Chemical Engineering and Processing 48 (2009) 493–506

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Chemical Engineering and Processing:

Process Intensification
journal homepage: www.elsevier.com/locate/cep

Generic modelling, design and optimization of industrial phosphoric acid

production processes
Athanasios I. Papadopoulos a,∗ , Panos Seferlis a,b
a
Chemical and Process Engineering Research Institute (CPERI), Centre for Research and Technology Hellas (CERTH), P.O. Box 60361, 57001 Thermi-Thessaloniki, Greece
b
Department of Mechanical Engineering, Aristotle University of Thessaloniki, P.O. Box 484, 54124 Thessaloniki, Greece

a r t i c l e i n f o a b s t r a c t

Article history: In the present work we address the systematic and effective design of industrial scale phosphoric acid
Received 2 November 2007 production processes through the implementation of an efficient process modelling and optimization
Received in revised form 7 November 2007 strategy. A generic and systematic framework is employed that aims to facilitate the modelling and identi-
Accepted 15 June 2008
fication of highly performing phosphoric acid production schemes through exploration of interactions and
Available online 1 July 2008
synergies among the participating processing components. The framework allows the employed models
to be independent of the processes they are expected to emulate as it is developed through use of generic
Keywords:
process modules, thus facilitating design variability and flowsheet interconnectivity. The employed mod-
Phosphoric acid production
Process design
elling and optimization approach is implemented on an industrial phosphoric acid production process.
Process optimization Design options of increased performance are proposed for the industrial process while useful design
Phosphoric acid production process insights into the interactions of the process components are generated.
modelling © 2008 Elsevier B.V. All rights reserved.

1. Introduction and simplified population balances as well as reaction kinetic data.

Phosphoric acid is produced in industrial scale when a phos-
phorous containing mineral reacts with a mixture of sulphuric
and phosphoric acids. The main by-product of this reaction is the
formation of calcium sulphate (gypsum) crystals, which are sepa-
rated from phosphoric acid at the end of the process together with
other by-products formed during the reaction. The phosphoric acid
production process involves intense interactions among solid and
liquid components and is sensitive to a number of factors such as
mineral characteristics, reactant compositions and process temper-
ature conditions, to name a few. The main challenge involved in
the process is to produce an aqueous phosphoric acid solution of
the highest possible concentration and purity in order to facilitate
the downstream production of high valued phosphoric acid prod-
ucts. In industrial practice, the achievement of this goal is largely
based on both engineering and empirical knowledge of the process
behaviour, while a number of process modelling and design efforts
have been reported in published literature with the aim to improve
the understanding and efficiency of the existing processes.
A comprehensive multi-reactor mathematical model for the
production of phosphoric acid using the hemihydrate (HH) process
was first presented in Ref. [1]. The model takes into account material
∗ Corresponding author. Tel.: +30 2310498363; fax: +30 2310498130.
E-mail address: spapadopoulos@cperi.certh.gr (A.I. Papadopoulos).
The authors discuss the effect of the recycled acid to feed sulphuric
acid flowrate ratio on the supersaturation conditions in the reactor
as well as its influence to nucleation and crystal growth phenom-
ena. The model remains at a theoretical level as no comparisons are
made with industrial or experimental data. A model for a single-
stage dehydrate (DH) process is presented in Ref. [2] based on the
model proposed by Ref. [1]. The authors discuss the effect of certain
assumptions regarding crystal growth and nucleation on the model
behaviour and compare their results to experimental data obtained
from a lab-scale pilot reactor. An extensive work is presented in Ref.
[3] that covers a large number of scientific and engineering issues
addressed in phosphoric acid production. A modelling approach is
proposed for the phosphoric acid production process that involves
short-cut mass and heat balances as well as design equations for
the process unit operations, while empirical knowledge drawn from
industrial practice is also incorporated into the developed models
to a large extent. A model is developed in Ref. [4] for the simula-
tion of a five-CSTR industrial unit employing the dehydrate method.
The mathematical representation of the process is similar to that of
Ref. [1] but also involves heat balances. The authors discuss the
effect of design parameters, such as recycle ratio and heat gen-
eration, in process performance and propose optimum operating
conditions within a limited range of process parameter values. An
industrial hemihydrate process is studied in Ref. [5] followed by
hydration tanks to allow the transition to a dehydrate process. The
employed process model consists of material and heat balances and

0255-2701/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2008.06.011
494 A.I. Papadopoulos, P. Seferlis / Chemical Engineering and Processing 48 (2009) 493–506
investigates the effect of several design parameters such as reac-
tor temperature and recycle ratio in process operation. A model
of the single-stage dehydrate process is developed in Ref. [6] in an
Aspen Plus process simulator. The model consists of simple reaction
kinetic representations based on assumptions regarding the rock
dissolution and crystallization phenomena. The authors compare
their findings to industrial data using several key process design
criteria. They conclude that even a limited description of the phe-
nomena occurring during the phosphoric acid production process is
sufficient to provide valid insights into the process. A model for the
simulation of a three-CSTR pilot plant for the single-stage dehydrate
method is developed in Ref. [7]. The proposed model combines ele-
ments of the work of Refs. [1,2] and proposes simplifications in the
reaction kinetic models. The authors perform parametric studies of
a set of process parameters in order to find the optimum operating
conditions of the pilot plant.
The existing published work on phosphoric acid production
modelling reveals several common characteristics. All the pre-
sented models manage to capture major phenomena occurring
during the phosphoric acid production process to a sufficient
extent, regardless of the design detail level employed. However,
they fall short of providing design flexibility as they are explicitly
oriented towards the design case they are expected to emulate.
The sets of mathematical equations employed for the represen-
tation of the processing tasks are case-specific, hence requiring
the manual addition of terms in case that new design options (i.e.
streams, materials, processes, etc.) are considered in the performed
design calculations. The reported attempts to address design issues
in the existing phosphoric acid production processes mostly focus
on the investigation of the process behaviour caused by the varia-
tion of certain operating parameters. Although such investigations
are useful for the optimal fine-tuning of the process under consider-
ation, they lack generality of application as they are case dependant.
Furthermore, they are unable to identify targets of increased pro-
cess performance through efficient exploitation of the interactions
among the various processing tasks comprising the production sys-
tems at hand. This can only be achieved through the synthesis and
optimization of complex process configurations that simultane-
ously account for varying process operating conditions as well as
structurally diverse processing options.
A number of generic process synthesis approaches have been
reported in published literature that address the design of pro-
cesses involving reaction and separation tasks. One such approach
is the work of Ref. [8] that proposes a generic heat/mass exchange
module in order to effectively model any investigated process
regardless of the employed processing task. The module is utilized
in the generation of process superstructures, therefore capturing a
large number of interactions and synergies among the participating
reactive and separation components. The generated superstruc-
tures are then optimized based on a process performance criterion
using deterministic optimization technology in the form of mixed-
integer non-linear programming (MINLP). A generic framework for
the synthesis of reaction–separation processes has also been pro-
posed in Refs. [9,10]. It is based on rich and inclusive superstructures
targeting all possible novel as well as conventional design options
generated during the optimization search. The authors use the
reaction/mass exchange (RMX) unit concept in order to effectively
model the targeted processes regardless of process type, number
of processing components or design detail in the models of the
reaction or separation units utilized. The generated superstruc-
tures are optimized using stochastic optimization methods with
the aim to address an increasingly extensive design space and iden-
tify highly performing design options. Despite differences ranging
from design philosophy to solution quality issues, applications of
these approaches have shown that optimization through system-
atic identification of process interactions and synergies is required
in order to explore and identify design targets of optimum perfor-
mance.
In this context, we report on the application of a systematic
process synthesis and optimization strategy in the design of phos-
phoric acid production processes. This is realized through a generic
modelling and optimization framework that facilitates the sys-
tematic identification of optimally performing design options. The
employed framework utilizes generic process modules, based on
the work of Refs. [9,10], that are sufficiently flexible to allow pro-
cessing schemes of varying structural and operating characteristics
to be modelled as multi-phase systems. Furthermore, it is able to
transparently capture the process phenomena involved in phos-
phoric acid production regardless of the modelled application.
The employed framework allows a large number of alternative
processing options to be screened using stochastic optimization
technology, based on a specified performance index representing
the targeted improvements in the process performance. An indus-
trial phosphoric acid production process is used as a test-platform
for the implementation of the employed framework with the aim
to exemplify features of the employed design strategy as well as to
generate diverse design insights for a real-life design problem.
2. Design problem and solution strategy
2.1. Description of “wet” phosphoric acid production process
The main process used in industrial practice for phosphoric acid
production is the “wet method”, which includes single-stage and
re-crystallization processes. The single-stage processes consist of
a single reaction-crystallization step and the most common routes
for phosphoric acid production in this case are the dehydrate and
hemihydrate processes. Re-crystallization processes involve the
addition of dilute sulphuric acid at the gypsum separation stage and
are implemented as a combination of the dehydrate and hemihy-
drate processes. Using the wet method, phosphoric acid is produced
in reactors that facilitate the mixing and contact of phosphate rock
with an aqueous solution of sulphuric and phosphoric acid. The
phenomenon can be described by the following two-stage reaction:
Ca3 (PO4 )2 ·CaF2 + 6H3 PO4 → 4Ca(H2 PO4 )2 + 2HF (1)
Ca(H2 PO4 )2 + H2 SO4 + nH2 O → 2H3 PO4 + CaSO4 ·nH2 O (2)
where the gypsum product can be dehydrate (n = 2), hemihydrate
(n = 0.5) or anhydrite (n = 0). Based on the description presented
in Ref. [7], in the first stage hydrogen ions from recycled phos-
phoric acid attack the phosphate ore particles (represented by
fluorapatite) to form monocalcium phosphate (Ca(H2 PO4 )2 ). In
the second stage, the formed monocalcium phosphate reacts with
sulphuric acid to form phosphoric acid and insoluble calcium sul-
phate (gypsum). As the phosphate ore particles dissolve in the
reactor, supersaturation of calcium sulphate occurs, leading to gyp-
sum crystallization that involves phenomena such as nucleation
and crystal growth. The slurry produced from the reaction sec-
tion is lead to a filter where the solid calcium sulphate crystals are
mechanically separated from the produced liquid phosphoric acid.
In this context most pilot or industrial production arrangements
reported in literature as well as process sequences employed in
industry (reported in Ref. [3]) utilize a number of interconnected
reactors and a filtering process that usually allows to recycle part
of the produced acid back to the reactors.
The above description shows that the industrial phosphoric acid
production is realized through a process where the exploitation
of the interactions and trade-offs among the various processing
components is of paramount importance in order to obtain high
 A.I. Papadopoulos, P. Seferlis / Chemical Engineering and Processing 48 (2009) 493–506 495

yields of phosphoric acid. The conditions of dissolution of the phos- obtained optimum process flowsheet is based on design insights
phate rock are affected by the recycle rate of the product, which generated during the performed optimization search. The pro-
in turn has a significant effect on the development of the calcium posed framework allows further design iterations to be performed,
sulphate crystals. The number and size of the employed reaction hence capitalizing on the gained knowledge by incorporating it yet
vessels also affect the production yield as well as the raw material again in process design. The iterative procedure allows process fea-
losses because of the effect they have on the residence time of the tures lacking a positive design impact to be removed, while useful
phosphate rock particles in the reactors. The size and shape of the features could be further explored by addition of refined design
gypsum crystals as well as the amount of unreacted solid phase constraints and biases.
residuals affect the performance of the filtering process, which
influences the composition and flowrate of the streams recycled to
2.3. Process representation and modelling concept
the reactors. These are only few of the manifold interactions among
the participating process components, indicating the multidirec-
A key element in the proposed design framework is the use
tional propagation of the phenomena occurring in the production
of generic process modules for the representation of phospho-
of phosphoric acid. As a result, the entire range of effects caused
ric acid production processes as they are expected to facilitate
by such interactions should be taken into consideration during the
both the development of inclusive process models as well as the
design stages of phosphoric acid production processes. Any poten-
identification of optimum design options. This work employs a
tial design approach should allow the development of models that
generic-modular reaction/mass exchange unit, called RMX unit
are able to transparently capture the existing process interactions as
[9,10], for a flexible and compact synthesis representation of
well as provide venues for the emergence of decision paths leading
the phenomena taking place in the phosphoric acid production
to optimum design options.
processes. The unit follows the shadow compartment concept
developed for reactor network synthesis by Refs. [13,14]. It con-
2.2. Modelling and optimization framework
sists of compartments in each phase or state present in the system
under investigation and the streams entering the compartments
In the present work, we employ the modelling and optimiza-
exchange mass across a phase or diffusion boundary. Each compart-
tion framework shown in Fig. 1 in order to systematically design
ment receives inlet streams within its state and exchanges mass
phosphoric acid production processes of increased performance.
with the compartments in other states across the state bound-
A bi-level iterative strategy is utilized, targeting both the efficient
aries. The effluents from the compartments either leave the unit
development of a comprehensive process model as well as the
or are recycled within the reaction unit compartment. Fig. 2 shows
systematic exploitation of this model in order to develop highly
a schematic representation of the RMX unit. Phenomena such as
performing process schemes. The phosphoric acid process model
mass or heat exchange, kinetic equations, vapor–liquid–solid equi-
is developed using generic process modules as they provide func-
libria, etc. are modelled within the compartments of Fig. 2. The
tionalities that facilitate both the model development and process
mixers and splitters preceding and following the compartments-
optimization stage. The modules (described in the following sec-
modules, respectively, act as mathematical sinks and sources of
tions) are represented by a highly inclusive set of equations in
incoming and outgoing process streams, thus facilitating the inter-
order to realize the unit operations taking place in the phospho-
connectivity of the modules.
ric acid production flowsheet regardless of the process task they
Let SEM be the set of RMX units comprising a phosphoric acid
are set to represent. The processes, represented by the employed
production flowsheet. The following set of equations provide a
modules, are interconnected by an all-inclusive network of process
generic representation of the mass balance implementation on the
streams. Simulations provide the opportunity to evaluate the devel-
flowsheet:
oped model features based on available industrial/experimental
process data. Features resulting to poor model performance will
become the target for further improvement. Furthermore, features • Mass balances for mixers:
that might lead to insights deemed unnecessary for the scope of the
performed investigation could be excluded from the iterations that 
SEM

follow. The iterative procedure will continue until a desired match Fn·i−1,p,c = SFi,p,c + SFRi,j,p Fn·j,p,c (3)
between the model results and the industrial/experimental data is j=1
achieved.
• Mass balances for the RMX units:
After ascertaining the validity of the developed process model,
it is used as a process simulator within the employed optimiza-
tion framework. The process design and optimization philosophy ac,i,p Mc 
SEPH
Fn·i,p,c = Fn·i−1,p,c + Fn·i−1,p,cLR Xi + MTi,p,l,c (4)
utilized in this work is based on previous work presented in Refs. aLR McLR
c,i,p l=1
[11,12] addressing reaction–separation and separation process opti-
mization, respectively, by use of stochastic search methods. Each MTi,p,l,c = aci,p,l · f (phase change operation) (5)
randomly generated state, representing a certain phosphoric acid
process scheme, is simulated using the developed model and is then • Mass balances for splitters:
evaluated in terms of objective function value and constraint vio-
 
lation. Following appropriate decision making guidelines imposed 
SEM
by the utilized optimization algorithm, a vast number of process SPj,p,c = 1− SFRi,j,p Fn·j,p,c (6)
schemes are screened until the termination of the algorithm and the i=1
identification of the optimum process configuration is reached. The
topology of the process stream network, the addition or removal • Total mass flowrates:
of processing tasks and the stream flowrates distribution can be
employed, among other design parameters, as design variables for 
SECOMP
tot
optimization. As a result, the interactions and trade-offs among the Fn·(i−1)+k,p = Fn·i−1+k,p,c (7)
participating process components are thoroughly explored and the c=1
496 A.I. Papadopoulos, P. Seferlis / Chemical Engineering and Processing 48 (2009) 493–506

Fig. 1. Proposed modelling and optimization framework.

• Volumetric flowrates: Fig. 3 shows the use of the variables employed in Eqs. (3)–(10) in
a potential processes scheme. For an RMX unit i each compart-
 SFi,p,c
SECOMP

SEM tot
SFRi,j,p Fn·j,p ment in a given phase p of a set of phases SEPH features an inlet
Qn·i−1,p = + (8)
SF
i,p,c n·j,p stream Fni−1,p,c originating from the preceding mixer and an outlet
c=1 j=1 stream Fni,p,c arriving at the following splitter, all in the same phase
tot p, while n = 2 is the total number of set of streams (SEST) entering
Fn·i,p
Qn·i,p = (9) and leaving the unit. Each inlet and outlet stream carries a number
n·i,p of components c belonging to a set of components SECOMP. Each
• Components concentration: mixer in phase p can receive a side feed of flowrate SFi,p,c , while
each splitter in phase p can provide a side product SPi,p,c . SFRi,j,p
Fn·(i−1)+k,p,c denotes the split fraction of an outlet stream Fnj,p,c originating from
Cn·(i−1)+k,p,c = (10)
Qn·(i−1)+k,p a unit j of the available SEM and entering the current unit i. The
mass transfer between the compartments is realized through the
term MTi,p,l,c which represents the mass that is being exchanged
∀i, j ∈ SEM; p, l ∈ SEPH; k, n ∈ SEST; c ∈ SECOMP between the current phase p and a different phase l of SEPH. The

Fig. 2. Schematic representation of RMX unit concept.

 A.I. Papadopoulos, P. Seferlis / Chemical Engineering and Processing 48 (2009) 493–506
Fig. 3. Description of a generic process scheme using variables of Eqs. (3)–(10).
MTi,p,l,c term can be activated or deactivated using a switch aci,p,l
that also represents the mass transfer direction between the com-
partments. As shown in Eq. (5), MTi,p,l,c is a function of a mass
transfer operation that must be defined explicitly and can represent
vapor–liquid–solid equilibria, design equations or diffusional mass
transfer, etc. In case of reaction, Xi represents the degree of conver-
sion in unit i, while ac,i,p represents the stoichiometric coefficients of
components c with molecular weight Mc . LR is a superscript denot-
ing the limiting reactant. The total flowrates of the input and outlet
tot
streams are denoted by Fn·(i−1)+k,p , where k = 1, n. Finally, the vol-
umetric flowrates of the input and outlet streams are Qni−1,p , Qni,p ,
respectively, and Cn·(i−1)+k,p,c denotes the components concentra-
tion.
2.4. Functionality of employed representation approach
The existence of mass exchange between the compartments in
different phases can be established or removed. This allows reac-
tion and mass transfer phenomena to be disassociated between
compartments by setting aci,p,l = 0. In this case the RMX unit
reduces to a well-mixed reactor (Fig. 4a). With appropriate manip-
ulation of the reaction and mass transfer terms of Eq. (4) it is
possible to implement a variety of combinations between the
compartments, such as the simultaneous existence of a reac-
tive and a non-reactive unit, with mass transfer in between
(Fig. 4b) or two non-reactive units with mass transfer (Fig. 4c).
By appropriately handling the sign of aci,p,l (+ or −) it is possi-
ble to indicate the direction of the mass transfer between the
compartments.
The features of the reactive and mass transfer terms in Eq. (4)
allow the isolation of states which can lead to different levels of
design detail in modelling of a phosphoric acid production flow-
sheet. Such an example is given in Fig. 5, where a single phase
reactive unit can coexist in the same flowsheet with a two-phase
non-reactive unit. Another important feature of the employed pro-
cess representation is the high degree of interconnectivity that is
allowed among the units utilized for the representation of a flow-
sheet. All possible combinations of connectivity among the units
comprising a flowsheet are realizable. Fig. 6 shows a fraction of the
potential connections among the modules, which include recycle
Fig. 4. Existence of reactive and non-reactive units in single and two-phase systems: (a) single phase reactive unit; (b) two-phase reactive–non-reactive unit; (c) (b) two-phase
non-reactive unit.
497
Fig. 5. Existence of single and two-phase units in the same flowsheet.
and bypass streams, side feed and side product options. Recycles
or bypasses are also realizable between different phases, provided
that there is an additional unit that allows the implementation of a
phase change operation. The implementation of more connections
is possible in Fig. 6, but is not shown in order to maintain the figure
clarity.
3. Phenomena representation in phosphoric acid
production processes
As previously discussed, the two major operations utilized in
phosphoric acid production are reaction and filtration. During the
reaction stage, as the phosphate rock enters the reactors it is
attacked by sulphuric as well as recycled phosphoric acid and con-
verts to phosphoric acid. This phenomenon as well as the associated
assumptions have been thoroughly discussed by Ref. [7], hence we
adopt the set of design equations proposed by Ref. [7] in order
to mathematically describe the dissolution of the phosphate rock
particles. As the phosphate rock dissolves, the supersaturation of
calcium sulphate leads to the formation of nuclei that gradually
grow into fully formed gypsum crystals. We employ the design
equations proposed by Ref. [7] to model the calcium sulphate super-
saturation and crystal growth rate, while the number of produced
nuclei as well as the specific surface of the crystals are modelled
using the equations proposed by Ref. [3]. Part of the water utilized
in the phosphoric acid production process is evaporated in the reac-
tors. The evaporation is largely attributed to the heat produced from
the dilution of sulphuric acid in the reaction slurry. We employ the
empirical approach proposed by Ref. [3] to model the evaporation
of water in the reactors.
498 A.I. Papadopoulos, P. Seferlis / Chemical Engineering and Processing 48 (2009) 493–506
Fig. 6. Potential combinations of interconnected RMX units in a flowsheet.
In published literature the filter is often modelled using mass
balances complemented by assumptions regarding the filtering
efficiency. In this work we propose the use of filter modelling equa-
tions that incorporate physical characteristics of both the slurry and
the filter components. In phosphoric acid production, a filter type
commonly utilized is the rotating vacuum filter. The filtration pro-
cess is realized in several stages as the filter rotates. In the first few
stages the slurry is washed each time using liquid obtained from
the preceding stage, while in the last stages fresh water is used.
Once the solids have been adequately drained they are removed
either by water or mechanically. In this context, the design equa-
tions presented in Ref. [15] can be applied in each filtering stage to
model the filter operation.
4. Industrial case study
The employed modelling and optimization framework is illus-
trated through an extensive case study of industrial interest as
actual operating data of an existing single-stage dehydrate phos-
phoric acid production process, similar to the one described in Ref.
[3], are available. The aim of the case study is to demonstrate the
application of the presented framework in the design of phosphoric
acid production processes as well as to investigate design scenarios
of interest to industrial users. We first discuss the implementation
of the employed framework in the efficient mathematical repre-
sentation of the industrial process at hand and then we present
details of the optimization strategy utilized for the investigation of
different design cases.
Fig. 7. Multi-phase model of the industrial phosphoric acid production process.
4.1. Representation of the phosphoric acid production plant
The main processes of the employed phosphoric acid production
plant consist of two CSTR reactors followed by a filtering process.
Fig. 7 provides a comprehensive multi-phase representation of the
phosphoric acid production plant utilized in the performed case
study. The reactors are represented as two-phase systems consist-
ing of a reactive slurry and a vapor phase compartment, while
the filter consists of a non-reactive slurry and a solid phase com-
partment. Two recycle streams originating from the filter slurry
phase are led to the mixers prior to the reactors where the reac-
tants in the form of phosphate ore and sulphuric acid are also
added (SF1 and SF2). The mixer prior to the filter receives the
equivalent amount of water (SF3) required for the filtration oper-
ation, while the produced gypsum crystals are separated from the
slurry into a solid phase. It should be noted that for reactor 2
the reaction representing the phosphoric acid production is given
by Eqs. (1) and (2). In reactor 1 a different representation of the
employed reaction is utilized, based on the provided industrial
data:
CaOP2 O5 CaF2 + 2H2 SO4 + 6H2 O → 2CaSO4 ·2H2 O
+ 2H3 PO4 + 2HF (dehydrate) (11)
CaOP2 O5 CaF2 + 2H2 SO4 + 3H2 O → 2CaSO4 ·0.5H2 O
+ 2H3 PO4 + 2HF (hemihydrate) (12)
 A.I. Papadopoulos, P. Seferlis / Chemical Engineering and Processing 48 (2009) 493–506
Fig. 8. Implementation of vectors (a) SFRi,j,p and (b) aci,p,l in the process.
Filter modelling, as discussed in Section 3.6, can be represented by a
series of processing stages where the incoming gypsum is subjected
to different treatment conditions. Such conditions mainly involve
the gypsum washing solutions that result from filter intrinsic recy-
cle streams and lead to component concentration differentiation
in recycle streams 1 and 2 of Fig. 7. In our modelling approach it is
assumed that the filter is a single-stage process without consider-
ing the intrinsic recycle streams. The effect of these streams on the
concentration of recycle streams 1 and 2 is emulated by assuming
that the mass fraction of the components included in these streams
is fixed (to the industrial operating specifications provided by the
available data), while their flowrates may vary. It is further assumed
that the produced filtrate consists only of liquid phase components.
The connectivity between the units depicted in Fig. 7 is realized
through the SFRi,j,p vector used in Eqs. (3)–(10). For the flowsheet of
Fig. 7 this vector has the form shown in Fig. 8a. Approximately 50%
of the mass flow of the slurry-phase filter outlet stream is recycled
to reactor 1, while 20% of the mass flow of the same stream is recy-
cled in reactor 2. The remaining 30% leaves the process through
the product stream and is calculated as a side product using the
splitter mass balance. The whole amount (100%) of the mass flow
leaving reactors 1 and 2 through the splitters following the reac-
tors is lead to the subsequent process units. The mass transfer
between the different phase compartments in each process unit
is realized though the aci,p,l vector shown in Fig. 8b. The elements
of the aci,p,l vector indicate the mass flow direction between the
compartments.
4.2. Optimization of the industrial phosphoric acid production
process
4.2.1. Overview of optimization approach
The employed modelling approach results in a process model
that will be used for the optimization of the existing phospho-
ric acid production process. As previously shown in Fig. 1, the
process model calculations are used for the estimation of a pro-
cess performance measure in the form of an objective function
subjected to constraints representing desired performance limits.
The employed performance measure and constraints are evalu-
ated by the utilized stochastic optimization algorithm, hence giving
rise to decision paths that will lead to optimal design options.
The aim of the performed optimization will be to seek targets
of high performance for the process at hand as well as propose
process schemes to realize these targets. The simple structure of
the existing process will be further enhanced by the incorpora-
tion of additional structural elements in the flowsheet, represented
as design variables in the optimization problem. As a result, con-
ventional and novel structural options will be investigated as
potential candidates of improved performance for the process
flowsheet.
499
4.2.2. Objective function formulation
A key parameter of the process that can be improved is the mass
fraction of the phosphoric acid in the filter product stream, as less
energy will be required for further concentration of phosphoric
acid after the filter in order to produce high valued phosphorus
containing products. This can be combined with reduction of phos-
phoric acid losses in the filter gypsum stream and reduction of
sulphuric acid contained at the product stream, so that product
purity increases. Therefore, the objective is to maximize the amount
of phosphoric acid in the filter product stream, while we minimize
the amount of phosphoric acid lost in the gypsum stream as well as
the amount of water and sulphuric acid in the product stream. Eq.
(13) shows the employed objective function, which is formulated
based on the requirements of the utilized stochastic optimization
algorithm:
FPG O FHPr O FHPr SO
Min J = 2 5 2 2 4
(13)
FPPrO
2 5
The employed constraints are represented by Eqs. (14)–(18). The
mass fraction of gypsum in the gypsum outlet stream and of phos-
phoric acid in the product stream must exceed those of the existing
industrial process (base case). Furthermore, the flowrates of the
sulphuric acid in the gypsum and product streams are not allowed
to exceed that of the available industrial process. Finally, the mass
fraction of the sulphuric acid in the product stream must not exceed
1.5%:
I
xG ≥ xG (14)
xPPr O ≥ xPPr O
I
(15)
2 5 2 5
FHG ≤ FHG ISO (16)
2 SO4 2 4
FHPr SO ≤ FHPr ISO (17)
2 4 2 4
FHPr SO ≤ 0.015F Pr (18)
2 4
The above set of constraints and objective function are used in
order to guide the optimization search towards processing schemes
that improve the performance of the employed industrial pro-
cess. Additionally, it allows the generation of insights by enhancing
diversity in the designed processing options. Following the utilized
modelling and optimization framework, the generation of design
insights through the realization of sequential design iterations, as
discussed in Section 2.2, might eventually lead to relaxation or
enhancement of the constraints in order to identify potentially use-
ful trade-offs among the designed processing schemes.
4.2.3. Design variables
Existence of additional processing tasks and recycle/bypass
streams, range of operating parameters and distribution of stream
flowrates among the processing components are used as design
variables in order to generate diverse combinations of processing
schemes during the performed optimization. The functionality of
the employed design and optimization framework is not limited by
any physical or artificial constraints as any type, number or com-
bination of the previously described design options can be varied
within any desired value range during the optimization search. In
this context, we apply upper and lower bounds in the employed
design variables in order to control the design complexity but also
to take into account the ease of implementation of the proposed
designs from an industrial perspective. An optimization search
launched within close proximity of the available process data is
likely to lead to process schemes that are easier to be considered for
implementation by industrial users. On the other hand, a broader
500 A.I. Papadopoulos, P. Seferlis / Chemical Engineering and Processing 48 (2009) 493–506
optimization search is expected to result in schemes of higher per-
formance but also increased design complexity. Other than the
implementation of bounds in process operating parameters, we
consider an upper bound on the processing tasks comprising the
process flowsheet, such as reactors and filters. We further con-
sider upper and lower bounds in the active recycle/bypass streams
(i.e. available to carry material through the flowsheet) as well as to
the flowrate distribution of these streams. In other words different
combinations among the elements of the SFRi,j,p vector are investi-
gated and optimized, with the aim to identify the combination that
reaches the highest possible improvement limits over the existing
process. The employed upper and lower bounds are reported in
Appendix B.
4.2.4. Optimization through Simulated Annealing (SA)
A stochastic optimization method is used in this work in the
form of SA [16]. SA is a statistical cooling optimization tech-
nique that generates a biased random search and employs Monte
Carlo simulations under a variable probability schedule. In SA, the
employed process model is used to simulate biased random transi-
tions implemented on the design variables, hence resulting to the
sequential generation of diverse processing schemes. Each newly
generated processing scheme is evaluated based on a probability
schedule that is a function of the utilized performance measure
(objective function) and an SA algorithmic variable called anneal-
ing temperature. While in high annealing temperature, a processing
scheme that may improve or deteriorate the performance of the
previously evaluated design is probabilistically accepted as a poten-
tially optimum design option, therefore giving rise to formerly
unexplored search directions. A pre-specified number of objective
function evaluations are performed under constant temperature in
order to ensure the implementation of sufficient design diversifi-
cation in the optimization search. As the annealing temperature is
gradually reduced, with a rate that accounts for the performance
of the already investigated process schemes, the performed search
is intensively steered within close proximity of highly performing
design options. The optimization search terminates based on a sta-
tistical termination criterion that aims to ensure that the optimum
solution has been identified. In this work SA is implemented fol-
lowing its adaptation for the design of separation processes by Ref.
[12]. Further applications of SA in the chemical engineering domain
include work in molecular design [17,18] and in reaction/separation
process synthesis [11], to name a few.
5. Modelling and optimization results for the employed
industrial process
The implementation of the employed modelling and design
framework using the available industrial data is organised in five
modelling and design tasks. Initially, a model of the available
Table 1
Comparison of model predictions with industrial data
Industrial data
P2 O5 in product (%) 30.5
P2 O5 output of reactor 1 (%) 16.0
P2 O5 output of reactor 2 (%) 20.0
Total flowrate of product stream (t/h) 59.41
Total flowrate of gypsum stream (t/h) 111.41
Total flowrate output of reactor 1 (t/h) 149.31
Total flowrate output of reactor 2 (t/h) 217.85
Total flowrate output of recycle stream 1 (t/h) 101.16
Total flowrate output of recycle stream 2 (t/h) 41.6
Density in reactor 1 (kg/m3 ) 1482
Density in reactor 2 (kg/m3 ) 1537
phosphoric acid production plant is calculated in order to test
the validity of the employed approach. The developed model is
then subjected to optimization using a number of design and
operating options as design variables, with the aim to investi-
gate structural process alterations that could increase the process
performance. The first design case investigates the effect of intro-
ducing additional recycle and bypass streams in the existing
industrial process. In the second and third cases the existing pro-
cess flowsheet is further enhanced with the addition of a reactor
and an intermediate filter, respectively, and the added compo-
nents are investigated with respect to their interactions through a
comprehensive stream network. In the final design case, the com-
bined dehydrate–hemihydrate production of phosphoric acid is
addressed and compared to industrial data.
5.1. Modelling of the phosphoric acid production plant
In Table 1 we present the results obtained for the model pre-
sented in Fig. 7. These results are compared with the available
industrial data in terms of key process stream flowrates and compo-
sitions. Results show a relative difference in the range of 0.01–4.5%,
with most values being in the range of 0.2–2.95%. It appears that
there is a close match between the industrial and model calcu-
lated data. A similar relative difference range (0.42–3.46%) between
model calculated and phosphoric acid pilot plant data is reported
by Ref. [7], who use similar design equations to the ones employed
in this work. According to Ref. [3] the degree of conversion in indus-
trial phosphoric acid production processes ranges from 85% to 95%.
In this work, the model calculated degree of conversion is well
over 95% while the industrial process under investigation presents
a degree of conversion of approximately 90%. In order to achieve a
realistic representation of the process at hand we employ a value of
90% for the degree of conversion in the performed calculations. Fur-
ther data used in the model calculations are reported in Appendix
D.
5.2. Optimization of the industrial phosphoric acid production
unit
5.2.1. Case A: existing process flowsheet
At first we consider the current process structure with the
addition of streams recycle 3 and bypass 1 shown in Fig. 9. The two-
phase modelling approach is maintained for the process shown in
Fig. 9, however we only show the slurry-phase compartments in
the reactors in order to preserve the clarity of the figure. The vapor
phases of the process representation remain identical to those of
Fig. 7. The design variables for optimization are represented by the
split fractions of the streams connected to splitters 1, 2 and 3. The
upper and lower bounds employed in the performed optimization
search are reported in Table 2 for each stream.
Model predictions Relative difference (%)
31.4 2.95
15.7 1.87
20.9 4.5
60.9 2.5
111.47 0.05
148.65 0.44
217.82 0.01
104.0 2.8
42.32 1.73
1479 0.2
1542 0.33
 A.I. Papadopoulos, P. Seferlis / Chemical Engineering and Processing 48 (2009) 493–506 501

Fig. 9. Process structure considered for case A.

Table 2 tion would potentially lead to enhancement of problems associated

Upper and lower bounds in design options investigated in case A
with gypsum handling and disposal, due to high moisture content,
Stream Case A (%) Base case (existing process) (%) and would require incorporation of such process models in the
Recycle 1 30.0–70.0 50.2
existing phosphoric acid production model in order to identify the
Recycle 2 0.0–40.0 20.4 optimum gypsum dilution limit. This investigation demonstrates
Stream 1, stream 2 80.0–100.0 100 the improvements that can be implemented in the existing process
Recycle 3 0.0–20.0 – by identifying certain simple, yet important, trade-offs. The pro-
Bypass 1 0.0–20.0 –
cess configuration options that correspond to the improved results
of cases A.1, A.2 and A.3 also involve recycling from reactor 2 to reac-
Table 3 tor 1 as well as bypass of reactor 2, to a limited extent. Although
Process optimization results for case A the employed recycle/bypass flowrates are low, the consideration
of these streams in the optimization search is important for the
Base case Case A.1 Case A.2 Case A.3
identification of the reported process performance limits.
P2 O5 in product stream (%) 31.5 32.3 33.3 33.8
Gypsum in filter outlet stream (%) 59.8 58.8 57.7 57.3
Recycle 1 (%) 50.2 47.4 50.4 49.3 5.2.2. Case B: addition of a reactor in the existing process
Recycle 2 (%) 20.4 24.9 22.6 24.1
flowsheet
Stream 1 (%) 100 98.0 100 100
Stream 2 (%) 100 99.4 97.9 97.8 In case B.1 we investigate the option of adding a reactor to the
Recycle 3 (%) – 0.6 2.1 2.2 existing process configuration in order to increase the residence
Bypass 1 (%) – 2.0 0.0 0.0 time of the reaction mixture in the process (Fig. 10). In particu-
lar, case B.1 is developed by identifying optimum targets for the
flowrates of recycle streams 1 and 2, in order to investigate the
The obtained results are reported in Table 3. In the case that the impact of the addition of reactor 3 in the process flowsheet. The
lower bound of the gypsum mass fraction constraint (Eq. (14)) is design results of a case where the volume of reactor 3 is identical
set to the value of 59.8%, which represents the operating status of to that of reactor 2 are compared to those where the volume of
the existing process, the optimization search identifies the exist- reactor 3 is an additional design variable.
ing process configuration as the optimum solution. In other words, The optimization results for the process of Fig. 10 are shown in
the existence of recycle or bypass streams combined with recon- Table 4. The mass fraction of phosphoric acid in the product stream
figuration of the filter recycle flowrates do not enable the increase increases by 2.3% compared to the base case, when the volume of
of the P2 O5 in the product stream with the desired simultaneous reactor 3 is assumed identical to that of reactor 2. This is attributed
increase of the gypsum filter output stream mass fraction. Gradual to the increased phosphoric acid flowrate in the product stream
relaxation of this constraint to lower values shows an important while the water flowrate has decreased significantly. It is also worth
trade-off between the mass fraction of P2 O5 in the product stream noting that a different design pattern emerges for the phosphoric
and the mass fraction of gypsum in the filter outlet stream. The P2 O5 acid flowrates recycled from the filter to the reactors, compared to
mass fraction can increase by approximately 2% for a maximum case A. The flowrate of recycle stream 1 has decreased compared
2.5% reduction of the gypsum mass fraction. Further gypsum dilu- to case A, while the flowrate of recycle stream 2 has increased. On

Fig. 10. Process flowsheet investigated in case B.1.

502 A.I. Papadopoulos, P. Seferlis / Chemical Engineering and Processing 48 (2009) 493–506
Table 4
Optimization results for case B.1
% of filtrate recycled to reactor 1 (recycle 1)
% of filtrate recycled to reactor 2 (recycle 2)
P2 O5 in product (%)
Reactor volume (m3 )
P2 O5 flowrate in product (t/h)
H2 O flowrate in product (t/h)
Fig. 11. Optimum process flowsheet for case B.2.
the other hand, it appears that for a reactor 3 volume of 176 m3 the
mass fraction of phosphoric acid in the product stream reaches a
maximum of 35.3%, which is mostly attributed to the significant
reduction of the water flowrate. This decrease in reactor 3 volume
clearly implies reduction in investment costs associated with the
installation of the new reactor, while optimum operating condi-
tions are achieved. It is also worth noting that there is a significant
change in the process structure as the filter recycle stream to reactor
2 is practically eliminated.
In case B.2 we employ a large number of connectivity options in
the flowsheet as design variables for optimization. Fig. 11 shows the
design results for the employed process structure. Table 5 shows the
optimal results obtained for the flowsheet of Fig. 11. The proposed
process flowsheet leads to a 5–6% increase in the mass fraction of
phosphoric acid compared to the base case. This is mainly achieved
by a significant decrease in the flowrate of water in the product
stream. The designed reactor 3 volume is further decreased com-
pared to case B.1, while the extensive flowsheet integration induced
by the employed network of streams leads to a highly performing
process scheme.
5.2.3. Analysis of results obtained in case B
In industrial practice, the phosphoric acid mass fraction in the
product stream presents an upper limit of approximately 32%.
This limit is mainly due to the existence and growth of the solid
crystals in the reaction liquid that after a certain point block the
reaction from proceeding by causing phenomena known as rock
Table 5
Design results for process flowsheet of Fig. 12
Case B.2
Fixed reactor Variable reactor 3
3 volume volume
P2 O5 in product (%) 36.2 37.6
Reactor volume (m3 ) 250 156
P2 O5 flowrate in product (t/h) 20.091 20.147
H2 O flowrate in product (t/h) 34.978 32.101
Case B.1 Base case
Fixed reactor 3 volume Variable reactor 3 volume
47.7 67.8 50.2
25.3 0.4 20.4
33.8 35.3 31.5
250 176 –
20.090 20.227 19.147
39.261 36.867 40.204
coating or blinding [19]. The exact design limits invoked by such
phenomena are not known a priori as they depend on a number
of design-operating factors and their arbitrary incorporation into
the optimization constraints would possibly bias the optimization
search towards presumably optimal options. While the predictive
capabilities of the employed process models for operating condi-
tions noticed in industrial practice have been proven, predictions
indicating process performances that significantly exceed available
industrial data must be further evaluated. Process design schemes
that predict a value of phosphoric acid mass fraction in the product
stream slightly over 33% could be deemed valid as a result of the
proposed design-operating modifications. They, further, lie within
acceptable deviation limits between process model predictions and
real-life industrial conditions. On the other hand, the phosphoric
acid mass fraction in the product stream is over 35% in case B.2,
as well as in case B.1 when variable reactor 3 volume is consid-
ered. In these cases it is necessary to investigate whether such
model predictions could be achieved under industrial processing
conditions.
In view of the above, we employ the transition point [5] as a
first indicator of the conditions within the reactors. The transition
point is defined as the temperature in which equilibrium is installed
between the hemihydrate and dehydrate form of the crystals within
the reactor and conversion of crystals from one form to the other
takes place. Fig. 12 shows that the transition temperature in cases
B.1 and B.2 lies within the range of 88–93 ◦ C while the temperature
in the reactors is 80 ◦ C for the performed calculations. As a result,
the reactors operate under dehydrate conditions and there is no
transition to hemihydrate operation, that would justify under real-
life conditions, the increased value of phosphoric acid mass fraction
in the product stream.
Base case The degree of supersaturation [7] is employed in order to inves-
tigate the crystallization conditions within the reactors. The degree
of supersaturation calculated for each one of the investigated cases
31.5 (B.1 and B.2 for fixed and variable volumes, respectively) is divided
– by the degree of supersaturation calculated for the existing indus-
19.147 trial process (base case). As a result, when this ratio is close to unity,
40.204
the supersaturation conditions within the reactors are similar to the
 A.I. Papadopoulos, P. Seferlis / Chemical Engineering and Processing 48 (2009) 493–506
Fig. 12. Transition temperature for cases B.1 and B.2.
Fig. 13. Ratio of supersaturation degree in investigated design cases.
conditions in the existing industrial process. Fig. 13 shows that in
case B.1 the deviation of the predicted supersaturation for the opti-
mum designs (Table 4) from the base case is not significantly high,
compared to the deviations noticed in case B.2. When fixed reactor
3 volume is considered in case B.1 the supersaturation in reactor 1
is approximately 50% higher than in the base case, while for reactor
2 it is approximately 50% lower. This implies that reactor 2 compen-
sates for the unreacted residual of reactor 1. When variable reactor
3 volume is considered (in case B.1) the supersaturation conditions
in both the reactors are very similar to those of the base case. This
indicates that there is limited additional blocking of the reaction
and the predicted optimal results (Table 4) would be approximately
valid under real operational conditions. On the other hand, in case
B.2 the calculated supersaturation in reactor 1 presents a significant
deviation from the base case, indicating high rates of spontaneous
nucleation and possible blocking of the reaction.
Similarly to the degree of supersaturation we investigate the
ratio of the produced crystal surface area, which is used as a mea-
sure of crystal size. In industrial practice it is important to maintain
the crystal size within certain limits in order to facilitate the reac-
tion and filtration processes. Such limits are not strict mathematical
bounds but the result of effective process fine-tuning achieved for
Fig. 15. Addition of an intermediate filtration unit.
503
Fig. 14. Ratio of crystal surface area in investigated design cases.
the specific operating conditions of each process. When a fixed
reactor 3 volume is considered in case B.1, results (Fig. 14) show
that the produced crystals are of similar surface to the crystals
produced in the base case and it is expected that similar reaction
and filtration conditions will be achieved. For all other cases the
produced crystal surface area deviates from the base case, indicat-
ing potential deviations in the reaction and filtering conditions as
well.
From the above investigation into the designed process oper-
ating conditions, as compared to those of the base case, it can
be concluded that a phosphoric acid mass fraction of over 35%
would possibly not be achievable under real production condi-
tions. However, the phosphoric acid design options identified in
the investigated design cases unveil the utilized model limitations.
Although the employed set of design equations enables a sufficient
representation of the phenomena present in a real-life process,
more elaborate models are required for processes such as crystal-
lization and filter operation under limiting operating conditions
such as the ones presented in cases B.1 and B.2. Despite such limi-
tations the obtained designs maintain their usefulness as a number
of transparent design insights can be drawn and utilized in further
design attempts using improved process models. It appears that
the addition of a reactor with volume identical to that of reactor 2
(case B.1) in the existing process provides exactly the same phos-
phoric acid mass fraction result as in case A.3. This indicates that
investing on the installation of a new reactor without the inten-
tion of effectively integrating it with the existing process flowsheet
by consideration of recycle and bypass options is not advisable.
Furthermore, the decision regarding the volume of an additional
reactor should be the result of design through optimization, as it is
possible to achieve improved production regimes using reactors of
reduced size.
5.2.4. Case C: addition of intermediate filtration in the existing
process flowsheet
In case C we investigate the option of adding a filter between
reactors 1 and 2 in the existing process (Fig. 15). Operational charac-
504 A.I. Papadopoulos, P. Seferlis / Chemical Engineering and Processing 48 (2009) 493–506

Table 6 Table 7
Design results for case C Design results for case D

Case C.1 Case C.2 Base case DH–DH DH–HH HH–DH HH–HH

P2 O5 in product (%) 31.5 33.5 31.5 P2 O5 in product (calculated) (%) 31.5 38.5 31.4 38.0
Filter 1 surface area (m2 ) 45 24 – P2 O5 flowrate in product (t/h) 19.147 19.189 19.174 19.216
Filter 1 vacuum pressure (kPa) 36 36 – H2 O flowrate in product (t/h) 40.204 29.199 40.521 29.960
Filter 2 surface area (m2 ) 34 22 63 H2 SO4 flowrate in product (t/h) 1.445 1.446 1.464 1.447
Filter 2 vacuum pressure (kPa) 30 32 40 % of filtrate recycled to reactor 50.2 59.6 53.7 64.2
% of filtrate recycled to reactor 1 from 70 54.9 50.2 1 (recycle 1)
filter 2 (recycle 1) % of filtrate recycled to reactor 20.4 13.5 15.7 0.07
% of filtrate recycled to reactor 2 from 0.2 11.8 20.4 2 (recycle 2)
filter 2 (recycle 2) P2 O5 in product (industrial 30–32 36–42 30–32 38–55
% of filtrate recycled to reactor 1 from 0.0 6.1 – [20]) (%)
filter 1 (recycle 3)
P2 O5 flowrate in product (t/h) 17.995 16.857 19.147
H2 O flowrate in product (t/h) 37.765 33.474 40.204 phoric acid and water flowrates in the product stream compared to
H2 SO4 flowrate in product (t/h) 1.371 0.1 1.445 case C.1. Additionally, large quantities of sulphuric acid are removed
from the product stream in case C.2, which is very important as the
purification requirements of the product from sulphuric acid will
teristics of the filters, such as applied vacuum pressure and filtering be significantly reduced. It is also observed that the added filtering
surface, are treated as design variables. The option of recycle stream surface area in case C.2 is 46 m2 which is significantly lower than
3 from filter 1 to reactor 1 is also considered as design variable, the 63 m2 required in the base case and the total of 79 m2 in case C.1.
together with the flowrates of recycle streams 1 and 2. The aim Overall, a clear conclusion that can be drawn from this case is that
of this case is to set the design specifications for filter 1 and recy- a significant reduction can be achieved in the filtering surface area,
cle stream 3, while re-adjusting the specifications of the already but at the expense of the plant production capacity. This provides
existent filter 2 and recycle streams 1 and 2. the incentive to further investigate the presented design scenarios
The obtained results for two design scenarios (C.1 and C.2) are using economic terms.
shown in Table 6 in comparison to the base case. The difference
between the two design scenarios is that in C.1 recycle stream 3 is 5.2.5. Case D: combined phosphoric acid production using the
not active, while in C.2 a maximum 10% of filtrate leaving filter 1 dehydrate and hemihydrate process
is allowed to be recycled through recycle stream 3. Results show In all the previously investigated cases it was assumed that
that case C.1 produces the exact same result as the base case in both reactors operated under dehydrate conditions. Existing indus-
terms of phosphoric acid mass fraction in the product stream. How- trial processes often combine the DH and HH process in the same
ever, the obtained mass fraction value is achieved in case C.1 with flowsheet by applying DH or HH reactive conditions in different
lower phosphoric acid and water product flowrates than in base processing stages. This can be easily modelled using the modelling
case. Less water in product implies reduced evaporation energy and design approach employed in this work, as shown in Fig. 16.
requirements, while less phosphoric acid leads to operation below We apply DH and HH reactive conditions in the flowsheet of the
the current plant output capacity. The reduction in the phosphoric process at hand and optimize the process flowsheet using the fil-
acid product flowrate, compared to the flowrate calculated for the ter recycle stream flowrates as design variables. The optimization
base case, is partly due to increased losses of phosphoric acid in results for the three processes (DH–HH, HH–DH, and HH–HH) that
the gypsum streams as well as to increased unreacted raw material emerge in addition to the already investigated DH–DH are shown
residuals in the two reactors. In this case, it is also observed that in Table 7.
recycle stream 2 is almost eliminated while 70% of the filter 2 filtrate The obtained results lie within the phosphoric acid production
is recycled to reactor 1. This is reasonable as the required phosphoric limits noticed in industrial practice [20]. The compositions of raw
acid previously introduced to reactor 2 from filter 2 is now replaced materials, utilities as well as flowrates employed in the DH–DH pro-
by the phosphoric acid produced by filter 1. In case C.2 the optimal cess provide a similar phosphoric acid mass fraction in the product
solution involves a 6.1% recycle of filtrate to reactor 1 which leads stream as in the case of HH–DH, with a reduced filter-to-reactor 2
to a 33.5% product mass fraction. This recycle decreases the phos- recycle flowrate required in the latter case. On the other hand, the
phoric acid quantity fed to reactor 2 from filter 1, which is replaced same process feed data applied in the DH–HH and HH–HH cases
by recycle 2 stream that is activated again. Despite the increased provide results that lie towards the lower end of the range noticed
phosphoric acid mass fraction, there is a further reduction in phos- in industrial phosphoric acid production. The employed DH–DH

Fig. 16. Combined DH and HH operating conditions for existing process.

 A.I. Papadopoulos, P. Seferlis / Chemical Engineering and Processing 48 (2009) 493–506 505

process appears to have a similar performance to the HH–DH pro- Table A.1
Available industrial process related data
cess, however the HH–DH process would run under a higher energy
consumption regime as it involves the production of hemihydrate Value
gypsum. In this respect, the incorporation of hemihydrate produc- Process data
tion in the existing process would only be worth considering as a Mineral flowrate entering reactor 1 (kg/h) 15,800
DH–HH or HH–HH combination. Mineral flowrate entering reactor 2 (kg/h) 14,650
Density of rock (kg/m3 ) 2200
DH reactor temperature (◦ C) 80
6. Concluding remarks HH reactor temperature (◦ C) 95
Reactor 1 volume (m3 ) 322
In this work we have presented a comprehensive modelling and Reactor 2 volume (m3 ) 250
Reactor 1 diameter (m) 10.54
optimization framework for the design of phosphoric acid pro-
Reactor 2 diameter (m) 7.35
duction processes. The framework concept is based on a bi-level Impeller speed (rph) 3000
iterative design strategy targeting the systematic development Impeller diameter (m) 1
of both inclusive process models as well as optimum process Average rock particle size (m) 4 × 10−4
schemes. Developed designs are validated based on available indus- Particle shape factor 0.55
Sulphuric acid entering reactor 1 (kg/h) 30,690
trial/experimental data and account for insights emerging from
Sulphuric acid entering reactor 2 (kg/h) 13,180
interactions and trade-offs among structural and operating flow- Sulphuric acid concentration (wt%) 98
sheet options. We analyze the functionalities of the employed Density of sulphuric acid (kg/m3 ) 1815
generic-modular RMX units and demonstrate their rich represen- Water feed in filter (kg/h) 101,109
Filtering surface area (m2 ) 63
tation potential. This potential is fully exploited by an effective
Vacuum filter pressure (kPa) 40
optimization framework that is based on the use of a stochastic
search algorithm in the form of simulated annealing. The employed Rock composition
P2 O5 in rock (%) 34
design and optimization approach is applied on an industrial phos-
CaO in rock (%) 52
phoric acid production flowsheet. We model the flowsheet at hand SO3 in rock (%) 2
as a two-phase-per-task process and use the connectivity features Moisture (%) 1.5
provided by the RMX unit representation to connect the reaction Solid phase impurities (%) 10.5
and filtering units. We further implement the employed optimiza-
tion framework on four extensive case studies. The results obtained
Subscripts and superscripts
from the case studies show that targets of increased process per-
c component of a set of components SECOMP
formance can be reached through a wide-ranging investigation
G gypsum stream
of the available design options. Useful insights are generated in
i, j RMX unit of a set of units SEM
each case regarding the predictive ability of the utilized process
I industrial
models as well as the implementation of the proposed design alter-
LR limiting reactant
ations in the investigated phosphoric acid production plant. Design
n the total number of streams entering and leaving a unit
options that can be considered for implementation in the existing
of a set of streams SEST
process flowsheet are proposed. Designs of amplified complex-
p, l phase of a set of phases SEPH
ity, yet increased performance, provide the incentives to further
Pr product stream
investigate these options using more detailed and accurate process
tot total
models.
Appendix B
Acknowledgement
Table A.1 provides the process related data used in the model cal-
The authors gratefully acknowledge the financial support of the culations. For all the presented cases the upper and lower allowed
European Commission under the ECOPHOS project (Contract No. values on the flowrate of the stream recycled from the final filter to
INCO-CT-2005-013359). reactor 1 is equal to 70% and 30% of the filtrate, respectively, while
for the stream recycled to reactor 2 it is 40% and 0%, respectively.
Appendix A. Nomenclature For all other recycle/bypass streams the maximum and minimum
allowed flowrates are equal to 20% and 0% of the stream leaving the
preceding splitter, respectively. In case C, the upper and lower lim-
ac stoichiometric coefficient of component c its for the filtering surface area are 63 and 23 m2 , respectively, and
aLR
c stoichiometric coefficient of limiting reactant component for the applied filter vacuum they are 20 and 60 kPa, respectively.
C concentration (kg/m3 )
F stream flowrate (kg/h) Appendix C. Supplementary data
Mc molecular weight of component c (kg/(kg mol))
McLR molecular weight of limiting reactant component Supplementary data associated with this article can be found,
(kg/(kg mol)) in the online version, at doi:10.1016/j.cep.2008.06.011.
Q volumetric flowrate (m3 /h)
SF side feed stream flowrate (kg/h) References
SFR split fraction of stream F
[1] F. Gioia, G. Mura, A. Viola, Analysis simulation and optimization of the
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