Ind. Eng. Chem. Res.

2002, 41, 3797-3805

3797

Metallurgical Process DesignsA Tribute to Douglas Conceptual

Design Approach
Andreas A. Linninger*
Laboratory for Product and Process Design, Department of Chemical Engineering,
University of Illinois at Chicago, Chicago, Illinois 60607

This case study illuminates a practical design problem for cleaner metallurgical manufacturing.
The task consists of assessing the feasibility of a novel low-waste process capable of eliminating
unwanted, hazardous waste streams in stainless steel production. The novel flowsheet evolves
gradually as prescribed by the decision hierarchy of Douglas (Douglas, J. M. AIChE J. 1985,
31, 353-362). Successively refined economic potential estimators discriminate inferior options
and discard process configurations with marginal economic performance early in the design cycle.
The complex liquid metal reaction network is optimized via a multiphase total Gibbs free energy
model. A bilevel mathematical program for the simultaneous optimization of economic
performance at equilibrium within specified operational bounds is presented. The article uses
the case study to elucidate methodological aspects in systematic decision making for metallurgical
process synthesis. Examples for the beneficial use of mathematical modeling and nonlinear
programming within a systematic design framework for a novel metallurgical process are offered.
Introduction
In process engineering, creative R&D efforts generate
a continuous stream of new potentially marketable
process ideas. Only a few inventions promise sufficiently
large economic incentives to justify full-scale process
development. It is evident that assessing the feasibility
of many new process concepts is a crucial activity for
innovative engineering businesses. To address this vital
design challenge, Douglas developed a hierarchical
process synthesis methodology for expeditious and
systematic flowsheet generation.1-2 Although perfected
for continuous petrochemical processes, this work confirms the merit of Douglas conceptual design procedure
for a batch metallurgical synthesis task. Its background
is introduced next.
Conventional stainless steel manufacturing leads to
unavoidable waste streams containing heavy metal
oxides (see Figure 1). In todays practice, these slags are
still deposited as waste in landfills.3-4 Slag dumping is
expensive and/or restricted when it contains certain
heavy metals. From the environmental and economic
points of view, it would be desirable to eliminate these
wastes, thus avoiding the need for their disposal. One
alternative to waste dumping consists of removal of
hazardous contaminants from the slag. After cleaning
and proper adjustment of their compositions, treated
slags can even serve as a precursor to a commercial
construction material. Hence, a new low-waste process, whose real identity is deliberately concealed for
confidentiality reasons, should address the following
goals: removal of toxic metallic species from the slag;
transformation of slag into a building material, thus
eliminating the need for landfill; and recovery of valuable metals for recycling to the stainless steel process.
In this article, we evolve an entirely new metallurgical
process and its corresponding flowsheet and assess its
economic performance using a modified version of
Douglas approach. Sections 1 and 2 investigate funda* To whom correspondence should be addressed. Tel.: (312)
996-2581. Fax: (312) 996-0808. E-mail: linninge@uic.edu.

Figure 1. Material streams in conventional stainless steel

manufacturing
Table 1. Stages of Hierarchical Decision Making for
Process Design (Douglas1)
name

design activities

level 1 batch vs
continuous
level 2
level 3
level 4
level 5
level 6

plant capacity, raw material flows, and

product specifications; principal reaction
routes and process options
input-output process streams, their phases and
composition
EP ) net balance of material values
recycle
reaction-separation system: reaction
structure
and phase equilibrium, Gibbs free energy
minimization f optimal material charge
detailed
separations design: recycle streams, gas
separations
cleaning for solid removal and treatment
of air pollutants
heat
energy and power integration of entire
integration
manufacturing site, pinch analysis
process
open process options, alternatives and
alternatives
variations, detailed kinetics and
transport limitations

mental process options and preliminary information.

The complex metallurgical reaction network is optimized using a thermostatic approach in section 3. We
demonstrate the formulation of the equilibrium problem
and selection of optimal key design variables via a
bilevel mathematical program that ensures optimal
economic, thermodynamic, and operational targets. Section 4 outlines the completion of the conceptual design
of the new process. The article closes by drawing
conclusions from this work for metallurgical process
design.
Level 1. Preliminary Information
Table 1 depicts Douglas decision hierarchy adopted
for this case study. The first phase concerns the gather-

10.1021/ie0107901 CCC: $22.00 2002 American Chemical Society

Published on Web 03/23/2002

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Ind. Eng. Chem. Res., Vol. 41, No. 16, 2002

Figure 2. Conceptual objectives of a low-waste process.

ing of preliminary information on the primary chemical

reaction routes and available process options. The
reaction chemistry of liquid metal mixtures has several
distinctive features, including (i) large numbers of
reaction pathways between reduction and oxidation of
metallic species and their oxides (ii) and highly nonideal
phase behavior. Strong repulsive forces between liquid
mixtures of metals and their oxides lead to almost
perfect separation between the alloy and the ionic phase,
i.e., steel and slag. Proper slag conditioning for low
viscosity and density furthers the separability between
metals and slags.5 This clean phase separation is
essential in steel manufacturing routes in which deliberate formation of an oxide phase helps remove unavoidable impurities from the high-quality steel product.
The natural separation between metal and slag also
benefits our new process technology.
A typical conventional stainless steel plant produces
800 000 tons of steel per year. This plant also discharges
200 000-250 000 tons of slags and dusts per year (see
Figure 1). The formation of slags in the stainless process
itself cannot be circumvented because of the high quality
demand on stainless steels. A new secondary process
should tackle the need for landfill of waste loads for
economic and ecological reasons, as depicted in Figure
2. Hence, the main objective of the new process aims at
eliminating heavy-metal-contaminated slags from the
life cycle of stainless steels by their transformation into
a useful building material. Demanding an available
operability of approximately 6000 h/year, we arrive at
an hourly production rate above 40 tons/h. This rather
small expected capacity puts the new process in the
batch category. We will therefore consider a single plant
similar in size and operation to a small electric arc
furnace used in mini-mills.6
The physical properties of slags impede selective
physical separation of unwanted oxides by extraction.
Slags build strong networks of large polymerized ions,
predominantly silicate ions, as well as corresponding
cations and anions from manganese oxide, iron oxide,
manganese, and phosphorus. Because of the strong
linkage of the slag matrix, extraction or other physical
purification of the heavy metal oxides is impractical.
This peculiarity of metallurgical processes impacts the
separation process design in the later phases. It will lead
us to designing a reactor-separator for the desired
chemical reactions with simultaneous phase separation
between metal bath and slag.
A promising process option displaces unwanted oxides
via chemical reactions. A reduction reaction exchanges
the unwanted metal oxide complex (MxOy) with the
oxide of a suitable reduction agent (RzOy) as specified

Figure 3. Schematic Richardson diagram showing oxidation

potentials of important metals and their oxides.

in eq 1. Because of the phase separation between the

liquid metal and its oxide, enclosures are used to
distinguish between the metallic [ ] and oxidic ( ) phases.

(MxOy) + z[R] S x[M] + (RzOy)

(1)

where M represents the metals Fe, Mn, Si, Al, Ti, V, ...;
R represents a reduction agent, ...; and x, y, and z are
stoichiometric coefficients.
The reduction agent R is typically a metal of lower
oxygen potential than metal M. Typical key metals
involved in most metallurgical processes include iron
(Fe), silicon (Si), manganese (Mn), and aluminum (Al).
In addition, we often find precious metals such as Ti,
Ni, V, and Cr. Their corresponding oxides form highly
nonideal liquid solutions, e.g., Al2O3, SiO2, FeO, V2O5,
etc. The choices for suitable reaction agents R for a given
metal M can be studied with the help of the Richardson
diagram.3 It is depicted schematically in Figure 3 and
explains the stability of metals and their oxides as a
function of temperature. Metals with low oxidation
potentials can reduce oxides located higher in the
Richardson diagram. Lower oxidation potentials indicate more stable oxides. Hence, silicon can reduce the
oxides of iron. Aluminum (Al) can, in turn, reduce silicon
oxide. The strongest reduction agents are calcium (Ca)
and magnesium (Mg).
The preliminary analysis of the oxidation potentials
points toward an opportunity for hazardous oxide
elimination by chemical reactions of the type given in
eq 1. In addition, the reduction reaction will release the
corresponding elemental metal trapped in the harmful
oxides. In effect, this reaction route also recycles valuable metallic alloys that would otherwise end up wasted
in landfills. A critical advantage of this route further
lies in the inexpensive and potentially total separation
between the slag and the recycled metals, i.e., treated

Ind. Eng. Chem. Res., Vol. 41, No. 16, 2002 3799

Figure 4. Input-output structure of the low-waste process.

Table 2. Partial List of Cost Basis for a Low-Waste
Process
group
product
benefits
reduction
agents
additives
electricity

stream name
slag benefit
recovered iron
recovered Ni
carbon
metal1
metal2
lime
dolomite
quartz
energy cost
energy efficiency

stream
label

unit price
($/ton)

S1
P2
P2
R1
R2
R3
A1
A2
A3

60
115
8.000
100
540
1540
60
60
15
$4/MBU
) 0.8

waste stream and raw material recycle. Hence, we shall

pursue the process design task for the low-waste process
based on the replacement reactions given above.
Level 2. The Input-Output Analysis
The central decisions in the input-output (I/O) analysis aim at identification of all chemical compounds and
their categorization into input and output streams. The
principal input to the low-waste process is the primary
waste slag from steel manufacturing, S1 (see Figure
4). The process requires a metallic phase to start each
batch (M1) to allow for a sufficiently large phase
exchange area. The desired chemical reactions are
engaged by adding a suitable reduction agent R. Additives (A) are needed to induce the desired phase separation between slag and metals and to meet the desired
product compositions. When done properly, slag and
metallic phase will perfectly desegregate already in the
reactor-separator furnace without the need for additional separator units. Hence, the new low-waste
furnace will have two product streams: chemically
altered slag (P1) and recovered metals (P2). The principal
product leaves the process as clean slag (P1). The
byproduct gathers the recycled metals (P2). An off-gas
stream (O) collects the gaseous byproducts composed
predominately of the oxides of carbon and hydrogen,
e.g., CO, CO2, and H2O. Off-gas rich in CO or H2 is
highly reactive, offering the possibility of recycle to the
reactor. Alternatively, it could be purged. In the absence
of quantitative criteria to justify either choice now, we
opt for the process option without gas recycle. The
recycle configuration of reactive synthesis gas rich in
CO and H2 is recorded as a possible process alternative.
Economics of the I/O Structure. Douglas recommends repeated estimation of the economic potential
(EP) for the novel process. This first EP estimate
accounts for product value minus raw material cost, as
raw materials typically make up 35-80% of the process
manufacturing cost.2 Conducting this first input-output
analysis using cost data for the processing streams given
in Table 2, it becomes clear that all process alternatives
based on pure elemental reduction agents such as
precious metals (R2 and R3) are not economically viable.

This conclusion can be explained by the high cost of such

agents compared to the rather inexpensive products.
This early result of the I/O analysis triggered an
obligatory search for alternative, cheaper reduction
agents!
The need for better reduction agents resulting from
the I/O analysis points back to the Richardson diagram
introduced in Figure 3. It also displays the oxidation
potential of carbon, shown as a straight line with
negative slope representing the equilibrium of elemental
carbon and its oxide CO according to the equilibrium
reaction

[C] + 2O2 S 2CO

(2)

For direct reduction with carbon, a strong increase in

reactive strength can be observed at high temperatures.
At temperatures above 1600 C, carbon reacts with the
undesired heavy metal oxides identified by a gray band
in Figure 3. Hence, carbon could serve as an inexpensive
reactant capable of reducing even very stable oxides.
We conclude that direct reduction of undesired hazardous oxides with carbon is feasible above 1600 C. As a
consequence, the candidate list of reaction agents was
augmented with carbon sources such as coal or coke,
leading to a redesigned input-output structure. Reevaluating the EP for carbon-based chemistry exposes
strong economic incentives, thus allowing the advancement of the process into the next stage.
Level 3. The Recycle StructuresThe Reactor
Separator Furnace
The recycle structure analysis investigates the feasibility of chemical reactions and examines the reaction
mechanisms in detail. It also determines the number
and operating ranges of the required reactors, as well
as the need for internal recycle streams and subsequent
separations. For the low-waste process, a reaction
temperature high enough for effective heavy metal
reduction, but below the melting temperature of reactor
linings, can be established. A suitable operation window
opens between 1600 and 1900 C, with reduction reactions taking place in the liquid phase. These considerations lead to a single lined furnace-type reactor. This
furnace also separates the oxides (P1) from the recyclable alloys (P2). The key decisions for controlling both
the optimal reaction and phase separation are tied to
the choice of reactants. An overview of recycle structure
decisions specific to metallurgical processes is presented
in Table 3. Hence, the following key questions need to
be addressed for the reactor-separator design: (1) What
is the ideal mixture of reduction agents and additives
capable of triggering the desired reactions? (2) Which
charge mixture ensures phase separation within the
reactor-separator, as product purification via peripheral physical separators is impractical?
The clean phase separation of slag and metal that can
be achieved in liquid metal reactors avoids the need for
further product purification steps. The off-gases, however, are often loaded with dusts. Proper gas cleaning
is mandated for environmental reasons.6 Hence, the
recycle structure of the low-waste process foresees a gas
cleaning system with dust recycle. Two possible recycle
structures are depicted in Figure 5.
Unfortunately, there are no reliable heuristics to
answer the convoluted recycle structure questions for
new metallurgical processes.7-8 Hence, we shall develop

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Ind. Eng. Chem. Res., Vol. 41, No. 16, 2002

Table 3. Decision Hierarchy and Guidelines for Metallurgical Process Design

size
phases of product
product delivery
product quality improvement
necessary byproducts

raw materials
metal sources
reduction agents
additives

oxidation potentials
number and operation
of reactors
recycle streams
raw materials

Level 1. Preliminary Information

batch or continuous tapping
solid: reduction by roasting process (e.g. MIDREX), reduction furnace cascade
liquid: blast furnace, coal gasification (COREX), electric arc process, plasma furnace
gas: vapor decomposition, precipitation after evaporation
delivered in solid form (roast sinter), as alloy (solid, liquid) or oxide (slag, ceramic)
secondary metallurgy (yes/no), deploy sequence of reactors
off-gas? when reactions produce CO, CO2, H2, H2O
slag? removal of impurities
dusts? unavoidable solid elutriation when using powdered charges/large amount of coal
wastewater? follows from the need to scrub NOx, SOx, or halogenated compounds
natural ores, scrap (recycled metals), recycled dust
gaseous: carbon monoxide, hydrogen (synthesis gas)
solid: carbon (coal, coke, anthracite), metallic (Al, Si, Mn)
CaO (dolomite, lime), Al/Al2O3 (bauxite), quartz (SiO2)
slags (conditioning of products)
Level 2. Input-Output Structure Decisions
sequence of oxides to reduce, sequence of metals to refine
Is a reactor cascade needed (e.g., roasting)?
reduction in the liquid phase (indirect with CO/H2; direct with elemental carbon, coal)
Is refinement of carbon or impurities needed (e.g., desulfurization, de-hosphorization)?
Compare to product specs
Recycle or purge metallic charge (sump)?
Should synthesis gas be recycled? If CO/H2 > 90%; otherwise, consider CO2 removal
Should postcombustion of off-gas be used? If CO/H2 content is too low for reduction
Should oxygen supply be purified (air vs pure O2)? Function of reactor temperature
Can air/gas supply to burners be preheated? Note as process optimization option
Can solid charge (ore, coal, metals,...) be preheated?

Level 3. Recycle Structure Decisions

Is (partial) solid-phase reduction needed? Make use of recycled/reused off-gas stream
Use operating conditions of a cascade? Function of the equilibrium concentrations
Phase separation in liquid reaction? Which additives are necessary to ascertain the desired phase split/desired product purity?
Do Gibbs free energy analysis
Is solid recycle of dust (cyclone) needed?
What are the energy requirements for the reactor?
heating: gas burners, solid coal dust burners, off-gas burners, recycled off-gas (postcombustion)
cooling: cooling panels in the freeboard, if the off-gas temperature is excessive for off-gas duct
Which reactant has the highest impact on economic potential? Can it be replaced?
Level 4. Separation Design
Is product quality adjustment necessary? Do secondary metallurgy, e.g., laddle furnace
Is solid gas cyclon needed? Economic reasons if 5-10% of solid streams are leaving
Does the off-gas need chemical cleanup of gaseous contaminants (NOx, SOx, halogens)?
Use acid/basic wash solution in scrubber
Particulate removal? Use bag filter or E-filter
Remove fine dust alongside air pollutants? Consider aerosol-based cleaning process, e.g., AIRFINE
Are emissions clean? Send to flare
Can off-gas be reused for heating purposes? Send to gas burners after filtration

Figure 5. Alternative recycle structures for the low-waste process.

a quantitative mathematical framework to conduct the

recycle structure analysis of metallurgical processes,

relying on readily available computers and mathematical software. Subsection 3.1 discusses equilibrium models suitable for metallurgical reactor-separator design.
The economics that can be achieved with optimal
material charges are analyzed in subsection 3.2.
3.1. Equilibrium Thermodynamics of Metallurgical Reaction Networks. A challenge in metallurgical reaction networks rests in the large number of
possible chemical reaction pathways coupled to the
nonideal multiphase solution behavior. The formation
and disappearance of crystalline phases compound the
difficulty of the problem. An important conclusion for
metallurgical reaction network design is the coupling
of equilibrium reaction pathways and the phase stability
problem.9 The law of mass action relies on equilibrium
constants. Hence, it requires explicit enumeration of all
prevailing reactions and stable phases, a piece of
knowledge typically not available in the conceptual
design phase.10 A far more robust model suitable for
conceptual process design can be derived by means of
the total Gibbs free energy of a system.
Reactive phase equilibrium using Gibbs free energy
minimization can resolve problems encountered with

Ind. Eng. Chem. Res., Vol. 41, No. 16, 2002 3801

the law of mass action. It is an exercise in applied

thermodynamics to prove that the mass action law
expresses but a special case of the optimality conditions
for G minimization assuming known reaction pathways and stable phases.10 However, reaction models
based on equilibrium constants offer no criteria for
checking the validity of the underlying assumptions. In
contrast to the law of mass action, minimization of the
total Gibbs free energy requires no a-priori wisdom of
the reaction pathways or of the distribution of species
into the oxide and metallic phases, and it can also
accommodate criteria for phase stability.11-12
The compact Gibbs free energy formulation entitled
problem A in 3-5 represents equilibrium thermodynamics for a wide range of the process parameters. Its
only limitation lies in species or atoms unaccounted for
in the formulation (Ic, Ip) and the inherited shortcomings
of the solution models deployed for each phase (aki ). In
particular, the equilibrium composition of the product
streams (nki ) can be computed by solving problem A for
any specification of the input streams, e.g., slag, metal
charge, reduction agents, and additives (bj). Once again,
we follow Douglas arguments that economics dictate the
best combination of charge materials, as discussed in
the next subsection.
Problem A

min G )
k

ni

nki (g0i + RT ln aki )

nki ki ) kI

kI iI
iI

(3)

kI iI

) bj j ) 1, ..., NE

(4)

nki g 0

(5)

ckij

nki

Gibbs free energy minimizationsthe subordinate

objectivesensures chemical equilibrium among the
product streams, i.e., metallic bath, slag, and off-gas.
The activities for the complex solutions rely on the
experimental data fitted to models of the regular solution theory and atom interaction parameters.4,15-17 A
detailed discussion of the solution thermodynamics of
metallic solutions is beyond the scope of this article but
can be found in the Appendix and elsewhere.18
Hence, G minimization rigorously captures all possible reactions among all compounds and the equilibrium distribution of species into the multiple nonideal
phases, i.e., liquid metal, liquid oxides, gas, and pure
precipitated solids. The constraints safeguard the product specifications and/or desired operational limitations.
In the low-waste process, they are needed to enforce the
exact target composition of the desired building material
and proper slag basicity, as well as to delineate lower
and upper bounds for the furnace temperatures. Additional constraints accommodate complementary operational requirements such as prescribed ratios among
raw material blends; addition of flux to ensure low
viscosity; and density of the slag and safety related
constraints, e.g., avoidance of explosions triggered by
vigorous reactions.
Problem B

max EP ) vbmS1 +
nki ,fki

vifki - vecQ
vinki - kR

iI

kP iIc

s.t.

3.2. Economics of the Reactor-Separator Furnace. The reactive equilibrium of the reactor-separator
can be controlled by different choices of reactants
appearing on the right-hand side of the constraints in
eq 4. It was established above that the costs of reduction
agents and additives impact the overall cost most
significantly. Hence, the analysis of the recycle structure
EP entails sensitivity studies for different charge policies because of the dominance of raw material cost. In
principle, the sensitivity functions can be obtained by
repeated evaluations of problem A. However, the large
number of different types of reactants, the complex
coupling between reactions, and the possibility of introducing unwanted phases call for a more efficient
mathematical procedure.
Fortunately, mathematical programming embedded
within the decision framework offers yet another elegant
modeling opportunity. Problem B, given in 6-10, expresses the maximum EP that can be attained for any
equilibrium reactor-separator. It constitutes a bilevel
nonlinear optimization problem.13,14 The economic potential, its principal objective, accounts for (i) benefits
for avoiding slag deposition at landfill, S1, and (ii) the
recovery value of the recycled metals (P2) and the value
of the cement byproduct (P1). The EP diminishes with
the cost for (iii) reduction agents and additives and (iv)
energy. The program can choose the optimal feed blend
of reduction agents and additives (fki ) to give maximum
economic performance for the desired product specification. In addition, the reaction temperature (T) and
pressure (P) can be treated as either open design
variables or as adjustable parameters.

s.t.

min

equilibrium
amounts

ckij nki ) bj

kI iI
p

(6)

G(nki ,P,T)
j ) 1, ..., NE

(7)
(8)

(nki ) e 0

(9)

(nki ) e 0

(10)

Solution Approach. The bilevel problem B is a

highly nonlinear mathematical program that cannot be
solved directly. It is transformed into a single-level
problem by replacing the thermodynamic equilibrium
subproblem with its analytical optimality conditions.19
The introduction of appropriate Kuhn-Tucker (KT)
multipliers for the second-stage objective (i.e., Gibbs free
energy minimization) circumvents the double optimization. The resulting single-level nonlinear program,
entitled problem C in 11-15, augmented with the
Lagrangian multipliers j can be solved numerically
with commercial optimization software.
Problem C

max EP ) vbmS1 +

nki ,fki ,j

vinki - vifki - vecQ

kPiI
kRiI
c

ckij ) 0
iI kI

s.t. (g0i + RT ln aki ) - j

ckij nki ) bj

kI iI
p

(11)

(12)

j ) 1, ..., NE

(13)

(nki ) e 0

(14)

(nki ) e 0

(15)

3.3. Results of the Optimal Reaction-Separation

Network. The bilevel optimization constitutes a com-

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Ind. Eng. Chem. Res., Vol. 41, No. 16, 2002

Figure 6. Composition chart for optimal charge (the legend is

kept schematic for proprietary reasons).

Figure 7. Cost distribution for optimal charge.

pact mathematical model for the process performance

as a function of key design variables, i.e., different
material charges, temperatures, and pressures. An
analysis of the solutions obtained by the mathematical
program rendered the optimal material charges for two
distinct operational modes: (i) carbon-based reduction
and (ii) metal-based reduction.
Figure 6 shows the composition chart for optimal
carbon-based process. It illustrates the fate of each
species in terms of its amount normalized to 1 ton of
reference slag input (S1). With a suitable amount of
metallic charge M1 and a small quantity of reduction
agent R1, 900 kg of product P1 can be attained in
accordance with the specifications. The main product
P1 is essentially a cement with a SiO2-Al2O3-CaOMgO matrix. The byproduct P2 amounts to approximately 150 kg/ton containing the recovered heavy
metals. The expected off-gas is comparably small. The
additives lime and dolomite are necessary to meet the
basicity requirements. It should be noted that the
specifications for the building material could not be met
with the original set of additives. Hence, additional
resource streams supplying the needed compounds were
incorporated into the process input-output list. Figure
7 breaks down the cost contributions corresponding to
raw material and product values. The true value of the
economic potential cost was camouflaged by the use of
virtual monetary units, rather than dollars per ton, for
proprietary reasons.
The computations also revealed that liquid iron oxide
(FeO) had to be eliminated from the slag prior to the
chemical removal of unwanted heavy metal oxides. This
effort requires more reduction agent than anticipated

Figure 8. Economic potential for different reactor temperatures.

for heavy metal reactions only. The reason rests in the

higher oxygen potential of FeO as seen in the Richardson diagram (see Figure 3).
Because carbon is the cheapest reduction agent, pure
economics would dictate reduction with carbon only.
Reduction agents such as Ca, Mg, Si, and Al are chosen
only to meet the product quality constraints because of
their higher costs. In the final process design, these
strong reaction agents might be needed to expedite
reaction kinetics. Another avenue toward satisfying the
product specifications lies in mixing in more additives.
In each of the computations, process economics prescribe
the minimal amount of additives, as their addition costs
money.
Influence of Reaction Temperature. Higher reaction temperatures increase the reduction potential, thus
favoring the replacement of unwanted oxides. On the
other hand, higher temperatures diminish the lifetime
of the furnace lining, thus inflating the capital cost.
Figure 8 depicts the cost performance resulting from
these conflicting influences and points toward an effective reaction temperature range. Even though it is
tempting to read the optimum reaction temperature
from the graph, this would be premature. The results
so far are rigorous in the mathematical sense, but they
have to be considered approximate by virtue of the
simplified modeling assumptions.
The two-level problem formulation introduced in
problems B and C render optimum results by a simultaneous consideration of process economics, equilibrium
reactions, and constraints imposed on the desired
product. The compact problem representation permits
sensitivity analysis for different scenarios with little
extra effort. A typical result is shown in Figure 9, which
illustrates the minimum carbon requirement for maximum profit at different temperatures. The simple equilibrium model alone would require a tedious trial-anderror procedure. In light of the innumerable possibilities
for varying the operation of the reaction network and
design constraints, techniques based on simple graphical heuristics, spreadsheets, or hand calculations appear
completely inadequate for the task.
4. Finalizing the Conceptual Process Design
4.1. Level 4. The Detailed Separation Structure.
A particular characteristic of metallurgical processes
stems from the impracticality of physical product purification, as explained in section 2 of this paper. Hence,
the principal mode of attaining the desired product
specification employs chemical reactions. In case the

Ind. Eng. Chem. Res., Vol. 41, No. 16, 2002 3803

Figure 9. Sensitivity of carbon requirement to temperature.

clearly beyond the scope of this paper. The interested

reader is referred to work in the open literature.20,21
Level 6 investigates process alternatives such as the
process alternative with gas recycle. The detailed flowsheet and its refined economics gradually emerge.
Further detailed results have to be omitted for proprietary reasons. The knowledge of the extent of economic
incentive for this enterprise provides valuable insights
into decisions and planning for further investment. The
swiftness and low engineering effort required to conduct
such a feasibility study underscore the strength of
Douglas systematic approach for process synthesis.
The preliminary results rooted in equilibrium thermodynamics warrant the advancement of the process
to the pilot-plant stage. A crucial point in the subsequent phases will concern reaction kinetics and transport limitations. This ongoing research must involve
further experimental trials alongside refined dynamic
process modeling.
Conclusions and Significance

Figure 10. Separation structure of the low-waste process.

principal reactor-separator does not yet satisfy the final

purity specifications, further adjustments can be realized via secondary reaction metallurgy. Examples for
product quality correction in subsequent metallurgical
processes include desulfurization and dephosphorization
in laddle furnaces, as well as high-quality application
in vacuum and plasma furnaces. In the low-waste
process, however, the product specifications can be met
in a single reactor-separator, rendering further separators unnecessary.
Solid particulates elutriated from the furnace with the
off-gas stream constitute an exception. Their treatment
is dictated by environmental legislation. Because the
amount of solid lost does not significantly affect the
economics of this plant, it will not be discussed further
in this article. Options for the selection of a gas cleaning
system, which slightly inflates the capital cost of the
new process technology, are given in Table 3. Table 3
also provides guidelines for decision making specific to
metallurgical process design. As a consequence, the
separation structure analysis (level 4) adds a gas
cleaning system and contributes estimates for the
required capital charges (see Figure 10).
4.2. Level 5 and Higher. For the low-waste process,
energy integration (level 5) has a minor importance
because of the marginal contribution of the energy cost,
as can be inferred from Figure 7. The low demand for
energy is due to the almost-balanced overall reaction
enthalpy of the metallurgical reaction network and the
introduction of the slag (S1) and metal (M1) in the liquid
state. In some cases, the chemical energy of the off-gas
(O) needs to be exploited to improve the overall cost
efficiency of the process. In that situation, energy
integration couples the process to the energy demands
of the entire manufacturing site. Total power and energy
integration of the entire manufacturing process is

Classical metallurgical process design tends to emphasize the technical feasibility of operations. Traditional design strategies rely on generalized metallurgical thermodynamic relations such as those described in
the Richardson3 or the Rist4,5 diagram. Design heuristics
based on the thermodynamics alone offer little insight
into the economics of a specific process. The costeffective design of reaction-separation networks was
shown to be a strong function of the material choice
charged to the process. A bilevel mathematical program
considering process economic, thermodynamic, and
operational constraints simultaneously addressed the
lack of design guidelines for such a complex reactionseparation problem. Thus, the economic performance of
the central reactor-separator furnace, its operating
parameters, and material charge were determined
optimally for an array of operational constraints. Difficulties in handling the multitude of unknown reaction
pathways in heterogeneous metallurgical reactionseparation networks were effectively overcome via a
total Gibbs free energy model embedded in the economic
master problem. The bilevel program presented here is
suitable for design problems involving large numbers
of economical and ecological targets. Its use in conjunction with a systematic metallurgical process design
framework is first reported here to the best of the
authors knowledge.
Systematic decision making combined with powerful
G minimization offers a fast and more accurate
conceptual design procedure. The approach presented
here challenges current industrial practice, which relies
on repeated performance calculations with flowsheet
simulators or custom-built spreadsheet modules. In that
mode, it is difficult to arrive at optimal charge mixtures
that also satisfy all quality constraints with a reasonable number of computations. The lack of adequate
models for standard unit operations of metallurgical
reactors further weakens that popular design routine.
The clear role of economics in driving the innovative
search for new process options is a key feature in
Douglas approach that is lacking in other design
philosophies. Although expert developers and engineers
have invented ingenious designs in the past, new
business constraints such as consideration of uncertain
raw material prices and shorter development cycles

3804

Ind. Eng. Chem. Res., Vol. 41, No. 16, 2002

favor systematic procedures complemented with mathematical models.

A case study confirmed the effectiveness of the
proposed decision framework for a novel low-waste
process. The gradual evolution of the entirely novel
metallurgical process route followed the hierarchical
design methodology developed by Douglas. The lack of
design heuristics for complex metallurgical reaction
networks was overcome via a simultaneous optimization
of economics and Gibbs free energy. The example also
demonstrates the validity of the fundamental decomposition principle proposed by Douglas for applications
in metallurgical processes.
Dedication
This article is dedicated to Professor James Douglas,
who shared fun and experience in process design with
so many engineers and whose textbook raised our senior
design courses from chaos to an exciting teaching and
learning experience.
Nomenclature

energy
Gibbs free energy of mixing, and RT ln i ) gexcess
i
is the excess Gibbs free energy of mixing.
The use of empirical data available in the literature
within a Gibbs free energy minimization requires the
thermodynamic relations in eqs A2-A4. The derivation
departs from a Taylor expansion of the activity coefficient around infinite dilution of a compound (Xi) in a
bulk solvent, typically iron. At constant temperature
and pressure, the expansion around the infinite-dilution
coefficients (0i ) accounts for the influence of other
species j on the activity coefficient of compound i (i.e.,
ln i/Xj). In a first-order approach, higher-order terms
O(X2) are neglected. Hence, eq A3 introduces the firstorder interaction coefficients ji. The coefficients ji
measure the impact of a solute j on the activity coeffient
of a solute i in an infinitely dilute solution in iron.
Typcially, components i and j are elemental metals
dissolved in a concentrated liquid iron mixture, e.g.,
liquid steel or pig iron. Values for the interaction
parameters can be found in the open literature.9,16,17

RT ln i ) RT ln 0i |T,P,X1f1 +
n

Roman Symbols
aki ) activity of compound i in phase k
bj ) atoms of type j entering with the feed streams
cki ) stoichiometric coefficient of atom j of compound i in
phase k
EP ) economic potential
fki ) feed of species i in stream k
g0i ) standard specific Gibbs free energy of compound i
mS1 ) mass of slag mixture S1
nki ) amount of compound i in phase k
NE ) number of atoms in the system
P ) reaction pressure
Q ) net energy requirement
T ) reaction temperature

RT

j)2

ln i
Xj

Xj + O(X2) (A2)
T,P,X1f1

Alternatively
n

ln i ) ln 0i +

jiXj + O(X2)

j)2

(A3)

where

ji ) RT

ln i
Xj

(A4)

T,P,X1f1

Greek Symbols
vi ) price of compound i
b ) benefit for avoiding landfill
ec ) energy price
ki ) chemical potential of compound i in phase k
j ) Lagrangian multiplier for atom balance constraint j
, ) vector function for operational and additional
constraints
Index Sets
R ) {M1, S1, A, R} ) index set of feed material stream
(input)
P ) {P1, P2} ) index set of products P1 and P2 (output)
Ic ) {Fe, FeO, ...} ) index set of species in the system
Ip ) index set of distinct phases in the system

Appendix. Excess Gibbs Free Energy

Nonideal solution effects in liquid metallic solutions
can be quantified via excess Gibbs free energy models.
The chemical potential of a compound in solution can
be written as follows

i(T) ) g0i (T) + RT ln ai ) g0i (T) + RT ln xi +

RT ln i (A1)
where g0i (T) is the Gibbs free energy of the pure species
solution
is the ideal
at standard pressure, RT ln xi ) gideal
i

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Received for review September 24, 2001

Revised manuscript received February 5, 2002
Accepted February 6, 2002
IE0107901