Mineral Processing and Extractive Metallurgy

Transactions of the Institutions of Mining and Metallurgy

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

Principles and applications of mathematical and

physical modelling of metallurgical processes

Hong Yong Sohn

To cite this article: Hong Yong Sohn (2020): Principles and applications of mathematical and
physical modelling of metallurgical processes, Mineral Processing and Extractive Metallurgy, DOI:
10.1080/25726641.2019.1706376

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MINERAL PROCESSING AND EXTRACTIVE METALLURGY
https://doi.org/10.1080/25726641.2019.1706376

RESEARCH ARTICLE

Principles and applications of mathematical and physical modelling of

metallurgical processes
Hong Yong Sohn
Department of Materials Science & Engineering, University of Utah, Salt Lake City, UT, USA

ABSTRACT ARTICLE HISTORY

This article reviews the principles and methods for formulating mathematical or physical Received 9 October 2019
models that are useful in the design, analysis and optimization of metallurgical processes. Revised 5 December 2019
Mathematical models based on first principles are emphasised. Examples of developing new Accepted 6 December 2019
processes based on a first-principle mathematical model or a physical model are presented.
KEYWORDS
Cautions and pitfalls associated with the formulation and application of mathematical Computational fluid
models are discussed. The reader is encouraged to carefully examine correctness of the dynamics; equilibrium
approach and assumptions made in the formulation in order to avoid an erroneous modelling; flowsheet; heat
application of a model. For complex processes requiring harsh conditions, physical models and mass transfer; modelling;
are useful. The interpretation and utilisation of the results from physical models can be process simulation; reaction
difficult and sometimes even misleading. This problem is greatly assuaged by combining engineering; Sohn’s Law
physical modelling with mathematical modelling. For example, the use of computational
fluid dynamics greatly improves the physical modelling of systems involving complex fluid flow.

Nomenclature rg Original radius of a grain

Universal gas constant
am Raoultian activity of species M Ri Molar rate of production of species i per unit volume
Ag , Ap External surface area of an individual grain and the Re Reynolds number
pellet, respectively Sf Net source term of dependent variable ϕ
b Number of moles of solid reactant reacting with one Sv, S0v Surface area per unit volume of the solid at any time
mole of fluid reactant and its initial value, respectively
cp Heat capacity Sc Schmidt number

km dp
Ci Molar concentration of fluid species i Sh* Modified Sherwood number, ;
Cib Molar concentration of fluid species i in the bulk Time

De  
bkCAn 0 Ag
Di−mix Diffusion coefficient of species i in the vapour mixture t∗ Dimensionless time ; t
E(t) Residence time distribution response of a reactor to a Absolute temperature rm F g Vg
pulse input u Mixture velocity vector
f (w) Relative variation of the specific surface area Sv with vi Velocity component in the direction i (m s−1), or mol-
solid conversion ecular volume of species i
Fg , Fp Shape factor for grains and pellet, respectively (=1, 2 V g , Vp Volume of an individual grain and pellet, respectively
and 3 for flat plates, cylinders and spheres, w Local fractional conversion of the solid reactant, or
respectively). solid weight per unit volume of the bed
g(X) Conversion function for the system rate-controlled by Wi Weight of phase i
the reaction of individual grains x Matte grade in %
h Heat-transfer coefficient xi Mole fraction of fluid species i
Reaction constant or thermal conductivity Fractional conversion of solid reactant
(kn,M)i Volatilization constants
km External mass-transfer coefficient
K Equilibrium constant Greek Symbols
L Distribution coefficient: LIM = [%M]Cu/[%M]mt; LIIM =
[%M]cu/[%M]sl; LIIIM = [%M]mt/[%M]sl a Factor defined in Figure 11
mi Mass flow rate of phase i aB Fraction of pellet volume occupied by solid reactant B
(−ṁA ) Molar rate of consumption of the fluid reactant A per γo Raoultian activity coefficient at infinite dilution
unit area Gwm Mixture effective transport coefficient
[%M]i % of species M in phase i 1 Emissivity
ni Number of moles of species i m Gas viscosity
Ni Molar flux of fluid species i r Mass density
p(X) Conversion function for the system rate-controlled by rB Molar density of solid reactant B
pore diffusion ŝ2 Generalised
 fluid-solid  reaction modulus


2
pi Partial pressure of species i aB kCAn−1 Fp A g V p
pT Total pressure ; 0

τ 2De Fg Vg Ap
Pr Prandtl number
rc Position of the reaction interface within a grain Average residence time in a reactor
w Generic dependent variable (various)

CONTACT Hong Yong Sohn h.y.sohn@utah.edu Department of Materials Science & Engineering, University of Utah, Salt Lake City, UT 135 S 1460 E
RM 412, USA
© 2020 Institute of Materials, Minerals and Mining and The AusIMM Published by Taylor & Francis on behalf of the Institute and The AusIMM
2 H. Y. SOHN
Subscripts
b Bulk
B Solid reactant B
e Equilibrium
Fg , Fp Shape factor for grains and pellet, respectively (=1, 2
and 3 for flat plates, cylinders and spheres,
respectively).
g Grain
mt Matte
p Pellet
sl Slag
Operators
∇ Nabla∂ operator
∂ ∂ in Cartesian coordinates;
∇ = dx + dy + dz
∂x ∂y ∂z
General approach to mathematical
modeling
A process model consists of process steps of similar nature
as common blocks. Thus, a process model is a description
of a process as an abstract combination of these blocks and
is used to describe how the actual process works. Since one
wants to obtain quantitative results from the model, the
behaviour of the block is typically described by mathemat-
ical equations representing the process taking place
together with known properties and knowledge about the
process. The purposes of process models are to describe,
explain, and/or predict what happens in a process. The
major individual objectives include: to increase fundamen-
tal understanding of a process; to assist in scale-up; and to
be used in process control and optimisation.
The development of a process model starts with the
definition of what aspects of the process one wants to
simulate. This is followed by the determination of
which phenomena must be included and which to sim-
plify or ignore. Next, the type and complexity of the
model must be chosen. The purpose of the model
should dictate what phenomena are included, and con-
sequently how complex the model should be. The next
step is to model phenomena in proportion both to their
importance to the problem and to how well they are
understood mechanistically. Important phenomena
that are well understood should be included in detail.
Overly complex models are too difficult and time con-
suming to solve; on the other hand, unreasonable sim-
plifications lead to erroneous conclusions.
Mathematical equations that make up a process model
are obtained by applying the laws of mass, energy, and
momentum conservation. In a model that deals with
the global behaviour of a unit operation or process within
the overall system, these conservation laws are applied
macroscopically to the entire unit (Himmelblau and
Riggs 2004). This type of a model describes the global
average behaviour of the process, but cannot simulate
the details of what happens at different positions within
the unit. Thus, the macroscopic model may describe
the average temperature, average composition, and
average velocity in a reactor, but cannot describe how
these properties vary with position within the reactor.
Thus, important questions such as how large the unit
must be or whether conditions for a local hot spot or
excessive erosion may be created cannot be correctly
answered by such a model.
To be able to describe these details, the conservation
laws must be applied to a very small portion of the unit –
the smaller the control volume, the more accurate the
results. Thus, a microscopic model that can describe
the continuous variation of the system properties is
based on an infinitesimally small control volume,
usually giving rise to differential equations (Bird et al.
2002). A balance is performed on the quantity (quantity
of species, heat, or momentum) to be conserved over
such a control volume, as follows:
⎡ ⎤ ⎡ ⎤
Input across Output across
⎣ boundary of ⎦ − ⎣ boundary of ⎦
control volume control volume
⎡ ⎤
Net generation
+⎣ within ⎦
control volume
⎡ ⎤
Accumulation
=⎣ within ⎦ (1)
control volume
These balance equations yield the governing equations
for concentration, temperature, and velocity in terms
of position and time. The solution of these governing
equations has become convenient with the availability
of many powerful commercial software packages.
These include process simulation programmes that
mainly solve material and energy balances for complex
flow sheets that include chemical reactions, thermo-
chemical software, and fluid-flow solvers.
The results of the model predictions, especially for
problems with complex model equations such as those
involving fluid flow, must be verified by testing the pro-
gramme under appropriate conditions that will yield
known solutions. Once the process model is verified, its
predictions should be compared with experiments and
any disagreements must be reconciled either by modify-
ing the model equations or by repeating the experiments.
Reliable results can only be obtained by engineering and
operational judgment, careful examination of input par-
ameters and assumptions, and laboratory, pilot-plant or
plant operating data.
Of particular relevance in highly intense processes is
the development of mathematical formulations capable
of reproducing the important phenomena occurring in
the process units. Mathematical tools of this kind are use-
ful because they provide a quantitative description of the
process behaviour, thus eliminating subjective and often
fallible human judgment. Upon validation with exper-
imental data, well-constructed mathematical models can
be used to simulate the process behaviour under different
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY 3

conditions, thus replacing test runs that are costly and and removing the turbulent components. The Reynolds
time-consuming in industrial or even pilot plants. stress terms −ru′ u′ are typically related to the time-aver-
When the overall balance principle expressed in aged velocity terms through a turbulence model. For
Equation (1) is applied to the transport of momentum, example,
energy, and species in a process, which in general involves Realisable k-ε model:
fluid flow, the following general equation is obtained:
2
∂
+ ∇†(ruf) − ∇†(Gf ∇f) = Sf −ru′ u′ = mt [∇u + (∇u)T ] − (rk + mt ∇ · u)I (10)
∂t (rf) (2) 3
where ϕ is any dependent variable (for total mass balance,


 
ϕ = 1), Gf is the coefficient for the diffusive transfer, and ∂(rk) mt
Sϕ is the source term. + ∇ · (rku) = ∇ · m+ ∇k + Gk
∂t sk
In a typically turbulent fluid phase of a chemically
+ Gb − r1 − YM + Sk (11)
reacting system, the conservation principles expressed
by Equation (2) take the following forms:
In Vector Form:

 
∂(r1) mt
Continuity: + ∇ · (r1u) = ∇ · m+ ∇1
∂t s1
∂r 12
+ ∇ · (ru) = Sp (3) + rC1 S1 − rC2 √
∂t k + n1
Momentum: 1
+ C11 C31 Gb + Sk (12)
k
∂(ru)
+ ∇ · (ruu) = −∇p + ∇ · (t) + ∇
∂t In modelling typical real systems, the rectangular
· (−ru′ u′ ) + rg + F p (4) coordinate system is typically used, and the above
equations take the following forms, using the Einstein
where summation convention:

 Continuity:
2
t = m (∇u + (∇u) ) − I∇ · u
T
(5)
3
∂r ∂
+ (rui ) = Sp (13)
Energy: ∂t ∂xi
∂(re)
+ ∇ · (reu) = ∇ · (keff ∇T) + ∇ · (t · u) Momentum:
∂t
− ∇ · ( pu) + rg · u + Qr ∂(rui ) ∂ ∂p
+ (rui uj ) = −
+ Sg (6) ∂t ∂xj ∂xi



where ∂ ∂ui ∂uj 2 ∂ul
+ m + − dij
∂xj ∂xj ∂xi 3 ∂xl
p 1
e = hg − + u·u (7) ∂
r 2 + (−ru′ i u′ j ) + rgi
∂xj
Species m: + F p,i
∂(rYm ) (14)
+ ∇ · (ruYm ) = −∇ · J m + Rm + S p,m (8)
∂t
Realisable k-ε model:
where



 
mt ∇T ∂(rk) ∂ ∂ mt ∂k
J m = − rDm,mean + ∇Ym − DT,m (9) + (rkui ) = m+ + Gk
Sct T ∂t ∂xi ∂xi sk ∂xi
In the above equations, S represents the source term from + Gb − r1 − YM + Sk (15)
another phase, if any, per unit volume, and F represents
the drag component due to the presence of another

 
∂(r1) ∂ ∂ m ∂1
phase, if any. u denotes the time-averaged velocity vector; + (r1ui ) = m+ t
∂t ∂xi ∂xi s1 ∂xi
I = identity tensor; e = specific internal energy; keff = effec-
tive thermal conductivity; Ym = mass fraction of species m; 12
+ rC1 S1 − rC2 √
Jm = diffusive flux; Rm = molar rate of generation of species k + n1
m per unit volume. These equations are also valid in a 1
+ C11 C31 Gb + Sk (16)
laminar flow system by keeping the molecular properties k
4 H. Y. SOHN

Energy: Edition (Stull and Prophet 1971); Thermochemical


∂(re) ∂ ∂ ∂T ∂
+ (rui e) = keff + (tij uj )
∂t ∂xi ∂xi ∂xi ∂xi
∂
− ( pui ) + rgi ui + Qr
∂xi
+ Sg
Species m:
∂(rYm ) ∂ ∂Jm,i
+ (rYm ui ) = − + Rm + S p,m
∂t ∂xi ∂xi
in which ui denotes the time-averaged velocity com-
ponent in the i-direction; dij = Kronecker delta.
These equations are also valid in a laminar flow system
by keeping the molecular properties and removing the
turbulent components.
Constitutive components of mathematical
modeling
In order to apply the above general modelling
equations to specific processes, it is necessary to have
the physical, transport and chemical properties of the
materials involved as well as the knowledge of the prin-
ciples and behaviour of subprocesses. The latter may
require developing submodels. We will discuss this
further below.
First, it is realised that the continuity and species
equations are related because the sum of the masses
of all the species in the system gives the total mass. Sec-
ondly, if the process does not involve fluid flow, the
momentum equations are not necessary. Further, if
the process is isothermal, the energy equation is not
needed, and if the process involves just a pure phase,
the species equation is unnecessary. Depending on
which equations are needed, the corresponding phys-
ical, transport and chemical properties must be known.
Physical, transport and chemical properties
Many sources are available from which these properties
can be found. Here only some limited sample refer-
ences are listed:
Physical, transport and chemical properties: Perry’s
Chemical Engineers’ Handbook (Green and
Southard 2019); CRC Handbook of Chemistry
and Physics (Rumble 2017); Transport Properties
of Chemicals and Hydrocarbons (Yaws 2015);
Yaws’ Handbook of Thermodynamic and Physical
Properties of Chemical Compounds (Yaws 2003);
The Properties of Gases and Liquids (Poling
et al. 2001).
Thermodynamic properties: Thermodynamic Data for
Mineral Technology (Pankratz et al. 1984);
JANAF Thermochemical Tables. Second
Properties of Inorganic Substances (Knacke
et al. 1991); Metallurgical Thermochemistry
(Kubaschewski and Alcock 1967).
(17) Submodels
Before constructing a mathematical model for an entire
process or for the purpose of examining a specific por-
(18) tion of the overall process, it may be necessary to
develop a model for subprocesses. Some examples
will be discussed here.
Mass and heat transfer processes
Metallurgical processes typically involve interactions
between different phases involving heat and mass
transfer. Mass transfer process between phases has
been extensively studied. Let us consider the process
in which material is being transferred from a surface
into a moving fluid stream. Let i denote the transferred
species, the molar concentration of which is then desig-
nated by Cis and Cib at the surface and in the bulk of the
fluid stream, respectively. Then, the molar rate at
which a species is transferred from the solid surface
into the fluid per unit area is given by
Ni = km (Cis − Cib ) (19)
where km is the mass transfer coefficient. Some authors
have expressed the concentrations in terms of partial
pressures or mole fractions, leading to mass transfer
coefficients that are different from the above.
Frequently, the mass transfer coefficient is expressed
in terms a Chilton-Colburn jD, factor, which is
defined as
jD = Sh/ReSc1/3 (20)
where Sh ; kmL/D is the Sherwood number; Re ;
uρL/μ the Reynolds number; and Sc ; μ/(ρD) the
Schmidt number. L is a characteristic dimension, e.g.
the diameter of a spherical body; μ/ρ is the kinematic
viscosity; D is the diffusivity; u is the linear velocity
of the fluid stream flowing past the solid (measured
outside the boundary layer surrounding the solid); ρ
is the mass density of the fluid.
Mass Transfer involving Single Solid Bodies: Because
of the industrial importance of operations involving
mass transfer from drops or solid bodies, tyoically
represented by spheres, this topic has been much
investigated. One of the early studies was that of
Ranz and Marshall (1952), who developed the follow-
ing equation:
Sh = km d/D = 2.0 + 0.6Re1/2 Sc1/3 (21)
The definition of Sh for a spherical drop or solid body
is most appropriate by taking its characteristic dimen-
sion to be the diameter, as indicated in this equation.

Much of the earlier work on this topic was reviewed
by Rowe and Claxton (1965), who proposed the follow-
ing correlations:
Sh = 2.0 + 0.69Re1/2 Sc1/3 for air (22)
Sh = 2.0 + 0.79Re1/2 Sc1/3 for water (23)
with analogous expressions for heat transfer.
Mass Transfer in Packed Beds: There are different
types of transport phenomena in multi-particle sys-
tems: One is the transfer between the particle assem-
blage and the surface of another object such as the
wall of the vessel or a tube immersed in the particle
bed, and the other is the transfer between the particles
and the fluid flowing through them. The mass transfer
rate between particles and fluid in packed beds is typi-
cally described with a correlation equation of the form
Sh = f (Re, Sc, geometric factor) (24)
Examples of published correlations include those by
Wakao and Kaguei (1982); Selman and Tobias
(1978); Wakao and Funazkri (1978); and Petrovic
and Thodos (1968). Much more extensive investi-
gations have been reported on heat transfer than on
mass transfer. Fortunately, an analogy between mass
transfer and heat transfer can be used for estimating
mass transfer coefficients from heat transfer corre-
lations in packed beds (Rosner 2000; Bird et al. 2002).
Mass Transfer in Fluidised Beds: There are a number
of different regimes of fluidisation: bubbling, turbulent,
fast fluidisation, and dilute-phase flow (Gupta and
Sathiyamoorthy 1999). Different mass transfer charac-
teristics are present in different fluidisation regimes.
For example, in a bubbling bed, mass transfer involves
transfer between the particles and the fluid in the emul-
sion phase; between the emulsion and the cloud phases;
and between the cloud and the bubble phases (Mak-
kawi and Ocone 2011). As mentioned above in the dis-
cussion of mass transfer in packed beds, much more
extensive investigations have been reported on heat
transfer than on mass transfer in fluidised beds. An
analogy between mass transfer and heat transfer can
also be used for estimating mass transfer coefficients
in a fluidised bed from heat transfer coefficient corre-
lations (Rosner 2000; Bird et al. 2002).
Some correlations combine effects of the individual
steps, and thus caution must be taken in using corre-
lations to recognise the accompanying assumptions.
In designing a fluidised bed, a Sherwood number cor-
relation with the same assumptions used in developing
it must be used. Thus, the Sherwood numbers esti-
mated just for the emulsion phase must be used in
combination with mass transfer between different
phases, while a Sherwood number correlation for the
overall bed without taking into consideration the indi-
vidual features like the bubbling, channelling and dis-
persion should be used in combination with a
MINERAL PROCESSING AND EXTRACTIVE METALLURGY 5
material balance equation that does not separately
recognise these features. This approach may be suitable
for non-reacting systems such as evaporation and
adsorption processes, but may not be applicable for
chemically reacting systems, especially at low fluid
flow rates.
For correlations of mass transfer coefficients under
different assumptions and in various phases of a
fluidised bed, the reader is referred to literature sources
(Kunii and Levenspiel 1991; Gupta and Sathiya-
moorthy 1999; Makkawi and Ocone 2011).
For liquid–solid reactions limited by diffusion
through the mass transfer boundary layer, the hydro-
dynamic flow regime at the reacting surface is of
importance in understanding the reaction kinetics.
Mass transfer in an aqueous phase containing ionic
species has been analysed in detail by Newman
(1973) and Bockris and Reddy (1970). In such a sol-
ution, mass is transferred by
. diffusion, i.e. motion of both charged and uncharged
species due to concentration gradients,
. migration, i.e. motion of charged species in an elec-
trical field, and
. convection, i.e. transfer of mass due to the bulk
motion of the liquid phase.
Pore Diffusion: Diffusion through pores of a solid
matrix often plays an important role in fluid-solid reac-
tions. A comprehensive treatment of this topic was
proposed by Mason and Marrero (1970) and Mason
et al. (1967), for which the reader is referred to the orig-
inal papers or other references (e.g. Szekely et al. 1976).
A convenient approach involves the use of the follow-
ing equation:
1/DABeff = (t/1)[1/DAB + 1/DAK ] (25)
where ε is the porosity of the solid, τ a tortuosity factor
characteristic of the solid, DAB the molecular (ordin-
ary) diffusivity for the pair A-B, and DAK the Knudsen
diffusivity of A.
Convective Heat Transfer between a Solid Body and
a Fluid Stream: The subject of heat transfer has been
investigated widely and is extensively covered in
many engineering texts (e.g. Szekely et al. 1976;
White 1988; Hagen 1999; Bird et al. 2002; Kaviany
2002; Holman 2010).
Let us consider a solid body the surface temperature
of which is at Ts in contact with a moving fluid stream,
which has a bulk temperature Tb. The heat flux from
the solid surface is related to Ts and Tb according to
q = h(Ts − Tb ) (26)
where q is the heat flux (rate of heat transfer per unit
area of external surface), and h the heat transfer coeffi-
cient. As for mass transfer coefficients, in most cases we
6 H. Y. SOHN
have to rely on empirical correlations for the heat
transfer coefficient.
The Ranz and Marshall (1952) correlations for heat
transfer is given by
Nu = 2.0 + 0.6 Re1/2 Pr1/3 (27)
Moreover, the previously given relationship for jD, the j
factor for mass transfer [Equation (20)], may also be
used for estimating the heat transfer coefficient by
assuming that
jD ≃ jH (28)
where
jH = (hL/k)Pr−1/3 Re−1 (29)
and k is the thermal conductivity of the fluid, L the
same characteristic dimension used for mass transfer,
and Pr the Prandtl number.
Heat Transfer in packed beds: There are different
types of heat transfer phenomena in a packed bed:
Heat conduction through the packed solids, heat trans-
fer between the particles and the wall of the vessel or a
tube immersed in the bed, and the other is the transfer
between the particles and the fluid flowing through
them (Balakrishnan and Pei 1979; Wakao and Kaguei
1982; Naterer 2003).
The heat transfer rate between particles and fluid in
packed beds is usually described with a correlation
equation of the form
Nu = f (Re, Sc, geometric factor) (30)
Examples of published correlations include those in
Kunii and Levenspiel (1991); Wakao and Kaguei
(1982); Balakrishnan and Pei (1979); and Whitaker
(1972).
Heat Transfer in fluidised beds: Like mass transfer in
fluidised beds, there are different types of heat transfer
processes: One is heat transfer between the particle
assemblage and the surface of the wall of the vessel
or a tube immersed in the bed, and the other is the
transfer between the particles and the fluid flowing
through them such as between particles and interstitial
fluid; emulsion and cloud phases; and cloud-bubble
phases.
In the design of a fluidised bed a Nu number corre-
lation with the same assumptions as those in its devel-
opment. Thus, the Nu numbers estimated for just the
emulsion phase must be used for heat transfer between
different phases, while a Nu number correlation for the
overall bed without accounting for the individual fea-
tures like bubbling, channelling and dispersion should
be used together with a heat balance equation that does
not separately take into consideration these features.
Again, this approach may be suitable for non-reacting
systems such as heating and drying processes, but may
not be applicable for chemically reacting systems,
especially at low flow rates of the fluid.
For correlations of heat transfer coefficients under
different assumptions and in various phases of a
fluidised bed, the reader is referred to literature sources
(Kunii and Levenspiel 1991; Molerus and Wirth 1997;
Gupta and Sathiyamoorthy 1999).
Thermal Radiation: At high temperatures radiation
may become an important mechanism for heat trans-
fer. The rate at which a solid surface emits radiation
is given by the Stefan–Boltzmann equation:
qR = 1̃s Ts4 (31)
where qR is the heat flux emitted by the surface, 1 the
emissivity, σ the Stefan–Boltzmann constant, 1.3553 ×
10−12 cal/(cm2·s·K4), and Ts the surface temperature in
absolute degrees. The description of radiation exchange
between surfaces of irregular geometries is a difficult
problem. For a detailed discussion, the reader is referred
to the literature (e.g. Sparrow and Cess 1978; White
1988; Modest 2013). It is noted here that a simple
equation exists for the radiant flux received by a piece
of solid in a large transparent space:
q′R = 1̃s(TE4 − Ts4 ) (32)
where TE is the temperature of the walls and q′R the net
flux received by the solid surface. Equation (32) is in
many cases a satisfactory approximation for a piece of
solid in a furnace, among other situations.
For combining the effects of radiative and convec-
tive heat transfer, the following procedure is often used:
hr = 1̃s(TE2 + Ts2 )(TE + Ts ) (33)
so that
q′R = hr (TE − Ts ) (34)
Conductive Heat Transfer in Porous Solids: The conduc-
tion of heat is described by the following Fourier’s law:
qy = −k ∂T/∂y or q = −k∇T (35)
The thermal conductivities of gases, liquids, and solids
are well known (Yaws 1995; Weast 1999; Poling et al.
2001; Bird et al. 2002). In contrast, the conductivity in
a porous solid is difficult to estimate. Typically, an effec-
tive conductivity is defined for the entire porous solid.
There are methods for estimating the effective conduc-
tivity, as follows:
(a) The material is made up of a solid matrix contain-
ing closed voids. Thus, the thermal conductivity ke
of a commonly available refractory may be esti-
mated by (Francl and Kingergy 1954)
ke = ks (1 − 1) (36)
where ks is the thermal conductivity of the solid
phase, and ε is the voidage.

(b) The material is made up of a continuous fluid
phase and dispersed solid pieces that are in contact
with their neighbours. The conduction takes place
through the fluid in the vicinity of the contact
points, and the estimation of the effective conduc-
tivity is difficult.
More advanced techniques for estimating the
effective thermal conductivity of a porous solid
have recently been advanced. An example is that of
Wang et al. (2007), who obtained the effective ther-
mal conductivity of a random porous solid by solving
the energy transport equation with complex multi-
phase porous geometries. The structure of a porous
solid was generated with a random internal mor-
phology and structure generation-growth method,
and the conjugate heat transfer among different
phases was solved by applying a lattice Boltzmann
algorithm.
Heterogeneous chemical reactions and mass
transfer
Chemical changes in most metallurgical processes
involve heterogeneous reactions, which take place at
phase boundaries. Most such reactions are of fluid-
solid type, although liquid–liquid interactions are
important in high-temperature systems involving mol-
ten phases and in solvent extraction. Since the prin-
ciples involved in the coupling of interfacial reactions
and mass transfer are common to any heterogeneous
interactions, we will use the following type of fluid-
solid reactions to discuss how heterogeneous reactions
are coupled with mass transfer:
A(f ) + bB(s) = cC(f ) + dD(s) (37)
At the fluid-solid interface, the following relationship
holds:


 (CAb − CAe ) =
molar flux external surface
×
of species A area of solid


stoichiometric
× with the progress of reaction.
coefficient


molar rate of
= (38)
consumption of B
Thus, we have, after some rearrangement
b(−NA )S = −bSkmA (CAs − CAo )
= −aB rB (dV/dt) = −aB rB S(drc /dt) (39)
where V and S denote, respectively, the volume and
surface area of the solid object at any time, αB is the
volume fraction of the solid occupied by solid reactant
B, ρB is the true molar density of the solid reactant B,
and rc is distance normal to the surface of the solid
toward the fluid phase. The subscripts s and b denote,
respectively, the solid surface and the bulk fluid phase.
MINERAL PROCESSING AND EXTRACTIVE METALLURGY 7
Here, the flux is defined in the direction extending
from the solid into the bulk fluid.
Equation (39) can be simplified as
(−NA ) = −kmA (CAs − CAb )
= −(1/b)aB rB (drc /dt) (39A)
and similarly for fluid species C
NC = kmC (CCs − CCb ) = (c/b)aB rB (drc /dt) (39B)
We will now illustrate the general procedure for
obtaining the conversion rate in terms of the bulk con-
dition for a mass-transfer-controlled reaction. For sim-
plicity, we will formulate the problem for the case of c
= 1 and kmA = kmC. In this case, the conditions at the
solid surface are close to equilibrium. Thus,
CAs = CAe = CCs /K (40)
where CAe is the equilibrium concentration of A.
Further, from stoichiometry with c = 1 and kmA = kmC
= km,
CAs + CCs = CAb + CCb (41)
Simultaneous solution of the above equations yields
CAs = CAe = (CAb + CCb )/(1 + K) and CCs
= CCe = (CAb + CCb )[K/(1 + K)] (42A&B)
Substituting CAs in Equation (39A), we obtain the fol-
lowing equation for the conversion rate in terms of the
known bulk concentrations:



drc bkm K
− = (CAb − CCb /K) (43)
dt aB rB 1 + K
It is noted from Equation (42A & B) that the concen-
tration driving force for an equilibrium-limited, mass
transfer-controlled reaction becomes


K
(CAb − CCb /K) (44)
1+K
The mass transfer coefficient km is in general depen-
dent on the size of the solid, which in turn may change
Flowsheet based process modelling
Metallurgical plants have many component processes
that are interconnected and usually operate on a con-
tinuous basis. In an industrial process, the conversion
of raw materials into final products requires multiple
steps. Thus, the overall process must be divided into
individual steps that provide intermediate changes.
These are carried out through heating/cooling, separ-
ation/mixing, particle size reduction/enlargement,
and chemical reactions. Once individual steps have
been selected, they must be interconnected to obtain
the overall result. Thus, the synthesis of a process
8 H. Y. SOHN
involves two broad activities. First, individual
process steps are selected. Second, these individual
steps are integrated to form an overall process that
achieves the desired result. A flowsheet constructed
from the integrated steps then forms the basis of a
mathematical model that is capable of describing the
behaviour of the process when it is practiced in the
full scale. The model requires the operating conditions
for the input feed materials and then predicts the con-
ditions for the products, byproducts, waste streams,
and emissions as well as the yields and energy con-
sumption or generation.
The availability of large computing power, together
with simulation software packages like Aspen Plus
(Dyment and Mantrala 2015; Al-Malah 2017), MET-
SIM (Pinegar et al. 2011, 2012, 2013a, 2013b), HSC
Sim (Coleman and Lamberg 2010; Outotec 2019), to
name but a few among many others, has made
flowsheet simulation a powerful tool the design, analy-
sis, and optimisation of industrial operations.
Flowsheet modelling can further serve a basis for
evaluating the economic feasibility of a new process.
The reader is referred to the literature for more com-
prehensive discussion on this topic (e.g. Spencer and
Scriba 2008; Pinegar et al. 2011, 2013b; Kennedy 2014).
Here we will use an example of flowsheet modelling
and economic feasibility analysis of a novel flash iron-
making technology (Pinegar et al. 2012, 2013b).
Process Simulation for a Novel Flash Ironmaking
Technology: The Flash Ironmaking Technology (FIT)
was developed as a novel ironmaking technology by
Sohn (2007, 2014) at the University of Utah to over-
come current ironmaking shortcomings. This technol-
ogy is based on gaseous reduction of fine iron ore
particles using gaseous fuels/reductants (Sohn 2007;
Sohn et al. 2009). The process avoids the problems
associated with cokemaking and the use of iron ore pel-
lets or mm-size particles, such as particle fusion, stick-
ing or disintegration of pellets.
Pinegar et al. (2011, 2012, 2013a) constructed and
simulated flow sheets for several versions of this pro-
cess using commercially available software METSIM.
A flow sheet for annual iron production of 1 million
tonnes of iron using partial combustion of natural
gas is shown in Figure 1. In this version, natural gas
is partially burned to generate process heat and a redu-
cing gas mixture of H2 + CO with the recycling of
unreacted hydrogen obtained after the off-gas goes
through the water-gas-shift reaction and the pressure
swing adsorption (PSA) process to bleed of CO2. This
mode of the process was termed the Reformerless
Flash Ironmaking Process. Summaries of material
and energy balances for a flash ironmaking process at
this production rate are shown in Tables 1 and 2.
[See Sohn and Olivas-Martinez (2014) for a discussion
on the computation of ‘energy requirement’.] Material
and energy flows for a standard case with the stream
values and conditions are given in Figure 1. As
shown in Tables 1 and 2, the Reformerless Flash Iron-
making Process generates 0.98 tonne CO2 per tonne of
hot metal, and requires 14.7 GJ of energy per tonne of
molten iron. Compared with the average blast furnace
process, this carbon dioxide emission level is 39% less
and the energy requirement is 32% less. Economic
feasibility was also evaluated (Pinegar et al. 2013b).
Reaction engineering models
This section describes mathematical models for indi-
vidual unit operations or unit processes within an
overall metallurgical process, typically taking into
account heterogeneous chemical reactions and mass/
heat transfer. Such models form the basic building
blocks for models for an overall process, which in
turn are a component of process models for an entire
plant.
Since most metallurgical reactions are hetero-
geneous and typically involve solids, the discussion
will start with modelling fluid-solid reactions taking
place within a single piece of solid. Heterogeneous
reactions occur at phase boundaries and thus always
accompany transfer of mass and heat.
The overall fluid-solid reaction involves a combi-
nation of the following steps:
(1) Transfer of fluid reactants and products between
the bulk and the external surface of the solid
particle.
(2) Diffusion of the fluid reactants and products
within the pores of the solid, if the solid contains
open porosity.
(3) Chemical reaction between the fluid reactant and
the solid at the fluid-solid interface.
(4) Transfer of the reaction heat within the solid.
(5) Transfer of heat between the external surface of the
solid and the surroundings by convection and
radiation.
(6) Changes in the structure of the solid due to chemi-
cal reaction and heat.
The rate-controlling step depends on reaction con-
ditions, and thus the rate parameter obtained under a
given set of conditions may not be applicable under
another set of conditions. Furthermore, there may
not be a single rate-controlling step and several steps
may have comparable effects on determining the over-
all rate. The relative importance of these steps can also
change in the course of the reaction. Therefore, under-
standing how the individual steps interact with each
other is important in determining not only the rate-
controlling step under given reaction conditions but
also whether more than a single step must be con-
sidered in determining the rate over the entire duration
of the reaction (Szekely et al. 1976).
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY 9

Figure 1. Material and energy flows for a commercial-scale reformerless flash ironmaking process producing 1 million tonnes of
molten iron annually. In this flow sheet, BFW stands for boiler feed water; PSA for pressure swing adsorption; and WGS(R) for water-
gas-shift (reactor) [Adapted from Pinegar et al. (2012).]

Table 1. Material balance for the Reformerless Flash Ironmaking Process compared with that of the average blast furnace process
for a plant with an annual iron production rate of 1 million tonnes (Pinegar et al. 2012).
Reformerless flash ironmaking
process BF process
INPUT (tonnes/tonne of hot metal) Natural gas 0.37
Oxygen 0.78 0.68
Iron ore 1.46 (magnetite) 1.43 (hematite)
Flux 0.06 0.29
Nitrogen 2.21
Coke 0.46
Fresh water 2.61
Air 1.61
Total 6.89 5.07
Cooling water 20.8 22.3
OUTPUT (tonnes/tonne of hot metal) Hot metal 1.00 1.05 (contains 4.5% C)
Slag 0.14 0.21
Condensed water vapour in slurry 0.83
Hot water not used 1.87
Steam not used 0.51
Total discharged gas 2.54 3.81
Carbon dioxide 0.98 1.60*
Nitrogen 1.25 2.21
Total 6.89 5.07
Cooling water in slurry 20.8 22.3**
Carbon dioxide from CaCO3 and MgCO3 calcination 0.04
*This number does not include the carbon dioxide emission from ore/coke preparation.

Because the transfer of mass and, in some systems,
heat constitutes an important aspect of a fluid-solid
reaction, the quantitative analysis of the overall
rate must necessarily take into account the geometry
and structure of the solid before and during the
reaction. The most important group of reactions in
metallurgical processes consists of those in which a
solid reacts with a fluid to produce a coherent layer
of porous products. Therefore, this discussion will
mainly be concerned with this type of reactions,
10 H. Y. SOHN

Table 2. Energy requirements for the Reformerless and hydrogen-based Flash Ironmaking Process compared with that of the
average blast furnace process for a plant with an annual iron production rate of 1 million tonnes (Sohn and Olivas-Martinez 2014).
Flash ironmaking – natural gas Hydrogen Blast furnacea
INPUTb Fuel combustionc 19.22 14.05 13.6
(GJ/tonne Fe) Pelletizing/ Sintering/ Cokemaking 3.01/0.65/2.02
Limestone calcination 0.26 0.26
Total 19.48 14.31 19.28
OUTPUTd Heat recovery 4.77 2.80 1.32
(GJ/ tonne Fe) Total 4.77 2.80 1.32
NET = INPUT – OUTPUT (GJ/ tonne Fe) 14.7 11.5 18.0
a
Calculated based on material balance following the same procedure as that for flash ironmaking.
b
All raw materials are considered to enter the system at room temperature (25°C).
c
Fuel combustion energy input in this case is the heat of combustion of the entire fuel + reductant.
d
Energy output is the useful heat recovered (plus any heating values which in this case are zero because we considered fully oxidised species) in both flash
ironmaking processes and blast furnace.



which is represented by the following general (DA /d)dp DA kmA dp
equation: Sh∗ ; =
DeA DeA DA


A(f ) + bB(s) = cC(f ) + dD(s) (45) DA
= Sh (49)
DeA

gFp (X) ; 1 − (1 − X)1/Fp ;

Reaction of an initially non-porous solid (the
conversion function for reaction control (50)
shrinking-core system)
In this type of fluid-solid reactions, the reaction typi-
cally progresses in a topochemical manner from the
outer surface of the solid towards its interior, as and
shown in Figure 2. The reaction produces a coherent
Fp (1 − X)2/Fp − 2(1 − X)
porous product layer around the unreacted part of pFp (X) ; 1 − ;
the solid, with the chemical reaction taking place at Fp − 2
the sharp interface between the two parts. This shrink- conversion function for (51)
ing-core scheme has been applied to a wide range of pore-diffusion control
systems. Szekely et al. (1976) generalised the results (Sohn and Sohn 1980)
of many investigators and formulated the following
equation incorporating chemical kinetics, pore diffu- ; X 2 for Fp = 1 (51A)
sion, and external mass transfer for three basic geome-
tries of the solid: ; X + (1–X)Ln(1–X) for Fp = 2 (51B)

gFp (X) + s2s [pFp (X) + 4X/Sh∗ ] = t∗ (46) ; 1 − 3(1 − X)2/3 + 2(1 − X) for Fp = 3 (51C)
where Fp is a shape factor (= 1, 2, or 3 for a flat plate, a It can be seen that chemical reaction controls the over-
long cylinder, or a sphere), and all rate when s2s < 0.1 or 0.01 depending on the level



 error that can be accommodated (< 10% or < 1%,
bk Ap CCb
t∗ ; CAb − t (47) respectively). On the other hand, pore diffusion and
aB rB Fp Vp K
external mass transfer control the overall rate [gFp (X)



 becomes negligible] when s2s > 10 or 100. These criteria
k Vp 1
ss ;
2
1+ (48) apply equally for all geometries of the solid when the
2DeA Ap K
fluid-solid reaction modulus s2s is defined as above.
Other definitions of the modulus have been used in
the literature, but the numerical criteria for the rate
controlling steps then become dependent on the
shape of the solid (Szekely et al. 1976).
Individual forms of Equation (46) have been used for
various metallurgical reactions (McKewan 1960; Kawa-
saki et al. 1962; Themelis and Gauvin 1963; St. Clair
1965; Seth and Ross 1966). This shrinking-core model
is attractive for its conceptual and mathematical simpli-
Figure 2. Reaction of an initially nonporous solid that forms a city. It should be noted, however, that its validity is lim-
coherent layer of porous product (the shrinking-core reaction ited to the reaction of a nonporous solid occurring at a
system). [Adapted from Sohn (1991).] well-defined sharp reaction interface. In general, an

Figure 3. Reaction of an initially porous solid. [Adapted from
Szekely et al. (1976).]
improper application of the shrinking-core model to a
porous solid results in an erroneous analysis of exper-
imental data. Thus, one may obtain incorrect depen-
dence of the rate on reaction conditions and physical
parameters such as temperature, reactant concen-
tration, and particle size. The proper analysis of the
reaction of porous solids is discussed below.
Reactions involving an initially porous solid
Many solid reactants are porous, allowing diffusion and
chemical reactions to occur simultaneously in the porous
solid. The progress of reaction in a porous solid is illus-
trated in Figure 3. The reaction in general takes place
throughout the pellet volume, and the concentration of
the fluid reactant decreases as it diffuses into the interior
of the solid while reacting on its path. The reaction given
by Equation (45) taking place in a porous solid can be
described mathematically by starting with the diffusion
equations for the fluid, combined with the energy
equation if a substantial heat effect is involved.
The conservation of fluid species per unit volume of
the pellet (including the pore space) is given by
∇ · Ni = Ri ; i = A or C (52)
This equation incorporates the pseudo-steady-state
approximation, i.e. the accumulation term can be neg-
lected (Bischoff 1963, 1965).
For fluid-solid reactions in general, the molar rate of
consumption of the fluid reactant per unit area of the
reaction interfaces is given by the following Lang-
muir–Hinshelwood-type equation:
k(CAm − CCn /K)
( − ṁA ) = j low concentrations. It was further assumed that the diffu-
1 + K1 CAi + K2 CC
A − pC /Kp )
kp (pm n
= (53)
1 + K ′ 1 piA + K ′ 2 pC
j
MINERAL PROCESSING AND EXTRACTIVE METALLURGY 11
Many reactions can be described by a simple kinetic
expression with m = n = 1 and K1 = K2 = 0 in
Equation (53).
The molar rate of consumption of the solid reactant
per unit volume of the solid is expressed by
∂w
rB = b( − ṁA )Sv = b( − ṁA )S◦v · f (w) (54)
∂t
where w is the local fractional conversion of the solid
reactant and S0v is the initial surface area per unit
volume of the solid.
The fluxes of gaseous species may for a binary mix-
ture or by using an effective binary diffusivity be writ-
ten as follows:
n
Ni = −CT Dei ∇xi + xi Nj (55)
j=1
The rate of production of fluid species i per unit volume,
Ri, is related to the rate of reaction of the solid reactant
through the reaction stoichiometry, as follows:
aB rB ∂w
RA = = −aB (ṁA )S0v f (w) (56A)
b ∂t
caB rB ∂w
RC = = caB (ṁA )S0v f (w) (56B)
b ∂t
When temperature in the solid changes during the reac-
tion, the conservation of energy is described by
∂T
rcp = −∇ · q + ( − DH) · ( − RA ) (57)
∂t
Simultaneous solution of Equations (52)–(57) produces
the fluid species concentrations as functions of position.
The local conversion of solid, w, can then be calculated
as a function of time by integrating Equation (54)
together with Equation (53). The overall conversion X
is then obtained by integrating the local conversion
over the entire solid.
The Grain Model: This model pictures the porous
solid to be made up of fine non-porous grains of a uni-
form size each of which reacts according to the reac-
tion-controlled shrinking-core process, as shown in
Figure 4 (Sohn and Szekely 1972; Szekely et al. 1976).
This picture is somewhat unrealistic and restrictive
but gave an early basis for incorporating solid structure
in the analysis of fluid-solid reactions in porous
solids. In addition, this model also provided an early
basis for more realistic and less restrictive approach to
the description of fluid-solid reactions, as will be dis-
cussed later.
The generalised grain model developed by Sohn and
Szekely (1972) was constructed for an isothermal reac-
tion with equimolar counter-diffusion or diffusion at
sion in the product layer around an individual grain
offers little resistance to the overall rate. This assumption
is valid for small grains but can readily be relaxed (Sohn
12 H. Y. SOHN

under the bulk conditions controls the overall rate

when ŝ < 0.1 or 0.01 depending on the level of toler-
able error (< 10% or < 1%, respectively), and pore
diffusion and external mass transfer control the over-
all rate [gFp (X) becomes negligible] when ŝ > 10 or
100.
The above analysis of the grain model was made for a
constant effective diffusivity. In many fluid-solid reac-
tions, the product solid layer has a substantially different
effective diffusivity than that of the reactant. One of the
simplified methods of incorporating this structural
change is to assign different effective diffusivities to
the completely and partially reacted zones. Sohn and
Perez-Fontes (2010) and Szekely and Sohn (1973)
reported the results of computation for this two-diffu-
sivity system.

Figure 4. The grain model for an initially porous solid.
[Adapted from Sohn (1991).]
and Szekely 1974). Sohn and Szekely (1972) considered
porous solids in which the pellet and the grains may
each have the shape of a flat plate, a long cylinder, or a
sphere – nine possible combinations.
Sohn’s law of additive reaction times
Based on the conversion-vs.-time relationships for por-
ous and nonporous solids discussed above, Sohn
(1978) formulated the ‘Law of Additive
Reaction Times’. This law states for an isothermal reac-
tion that:

Time required to attain

Time required Time required to attain the the same conversion under
to attain a  same conversion under the conditions + the rate control by inter-grain
certain conversion of rapid inter-grain pore diffusion pore diffusion and external
mass transfer
(61A)

For systems in which the effective diffusivity

remains unchanged during the reaction, Sohn and Sze-
kely (1972) obtained the following approximate con- or mathematically
version-vs.-time relationship:
t  t(X)|ŝ 0 + t(X)|ŝ 1 (61B)
tg∗  gFg (X) + ŝ2 [pFp (X) + 4X/Sh∗ ] (58)

where  a · g(X) + a · ŝ2 [ pFp (X) + 4X/Sh∗ ] , (61C)




bk Ag CCb
tg∗ ; CAb − t (59) where a is a constant term containing the reaction-rate
rB Fg Vg K
constant.1 In general, the term t|ŝ 0 is related to f (w)


2

aB Fp k Ag Vp 1 in Equation (54) by (Sohn 2004a, 2004b)
ŝ ;
2
1+ (60)
2De Fg Vg Ap K
x
and gi(X ) and pi(X ) have been defined in Equations (50) rB dw
t(X)|ŝ 0 =
and (51), except in this case the g function is defined b( − ṁA )b S0v f (w)
0
with the shape factor of the grains.
x
The definition of the generalised fluid-solid reac- rB dw
=
tion modulus ŝ given above makes the criteria for bkSv (CAb − CCb /K)
0 f (w)
the controlling steps the same as those for an initially 0

nonporous solid and independent of the shapes of = a · g(X) (62)

the grains and pellet (Sohn and Szekely 1972; Szekely
et al. 1976). Thus, the reaction of individual grains in which ( − ṁA )b is ( − ṁA ) at bulk conditions. From
1
Note that kS◦v in this derivation is equivalent to k·ρB in Sohn [1978].

Figure 5. Graphical representation of Sohn’s Law of Additive Reaction Times. [Adapted from Sohn (1991).]
Equation (46) or (58), the term t|ŝ 1 is given by

2

Vp aB rB Fp 1 cation of this Law by Patisson et al. (2006) and Dus-
t(X)|ŝ 1 = 1+
Ap 2bDe (CAb − CCb ) K
(63)
× [ pFp (X) + 4X/Sh∗ ]
= a · ŝ2 [ pFp (X) + 4X/Sh∗ ]
Figure 5 illustrates how this Sohn’s Law of Additive
Reaction Times can be applied in general solely based
on information on the chemical reaction rate in the
absence of the resistance due to intra-pellet diffusion
and that on the rate controlled by intra-pellet diffusion.
Equations (46) and (58) are examples of the mathemat-
ical expressions of this law. This law is exact for the
reaction of a nonporous solid that follows the shrink-
ing-core scheme. It is approximately valid for the reac-
tion of an initially porous solid with a constant effective
diffusivity. In the latter case, the exact solution must in
most cases be obtained by numerical solution of the
governing differential equations.
Because it is expressed in the form of a closed-form
equation and explicit in time, Sohn’s Law of Additive
Reaction Times is extremely useful in the analysis of
multi-particle systems involving particle size distri-
bution and changes in fluid concentration and solid
temperature. Thus, it yields the instantaneous conver-
sion rate dX/dt as a function of solid conversion (X )
and other conditions. This allows the application of
the solution to systems in which conditions change
with time and/or position in the reactor as long as
the temperature within a particular pellet is uniform
at any given time but may change with time (Sohn
1978). Sohn (1978) has further shown that this law is
valid for any functional dependences of rate on solid
conversion.
Sohn’s Law of Additive Reaction Times has been
applied to a wide range of fluid-solid reaction systems
and has shown wide applicability and significant
advantages (Sohn and Szekely 1974; Sohn 1978; Sohn
and Braun 1980, 1982; Sohn and Kim 1984;
MINERAL PROCESSING AND EXTRACTIVE METALLURGY 13
Sohn and Chaubal 1986; Sohn and Xia 1986, 1987;
Sohn and Baek 1989; Sohn and Wall 1989). The appli-
soubs et al. (2002, 2003a, 2003b) is noteworthy in
that it was found to have many advantages over other
models when modelling a complex reaction system in
a multiparticle moving bed furnace.
It is stressed that this law was developed based on
the reaction modelling of an initially porous solid,
thus providing an example of the benefit of mathemat-
ical modelling, even based on simplification, beyond
describing the reaction of an individual piece of solid.
Furthermore, such mathematical modelling of various
types of fluid-solid reactions has enabled Sohn
(2004a, 2004b) to develop a quantitative theory on
the effect of equilibrium limitation on fluid-solid reac-
tion kinetics and apparent activation energy.
Development of new process schemes resulting
from first-principle-based modelling – gas-solid
reaction-rate enhancement by pressure cycling
A carefully constructed mathematical model based on
first principles not only is useful for designing, analys-
ing and optimising a process but can even suggest the
development of a new, improved process. Gas–solid
reactions are, in general, carried out under the con-
ditions in which pore diffusion of gaseous species sig-
nificantly affects or controls the overall rate. Pore
diffusion is a slow process compared with bulk flow.
The pumping action created by the pressure cycling
increases the transfer rate of gas into and out of the
solid thereby increasing the overall rate. Sohn and
Chaubal (1984) theoretically evaluated the effect of
pressure cycling on gas–solid reaction rates. Sohn
and Aboukheshem (1992) determined the effect of
pressure cycling by experiments with the hydrogen
reduction of nickel oxide and compared the results
with a similar mathematical model written for this par-
ticular system. The work by these latter authors will be
described below.
14 H. Y. SOHN

Consider a porous pellet of nickel oxide reacting high permeability and the boundary condition
with hydrogen according to
U = 0, at r = 0 (73)
H2 (g) + NiO(s) = H2 O(g) + Ni(s) (64)
we obtain
which can be written in a general form as 1r ∂P
U =− (74)
A(g) + bB(s) = cC(g) + dD(s) (65) 3P ∂t

A mass balance including bulk flow due to pressure Since

changes on the concentration of the gaseous reactant PA = xA · P, (75)
(A = H2) in a porous solid is described by
Equation (66) can now be combined with Equations
∂CA (71) and (74) to give the following equation in terms
1 + ∇ · (CA V) − ∇ · (DaA CT ∇xA ) + vA
∂t of the mole fraction of the gaseous reactant:
=0 (66)

2  
∂xA 1 ∂ xA 2P ∂xA 1r ∂P ∂xA
= Da P 2 + + − Rg TvA
in which the first term represents the variation of gas ∂t 1P ∂r r ∂r 3 ∂t ∂r
concentration with time, the second term the (76)
pressure-driven bulk flow of the gas, the third term
the dispersion effect associated with the bulk gas flow According to Edwards and Richardson (1968), the dis-
through the solid interstices, and the fourth term the persion coefficient is given by
consumption rate of the gaseous reactant by local 0.5Udg
reaction. Da = De + (77)
9.71DAC
An expression similar to Equation (66) can be writ- 1+
Udg
ten for the product gas (C = H2O):
The boundary conditions for Equation (76) are
∂CC
1 + ∇ · (CC V) − ∇ · (DaC CT ∇xC ) + vC
∂t ∂xA
= 0, at r = 0 (78)
=0 (67) ∂r

For Reaction (64), ∂xA

−De = km (xA − xAo ), at r = rp (79)
∂r
vc = −vA (68)
and Sohn and Aboukheshem (1992) applied the follow-
and the dispersion coefficients are assumed the same: ing pressure wave:
DaA = DaC = Da (69) P = Po (1 + A′ sinvt) (80)

Summation of Equations (66) and (67) using Equations The local rate of consumption of hydrogen per unit
(68). and (69) yields the following overall continuity volume is related to the local rate of reaction of nickel
equation: oxide as follows:
∂CT vA = −n1o · ∂Y/∂t = n1o · f (Y, pA , pC , T) (81)
1 + ∇ · (CT V) = 0 (70)
∂t
in which Y represents the local unreacted fraction of
where V represents the superficial velocity vector the solid reactant.
resulting from the external pressure cycling. The ideal The kinetics of hydrogen reduction of fine nickel
gas law relates pressure and concentration: oxide particles was described by the following nuclea-
tion and growth kinetics (Sohn and Kim 1984; Sohn
P = C T Rg T (71)
and Aboukheshem 1992):
The gas velocity is dependent on permeability. The
mbkxA PY(−LnY)1−1/m
NiO pellets used in this work are sufficiently permeable f (Y, pA , pC , T) = (82)
Rg Tn1o
that pressure is uniform throughout the solid at any
given moment. Substituting Equation (71) into The overall conversion is then calculated by
Equation (70) and considering symmetry in the angu- 
lar directions, 3 rp
X= 3 (1 − Y) · r3 dr (83)
rp 0
∂P ∂P P ∂(r2 U)
1 +U + 2 =0 (72)
∂t ∂r r ∂r Sohn and Aboukheshem (1992) varied the frequency
and amplitude of pressure wave in the ranges, respect-
in which U is the superficial linear velocity in the radial
ively, of 0–20 Hz and 0–0.67 atm. Even with this rela-
∂P
direction. Integrating Equation (72) with = 0 for tively moderate level of pressure cycling, the overall
∂r

Figure 6. Computed rate-enhancement effect of an acoustic
wave (ŝ = 10; 653 K). (- - -) constant pressure of 86.1 kPa (1
atm); (—) under acoustic wave [frequency = 100 Hz; ampli-
tude = 6.9 kPa (0.068 atm)].
rate of reaction increased significantly, even when the
effect of pore diffusion was rather moderate (ŝ = 10)
due to the limitations in the apparatus, as shown in
Figure 6. These authors also showed that the math-
ematical model yielded results that agreed well with
the experimental results. The pressure cycling is also
expected to enhance external mass transfer.
Based on their experimental and theoretical investi-
gations, Sohn and Aboukheshem (1992) summarised
the effects of the external pressure cycling on overall
gas–solid reaction rate as follows:
(1) The pressure cycling increases the reaction rate
when the overall rate is influenced by the diffu-
sional resistance. The stronger the diffusional
effect, the greater the rate enhancement by
pressure cycling.
(2) The overall rate increases with the frequency and
amplitude of pressure wave.
(3) The effect of pressure cycling was significant even
under a moderate pore diffusion effect. Much
greater effects of pore diffusion are readily pro-
vided at higher temperatures, where the effect of
pressure cycling has been calculated to be much
greater.
(4) Even a low-amplitude pressure wave like an acous-
tic wave can significantly increase the rate of a gas–
solid reaction by using high frequency of the wave.
Complex fluid-solid reactions
The ideas and principles discussed in the previous sec-
tions have been applied to the quantitative analysis of
complex fluid-solid reaction systems. Examples are
listed below. The reader is referred to the references
given in each case for further details.
MINERAL PROCESSING AND EXTRACTIVE METALLURGY 15
A. Solid–Solid Reactions Proceedings through Gaseous
Intermediates with a Net Production of Gases
(Sohn and Szekely 1973).
B. Solid–solid reactions proceeding through gaseous
intermediates with no net production gas (Sohn
and Kim 1987, 1988; Soepriyanto et al. 1989).
C. Successive gas–solid reactions in which the reactant
gas reacts with the first solid, producing an inter-
mediate gas which in turn reacts with the second
solid (Sohn and Rajamani 1977; Rajamani and
Sohn 1983; Sohn and Won 1985).
D. Staged reaction of a solid with a gas in which the
solid forms a series of thermodynamically stable
intermediate phases: (Sohn and Chaubal 1984).
E. Simultaneous reactions between solid reactants and
fluids (Sohn and Braun 1980; Sohn and Braun
1984; Lin and Sohn 1987; Paul et al. 1992).
Modelling of unit processes
In the above sections, the discussion was mainly con-
cerned with the analysis of reactions taking place in a
piece of solid. The eventual objective for studying a single
piece solid is to apply the results to the analysis and design
of multi-particle systems of industrial importance. The
extension of single-particle studies to multi-particle sys-
tems will depend on the nature of the particulate assem-
blages, the mode of fluid-solid contacting, and the spatial
variation of the fluid properties within the system.
In the previous sections, all the analysis and derivations
were done for the cases in which the bulk concentration of
the fluid reactant(s) is maintained constant. In practice the
fluid concentration outside a piece of solid tends to vary
with the progress of reaction, as in a packed-bed reactor
or a closed batch system. However, the derivations made
with constant bulk concentrations are applicable to the lat-
ter situation because the fluid phase in the interior of the
solid responds to the concentration changes in the bulk
much faster than the changes in the solid phase. This is
related to the justification of the pseudo-steady-state
approximation in fluid-solid reaction analysis.
In applying rate data obtained for single solids to
multi-particle systems, the following issues must be
taken into consideration:
(a) Physical nature of the assembly
In the analysis of multi-particle assemblies such as
packed beds, fluidised beds, and flash reactors, attention
must be paid to the fluid flow in the system. In packed or
fluidised beds the heat and mass transfer coefficients are
affected by the presence of the other particles.
(b) Contact time or residence time in the reaction
environment
16 H. Y. SOHN

In single-solid studies the reaction time is well-

defined. In most systems involving particle assemblies,
only the average contact time is known and there may
be a spread of residence times for both the solids and
the fluid. With more advanced computational tech-
niques, it has become easier to follow a group of par-
ticles or even an individual particle as they move
through multi-particle reactors.

(c) The effect of spatial variation of fluid composition

In experiments on the reaction of single solids, the

fluid concentration can be maintained constant. The
situation is more complicated in most multi-particle
assemblies, in which the solid particles are in contact
with a fluid at varying temperature and composition.
With the development of high-speed, high-capacity
computers and techniques, complicated processes have
become easier to analyse and model. Examples in the Figure 7. A schematic diagram of the bubbling fluidised bed.
[Adapted from Zhou and Sohn (1996).]
field of metallurgical process modelling are discussed
below.
the following equations:
A. Flash smelting process
dCAb
−fg,b Ub = dKbe (CAb − CAe ) + fg,b ( − rg,b ) (84)
The flash smelting process is important in the pro- dZ
duction of nonferrous metals from sulfide minerals.
In this process, fine mineral particles are injected into dCAe
and burned in the furnace with tonnage oxygen or −fg,e Ue = dKbe (CAe − CAb ) + fg,e ( − rg,e ) (85)
dZ
air enriched with oxygen. The design of a flash-smelt-
ing furnace is complex mainly due to the difficulty of where fg,j is the fraction of the bed volume occupied by
quantifying the turbulent fluid flow, convective heat the fluid in phase j; Kbe is the interchange coefficient
and mass transfer, chemical reactions, and radiative between the bubble and emulsion phases based on the
heat transfer. Modelling of such complex processes in bubble volume; and ri,j is the consumption rate of
which fluid flow is the main component is conveniently fluid reactant i per unit volume of the fluidised bed in
performed by computational fluid dynamic technique. phase j; and δ, the fraction of the bed volume occupied
Modelling of a flash smelting process is discussed in a by the bubbles, is given by (Kunii and Levenspiel 1991),
subsequent section.
⎧ U −U Umf
⎪
⎪
0 mf
when Ub 
B. Fluidised-Bed Reactors for Fluid-Solid Reactions ⎨ U +U 1mf
b mf
d= (86)
⎪
⎪ U0 − Umf Umf
⎩ when Ub  5
Fluidised-bed reactors are often used in metallurgi- Ub 1mf
cal processes, such as the roasting of sulfide minerals
and the gaseous reduction of oxide minerals. In a The following experimentally determined rate
fluidised-bed reactor, solid particles are dragged expression for the chlorination of rutile (Sohn et al.
upward by bubbles and descend by gravity in the emul- 1998) was used:
sion phase, as shown schematically in Figure 7. Par-
ticles may be fed continuously and discharged dr
= −kv (RT)1.29 Cco CCl2 .
0.55 0.74
(87)
through an overflow pipe. dt
Zhou and Sohn (1996) investigated the fluidised-bed
chlorination of rutile by CO–Cl2 mixtures, using the Assuming steady state, an overall mass balance of
bubble assemblage model to describe the bed behav- the solid yields (Kunii and Levenspiel 1968; Levenspiel
iour. The model assumes that the solid particles are et al. 1968)
well mixed throughout the bed, but the fluid reactant
concentrations vary with the bed height. rate of solid consumption in
The fluid flowing through the bubble and emulsion F0 − F1 − F2 = size interval rto r + dr
phases exchanges mass between the two phases. The all r in the whole bed
mass balances for the fluid in these two phases yield (88)
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY 17

and in terms of rate gives,

⎛ ⎞ ⎛ ⎞ ⎛ ⎞
Solids solids solids
⎜ ⎟ ⎜ ⎟ ⎜ ⎟
⎝ entering in ⎠ − ⎝ leaving in ⎠ − ⎝ leaving in ⎠
⎛ ⎞ the feed overflow carryover
Rate of mass consumption ⎡⎛ ⎞ ⎛ ⎞⎤
⎜ in the size interval rto ⎟ solids shrinking solids shrinking
⎜ ⎟ ⎢⎜ ⎟ ⎜ out of the ⎟⎥
⎝ r + drper unit ⎠ ⎢⎜ into the ⎟ ⎜ ⎟⎥
+⎢⎜ ⎟−⎜ ⎟⎥
volume of the bed ⎣⎝ interval from ⎠ ⎝ interval to ⎠⎦
⎛ ⎞
rate of mass consumption a larger size a smaller size
⎜ in the size interval rto ⎟ ⎛ ⎞
=⎜ ⎟ solids
⎝ r + drin bubble phase ⎠ ⎜ consumption ⎟
⎜ ⎟
per unit volume of the bed ⎜ ⎟
⎛ ⎞ − ⎜ due to the ⎟
⎜
⎟ = 0.
rate of mass consumption ⎜ ⎟
⎜ in the size interval rto ⎟ ⎝ shrinkage within ⎠
+⎜ ⎝ r + drin emulsion phase ⎠.
⎟ (89)
the interval
per unit volume of the bed (91)
The formulation of the quantitative expressions of the
various terms in the above conceptual balance
equations is described elsewhere (Zhou and Sohn
In the bubble and emulsion phases, 1996).
Zhou and Sohn (1996) carried out batch exper-
iments using a deep fluidised bed. The model yielded
the particle-size distribution and the amount of solids
in the bed as functions of time. The mathematical
⎛ ⎞ model was verified with the results of experiments
Rate of mass consumption
⎜ in the size interval rto ⎟ under conditions in which both the kinetics and
⎜ ⎟
⎜ ⎟ mass-transfer effects play a significant role. In this
⎝ r + drin bubble phase ⎠
way, generally valid verification of the model was
per unit volume of the bed obtained.
⎛ ⎞ Examples of the model predictions compared with
number of particles in
⎜ the interval rto r + dr ⎟ the experimental results are shown in Figure 8 for a
⎜ ⎟
= r⎜ ⎟ (90) feed with a wide size distribution. It is seen that the
⎝ in bubble phase per ⎠
mathematical model yields results that are in good
unit volume of the bed agreement in terms of overall conversion vs. time.
⎛ ⎞ ⎛ ⎞ The calculated results of the particle size distributions
rate of volume
⎜ decrease for ⎟ ⎜yb wP1 (r)dr dV ⎟ in the bed and in the elutriation are given in Figure 9.
⎜ ⎟ ⎟.
×⎜ ⎟ = r⎜
⎝
4 
⎝ one particle in ⎠ 3 dt ⎠ C. Bottom-gas-injected solvent extraction process
r pr
bubble phase 3
Solvent extraction is used to separate, purify, and
concentrate metal values in aqueous solutions (Ricci
1980; Lo et al. 1983; Blumberg 1988). The widely
used mixer-settler contactor is operated under the con-
In the preceding equations, Fo is the feed rate of ditions of near equilibrium between the organic and
solids with a particle-size density function of Po(r); aqueous phases. However, it has complicated struc-
F1 is the withdrawal rate of solids with a particle- tures of impellers, inter-stage pumping, and piping.
size density function of P1(r); F2 is the Furthermore, its maintenance is difficult, especially
elutriation rate of solids with a particle-size density for the processing of corrosive and/or solid-laden
function of P2(r); ρ is the mass density of solid; yb liquids (Laddha and Degaleesan 1978).
is the fraction of the entire solid present in the A new solvent extraction process without these pro-
bubble phase; w is the solid weight per unit volume blems is the SOHNEX process (Sohn 1997; Sohn and
of the bed; r is the particle radius; and V is the Doungdeethaveeratana 1998). The process uses a
volume of a particle. cylindrical contactor, in which the liquid–liquid emul-
Using the population balance approach, the mass sion is generated by bottom-blowing of gas, as shown
balance of solid in the particle-size interval r to r + dr in Figure 10. The gas jet generates an emulsion of the
18 H. Y. SOHN

mixed reactor. The flows around each plume were

described as recycling plug-flow reactors (Iyer and
Sohn 1994). The model has a single parameter α
(Figure 11), the throughput fraction through a reactor
unit, which was determined by matching the exper-
imental residence-time distribution with the reactor
model.
The residence-time distribution response E(t) of a
plug-flow reactor to a pulse input, applied to the
lower recycling reactor is
E(t) = d(t – tP ). (92)
where δ is the Dirac delta function and τP is the average
residence time in the reactor.
The E(t) of a perfectly mixed reactor to a pulse input
is given by


t
E(t) = t−1
C exp − (93)
tC
Figure 8. Experimental data vs. model prediction for the
fluidised-bed chlorination of rutile particles with a wide size where τC is the average residence time of the perfectly
distribution. (The feed particle size distribution can be found mixed reactor. The residence-time distribution for the
in Figure 9.) [Adapted from Zhou and Sohn (1996).] recycling reactor in the aqueous phase is
E(t) = a(1 − a)n {d[t – tp –n(tP + tR )]} (94)
where τR is the average residence time of the upper


t − tP
recycling reactor, and n = integer . Consid-
tP + tR
ering a perfectly mixed reactor with a normalised
input function Y(t) such that
1
Y(t)dt = 1, (95)
t=0

the residence-time distribution response to the input

introduced between time θ and θ + dθ is given by


−1 t−u
dE = tC [Y(u)du] exp − . (96)
tC
Therefore, the residence-time distribution at any
time t is

t t−u
−
E(t) = t−1
C Y(u)e
tc d u. (97)
u=0
Figure 9. Calculated particle-size distribution in the bed and
elutriation for the fluidised-bed chlorination of rutile particles. The equations for various combinations of reactors is
[Adapted from Zhou and Sohn (1996).] obtained by combining the responses of the individual
reactors. The residence-time distribution of the first
organic and aqueous phases for rapid mass transfer. recycling reactor unit and perfectly mixed reactor com-
The two liquids then disengage and flow in the oppo- bination is given by
⎧ ⎡ ⎤⎫
site directions before entering another mixing zone. t −t−u
n ⎪
⎨ t−t −
⎪
⎬
This unit has no moving parts or other internal struc- n−1 ⎢ −tp1 −1 t ⎥
E1 (t)= a(1− a) ⎣ e tC1 Y(u)e C 1 d u⎦
tures. Thus, the process is simple and efficient (Zaidi ⎪
i=1 ⎩ u=0 ⎪
⎭
and Sohn 1995).
(98)
The fluid flow and mixing patterns in this reactor

were modelled by an ideal-reactor-network model, as t − tP1
where τ = (2i + 1)τP1 and n=integer , with the
illustrated in Figure 11 (Iyer and Sohn 1994). In this 2tP1
model, the plume region was represented as a perfectly assumption of equal residence times in the upper and
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY 19

Figure 10. Sketch of the SOHNEX solvent extraction process. [Adapted from Sohn and Doungdeethaveeratana (1998).]

Figure 11. Ideal-reactor-network model of the gas-injected solvent extraction process. [Adapted from Iyer and Sohn (1994).]

lower recycling reactors, i.e. τP = τR (Iyer and Sohn A comparison of experimental data with model
1994), whereas that for the recycling section after the results for aqueous-phase residence-time distribution
perfectly mixed reactor is given by is shown in Figures 12–14. There is an overall excel-

n lent agreement between the predicted and the exper-
E2 (t) = a(1− a)n−1 [E1 (t − t)] (99) imental results. The fluctuation in the E(t) value is
i=1 due to the behaviour of the idealised recycling reac-
tor. The recycling reactor output consists of pulses
where τ = τP1 + (2i + 1)τP2 and

 at intervals of (τP + τR) (Iyer and Sohn 1994). Even
t − tP1 − tP2
n =integer . for the largest value of α, for which the fluctuation
2tP1
is largest, the peak time and the average residence
These equations may be repeated for identical sec- time are predicted adequately.
tions along the reactor by using the output from the Iyer and Sohn (1994) developed a correlation for α
previous section as the input to the next section. against the experimental conditions characterised by
20 H. Y. SOHN

Figure 12. Calculated and experimental residence time distri- Figure 14. Calculated and experimental residence time distri-
butions in the aqueous phase of gas-injected two-liquid con- butions in the aqueous phase of gas-injected two-liquid con-
tacting. [α = 0.025. Test conditions can be found in Iyer and tacting. [α = 0.644. Test conditions can be found in Iyer and
Sohn (1994).] Sohn (1994).]

For the organic phase, the model equations are simi-

lar to those for the aqueous phase. The output from the
first recycling reactor and perfectly mixed reactor set is
identical to Equation (99). For the plug flow reactor
unit after the perfectly mixed reactor, the residence-
time distribution is given by

E2 (t) = 0 for 0 , t , tP1

= E1 (t − tP2 ) for t . tP2

These equations can also be extended, as for the aqu-

Figure 13. Calculated and experimental residence time distri-
butions in the aqueous phase of gas-injected two-liquid con-
tacting. [α = 0.225. Test conditions can be found in Iyer and
Sohn (1994).]
eous phase, to subsequent identical sections along the
reactor by using the output from the previous section
as the input to the next section. A comparison of the
calculated with the experimental results for the organic
phase is presented in Figure 16.

a single dimensionless parameter ε defined based on

dimensional analysis:
 

 2 2
r1 QL1 h1 h2 r2 pdinj
1= 1+ . (100)
rg Qg L h1 r1 4A1

where ρ is mass density, Q the volumetric flow rate, h

the liquid depth, L the distance between the adjacent
gas injectors, A the cross-sectional area perpendicular
to the liquid flow, and the subscripts 1 and 2 denote,
respectively, the aqueous and the organic phases. The
correlation is given by
a = 0.2 log10 1 + 1.623, for 8 × 10−9 , 1
, 2 × 10−5 (101)

The correlation for α was tested for a much larger

unit (1 m diameter and 7.2 m length) to test its applica-
bility for scaling-up (Iyer and Sohn 1994). A comparison
between the experimental and the calculated results is
shown in Figure 15, indicating good agreement.
Figure 15. Calculated and experimental residence time distri-
butions in the aqueous phase of a large-scale model of gas-
injected two-liquid contacting. [α = 0.181. Test conditions can
be found in Iyer and Sohn (1994).]

Figure 16. Calculated and experimental residence time distri-
butions in the organic phase of gas-injected two-liquid con-
tacting. [β = 0.601. Test conditions can be found in Iyer and
Sohn (1994).]
The parameter β for the recycling part of the organic
phase was correlated against the experimental con-
ditions characterised by a single dimensionless par-
ameter γ defined by
 2 2 m fd [%M] fd = mmt [%M]mt + msl [%M]mt /LIII
r2 QL2 h1 h2 r2 pdinj
g= 1+ . (103)
rg Qg L h1 r1 4A2
and the correlation equation is
b = 0.288 × 10(2.46× 105g), for g
, 1.4 × 10−6 (104)
Thermodynamic equilibrium process
modelling
Smelting processes operate at high temperatures where
chemical reactions are rapid and therefore largely pro-
ceed near the equilibrium conditions. Kellogg (1967),
Nagamori and coworkers (Chaubal and Nagamori
1982, 1988; Nagamori and Chaubal 1982a, 1982b;
Chaubal et al. 1984), Itagaki and Yazawa (1983), Ita-
gaki (1986), and Kim and Sohn (1996, 1997, 1998) con-
tributed significantly to the equilibrium modelling of
such processes. Examples of this approach are dis-
cussed below.
Minor-element behaviour in bath smelting of
sulfide minerals
The distribution of minor elements in bath smelting is
typically analysed under the following assumptions:
(1) A system composed of different phases is at equi-
librium conditions.
MINERAL PROCESSING AND EXTRACTIVE METALLURGY 21
(2) All the injected oxygen reacts completely with the
molten phases and fuels if used.
(3) The physical suspension of materials from another
molten phase does not affect the minor-element
behaviour.
A. Steady-State Operations
The smelting processes are becoming continuous with
the conditions in the vessel remaining constant with
time. Modelling of minor-element behaviour during a
steady-state operation will be described using the
work of Kim and Sohn (1996, 1998) on copper matte
smelting as an example.
The important impurity elements in copper smelt-
ing are Pb, Zn, Bi, Sb and As (Nagamori et al. 1975;
Kim and Sohn 1996, 1998). Matte is usually made by
a continuous process.
Assuming that all copper in the feed goes into the
matte phase, the following mass balances are estab-
lished:
m fd [%Cu] fd = x · mmt (105)
m fd [%Fe] fd = mmt [%Fe]mt + msl [%Fe]sl (106)
M
+ yM
T
no AM (107)
where
M = [%M]mt /[%M]sl
LIII (108)
and mfd, mmt and msl are the mass rates of feed, matte and
T
slag, respectively; x is the matte grade; yM is the mole frac-
tion of impurity M in the output gas (= pM /pT ) where pTM
T
is the sum of the partial pressures of all the gaseous
species containing the element M as defined below; LIII M
is the distribution coefficient of element M between
matte and slag; no is the total molar flow rate of output
gas; and AM is the atomic weight of element M.
The effective total pressure of all the M-containing
species is calculated by
pTM = pM + pM2 + bpMb Od + mpMm On
= (k1,M )i [M]i + (k2,M )i [M]2i + (k3,M )i [M]bi
+ (k4,M )i [M]ni
(109)
where i denotes a molten phase and the (kn,M)i are
functions of temperature, pO2 and pS2 that are com-
puted from the equilibrium between the gas and con-
densed phase i. In copper smelting only M, M2, MO
and MS are significant (Kim and Sohn 1998). Details
for computing (kn,M)i are given in Kim and Sohn
(1996, 1998).
22 H. Y. SOHN
C. Unsteady-state operations
Some smelting processes take place in time-depen-
dent batches. The analysis of impurity behaviour in a
transient process, such as the Peirce-Smith converting,
has been performed by Kim and Sohn (1996, 1998).
Specific examples of applying the above discussed
procedure of equilibrium modelling to copper matte
smelting and converting can be found in the literature
(Chaubal et al. 1984; Chaubal and Nagamori
1988; Chaubal et al. 1989; Kim and Sohn 1996, 1998).
Computational fluid dynamics modelling
This section discusses the principles involved in com-
putational fluid dynamic (CFD) modelling and pre-
sents examples of metallurgical process models based
on CFD. This tool allows the simulation of multiphase
fluid flow in complicated geometric systems, into
which other subprocesses such as heat and mass trans-
fer and chemical reactions can be incorporated. Indus-
trial processes have become amenable to more detailed
analysis and simulation, thanks to this versatile and
useful technique.
In traditional metallurgical process modelling, it was
possible to incorporate only the simplified aspects of
fluid flow, mixing, and heat/mass transfer into the
analysis of process rates and reactor design. As a result,
accurate and realistic incorporation and simulations of
many aspects of complex processes were not possible.
With the advent of high-speed, high-capacity comput-
ing devices and technologies, complex processes have
become amenable to more detailed analysis and mod-
elling. Developments that exemplify this in the field
of metallurgical process modelling are discussed in
this section.
The mathematical modelling of complex processes
using the computational fluid dynamic (CFD) tech-
nique requires quantitative description of the coupled
gas-phase transport and chemical reaction rate
equations, i.e. fluid flow, heat and mass transfer, and
reaction kinetics.
Governing equations
The governing equations in a process involving turbu-
lent fluid flow, including heat transfer, given in Section
1 are used in a CFD model. In addition, the following
subprocesses are incorporated into the basic fluid-
flow model when necessary:
. Radiative heat transfer
. Gas-phase reaction kinetics
. Gas-particle reaction kinetics
. Nucleation, growth, and coagulation of particles
. Population balance model to describe changes in
particles
An example of a CFD model of metallurgical processes
is presented below.
CFD modelling of flash smelting and converting
processes
An important example of a metal production process is
the flash smelting process in the production of nonfer-
rous metals from sulfide minerals. In this process, fine,
dried mineral particles and fluxes are injected into the
furnace with industrial oxygen or oxygen-enriched air.
The mineral particles are rapidly ignited and burn in
the turbulent gas jet.
The CFD modelling of flash smelting and convert-
ing processes is discussed here using the work of
Perez-Tello et al. (2001b) and Hahn and Sohn
(1990a, 1990b). A schematic representation of a flash
furnace for the purpose of CFD modelling is illustrated
in Figure 17. In developing a computer model of a
complex process such as a flash-smelting furnace, it
is necessary to start by first separating the overall pro-
cess into and obtaining good understanding of identifi-
able components. These components are then
assembled into the overall description of the process.
An important sub-process in flash smelting is the
gas-particle reactions, i.e. the oxidation of sulfur and
iron in the mineral particles. To describe the ignition
transient as well as the main combustion period follow-
ing the ignition, information on the intrinsic kinetics of
the mineral particle oxidation is needed. This infor-
mation is preferably obtained by carrying out separate
experiments (Chaubal and Sohn 1986).
Sohn and coworkers (Sohn et al. 1988; Sohn and Seo
1990; Perez-Tello et al. 2001a) carried out experiments
Figure 17. Schematic Representation of a Flash Furnace for
Mathematical Modelling Purposes. [Adapted from Perez-Tello
et al. (2001b).]
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY 23

Figure 18. Comparison of the calculated and measured results

from a laboratory flash furnace shaft. [Test conditions can be
found in Hahn and Sohn (1990).]

in a laboratory flash furnace under various experimen-

tal conditions. They also verified their CFD model
results against the independent measurements by
other research groups (Hahn and Sohn 1990a), provid-
ing further evidence of the dependability of the CFD
Figure 19. Comparison of the calculated and measured results
model. One can thus use the CFD model with much from an Outotec pilot flash furnace. [O2 (MexOy) denotes the
confidence to describe, analyse, and design the percent of input O2 used to produce metal oxides. Test con-
sulfide-smelting processes. An example is the appli- ditions can be found in Hahn and Sohn (1990).]
cation of this mathematical model to the description
of impurity behaviour (Seo and Sohn 1991), which is
(2) The smelting reaction is largely completed within
an important problem in any smelting processes.
fractions of a second and thus within a fraction
Figure 18 shows a typical comparison between the
of the furnace height typically used for most indus-
model predictions and measurements in terms of the
trial units. There are several reasons other than
SO2 concentration in the gas and sulfur content in
reaction rates for the larger furnace height than
the particles at various positions along the furnace
the calculated value, such as less reactive recycled
shaft (Hahn and Sohn 1990). The overall agreement
dusts and aggregates formed from the feed par-
is adequate. It is of interest that the model satisfactorily
ticles. However, the heights of industrial flash fur-
predicts the location at which the particles ignite. A
naces may, in general, be excessive. This has been
comparison between the computed and measured
verified by a commercial plant when they removed
data obtained by Outotec Co. in their pilot reactor is
the upper 3 m out of the original 13.5 m from their
shown in Figure 19. The upper figure shows the SO2
furnace without any undesirable effects. This work
and O2 concentrations along the axis from the burner,
has also been credited to be a critical factor in
as well as the amount of oxygen consumed in the oxi-
increasing the feed rate into a flash smelting fur-
dation of metal components. The second graph is for
nace, thereby doubling its capacity, without
the case in which the feed gas was preheated. The bot-
increasing the furnace size (Suzuki et al. 1998).
tom graph compares the temperature profiles for these
(3) Many ‘test runs’ can be performed with the com-
two cases.
puter model without the costly and time-consum-
The most significant features of the modelling of a
ing plant tests.
flash-smelting furnace are

(1) By providing a radial velocity component to the

Physical modelling
solid feed at the burner, particles distribute more
uniformly in the furnace, and hence a larger fur- The behaviour of a selected aspect of an industrial pro-
nace volume contributes to smelting. cess, especially one that requires harsh conditions, is
24 H. Y. SOHN
often investigated in a smaller scale at room tempera-
ture using model materials, typically water, air and/or
kerosene. Sometimes, low melting metals are used in
the physical models. Such a cold model is especially
useful for investigating high-temperature metallurgical
systems. The observations in such a model system have
traditionally been applied to the real process through
similarity analysis by the use appropriate dimension-
less groups such as the Reynolds number, the Froude
number, and the Euler (or Newton) number. More
recently, they are increasingly used as a means to
validate a comprehensive mathematical model of
the real process. Such a model is more reliable for
design, scale-up and optimisation of an industrial
process.
It is worth noting here that a physical model for one
process may also lead to a development of a new pro-
cess in a completely different field. An example is the
development of the Sohnex Process for solvent extrac-
tion discussed in Section 4.6(C). This process was
invented by Sohn (1997) while performing a cold
model study of the QSL leadmaking reactor (Queneau
1989; Queneau and Siegmund 1996) by recognising
that the requirements for good contact between the
two liquid phases in QSL while keeping the countercur-
rent arrangement of the two liquid phases are identical
to the requirements in a continuous solvent extraction
process.
There are a large number of investigations of phys-
ical modelling reported in the literature. Here, only a
limited number of examples in various groups of met-
allurgical processes are listed:
. Flash smelting furnaces: Yasuda and Sohn (1995);
Sutalo et al. (1998a, 1998b).
. Peirce-Smith converters: Fabritius et al. (2001);
Chibwe et al. (2013, 2011).
. Steelmaking tundishes: Mazumdar et al. (1997);
Rogler et al. (2005); Zheng and Zhu (2006);
Solorio-Diaz et al. (2007); Braun et al. (2010); War-
zecha et al. (2010); Chattopadhyay et al. (2011);
Merder and Pieprzyca (2012); Cwudziński (2014).
. Top blowing: Meidani et al. (2004); Zhou et al.
(2014); Park et al. (2010); Dyussekenov et al.
(2011); Chang and Sohn (2012).
. Continuous casting: Torres-Alonso et al. (2010);
Timmel et al. (2015).
. Ladle metallurgy: Sheng and Irons (1995); Guo and
Irons (2000); Pan and Björkman (2002); Xu et al.
(2010); Patil et al. (2010); Li et al. (2015); Liu et al.
(2017).
. Solid injection into liquid bath: Yamanoglu et al.
(1999); Park et al. (2010); Dyussekenov et al.
(2011); Chang and Sohn (2012).
. Emulsion formation: Zaidi and Sohn (1995); Lee
and Sohn (1996); Khajavi and Barati (2010).
. Bottom-gas-injected solvent extraction process, dis-
cussed above in Section 4.6(C): Iyer and Sohn
(1994); Sohn and Doungdeethaveeratana (1998).
Concluding remarks
The principles and techniques involved in formulating
mathematical models and how they are useful in the
design, analysis and optimisation of metallurgical pro-
cesses have been discussed. It is noted that a reliable
model of a process should be based on first principles
and contain carefully studied and understood com-
ponent steps. The reader is also encouraged to carefully
examine the correctness of assumptions made in the
formulation of a mathematical model in order to
avoid an indiscriminate and erroneous application of
a model. The use of physical modelling to understand
certain aspects of highly complex processes associated
with harsh conditions has also been discussed. It is
pointed out that the interpretation and utilisation of
the results from physical models is significantly
improved when they are combined with suitable math-
ematical models. Examples of developing new pro-
cesses based on a first-principle mathematical model
or a physical model have also been presented. Finally,
it is emphasised that reliable results can only be
obtained by judicious judgment, careful examination
of input parameters and assumptions, and laboratory,
pilot-plant or plant operating data.
Disclosure statement
No potential conflict of interest was reported by the author.
ORCID
Hong Yong Sohn http://orcid.org/0000-0002-6710-9508
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