser
beam, the shortage in water feed to the cooling unit
or to the laser head and the lack of air pressure in the
pneumatic valve lines are examples of detected
failures.
3. RESULTS
Before delivering the newly built LIBS analyzer to
the pellet plant, tests were conducted in COREM’s
pilot plant using a closed loop of circulating iron ore
slurry. Slurry flow (at 30 L/min) and homogeneity
were checked to satisfaction; control over the percent
solids in the slurry reached ±1% (around the 70%
level). Laser module toughness and watertightness
were successfully checked. Software and safety
devices were challenged over extended periods of
time. Applying the method of standard additions
(using compatible ores), calibration curves were built
to determine the measurement precision. Precision is
expressed as the smallest detectable variation in
absolute concentration (SDVAC). This indicator is
computed as the ratio of twice the standard deviation
of the measurements over the regression slope and
thus holds to a confidence level of 95%.
Results of pilot plant preliminary tests appear in
Table 1. Linear responses (R²) are excellent over the
concentration spans of each element measured. The
relative slope expresses the percentage of change of
the signal as a reaction to a 1% change in
concentration; it is an indication of the amplitude of
the response. It is thus seen that the manganese
response is strong while that of silicon is not. As can
be expected, this indicator is anti-correlated with the
precision obtained (SDVAC). The relative SDVAC
on the other hand weighs the response of each
element against its concentration in the ore; on this
basis, the quality of the silicon measurements is very
good compared to the other elements.
Table 1 Results of pilot plant preliminary tests
C Si Mg Ca
Concentration span 0.32 − 2.62 − 0.25 − 0.54 −
(%) 1.12 3.31 0.55 0.87
Relative stdev (%) 7.0 2.1 2.2 1.7
R² 0.9986 0.9906 0.9981 0.9970 0.9766
Relative slope 119 19 70 36
(% / %)
SDVAC (%) 0.07 0.21 0.09 0.07
Relative SDVAC 9.7 7.0 21.7 10.0
(%)
The instrument was shipped and installed at QCM’s
pelletizing plant in August 2005. QCM took charge
of the primary sampling of the process; and of the
transportation and disposal of the slurry after use.
The material to be measured was the output of the
ball mills, just prior to the final filtration and
pelletizing steps, and occurred as a slurry holding
some 72% solids. A primary sampling device was
installed on the process line to extract slurry at a rate
of about 150 litres per minute. A secondary sampler
was inserted after the LIBS measurement head to
extract samples for calibration purposes.
The analyzer was started and set to provide refreshed
concentration values every three minutes (each one
of the three acquisition windows is analyzed for one
minute). A connection was established between the
instrument’s command unit and the plant’s local
control system so that the LIBS data could be
exported, formatted and displayed on the operator’s
control screen. Local personnel was trained to look
over the instrument on a daily basis; COREM
remained as backup for servicing instrumental and
technical issues.
4.5
4
3.5
Concentration (% w/w)
3
2.5
2
1.5
1
Si LIBS
0.5
Si Chem
C LIBS
C Chem
0
9:30 10:30 11:30 12:30 13:30 14:30
Time
Fig. 2. Tracking of silicon and carbon concentrations
in the iron ore slurry on September 7, 2005.
Mn
0.11 −
0.32
One month after start-up, the tracking graph
reproduced in Fig. 2 was obtained. During the trial,
1.5 some perturbation of the process promoted the
variation of the concentrations of carbon and silicon.
The correlation between the LIBS and laboratory
273
results scores 0.91 for silicon and 0.96 for carbon.
0.01 During the first year of operation, the up-time for the
6.5 instrument was over 90% (excluding those periods
when the system was intentionally stopped). The
most time-consuming problem in the first months
was related to maintaining a steady flow of slurry;
pipe clogging and pipe wear were especially
troublesome; these problems were solved over time.
An optics alignment problem and a security failure
occurred which necessitated corrective actions. Apart
from these discrete events, the system only needed
regular maintenance (to change laser flashlamps bi-
yearly among other things). It is concluded that the
instrument needs only minimal supervision – less
than 10 hours a week on the part of QCM personnel –
in line with prospective specifications.
On-site performance evaluation of the analyzer was
done once the instrument and sample manipulation
were mastered. This consisted in determining the
accuracy of the measurements with respect to the
analyses produced by QCM’s chemistry laboratory.
The precision (smallest detectable variations in
concentration) determined for the measurements is
comparable to what was obtained in the preliminary
tests in COREM’s pilot plant. The accuracy though,
which was anticipated to hold within the precision
span, was at times not met. The most problematic
case was that of silica for which absolute biases
exceeding 0.25% were noted when comparing the
LIBS results with daily check tests.
 4. DISCUSSION
Calibration of the LIBS instrument is needed in order
to maintain the analyzer in a proper working state.
To this purpose, periodic calibration campaigns are
to be performed (a few times a year) by intentionally
upsetting the process. This is done by slowing down
slurry pumps, altering mill throughputs, temporarily
modifying additives feed, or by any other means that
will induce a sizable variation of the concentrations
of the components in the slurry solids. Taking a
number of samples during the event provides data to
compute a new calibration curve for each element
measured. Afterwards, daily checks serve to follow
the instrument’s routine level of performance; in this
case, only one sample is taken to establish the tuning
between the LIBS and the lab.
The accuracy problem observed (i.e. the fit to the
laboratory results) is limited to the comparison of
LIBS results with routine checks performed on a
daily basis. Indeed, when specific calibration
campaigns are run by intentionally perturbing the
process, the quality of the calibration curves and the
precisions obtained are very good (similar to results
from preliminary tests). It was observed though, that
daily check results line up on a slightly different
calibration slope. It is thus concluded that provoked
process upsets are not truly representative of real
process dynamics. This situation may arise from the
fact that over the short period during which a
perturbation occurs, long term variables such as
particle grain size and ore matrix composition remain
essentially constant; conversely, significant
excursions may be experienced on longer time
scales. Based on this reasoning, it was proposed that
practicable calibration curves should be constructed
by accumulating daily check results rather than
relying on calibration curves derived from
intentionally perturbed process situations.
In addition, it was found that calibration (for silica
especially) must be tailored to the current pellet type
in production in order to correctly account for the
different yields observed as a function of the pellet
composition. (Iron ore pellet plants produce pellets
of different “recipes”, varying in silicate content,
notably, to meet customer specifications.) It is
argued that the dual nature of the silicon-bearing
minerals in the slurry (silica in the native ore and
silicates in the additives) is responsible for this
situation. Indeed, indications to the effect that silica
yields less than silicates under LIBS excitation have
been accumulated but remain to be verified.
In spite of the slight bias in accuracy, the instrument
remains a very capable trend monitor for following
the chemistry of the ore in quasi real-time (three-
minute intervals between measurements). The on-
line measurements display a clear advantage over
conventional average-sampling and delayed
chemical assaying. Indeed, the continuous
measurements add up statistically to represent tons of
actual material as it flows by, compared to the minute
grams of slurry bleeded off the process line every 15
minutes and averaged over some 2 to 4 hours.
Any steady variation of the LIBS signal can readily
be interpreted as a deviation from a prior state. In this
manner, the process operator can bring down his
reaction time from hours to some 15 minutes or so,
thereby gaining timely and tighter control over the
process. This advantage, in turn, translates in
products of higher and consistent quality.
Furthermore, the on-line analyzer turned out to be a
very sensitive detector of various process upsets, like
mill failures, occasional use of recycled water, etc.
Also, the instrument is a powerful tool to study the
process itself. For example, establishing the grinding
kinetics of the ore (around 20 minutes) with respect
to the additives coke (15 minutes) and dolomite (18
minutes) was merely a straightforward task with the
on-line instrument.
5. CONCLUSION
An on-line analyzer based on Laser-Induced
Breakdown Spectroscopy was designed, assembled
and installed in an iron ore pellet plant. The field
application consists in measuring elements C, Si, Mg,
Ca and Mn in the solids embedded in a slurry; the
objective is to check compliance with prescribed
concentration levels. Tracking of these elements in
intervals of 3 minutes is a considerable enhancement
relative to the pre-existing situation (hours). The
precision achieved is sufficient to enable plant
operators to detect any process upsets and apply
corrective measures in a timely manner. The on-line
analyzer can also be used to study the process itself
by performing tests to determine process dynamics or
the response to some deliberate action. The LIBS
analyzer is up and running in the pellet plant since
September 2005.
ACKNOWLEDGEMENTS
A commitment for quality and close collaboration
between the research and industrial partners are two
factors that have significantly contributed to make
this project a success. The authors wish to thank
Steeven Dubord and Stéphane Morin from QCM for
their technical implication in looking over the
installed instrument. The devoted involvement in the
project of COREM’s Éric Proulx, Luc Tardif,
Frédéric Michaud, Pierre Laprade, Rémi Leclerc,
Daniel Mainville and Jean-Guy Chartrand is also
gratefully acknowledged.
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