minerals

Review
Sensors and Process Control in Copper Smelters: A Review of
Current Systems and Some Opportunities
Luis Arias 1 , Eduardo Balladares 2 , Roberto Parra 2, *, Daniel Sbarbaro 1 and Sergio Torres 1

1 Department of Electrical Engineering, University of Concepción, Concepción 4070371, Chile;

luiarias@udec.cl (L.A.); dsbarbar@udec.cl (D.S.); sertorre@udec.cl (S.T.)
2 Department of Metallurgical Engineering, University of Concepción, Concepción 4070371, Chile;
eballada@udec.cl
* Correspondence: rparra@udec.cl

Abstract: Despite the widespread and extended use of sensor systems in different industries, there
is an important gap to reach equivalent conditions in pyrometallurgical processes for primary
production. In the specific case of copper pyrometallurgy, the situation is particularly challenging
to incorporate the Industry 4.0 concept for the optimization of their operations. Currently, only
two instruments can be identified at the commercial level: the Noranda pyrometer and the Online
Production Control (OPC) system. The iron-making and steelmaking industries, however, present an
advanced level of control based on monitoring and sensing networks throughout the entire process.
This reality has served as a basis for developing a series of solutions based on radiometric sensors for
copper pyrometallurgy. We present two types of sensing concept. The first one is applied to smelting
and converting reactors based on the measurements of the radiation of the oxidation of different
copper and iron sulfides. The second one considers hyperspectral imaging of molten phases flow
during operations. The idea of this proposal is to transfer some commercial sensing technologies
already in use in the steelmaking industry. In this article, the fundamentals of the sensor design,
proofs of concept, and the initial industrial validations are reviewed. Finally, a discussion on the
contribution of this knowledge and development opportunities within the framework of Industry 4.0



are addressed.



Citation: Arias, L.; Balladares, E.; Parra,

Keywords: copper pyrometallurgy; sensing; spectral measurement
R.; Sbarbaro, D.; Torres, S. Sensors
and Process Control in Copper Smelters:
A Review of Current Systems and Some
Opportunities. Minerals 2021, 11, 1.
1. Introduction
https://dx.doi.org/min11010001
It is well accepted that modern industry requires a range of effective plant sensors and
Received: 21 October 2020 appropriate process control systems leading to a level of automation and third-generation
Accepted: 8 December 2020 process control for the highest efficiency [1]. This is the case of steelmaking plants, the oil
Published: 22 December 2020 and gas industry, chemical processes and the food industry to mention some examples.
In all of them, the 3rd industrial revolution has been adopted in their control systems.
Publisher’s Note: MDPI stays neu- In this set of industries, the copper pyrometallurgical processes can be considered as the last
tral with regard to jurisdictional claims step of the mining industry or the first one for manufacturing. Today, they face significant
in published maps and institutional challenges for establishing sustainable operations due to higher complexity in the ores to
affiliations. be treated and increasingly stringent environmental standards.
On-line sensors of important operational variables play a key role in the improvements
of operational standards. In copper pyrometallurgy, the degree of use of analytical instru-
Copyright: © 2020 by the authors. Li-
mentation for the monitoring and control of the process is limited, so that the information
censee MDPI, Basel, Switzerland. This available for the decision-making process during the operation is scarce. Currently, the
article is an open access article distributed control of copper smelters operations is mainly based on macroscopic mass and energy
under the terms and conditions of the balances, and the dynamics of the process depends, to a large extent, on the experience
Creative Commons Attribution (CC BY) of operators.
license (https://creativecommons.org/ This diagnosis is clearer if the iron and steel industry is taken as a reference, a process
licenses/by/4.0/). industry with clear similarities and analogies to copper pyrometallurgy. The steel industry

Minerals 2021, 11, 1. https://dx.doi.org/10.3390/min11010001 https://www.mdpi.com/journal/minerals

Minerals 2021, 11, 1 2 of 17

uses different types of sensor and well-developed control systems. This condition is
a key element in the operational versatility that these plants have, producing a wide
range of products with the same reactors and the same operators, and changing the
characteristics of the steel produced from one charge to another. Similarly, the consumption
of refractory materials in the steel industry is orders of magnitude lower than those of
copper pyrometallurgy, expressed per ton of metal produced. It should also be borne in
mind that the steel industry operates at a temperature higher than the temperature of the
copper pyrometallurgy, at least 300 ◦ C and with more aggressive chemical systems.
Even with the tremendous advance in the development of passive and active photonic
sensors such as hyperspectral imaging (HI) and different optic sensors, as simple as digital
optic pyrometers, there are still only two real-time analytical sensors specially designed for
the unique condition of the pyrometallurgical copper processes.
The direct study of the encrypted information in the spectral radiation produced by
combustion reactions facilitates the analysis of the process, due to the non-invasive and
wireless nature of the technologies used. This has enabled, for example, the estimation
of reaction temperatures and the observation of the main species of the reaction and its
concentrations. This concept has been successfully applied to the combustion of liquids or
gases [2] and pyrotechnic mixtures [3–5]. In these applications, the information provided
by online spectra has allowed investigation of morphological structures of flames, types
of reactions in mixtures pyrotechnics, the movement and burning of individual particles,
the processes of igniting powders, propagation of gas explosions, and in situ observations
of reactions in closed combustion chambers through optical fibers with optomechanics
adapted for these processes.
The application of optical spectroscopy to copper pyrometallurgy was discussed dur-
ing the Annual Meeting of the Minerals, Metals & Materials Society in Denver 1993 where
professor Queneau defined the advantage of the information that the operator can have,
where up to that time (until today) there had been no option to have the same information
“without sticking the head into the vessel”, this information was then developed in [6].
The maturity of the development of this type of sensor for the steelmaking industry is
clear today. The first development at the industrial scale was done early in the 1970s [7,8]
and gained real maturity in the 1980s [9,10]. This led to very robust process control of
the steelmaking processes and reactors. The use of spectral characteristics has also been
validated in the spatial recognition of phases of interest in the iron and steel making process,
as will be discussed in detail in Section 4.2.
Within copper smelters, the reality is that even the 3.0 industrial revolution (informa-
tion technology (IT) and automation) still has room for continued development. This cur-
rent state limits the ability to integrate Industry 4.0 developments for process optimization.
Indeed, the availability of analytical instrumentation for the monitoring and control of
the smelter processes is limited. Thus, the information available for operational decision-
making is mainly based on static mass and energy balances. The operational dynamics
continue to depend largely on the experience of ground operators. This condition is also re-
flected in the literature review (both on the eastern and western world) where the scientific
and technical information is related only with the two instruments that have gained indus-
try acceptance for operational monitoring and control in copper pyrometallurgical reactors.
The first one is the Semtech Online Production Control (OPC) system. The OPC
system was developed in collaboration with the Swedish company Boliden Mineral AB
to provide continuous online information on the status of the process in the Pierce Smith
converter (Equations (3) and (4)). The company started as a spin-off from the Physics De-
partment, Lund Institute of Technology at Lund University in 1987, and its first commercial
system was installed in 1994 at Boliden, already working [11]. The instrument is based on
spectrometric measurements to identify the presence of PbS and PbO in the off-gas of the
converter. The dynamic of these trace elements in the gas, increasing concentration of PbO
and decreasing concentration of PbS, signal when the process must be stopped (by stopping
the O2(g) injection in Equation (3)) [12,13]. Precise determination of the endpoint of O2(g)
Minerals 2021, 11, 1 3 of 17

injection is of great value to control the operation. It increases the operating time while
stabilizing the operation of the whole smelter due to the optimization of slag recirculation,
which at the same time diminishes its copper content increasing copper recovery.
The second is the Noranda Pyrometer [14], configured solely for bath furnaces using
blowing tuyeres. It has been on the market since the 1980s without any modifications
to the original design. By measuring radiation through an analog array, this instrument
monitors the temperature of the molten bath by applying Planck’s law for two fixed
wavelengths. In this case, more than the application of a radiometric measurement to
determine a temperature, which is quite trivial, the value of the instrument is in the design
and operation of an optical system that allows a direct and permanent field of vision of the
molten bath inside the reactor.
One option for the advancement of process monitoring and control systems in copper
smelters is to modernize the use of radiometric measurements since this approach has been
previously validated with both the OPC system and the Noranda Pyrometer.
The analysis presented in this article is based on the physicochemical characteristics
of the reactions that occur in the different reactors of the pyrometallurgical process for
copper concentrates to relate them with similar sensing processes present in other indus-
tries. The concept for the development of new sensors for copper smelters is based then,
in adopting and adapting principles already validated to the very particular conditions of
the chemical transformations of the primary production of copper from concentrates.

2. Pyrometallurgical Process Description

2.1. Basic Chemical Scheme for a Cu Smelter and Energy Released
The Cu pyrometallurgy process treats Cu concentrates to produce Cu anodes that are
then electro-refined by an electrochemical step in aqueous acid media. The Cu concentrates
are copper and iron sulfide minerals in the form of particles with sizes under 150 µm.
The elemental composition is around 25 to 30 wt% of Cu, 25 to 35 wt% of S, iron from 20 to
40 wt% and gangue (oxides). The smelter operation allows the selective oxidation of Fe
and S keeping the Cu in the final product. This oxidation is thermodynamically favored
by the high exothermic reactions that allow to melt the system. The overall chemical
transformations that occur in a Cu smelter can be represented by the following scheme:
(Cu,Fe,S) + O2(g) + (SiO2 -CaO)fluxes = Slag (2FeO*SiO2 + Fe3 O4 + CaO + others) + SO2(g) + Cu (1)
The fluxes diminish the liquidus temperature in the Fe-O system allowing the separa-
tion of the Cu metallic phases from the slag by density. The Cu smelter follows a two-step
process to achieve this overall transformation.
The first stage is aimed at melting the concentrate by the exothermic reactions control-
ling the oxygen mass balance to produce an intermediate phase called matte that is within
the Cu-Fe-S system and can be reasonable represented by the pseudo binary Cu2 S-FeS:
(Cu,Fe,S) + O2(g) + (SiO2 -CaO)fluxes = (2FeO*SiO2 + Fe3 O4 + CaO + others)slag + SO2(g) + (Cu2 S-FeS) (2)
This matte phase follows the oxidation in the same way in the second step:
(Cu2 S-FeS) + O2(g) + (SiO2 -CaO)fluxes = (2FeO*SiO2 + Fe3 O4 + CaO + others)slag + SO2(g) + Cu2 S (3)
The Cu2 S produced, also known as white metal, follows the oxidation, in this case to
eliminate the last remaining sulfur:

Cu2 S + O2(g) = 2Cu + SO2(g) (4)

The first step (Equation (2)) is called smelting and the second converting (Equations (3)
and (4)). The different smelting technologies induce similar chemical transformations but
differ in how the oxygen contact the concentrate. Until today, the best available technology
has been the flash smelting reactor where the concentrate is oxidized through a burner, with
clear similarities with coal combustion. A second important family for the smelting stage
is the bath smelting, where the concentrate is injected with air in a molten bath through
tuyeres. The bath smelting technology family is gaining increasing relevance due to the
Minerals 2021, 11, 1 4 of 17

development of new reactors in China, the so-called bottom blowing reactors that simplify
the injection of concentrates through tuyeres charging the concentrate from the top of the
reactor and blowing the enriched air from the bottom at high speed. For the converting
stage, the Peirce Smith converter is the most widely used in the world despite being a
reactor that has not undergone substantial improvements since its introduction in 1906.
Equation (2) takes place with different mineral sulfides species, the main ones being
Chalcopyrite (CuFeS2 ), Pyrite (FeS2 ) and Bornite (Cu5 FeS4 ). The oxidations of these species
are strongly exothermic as shown in Figure 1, where a mass and energy balance were
undertaken for two types of classic concentrate (Table 1) The adiabatic temperature of the
oxidative system is presented as a function of the Cu content in the matte as a target of
the control process. The energy and mass balance was developed using HSC 6.0 software
and database. Silica was the flux to form the slag assuming a target of Fe/SiO2 = 1.38.
Minerals 2021, 11, x
The chemical representation of the slag considers 2FeO*SiO5 of 19 2
, CaO*Al2 O3 *SiO2 and free
oxides to close the balance if needed.

2 000

1 900
Adiabatic temperature (K)

1 800

1 700

1 600
S/Cu=1; Cu=30.97%
S/Cu=1.15; Cu=29.247%
1 500

1 400
60 65 70 75 80
% Cu in matte

Figure 1. Adiabatic temperature of the reactive system during smelting (oxidation process) of con-
Figure
centrates 1 and 21. Adiabatic
(Table temperature
1). The enriched of the
air for the process reactive
has 65% system
O2(g) (pO2(g) = 0.65). during
smelting (oxidation process) of
concentrates 1 and 2 (Table 1). The enriched air for the process has 65% O2(g) (pO2(g) = 0.65).
2.2. Dynamic of the Oxidation of Sulfides
The temperatures obtained (Figure 1) are a useful reference to describe the thermal
Table
process 1. Chemical
of sulfides and mineralogical
minerals oxidation. The dynamics ofcharacterization of oftwo
the oxidation reactions concentrates used for calculation
those
species are extremely
presented fast, being
in Figure 1. completed in few milliseconds for particles of the size of
the ones from a concentrate. In this way, the generation of heat is also very fast which
could be a faster process than the heat transfer dynamic. So, if the temperature at the re-
action interfaceSpecies/Elements
could be measured, it would be verified that Concentrate 1
the reached temperature is Concentrate 2
effectively close to the adiabatic temperature.
FeS2 21.77 30.00
The mathematical modelling of the oxidation dynamics for different minerals parti-
CuFeS 2 40.00
cles has been developed by different researchers [15,16] and is a classical element for anal- 35.00
Cu2 S process for sulfide species. We have
ysis of the oxidation/combustion 15.00applied those mod- 15.00
CuS and other sulfide minerals as an example
els for chalcopyrite oxidation 3.93to have a reference 3.93
for the thermal evolution that a particle of concentrate follows during
Cu5 FeS 4.00the oxidation pro- 4.00
4
cess. The model takes into account the O2(g) partial pressure in the gas, the temperature of
Al O3 particle and the thermal properties3.00
the environment, the size 2of the of the different mineral
3.00
species. CaO 4.00 4.00
2.3. Fundamentals of the SiO 7.30 and Radiometric
2 Chemistry Processes for Designing Optical
Physical 5.07
Sensors Cu 30.972 29.241
Fe
In the case of high-temperature processes, the generation of 22.752
electromagnetic radia- 25.062
tion in the visible and near-infrared
S spectrum from the involved 30.972
phases has served to de- 33.624
velop and commercialize instruments that obtain information on the reactive process at
S/Cu 1.000 1.150
distance. In other words, the dynamic changes in the characteristics of spectral emission
have been related to the chemical process that is monitored. Examples directly related to
the copper smelting process are the combustion of fossil fuels (char, coal, fuel oil, natural
2.2. Dynamic of the Oxidation of Sulfides
gas, methane, etc.) and the characterization of molten phases in the iron and steel industry.
The characteristics of pyrometallurgical
The temperatures obtainedoxidation process1)forare
(Figure sulfide mineralsreference
a useful are to describe the thermal
depicted in Figures 1–3. One can conclude that the kinetics of the reactions, as well as the
process of sulfides minerals oxidation. The dynamics of
temperature rise of the process, is on the same order of magnitude as that of the oxidation the oxidation reactions of those
species are
and combustion extremely
of fossil fast,
fuels [17–19]. being
Therefore, it iscompleted in few
evident to analyze whichmilliseconds
solutions for particles of the size
have been developed to monitor and follow online real-time reactions of fossil fuel com-
of the ones from a concentrate. In this way, the generation of heat is also very fast which
bustion, which precisely correspond to the structure of Equation (2).
could be a faster process than the heat transfer dynamic. So, if the temperature at the
reaction interface could be measured, it would be verified that the reached temperature is
effectively close to the adiabatic temperature.
Minerals 2021, 11, 1 5 of 17

The mathematical modelling of the oxidation dynamics for different minerals particles
has been developed by different researchers [15,16] and is a classical element for analysis
of the oxidation/combustion process for sulfide species. We have applied those models
for chalcopyrite oxidation and other sulfide minerals as an example to have a reference
for the thermal evolution that a particle of concentrate follows during the oxidation pro-
cess. The model takes into account the O2(g) partial pressure in the gas, the temperature
of the environment, the size of the particle and the thermal properties of the different
mineral species.

2.3. Fundamentals of the Physical Chemistry Processes for Designing Optical and Radiometric
Sensors
In the case of high-temperature processes, the generation of electromagnetic radiation
in the visible and near-infrared spectrum from the involved phases has served to develop
and commercialize instruments that obtain information on the reactive process at distance.
In other words, the dynamic changes in the characteristics of spectral emission have
been related to the chemical process that is monitored. Examples directly related to the
copper smelting process are the combustion of fossil fuels (char, coal, fuel oil, natural gas,
methane, etc.) and the characterization of molten phases in the iron and steel industry.
The characteristics of pyrometallurgical oxidation process for sulfide minerals are
depicted in Figures 1–3. One can conclude that the kinetics of the reactions, as well as
the temperature rise of the process, is on the same order of magnitude as that of the
Minerals 2021, 11, x 6 of 19
oxidation and combustion of fossil fuels [17–19]. Therefore, it is evident to analyze which
solutions have been developed to monitor and follow online real-time reactions of fossil
fuel combustion, which precisely correspond to the structure of Equation (2).

(a)

(b)

Figure2. 2.
Figure Temperature
Temperature evolution
evolution for different
for different sizes 2of
sizes of CuFeS CuFeS2 (chalcopyrite)
(chalcopyrite) particles with particles
differ- with dif-
ferent
ent pO2(g)pOin 2(g) in the process
the process gas. The gas. The temperature
temperature of the was
of the environment environment
set at 973 Kwas
(700 set (a)973 K (700 ◦ C).
°C).at
pO = 0.8; (b)
(a)2(g)pO size(b)
= 0.8; of particle = 27 μm. = 27 µm.
size of particle
2(g)
 (b)

Figure 2. Temperature evolution for different sizes of CuFeS2 (chalcopyrite) particles with differ-
ent pO2(g) in the process gas. The temperature of the environment was set at 973 K (700 °C). (a)
Minerals 2021, 11, 1 6 of 17
pO2(g) = 0.8; (b) size of particle = 27 μm.

Minerals 2021, 11, x 7 of 19

(a)

(b)

Figure 3. Temperature evolution for CuFeS (chalcopyrite) and different minerals species for particle
Figure 3. Temperature evolution for CuFeS22 (chalcopyrite) and different minerals species for parti-
size
cle of of
size 27 27 and
µmμm andpOpO = 0.8. (a) Chalcopyrite at different Temperature of the environment (b) T
2(g) = 0.8. (a) Chalcopyrite at different Temperature of the environment (b)
2(g)
Tenvironment
environment973973KKand
andsize
sizeofofparticle
particle==27 μm.
27µm.

3. Sensors and Control in Cu Pyrometallurgy

3. Sensors and Control in Cu Pyrometallurgy
The accurate understanding of the physical chemistry of reactive and non-reactive
The accurate understanding of the physical chemistry of reactive and non-reactive
systems is of great value for designing sensors and has been the basis for development
systems is of great value for designing sensors and has been the basis for development in
in other industries. Despite of a good level of understanding on the physical-chemical
other industries. Despite of a good level of understanding on the physical-chemical fun-
fundamentals of oxidation and combustion of sulfides, until today the spectral analysis
damentals of oxidation and combustion of sulfides, until today the spectral analysis in-
involved in copper pyrometallurgy has been studied only within the research activities
volved
of the in copper
group pyrometallurgy
preparing has As
this paper. been studied
already only within
noted, the lackthe ofresearch activities for
instrumentation of
the group preparing this paper. As already noted, the lack of instrumentation
monitoring the dynamics of the process leads to almost non-existent or poorly performing for moni-
toring
controlthe dynamicsofofthe
strategies thesmelting
process leads to almost non-existent
and converting processes, where or poorly
the performing
human factor con-of
trol strategies of the smelting and converting processes, where the human
operators play an important role and imposes big instabilities. It is important to highlight factor of oper-
ators
that play an important
the variability on role and imposes big
the mineralogical instabilities. Itofisthe
characteristics important
copper to highlight that
concentrate is a
the
natural perturbation to the system where the characterization of this streamisisathe
variability on the mineralogical characteristics of the copper concentrate natural
basis
perturbation to theof
for the definition system where the characterization
the macroscopic mass and energy of balance
this stream is the
for the basis for
smelting the
rector.
definition of the macroscopic mass and energy balance for the smelting
If an online sensor can provide any information on the chemical evolution during the rector. If an online
sensor can provide any information
oxidation/combustion on theprovide
process, it would chemical evolution during
information the oxidation/com-
for fine-tuning online and
bustion
real-time process, it would
the smelting provide
furnaces. information
Thus, for fine-tuning
the productivity indexes will online and real-time
be improved the
by mean
smelting furnaces. Thus, the productivity indexes will be improved by
of higher stability of the operation, decreasing copper losses, and diminishing thermal andmean of higher
stability
chemical ofdeviation
the operation, decreasing
for their copper
set points. losses,of
A series and diminishing
proposed thermal
concepts andand chemical
results from
deviation for their set points. A series of proposed
initial industrial trials are discussed hereafter. concepts and results from initial indus-
trial trials are discussed hereafter.

4. Radiometric Proposals for New Instruments

4.1. Radiometric Measurements of Chemical Oxidation
The development of this family of “new instruments” has started by reproducing the
Equations (2)–(4) at laboratory level, adding online measurement of the spectral signal
through an optic fiber connected to a radiometer with further treatment using mathematic
tools. As was previously pointed out, there are two families of smelting reactors (Equation
Minerals 2021, 11, 1 7 of 17

4. Radiometric Proposals for New Instruments

4.1. Radiometric Measurements of Chemical Oxidation
The development of this family of “new instruments” has started by reproducing the
Equations (2)–(4) at laboratory level, adding online measurement of the spectral signal
through an optic fiber connected to a radiometer with further treatment using mathe-
matic tools. As was previously pointed out, there are two families of smelting reactors
(Equation (2)): bath smelting and flash smelting. For the sake of the length of this article,
we will refer specifically to developments, proof of concept, and preliminary tests at the
industrial level for flash smelting reactions and reactors.
Minerals 2021, 11, x 8 of 19

4.1.1. Experimental Set-Up

burner Aofvertical laminar
a flash smelting flow In
furnace. laboratory
this way, thereactor was
high rate used tofor
of oxidation simulate the oxidation condi-
sulfide min-
tions of the copper concentrates. The combustion of concentrates was carried out under
erals was reproduced at laboratory scale. The temperature and oxygen potential condi-
tions in the gas
controlled inside the furnace
conditions of feedwere
ratesimilar to those that typically
and combustion occur intothe
gas mixture concen- the physical and
simulate
trates burner at the industrial level, so the burning material was assumed to have charac-
chemical transformations that the concentrate particles have when they burn in the burner
teristics equivalent to the material that reaches the settler of the industrial furnace. The
of a flash
system smelting
to feed furnace.
the concentrate wasIn this way,
equipped withthe high rate of oxidation
a high-temperature for sulfide
optic fiber that was minerals was
reproduced
connected to aatVIS-NIR
laboratory scale. The temperature
spectrophotometer USB4000 (Ocean and Optis
oxygen Inc.,potential
Dunedin, conditions
FL, in the gas
USA) was
inside theused to acquire
furnace werethe similar
spectral data in the range
to those from 400–900
that typically nm with
occur an average
in the concentrates burner at
spectral resolution of ~0.22 nm; also, the spectrometer and optical circuit were calibrated
the industrial level, so the burning material was assumed to have characteristics equivalent
to measure the emitted radiation in absolute irradiance units (μW × cm−2 × nm−1). With
to the
such material
a set-up, that reaches
the reaction thereactor
zone of the settler of thetheindustrial
is within field of viewfurnace.
of the fiberThe system to feed the
allow-
concentrate
ing to follow the was equipped
spectral emissionwith
of theaoxidation/combustion
high-temperature of optic fiber
the copper that was connected to a
concentrate
VIS-NIR
(Figure 4). spectrophotometer
A detailed description of USB4000
the set-up(Ocean Optis Inc.,
and its operation Dunedin,
is presented FL, USA) was used to
elsewhere
[1–23]. the spectral data in the range from 400–900 nm with an average spectral resolution
acquire
The spectrum collected during the oxidation process was analyzed to obtain valuable
of ~0.22 nm; also, the spectrometer and optical circuit were calibrated to measure the
information to correlate the spectral information with the chemical process. The measured
emitted
spectra haveradiation in absolute
a continuous irradiance
part that follows Planck’s units × cm−and
(µWbehavior
radiation
2 × nm−1 ). With such a set-up,
discontinuous
the reaction
pattern that arezone oftothe
related the reactor
emission isfromwithin
atoms theand field of view
molecules formed ofduring
the fiber allowing to follow
the ox-
idation process. The temperature of the flame produced was also calculated
the spectral emission of the oxidation/combustion of the copper concentrate (Figure 4). using a clas-
sical Planck’s Law.
A detailed description of the set-up and its operation is presented elsewhere [1–23].

Figure 4. Experimental set-up [23].

Figure 4. Experimental set-up [23].
The results presented hereafter are the summary of different experimental campaigns
Thebeen
and have spectrum
reportedcollected
individuallyduring
in otherthe oxidation
articles process
or documents was
for the analyzed
public domain.to obtain valuable
information to correlate
It is the first time, thethey
however, that spectral information
have been with
integrated to give the chemical
a global process.
vision of what The measured
has been have
spectra developed at the laboratory
a continuous part level.
that This comprehensive
follows Planck’s view seeks to
radiation present the
behavior and discontinuous
concept that laboratory-level studies which reproduce the same chemical reactions of in-
pattern that are related to the emission from atoms and molecules formed during the
dustrial processes on a small scale are representative for studying the optical signals that
processes have.
Minerals 2021, 11, 1 8 of 17

oxidation process. The temperature of the flame produced was also calculated using a
classical Planck’s Law.
The results presented hereafter are the summary of different experimental campaigns
and have been reported individually in other articles or documents for the public domain.
It is the first time, however, that they have been integrated to give a global vision of what
has been developed at the laboratory level. This comprehensive view seeks to present
the concept that laboratory-level studies which reproduce the same chemical reactions of
industrial processes on a small scale are representative for studying the optical signals that
processes have.

4.1.2. Experimental Results: Temperature Measurements

Considering the continuous part of the spectrum, it is very clear that a calculation
for the flame temperature is possible by applying Planck radiation law. The mass balance
requires a model of reactions based on the mineralogical species that are oxidized in the
flame of the laboratory burner. This was achieved by performing a characterization using
automated mineralogy techniques (QEMSCAN® ) for the products generated. From this
information, a set of k chemical reactions were proposed and a calculation of their degree
of conversion allows us to close the mass balance to fit with the characterization of the
l species produced. Knowing the degree of conversion for each reaction we can apply
Equation (5) that corresponds to an energy balance and so on, estimating the temperature
of the flame.
k l +3 Z TCalc  
∑ i R,i,@TRef
n ∆H + Q Furnace = ∑ 4
m j × Cp j ( T )dT + σ × ε × A × TCalc 4
− Twall , (5)
i =1 j=1 TRef

where ni is the moles of a specie that reacts according to reaction i from the m reactions
defined; mj is the mole of one mineralogical specie from the l identified; TRef is the reference
temperature for the calculation of the enthalpy of the chemical reactions:∆HR,i,@TRef is the
enthalpy of reaction i at the the temperature of reference; QFurnace is the heat released by the
furnace to the environment; ε is the emissivity of the flame (understood as a reactive system
which considers gases and condensed particles, both Cu concentrate and liquid droplets of
sulfide and oxides, and as well solid oxides produced or coming from the gangue); A is the
area of the flame; σ is Stefan–Boltzmann constant; Twall is the temperature of the furnace
wall. Please note that j varies from 1 to l + 3, where 3 represents the 3 gases species: O2(g) ,
N2(g) and SO2(g) . In this case, the heat losses by the convective mechanism were neglected.
Equation (5) requires an estimate of the flame area and an estimate of the emissivity.
The emissivity is the emissivity of the whole reactive system, which is a mix of gases and
condensed/liquid phases with a space density much lower than the case of an industrial
burner. The emissivity was taken from Marin et al. [22] with a value of 0.28 × 10−3 .
This work presented a detailed model for the calculation of the emissivity with the same
experimental set-up used in this work.
The area of the flame was estimated through a set of photographs taken in a special
configuration of the set-up where the steel tube of the furnace was replaced by a quartz one,
and thanks to the characteristic of the furnace that can be open longitudinally (Figure 5).
The flame was approximated to a prolate spheroid, as described in Cartesian coordinates
by Equation (6). Its area, A is given by Equation (6) [24].

x 2 + y2 z2
1 ⇒ A = 2πa a + αc arcsen(α)
 
a2
+ 2 =
cq (6)
c2
where α = 1− a2
and A is the superficial area.
 Minerals 2021, 11, x 1
Minerals 2021, 11, 1 9 of 17

z
a x
a
y

Figure 5. Estimation of the flame volume; a = 3.4 cm and c = 5.86 cm and A = 174 cm2 [24].

The adiabatic temperatures calculated from the mass and energy balance were com-
pared with
Figure the temperature
5. Estimation measured
of the flame using
volume; Planck’s
a = 3.4 cm and law with
c = 5.86 cmtwo
andwavelengths (Figure
A = 174 cm2 [24].
6). This calculation takes the online spectrum from the radiometric measurement and
through a mathematical treatment of the signal eliminates the discontinuities of the spec-
z 2 was then used toapplyc the two wavelengths
x 2 + y 2 part 
trum. The continuous
2
+ 2 = 1  A = 2 πa  a + arcsen α 
algorithm, usingaan optimization
c method,chooses
( )
method. A second
α the best pair of wavelengths for the
calculation. The reported and calculated2 temperatures are on the same order of magni-
c
tudes as thosewhere
obtained α =by modeling
1 − 2 andthe A flash
is thecombustion
superficialforarea.
different mineral particles
(Figures 2 and 3). The results show a a very good agreement, which was expected due to the
accurate characterization of the products. Nevertheless, it seems that the error is depending
The adiabatic temperatures calculated from the mass and energy balance were
on the temperature itself. One source of error could be the evaluation of the size of the
pared with the temperature measured using Planck’s law with two wavelengths (F
flame, which is kept the same for different temperatures. At higher temperatures, the flame
Minerals 2021, 11, x 6). This calculation takes the online spectrum from the radiometric 11 measurement
of 19
must expand, and its transfer area increases, as well as the temperature, so radiation losses
through a mathematical treatment of the signal eliminates the discontinuities of the
are greater. Those two points go into the explanation for the error evolution.
trum. The continuous part was then used to apply the two wavelengths method. A se
algorithm, using an optimization method, chooses the best pair of wavelengths fo
2 100 calculation. The reported and calculated temperatures are on the same order of m
2 000
tudes as those obtained by modeling the flash combustion for different mineral par
(Figures 2 and 3). The results show a very good agreement, which was expected d
1 900 the accurate characterization of the products. Nevertheless, it seems that the error i
T measured (K)

pending on the temperature itself. One source of error could be the evaluation of the
1 800
of the flame, which is kept the same for different temperatures. At higher temperat
1 700 the flame must expand, and its transfer area increases, as well as the temperature, s
diation losses are greater. Those two points go into the explanation for the error evolu
1 600

1 500
1 500 1 600 1 700 1 800 1 900 2 000 2 100
T calculated (K)

Figure6.6.Comparison
Figure Comparisonbetween
betweenmeasured
measured(radiometric
(radiometricexperiments)
experiments)and
andcalculated
calculatedtemperature
temperaturefor
for laboratory combustion of concentrates by means of a mass and energy balance (Equation (5))
laboratory combustion of concentrates by means of a mass and energy balance (Equation (5)) [25].
[25].

4.1.3. Experimental Results: Molecular Identification of Oxides in the Flame

The discontinuous part of the spectrum is related to some species, atoms or mole-
 Minerals 2021, 11, 1 10 of 17

4.1.3. Experimental Results: Molecular Identification of Oxides in the Flame

The discontinuous part of the spectrum is related to some species, atoms or molecules,
that emit at a very specific wavelength. The discontinuities observed in the laboratory
and industrial measurements were analyzed to establish their relationship with species
typically obtained from the concentrated oxidation process. One goal is to develop the
capacity to correlate these discontinuities with the presence of species that are the ones to be
formed (Equation (2)) and others that would indicate an anomalous operation. The increase
of copper oxides (CuO and Cu2 O) and magnetite (Fe3 O4 ) is an unquestionable indicator
of the bad quality of the combustion-oxidation that occurs in the flame. Indeed, Cu oxide
should not be formed according to the scheme of Equation (2), and Fe3 O4 must stay under a
certain level. In industrial practice, the results of this anomalous condition can be identified
only after several hours according to the chemical analysis of the products, as it was shown
the oxidation process is on the time scale of milliseconds (Figures 2 and 3) so having the
information or not after several hours is of questionable utility.
If there is an increase in oxidized Cu, it represents a higher Cu content in the slag,
and consequently losses in the value for the process. Magnetite affects the viscosity of the
slag and the proper separation of matte and slag in the settler. Early identification of the
formation of these molecules in the flame would provide information to relate poor oxygen
distribution during the oxidation process and establish actions in the process control.
Toro et al. [26] have presented evidence of the FeO pick at laboratory scale by measure-
ments with a built-in developed spectrometer with a high sensitivity and a high spectral
resolution (Figure 7). Then, a second experiment was conducted measuring the spectra
with a low spectral resolution and a low-sensitivity commercial spectrometer, but enhanced
and analyzed with post-signal processing and multivariate data analysis such as principal
component analysis (PCA) and a multivariate curve resolution–alternating least squares
(MCR-ALS) method. In the same article, one can find the results from an experimental
plan to propose for the first time in the scientific literature the characteristic wavelength
for Fe3 O4 molecular emissions. The experiment was undertaken by the combustion of
Minerals 2021, 11, x pure pyrite (FeS2 ). This combustion test is very representative due to the possibility
12 of 19 to
produce Fe3 O4 in the laboratory furnace according to the control of oxygen potential in the
combustion chamber.

Figure
Figure 7. Spectral
7. Spectral FeOFeO emission
emission measurements
measurements andand reference
reference spectral
spectral features
features taken
taken from
from [26].
[26].

Insame
In the the same
scopescope
and and analyzing
analyzing datadata
fromfrom
thethe same
same set-up
set-up forfor combustion
combustion ofofcon-
concen-
trates, Arias at all [21] reported exploratory results depicted some spectral features related
centrates, Arias at all [21] reported exploratory results depicted some spectral features
to the presence of Cu O emissions at 606 nm and 616 nm.
related to the presence of xCuxO emissions at 606 nm and 616 nm.
4.1.4.4.1.4.
Experimental Results:
Experimental Identification
Results: Characteristics
Identification of theofCharge
Characteristics the Charge
The last result is related to the possibility to identify the characteristics of the
The last result is related to the possibility to identify the characteristics ofcharge
the charge
basedbased
on the
on analysis of the
the analysis spectrum
of the spectrumcollected. InIn
collected. this
thistopic,
topic,Marin
Marin[27]
[27]developed
developed the first
first algorithms applied to identify
identify three
three types
typesof
ofconcentrates
concentratescharacterized
characterizedbybytheir
theirS/Cu
S/Curatio
ratio (Figure 8). Then Díaz et al. [23] used the same approach to extend the identification
target to mineralogical species (Figure 9). The algorithms are based on principal compo-
nent analysis (PCA) applied on the spectral data showing high correlation features among
species with similar elemental compositions or the same type of concentrate. Classifica-
 In the same scope and analyzing data from the same set-up for combustion of con-
centrates, Arias at all [21] reported exploratory results depicted some spectral features
related to the presence of CuxO emissions at 606 nm and 616 nm.
4.1.4. Experimental Results: Identification Characteristics of the Charge
Minerals 2021, 11, 1 The last result is related to the possibility to identify the characteristics of the charge 11 of 17
based on the analysis of the spectrum collected. In this topic, Marin [27] developed the
first algorithms applied to identify three types of concentrates characterized by their S/Cu
ratio (Figure
(Figure 8). Then
8). Then Díaz
Díaz et et al.used
al. [23] [23]the
used
sametheapproach
same approach to the
to extend extend the identification
identification target to
target
mineralogical species (Figure 9). The algorithms are based on principal component compo-
to mineralogical species (Figure 9). The algorithms are based on principal analysis
nent
(PCA)analysis
applied(PCA) applied
on the ondata
spectral the spectral
showingdatahigh showing highfeatures
correlation correlation features
among among
species with
species with similar elemental compositions or the same type of concentrate.
similar elemental compositions or the same type of concentrate. Classification algorithms Classifica-
tion
werealgorithms
tested on were tested on
the spectral the spectral
data, data, and a classification
and a classification accuracy
accuracy of over 95% of over
was 95%
shown.
was
Detailed mathematical treatment of the spectrum and the mathematical developmentde-
shown. Detailed mathematical treatment of the spectrum and the mathematical of
velopment of identification
identification procedures can procedures
be followedcaninbe[23,27].
followed in [23,27]

Figure
Figure8.8.PC1–PC2
PC1–PC2scores
scoresfrom
fromprincipal
principalcomponent
componentanalysis
analysis(PCA)
(PCA)applied
appliedto tothe
theidentification
identification of
of
different types of concentrates [27]. Blend 1: Cu = 28.0%, Fe = 26.2% and, S = 27.1 with S/Cu = 0.96.
different types of concentrates [27]. Blend 1: Cu = 28.0%, Fe = 26.2% and, S = 27.1 with S/Cu = 0.96.
Minerals 2021, 11, x Blend 13 of 19
Blend2:2:Cu
Cu==28.3%,
28.3%,Fe
Fe==25.5%
25.5%and,
and,SS ==26.6
26.6with
with S/Cu
S/Cu==0.94.
0.94.Blend
Blend3:3:Cu
Cu==26.7%,
26.7%,FeFe==25.3%
25.3%and,
and,
S = 26.6 with S/Cu = 1.00. The composition is given in weight percent.
S = 26.6 with S/Cu = 1.00. The composition is given in weight percent.

Figure
Figure 9. 9. PC1–PC2
PC1–PC2 scores
scores from
from PCA
PCA applied
applied to to experiments
experiments with
with mixtures
mixtures of of pure
pure mineral
mineral species,
spe-
taken
cies, from
taken [23].
from [23].

These
These results
results provide
provide a very
a very interesting
interesting opportunity
opportunity toto integrate
integrate spectral
spectral measure-
measure-
ments
ments ofofa asmelting
smeltingfurnace
furnaceflame
flameinto
intooperational
operational control.
control. As
As previously
previously stated,
stated,the
thecontrol
con-
of a smelting furnace (flash smelting or bath smelting) is based on a macroscopic
trol of a smelting furnace (flash smelting or bath smelting) is based on a macroscopic mass and
mass
energy balance. These balances are carried out by charges that represent several hours
and energy balance. These balances are carried out by charges that represent several hours
of furnace operation. These charges are statistically characterized and, therefore, there
of furnace operation. These charges are statistically characterized and, therefore, there is
is always a deviation from the values that have been established to control the process.
always a deviation from the values that have been established to control the process. The
main variables of this control are the amount of oxygen indicated in Equation (2) and its
percentage in the process gas, which is the first control for a target temperature of the
operation. Having an online indicator whether of the type of charge (Figure 8) or, ideally,
based on information on their species (Figure 9) would allow establishing a mass and en-
Minerals 2021, 11, 1 12 of 17

The main variables of this control are the amount of oxygen indicated in Equation (2)
and its percentage in the process gas, which is the first control for a target temperature
of the operation. Having an online indicator whether of the type of charge (Figure 8) or,
ideally, based on information on their species (Figure 9) would allow establishing a mass
and energy balance online and adjusting the control variables based on this information.
The situation today is that the operator only knows the results of the operation several
hours later, having only the measurements of the temperature of the gas line as the most
relevant information for the control.

4.1.5. Preliminary Industrial Tests

To date, some measurements in an industrial environment made it possible to validate
some of the results proposed from the laboratory studies summarized in the previous
points. The setup considered the installation of an optical probe in the center of a burner in
an industrial flash smelting furnace, which is a location analogous to that of the laboratory
(Figure 10). The probe was installed in the space for the fuel lance that flash burners usually
have. The fuel lance is concentric to the concentrate burner and aims to provide a radiant
Minerals 2021, 11, x heat source from the center of the volume where the flame appears. The probe was placed 14 of 19
instead of the fuel lance. Due to the process of air and oxygen injection in this area, the
temperature is low enough to fit a standard optical probe.

Figure 10.
Figure 10. Position
Position of
of the
the probe
probe in
in aa industrial
industrial flash
flash smelting
smeltingburner.
burner.

The objective
A relevant of usingfor
objective this
theradiometric
operation of probe in the control
a smelting furnacestructure of a smelting
is to maintain a stable
furnace
process is
fortothe
provide
sulfideon-line and(Equation
oxidation real-time (2)).
information
In the caseonofthe combustion
a flash smeltingconditions
furnace, one of
the charge fed to the burner. As a first result, it can be precise that the probe
can say that the objective is to achieve stable combustion (Figure 11 shows a drawing of and its digital
system give an on-line
some conditions out oftemperature
standard). Itmeasurement,
is widely known which is any
that within the orders
instability of magnitude
in the flame pro-
of the values
duces a seriesobtained in the laboratory.
of disturbances This simple
into the operation, fact isthe
perhaps relevant because it
most relevant allows
being thethein-
validity
crease inofdust
the generation
experimental setup
that (Figure 4)accretions
can generate to be established
inside theinfurnace
order toorstudy
in thethe
gasflash
line
oxidation reactions
that are difficult of copper impacting
to handling concentrates.the reactor operating time.
A relevant objective for the operation of a smelting furnace is to maintain a stable
process for the sulfide oxidation (Equation (2)). In the case of a flash smelting furnace,
one can say that the objective is to achieve stable combustion (Figure 11 shows a drawing
of some conditions out of standard). It is widely known that any instability in the flame
produces a series of disturbances into the operation, perhaps the most relevant being the
 Figure 10. Position of the probe in a industrial flash smelting burner.

A relevant objective for the operation of a smelting furnace is to maintain a stable

Minerals 2021, 11, 1 process for the sulfide oxidation (Equation (2)). In the case of a flash smelting furnace,13 ofone
17
can say that the objective is to achieve stable combustion (Figure 11 shows a drawing of
some conditions out of standard). It is widely known that any instability in the flame pro-
duces a series of disturbances into the operation, perhaps the most relevant being the in-
increase
crease inindust
dustgeneration
generationthat
thatcan
cangenerate
generate accretions
accretions inside the furnace
furnace or
or in
in the
thegas
gasline
line
that are difficult to handling impacting the reactor operating time.
that are difficult to handling impacting the reactor operating time.

(a) (b) (c)

Figure 11. Some conditions out of standard for the flame. (a): well developed at a distance h; (b): h
Figure 11. Some conditions out of standard for the flame. (a): well developed at a distance h; (b): h
too
toofar
farfrom
fromthe
theburner;
burner;(c):
(c):hhtoo
toofar
farand
andnon-symmetric
non-symmetricflame.
flame.
The first objective was, therefore, to propose a parameter that would inform the
The first objective was, therefore, to propose a parameter that would inform the op-
operator about the stability of the flame, following the intensity measured by the probe
erator about the stability of the flame, following the intensity measured by the probe over
over time. If this measurement is below a certain threshold of reference for a certain period
time. If this measurement is below a certain threshold of reference for a certain period in
in a previous interval (for example, the last 60 or 90 min), the combustion could be out
a previous interval (for example, the last 60 or 90 min), the combustion could be out of
of standard, and the operator must take action to monitor the function of the burner as
astandard,
priority. and the12
Figure operator
gives anmust take action
example of thisto monitor being
indicator, the function of the burner
very relevant as a
to identify
priority. Figure 12 gives an example of this indicator, being very relevant
moments in which the measurement dropped abruptly, even without energy measurements, to identify mo-
Minerals 2021, 11, x ments in which the measurement dropped abruptly, even without energy measurements,
which may mean that the flame did not form or it is outside the field of view of the probe. 15 of 19
whichare
There may mean thatofthe
conditions flame
this typedid not form
where, or it isthe
however, outside
feed the field
of the of view of the
concentrate andprobe.
O2(g)
There are conditions
was maintained. of this type where, however, the feed of the concentrate and O2(g) was
maintained.

(a) (b)
Figure 12. Value
Figure overover
12. Value timetime
of the
of %
theof%“good combustion”
of “good during
combustion” the last
during 60 min.
the last In case
60 min. (a), the
In case
probe shows
(a), the variability
the probe shows the of this parameter
variability and as well
of this parameter anda no
as negligible proportion
well a no negligible of time with a
proportion
valueofunder the reference.
time with For the
a value under the(b) there is more
reference. stable
For the operation
(b) there andstable
is more with almost the and
operation entire day
with the parameter close to 100%.
with almost the entire day with the parameter close to 100%.

AAsecond
secondstage
stagefor
forthe
theanalysis
analysisofofthethecollected
collectedinformation
informationconsiders
considersthethedesign
designofof
onlinealgorithms.
online algorithms. Offline
OfflinePCAPCAwaswasalready
alreadyapplied
appliedin inthe
thepreviously
previouslydiscussed
discussedresults,
results,
whereititwas
where waspossible
possibletotoestablish
establishthat
thatthe
thesignals
signalsofofFeO,
FeO,CuOCuO x ,x ,
andand Fe
Fe O3
3 4 O 4 appear
appear ininthe
the
measuredspectra.
measured spectra.
Aswas
As wasdone
donefor
forlaboratory
laboratorytests
testsusing
usingPCA,
PCA,changes
changesininthe thecharge
chargefed
fedtotothe
thefurnace
furnace
wereidentified.
were identified. Figure 13 shows the the evolution
evolution in intime
timeof ofthe
thepassage
passagefromfromone onecharge
chargeto
another.
to another.This
Thisidentification
identificationisisrelevant
relevantsince
sincethe
thearrival
arrival ofof aa new type of of charge
chargeto tothe
the
burner
burnerisisestablished
establishedbybyaamethodology
methodologyconsidering
consideringthe themass
massbalance
balanceofofthe thehoppers,
hoppers,and and
the
thechange
changeof ofthe
thecontrol
controlparameters
parametersof ofthe
thefurnace
furnaceisisprogrammed
programmedaccordingly,
accordingly,without
without
having any field measurements of this process. The effective moment when the charge
changes is not certain. It was found that, in effect, this change differs at the start from the
program, having a difference of up to 25 min. The change itself takes at least 10 min, so
the furnace was in inappropriate control conditions for at least 35 min, and if the charge
 online algorithms. Offline PCA was already applied in the previously discussed results,
where it was possible to establish that the signals of FeO, CuOx, and Fe3O4 appear in the
measured spectra.
As was done for laboratory tests using PCA, changes in the charge fed to the furnace
Minerals 2021, 11, 1 were identified. Figure 13 shows the evolution in time of the passage from one charge to
14 of 17
another. This identification is relevant since the arrival of a new type of charge to the
burner is established by a methodology considering the mass balance of the hoppers, and
the change of the control parameters of the furnace is programmed accordingly, without
having
having any
any field
fieldmeasurements
measurements of ofthis
thisprocess.
process. TheThe effective
effectivemoment
moment whenwhenthe thecharge
charge
changes
changes is not certain. It was found that, in effect, this change differs at the start fromthe
is not certain. It was found that, in effect, this change differs at the start from the
program,
program, having
having aadifference
differenceofofup
uptoto2525min.
min.TheThechange
changeitself
itselftakes
takesatatleast
least10
10min,
min,so so
the
thefurnace
furnace was
wasinininappropriate
inappropriate control
controlconditions
conditions for
for at
atleast
least35
35min,
min,and
andififthe
thecharge
charge
changes
changes several
several times
times per
per day,
day,there
thereisisaarisk
riskofofthe
thefurnace
furnacehaving
havinginappropriate
inappropriatecontrol
control
parameters
parametersseveral
severalhours
hoursaaday.
day.

Figure 13. Two principal components (PC) showing the change of the charge from Blend 1 to Blend 2.
With circles are the evolution of those PC. The change was schedule at 08:00 and started at 08:10 and
took more than 9 min.

4.2. Non-Reactive Systems

The previous sections have shown that radiometric measurements can follow dynamic
aspects of the oxidation of sulfides and, in particular, mineral sulfides. The analysis of
the characteristics of these measurements, which are non-invasive, at a distance, and
with increasingly affordable components, can be extended for the application of spatial
recognition of the molten phases. Based on technological surveillance and prospecting of
the scientific and technical literature, there is no commercial instrument available for copper
smelters, that quantifies online and without contact the percentage of copper (% Cu) in the
molten metallic phases during tapping operations, nor the possibility of discriminating
the phases during tapping, which is of a superior interest for these operations. Indeed, the
discrimination of matte on the slag during slag tapping in smelting reactors or metallic
copper during slag tapping during the converting stage can impact Cu recovery for the
whole smelter. This action is, again, based solely and exclusively on the experience of
ground operators.
Just as a starting point for reactive system measurements was established in devel-
opments in the steel industry, development in spatial recognition of high-temperature
molten phases has also been established. In the last decade the spectral behavior of pig iron,
and slag in pig iron production processes in blast furnaces have been studied to estimate
tapping temperature [28,29]. The models presented describe the parameters contained in
the iron-slag mixture in the blast furnace tapping, essentially describing parameters such
as iron emissivity, tapping depth, slag layer thickness, slag absorption coefficients and
radiometric parameters such as reflectance at the iron–slag interface. The method consists
in determining a spectral range in which the spectral radiation of the molten phases tapped
is high, facilitating the detection by a silicon CCD camera, sensitive in the visible spectral
Minerals 2021, 11, 1 15 of 17

range and part of the near infrared. An optical filter centered at 650 nm was used together
with the optics, so the radiation emitted by the slag was partially filtered in the indicated
spectral range. The results confirm that the difference in emissivity of iron and slag at
650 nm allows a spatial distinction of the location of these phases, further identifying that
the radiation intensity of the molten iron remains practically constant during the process,
while the intensity of radiation from the slag is fluctuating. The fluctuation of this radiation
intensity would be due to the difference in the thickness of the slag layer, absorbing and
transmitting with variable percentages the radiation coming from the steel at high tempera-
ture. Moreover, the optical system has been calibrated with a high-temperature black body
radiator, allowing the temperature value to be estimated at 1500–1600 ◦ C. These results
confirm that by using appropriate spectral models, sensitive optoelectronic systems in the
spectral molten iron emission band and processing software, it is possible to obtain both
laboratory and industrial developments of reliable and robust systems. In addition, it is
now possible to find commercial instrumentation for the on-line detection of slag in the
steel industry (Slag Detection Systems, LAND instruments) [29]. This instrument measures
infrared radiation in the middle band (3–5 micrometer wavelength) with a narrow band
optical filter in 3.7 micrometers, generating a video in which the steel of the slag is clearly
discriminated in the image. Associated with the equipment, there is an algorithm specially
designed to calculate the percentage of slag.
This review shows that the possibility to apply spatial recognition of molten phases
is already a feasible development based on the same principles we have used until now
for reactive systems. The concept is to adopt the fundamentals the define the principle
and adapt them to the physical, chemical and optic properties of the molten phases of Cu
pyrometallurgy. Iron and copper have similar physical characteristics: bond microstructure
and comparable transport properties, especially of the molten phase. At the same time, the
steel making slag and the copper slag have similar oxide structure because they have the
same constituents: SiO2 , CaO, Al2 O3 , MgO and FeOx .

5. Final Remarks
In this first stage, the results obtained at the laboratory scale have been validated in the
industrial environment. It is important to point out that the experimental set-up designed to
replicate the fundamental phenomena of industrial reactors on a small scale is fully valid for
taking radiometric measurements during the evolution of the reactions. The radiometric
measurements are the subject of this proposal for the development of optoelectronic
sensors for the Cu pyrometallurgy, or in a wider scope, for non-ferrous metallurgy. These
radiometric measurements are specially adapted for the chemical processes that take place
in the reactors of a copper smelter. As previously specified (Figures 2 and 3), the scale of
the fundamental phenomena is in the order of milliseconds, even though the control of
the smelter is based on the monitoring of variables with a sampling rate in the order of a
minute. Optoelectronic sensors have the characteristics required to follow at this level the
oxidation phenomena that take place during all operational stages of a copper smelter.
Undoubtedly, the current reality of operational control in copper smelters presents a
considerable gap with the situation of other process industries, and very particularly with
the iron and steel industry. However, the new paradigm of Industry 4.0 could be a catalyst
to address these necessary developments and thus narrow the gap.
The developments presented require work to validate the instruments, not in their
functionality (which has already been demonstrated) but in their application, first, to create
tools of real value for the operators. The possibility of carrying out an online treatment of
the information is something very promising and so require different process calculations
to support the operators and tend to develop automatic control strategies. Those predictive
calculations require the generation of databases to evaluate different tools within the data
analytic techniques that, and in an accelerated manner, have been consolidated as an
applied alternative to solve complex problems. In particular, it is interesting to propose
the prediction of the output variables of the different reactors: chemical compositions
Minerals 2021, 11, 1 16 of 17

and temperatures of the molten phases that are produced in each one of them. From a
fundamental perspective, this objective is reasonable considering that the combustion
flame of sulfides carries information on the species participating in the oxidation, as was
demonstrated at the laboratory and industrial level. Consequently, it is plausible to expect
that the information from the flame radiation, perhaps combined with some other variables,
could predict the chemical characteristics of the products.
The reality of copper smelters is that the information systems must be able to incorpo-
rate information from different discrete variables, such as temperature and composition of
molten phases tapped out of the reactor to make batch and semi-continuous operations
compatible. Although this operation seems trivial it is a source of errors and inconsisten-
cies. The development of sensors that continuously measure the chemical composition of
the molten phases from the reactors will be of great help to have a uniform and unique
database to approach the analysis of modern techniques looking to optimize the processes
and the business of the smelter.
The results shown are part of a broad research program and progress has also been
made in the application of these concepts for bath smelting reactors. Although this part of
the study lags behind the application to flash melting furnaces, that represent over 50% of
smelting reactors in the world, the first results indicate that the signal from a molten bath
will be more stable and with a higher intensity than in the case of the sulfide oxidation
flame. Indeed, the flame is not a continuous volume, instead, the molten bath represents a
continuous domain for the field of view of the probe.

Author Contributions: Conceptualization: R.P., S.T. and D.S.; methodology: R.P. and S.T.; validation:
L.A., E.B. and S.T., formal analysis, L.A., E.B., R.P., D.S. and S.T.; writing—original draft preparation,
S.T. and R.P.; writing—review and editing: R.P. and funding acquisition, D.S., S.T., and R.P. All authors
have read and agreed to the published version of the manuscript.
Funding: This research was funded by ANID Agency grant ACM 170008 (Anillo Minería) and
FONDEF program grant IT16M 10029. Both FONDEF and ANID are Chilean government agencies.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data is contained within the article.
Conflicts of Interest: The authors declare no conflict of interest.

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