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chemical engineering research and design 8 9 ( 2 0 1 1 ) 706–721

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Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

Optimal synthesis of Fenton reactor networks for


phenol degradation

Ricardo F.F. Pontes a , José M. Pinto a,b,∗


a Chemical Engineering Department, Universidade de São Paulo, Av. Prof. Luciano Gualberto, Travessa 3,
380, 05508-900, São Paulo/SP, Brazil
b Othmer-Jacobs Department of Chemical and Biological Engineering, Polytechnic University, Brooklyn, NY 11201, USA

a b s t r a c t

There is an increasing need to treat effluents contaminated with phenol with advanced oxidation processes (AOPs) to
minimize their impact on the environment as well as on bacteriological populations of other wastewater treatment
systems. One of the most promising AOPs is the Fenton process that relies on the Fenton reaction. Nevertheless,
there are no systematic studies on Fenton reactor networks. The objective of this paper is to develop a strategy for
the optimal synthesis of Fenton reactor networks. The strategy is based on a superstructure optimization approach
that is represented as a mixed integer non-linear programming (MINLP) model. Network superstructures with mul-
tiple Fenton reactors are optimized with the objective of minimizing the sum of capital, operation and depreciation
costs of the effluent treatment system. The optimal solutions obtained provide the reactor volumes and network
configuration, as well as the quantities of the reactants used in the Fenton process. Examples based on a case study
show that multi-reactor networks yield decrease of up to 45% in overall costs for the treatment plant.
© 2010 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Keywords: Fenton process; Optimization; Reactor networks; Process synthesis; Wastewater treatment

1. Introduction no systematic approaches for optimizing AOPs comprised of


multiple reactors. The optimal synthesis of reactor networks
The Fenton process can be used to treat effluents containing can yield the optimal configuration of reactors, their optimal
aromatic compounds such as phenol (Eisenhauer, 1964; Kang volumes, as well as the amount and flow rates of reactants to
et al., 2002). Nevertheless, the major disadvantage of advanced be used in the process.
oxidation processes (AOPs), such as the Fenton process, with Pontes and Pinto (2009) review the literature that addresses
respect to conventional biological treatment processes, is the the optimal synthesis of reactor networks, for which there are
significantly higher operating cost due to the acquisition of two main approaches (Lakshmanan and Biegler, 1996): super-
reactants such as ozone and hydrogen peroxide or even UV structure optimization and attainable region targeting. The
light sources such as mercury lamps (Esplugas et al., 2002; first consists in the creation of a superstructure containing a
Pera-Titus et al., 2004). Many studies have been made targeting pre-determined number of reactors and connecting streams
AOP cost reduction (Esplugas et al., 2002; Rios-Enriquez et al., that is further optimized. Kokossis and Floudas (1990) pro-
2004; Moraes et al., 2004) that use solar radiation as an alter- posed a methodology in which the superstructure is composed
native to UV lamps. Duesterberg and Waite (2006) presented a by CSTRs and PFRs, generating a mixed integer non-linear pro-
study to optimize the quantities of reactants in a Fenton batch gramming (MINLP) model. The attainable region targeting is
process to degrade formic acid. Pontes et al. (2010) developed based on the concept developed by X. Horn and described by
a kinetic model for the degradation of phenol by the Fenton Glasser et al. (1987) and Hildebrandt et al. (1990), who devel-
process, which was used to analyze and optimize the quan- oped a methodology to obtain the attainable region for CSTRs
tity of used reactants (hydrogen peroxide and ferrous sulfide) and PFRs networks. However, their examples are limited to two
on the treatment efficiency and cost. Nonetheless, there are dimensions, i.e. reactions involving only two components.


Corresponding author. Present address: Praxair Inc., 39 Old Ridgebury Rd., Danbury, CT 06810, USA. Tel.: +1 203 837 2391.
E-mail address: Jose M Pinto@praxair.com (J.M. Pinto).
Received 5 March 2010; Accepted 26 August 2010
0263-8762/$ – see front matter © 2010 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.cherd.2010.08.017
chemical engineering research and design 8 9 ( 2 0 1 1 ) 706–721 707

Nomenclature
PVcp,T present value of capital cost during T years
f stream (US$)
FD effluent feed PVop,T present value of operational cost during T years
IN reactor inlet (US$)
BP by-pass PVTreat,T present value of treatment cost in a period of T
OT reactor outlet years
FN treated effluent rn rate of reaction n (mol L−1 s−1 )
R-Fe2T FeSO4 feed Rj consumption/production rate of component j
R-H2 O2 H2 O2 feed (mol L−1 s−1 )
j component Sarom overall concentration of aromatic compounds
k equipment (mol L−1 )
n reaction Sj concentration of component j (mol L−1 )
rt reactor Sj,f concentration of component j in stream f
(mol L−1 )
Parameters Vrt volume of reactor rt (L)
j,n stoichiometric coefficient for component j in Z objective function value
reaction n (dimensionless) Zb base case objective function value
Ak capacity of equipment k (L)
Caq,rt acquisition cost of reactor rt (US$)
Caq,rem acquisition cost of the excess iron removal sys-
tem (US$) The objective of this work is to develop a systematic
CFe2T acquisition cost of FeSO4 (US$ mol−1 ) strategy for the optimal synthesis of Fenton process reactor
CH2 O2 acquisition cost of H2 O2 (US$ mol−1 ) networks for the treatment of toxic effluents. This strategy
dop number of days in operation at the treatment establishes the reactor network topology, as well as equip-
plant (days year−1 ) ment capacity and stream composition. The pollutant studied
kn kinetic parameter for reaction n (L mol−1 s−1 , in this work is phenol, often present in industrial effluents.
except where otherwise indicated) Based on the mathematical model developed by Pontes et al.
FLang Lang factor (dimensionless) (2010), a superstructure optimization model is proposed that
iract actual annual interest rate (%) is composed of a network of Fenton reactors. The optimization
irinfl annual inflation rate (%) model has the objective of minimizing capital and operating
irnom nominal annual interest rate (%) costs for the treatment of an effluent stream contaminated by
MMj molar mass of component j phenol.
mphenol,FD phenol load in the feed stream (mol s−1 ) The structure of this paper is as follows. In Section 2,
ne factor related to the equipment type (dimen- the model of a reactor network superstructure that con-
sionless) tains multiple Fenton reactors is presented. In Section 3, the
NERT number of equations in a network of RT Fenton objective function is formulated aiming the minimization of
reactors overall treatment costs divided into capital, operation and
NFRT number of degrees of freedom in a network of depreciation. Section 4 presents a case study that contains
RT Fenton reactors performance and economical parameters for the network, fol-
NVRT number of variables in a network of RT Fenton lowed, in Section 5, by the corresponding optimal results for
reactors the synthesis of superstructures of one to three Fenton reac-
ny time period in which the equipment is depreci- tors. Finally, Section 6 presents the conclusions of the work.
ated (years)
P network parameter 2. Reactor network superstructure model
Pb base case network parameter
Pmax maximum value for the model parameter 2.1. Fenton reactor network model structure
Pmin minimum value for the model parameter
Sarom,max maximum overall concentration of aromatic The structure of the Fenton reactor model is based on the
compounds (mol L−1 ) Fenton process model developed by Pontes et al. (2010). The
T horizon for cost evaluation (years) stoichiometric model describes the reactions that take place
in the phenol degradation by the Fenton process, whereas the
Variables
kinetic model determines how fast these reactions occur. The
Ccp capital cost (US$)
flow model defines the design equations for the Fenton reac-
Cdp equipment depreciation cost rate (US$ year−1 )
tor. In this work, the network model is added to this hierarchy.
Ck acquisition cost of equipment k (US$)
The Fenton process reactor model is given in Appendix A,
Cop operational cost (US$ year−1 )
whereas the equations related to the superstructure network
Ff flow rate of stream f (L s−1 )
are presented in Appendix B.
ifrt binary variable that denotes the existence of
Since the model for the phenol contaminated effluent
the Fenton reactor rt in the network
treatment developed by Pontes et al. (2010) contains 53 reac-
PVdp,T present value of depreciation cost of the equip-
tions and 26 components, the method chosen for the optimal
ment in a period of T years (US$)
synthesis of a Fenton process reactors network was the super-
structure optimization.
708 chemical engineering research and design 8 9 ( 2 0 1 1 ) 706–721

Fig. 1 – Single reactor network superstructure.

The current work relies on the strategy developed by Pontes HPN5. Except for H2 O2 , the concentrations of the other com-
and Pinto (2009) to model the network superstructure, which ponents in stream R-H2 O2 are null;
includes the following equations:
Due to HPN2 and HPN3, variables Sj,BP and Sj,OT are not
- Mass balances for the feed stream splitter. included in this model. Also from Hypothesis HPN1:
- Mass balances for each reactor upstream mixer.
- Mass balances for each reactor downstream mixer. FIN = FOT (1)
- Mass balances for the final mixer.
- Mass balances for each reactor. Therefore, the mass balances for the stream mixers and split-
- Logical and non-negativity constraints. ters are given by:

FFD + FR−Fe2T + FR-H2 O2 = FIN + FBP (2)


In this section, the proposed mathematical models for
the superstructure of multiple Fenton reactor networks are
presented. Constraints related to effluent quality and non-
FFD · Sj,FD + FR-Fe2T · Sj,R-Fe2T + FR-H2 O2 · Sj,R-H2 O2 = FIN .Sj,IN
negativity are also detailed.
+FBP .Sj,IN ∀j (3)
2.2. Single Fenton reactor network superstructure
FBP + FOT = FFN (4)
Naturally, the simplest reactor network superstructure is the
one composed by a single reactor. According to the strategy FBP · Sj,IN + FOT · Sj,1 = FN · Sj,FN ∀j (5)
developed by Pontes and Pinto (2009), besides the inlet and
outlet streams, there is also the by-pass stream. The recycle From HPN4, the following equation is also valid:
stream, as shown in Pontes and Pinto (2009), is only contem-
plated by reactors with short-circuit, which is not previewed SFe2T,R-Fe2+ = SSO ∀j (6)
2+
4 T,R-Fe
for the Fenton reactor model developed by Pontes et al. (2010).
Normally, the FeSO4 and H2 O2 reactants are fed separately
The complete set of equations and variables that describe
from the contaminated effluent. Therefore, streams R-Fe2T,rt
the single Fenton process reactor network superstructure
and R-H2 O2,rt are defined in this model and each reactor is fed
model is presented in Appendix B. This model contains 161
independently.
equations, in which 105 are intrinsic to the Fenton process
Fig. 1 shows the single reactor network superstructure dia-
reactor and 56 to the network, and 194 variables, in which 106
gram.
are intrinsic to the Fenton process reactor and 88 to the net-
The superstructure model is composed by the kinetic and
work. Hence, the model has 33 degrees of freedom. Usually,
flow models for the Fenton reactor, which are described by
in an effluent treatment problem, the effluent feed stream
Pontes et al. (2010), as well as the mass balances for the splitter
flow rate (FFD ), its composition (Sj,FD ) and the reactant con-
(i) and the mixer (ii). The following hypotheses are made:
centrations in their respective feed streams (SFe2T,R-Fe2T and
SH2 O2 ,R-H2 O2 ) are given. Therefore, in a single Fenton process
HPN1. The contaminants in the effluent are in low concen- reactor network superstructure model, there are the following
tration, therefore there is no significant change in the four decision variables:
volumetric flow rate of the outgoing stream from that
of the incoming stream. - FR-Fe2T, FR-H2 O2 and FBP – stream flow rates (variables intrinsic
HPN2. The concentrations of the components in streams IN to the network);
and BP are identical (Sj,BP = Sj,IN ). - V – reactor volume (variable intrinsic to the reactor).
HPN3. The concentrations in the reactor outlet stream
are identical to the ones inside the reactor itself 2.3. Two Fenton reactors network superstructure
(Sj,OT = Sj,1 ).
HPN4. Except for FeSO4 , the concentrations of the other com- A multiple reactor network can yield an improved solution to
ponents in stream R-Fe2T are null. effluent treatment. Nevertheless, its superstructure represen-
chemical engineering research and design 8 9 ( 2 0 1 1 ) 706–721 709

Fig. 2 – Two reactors network superstructure.

tation becomes more complex, even for a two reactor network, −ii : FRF1 + FS2−1 + FR-Fe2T,1 + FR-H2 O2 ,1 = FIN1 + FBP1 (8)
as shown in Fig. 2.
Besides the by-pass stream, the superstructure renders fea- FRF1 · Sj,FD + FS2−1 · Sj,RM2 + FR−Fe2T,1 · Sj,R−Fe2T + FR-H2 O2 ,1
sible the existence of other streams. If stream Srt−rt exists,
· Sj,H2 O2 = FIN1 · Sj,IN1 + FBP1 · Sj,IN1 ∀j (9)
connecting reactor rt to rt provides a serial configuration to
the network. If both streams RF1 and RF2 exist, then the con-
figuration of the network is parallel. A mixed configuration −iii : FBP1 + FOT1 = FS1−2 + FRM1 (10)
occurs when more than one of the streams Srt−rt , RF1 and RF2
exist. FBP1 · Sj,IN1 + FOT1 · Sj,1 = FS1−2 · Sj,RM1 + FRM1 · Sj,RM1 ∀j (11)
In case of serial configuration, if the reactants feed are fed
only in the first reactor, there would be the need of excess −iv : FRF2 + FS1−2 + FR−Fe2+ ,2 + FR-H2 O2 ,2 = FBP2 + FIN2 (12)
concentration for pollutant degradation to take place not only
in the first reactor, but also in the second one. FRF2 · Sj,FD + FS1−2 · Sj,RM1 + FR−Fe2T,2 · Sj,R−Fe2T + FR-H2 O2 ,2
The following hypotheses are made for any component j
· Sj,H2 O2 = FIN2 · Sj,IN2 + FBP2 · Sj,IN2 ∀j (13)
and reactor rt:

−v : FBP2 + FOT2 = FS2−1 + FRM2 (14)


HPN6. The components concentrations in streams RFrt are
the same as the ones in stream FD (Sj,RFrt = Sj,FD ).
FBP2 · Sj,IN2 + FOT2 · Sj,2 = FS2−1 · Sj,RM2 + FRM2 · Sj,RM2 ∀j (15)
HPN7. The components concentrations in streams Srt−rt
are the same as the ones in streams RMrt (Sj,Srt−rt =
−vi : FRM1 + FRM2 = FFN (16)
Sj,RMrt ).
HPN8. The components concentrations in streams BPrt are
FRM1 · Sj,RM1 + FRM2 · Sj,RM2 = FFN · Sj,FN ∀j (17)
the same as the ones in streams INrt (Sj,BPrt = Sj,INrt ).
HPN9. The Fe2+ concentrations in any stream R-Fe2T,rt are
Due to HPN1, for any reactor rt:
identical, whereas the concentration for the other
components are null.
FINrt = FOTrt (18)
HPN10. The H2 O2 concentrations in any stream R-H2 O2,rt are
identical, whereas the concentration for the other
The complete set of equations and variables that describe
components are null;
the two Fenton process reactors network superstructure
model is presented in Appendix B. This model contains 349
Note that hypotheses HPN8, HPN9 and HPN10 replace HPN2, equations, in which 210 are intrinsic to the Fenton process
HPN4 and HPN5, respectively. reactors and 139 to the network, and 389 variables, in which
The mass balances for the mixers and splitters are: 212 are intrinsic to the Fenton process reactors and 177 to
the network. Hence, the model has 40 degrees of freedom, for
−i : FFD = FRF1 + FRF2 (7) which the network itself has 38 degrees of freedom. Usually
710 chemical engineering research and design 8 9 ( 2 0 1 1 ) 706–721

the values for FFD , Sj,FD , and SH2 O2 ,R-H2 O2 are defined; therefore, and the number of variables is given by:
the decision variables intrinsic to the network are:
NVRT = RT 2 + 164 · RT + 57 (28)
- FBPrt , FSrt−rt , FR−Fe2T,rt , FR-H2 O2,rt , rt = 1 and 2
- FRFrt , rt = 1 or 2 Therefore, the number of degrees of freedom, NFRT , is given
by:
2.4. Multiple Fenton reactors network superstructure
NFRT = RT 2 + 4 · RT + 28 (29)
From Fig. 2, the equations that describe a network with more
than two reactors can be derived. In a network with RT reac- Note that NERT is proportional to RT, whereas NVRT and NFRT
tors, the following equations are defined: are proportional to RT2 . Eqs. (27)–(29) are valid for RT > 1.
For the feed stream FD splitter: As in the two Fenton reactors network, the following
degrees of freedom are normally defined in a phenol contam-

RT inated effluent treatment problem: FFD , Sj,FD , SFe2T,R-Fe2T and
FFD = FRFrt (19) SH2 O2 ,R-H2 O2 . Therefore, there are the following decision vari-
rt ables:

For the upstream mixer from reactor rt: - For the network:
- FRFrt , rt = 1 . . . RT − 1

RT
- FR−Fe2T,rt , rt = 1 . . . RT
FRFrt + FSrt −rt + FR−Fe2+ + FR-H2 O2,rt = FBPrt + FINrt ,
- FR-H2 O2,rt , rt = 1 . . . RT
rt =
/ rt
- FBPrt , rt = 1 . . . RT
rt = 1, . . . , RT (20) / rt )
- FSrt−rt , rt = 1 . . . RT (rt =
- SH2 O2 ,R-H2 O2

RT
- Sj,Fe2T,R-Fe2T
FRFrt · Sj,FD + FSrt −rt · Sj,RMrt + FR−Fe2T,rt · Sj,R−Fe2T + FR-H2 O2,rt
- For each reactor:
rt =
/ rt
- Vrt , rt = 1 . . . RT
·Sj,R-H2 O2 = FBPrt · Sj,INrt + +FINrt · Sj,INrt , rt = 1, . . . , RT
∀j 2.5. Non-negativity constraints
(21)
For the downstream mixer from reactor rt: Except for the components formation/consumption rates,
all model variables must be non-negative. Therefore, it is

RT
necessary to add to the network superstructure model non-
FBPrt + FOTrt + = FSrt−rt + FRMrt , rt = 1, . . . , RT (22)
negativity constraints, which are listed in the Appendix.
rt =
/ rt


RT
2.6. Effluent quality constraints
FBPrt · Sj,FD + FOTrt · Sj,rt + = FSrt−rt · Sj,RMrt + FRMrt · Sj,RMrt ,
rt =
/ rt (23) It is necessary to add a constraint that imposes that the efflu-
rt = 1, . . . , RT ent treated in the Fenton reactor suits the demands from the
∀j environmental agencies.

Sarom = Sj · MMj ≤ Sarom,max (30)
For each reactor rt:
j ∈ {aromatic}

FINrt = FOTrt , rt = 1, . . . , RT (24)


CONAMA (Brazilian National Environmental Council) stan-
dards impose a maximum value for total phenols in disposed
For the final mixer: effluents of 0.5 mg L−1 , which is used in this work as an upper
bound. The EPA (Environmental Protection Agency) standards

RT
FRMrt = FFN (25) impose an even stricter upper bound for phenol of 0.3 mg L−1
rt
(EPA, 2006). This paper considers that the constraints set by
the EPA and the CONAMA refer to total aromatic component

RT concentration.
FRMrt · Sj,RMrt = FFN · Sj,FN ∀j (26) CONAMA (2005) also sets the maximum value for dissolved
rt iron in the effluent at 15.0 mg.L−1 , while EPA (2006) sets this
value at 1.0 mg.L−1 . Since most of the Fenton treatment pro-
Therefore, the model of a network superstructure contain- cesses (Pontes et al., 2010) generate effluent streams with
ing RT Fenton reactors (RT > 1) has 55RT + 29 equations intrinsic higher iron concentration, an iron removal system has to be
to the network. The network contains (RT2 + 58RT + 57) vari- incorporated to the plant.
ables. Appendix B presents the equations and variables
intrinsic to the network of multiple Fenton reactors. 3. Cost estimation for Fenton process
Hence, the number of equations for the superstructure treatment
model is given by:
For the optimal synthesis of a reactor network three cost
NERT = 160 · RT + 29 (27) items are considered in this work: capital, operation and
chemical engineering research and design 8 9 ( 2 0 1 1 ) 706–721 711

depreciation. The capital costs contemplate the direct and a T-year horizon is made:
indirect costs in the acquisition of equipment (reactors and
iron removal system) involved in this kind of operation. The ny = T (35)
operational costs contemplate the reactants acquisition costs.
Finally, the depreciation costs are relative to the depreciation 3.1. Present value calculation
itself of the equipment used in the treatment. The objective
function used in this paper minimizes the sum of the three For the present value calculation of the Fenton process treat-
costs above. ment, it is necessary to calculate the present values for the
For the calculation of direct and indirect capital costs Ccp capital, operation and depreciation costs over a T-year hori-
of the phenol contaminated effluent treatment by the Fenton zon.
process, the Lang factor method (Turton et al., 2003) is used: It is assumed that the capital cost is spent at the start and,
 RT  therefore, the capital cost present value PVcp,T is the capital
 cost itself according to Eq. (36):
Ccp = FLang ifrt · Caq,rt + Caq,rem (31)
rt=1
PVcp,T = Ccp (36)

According to Turton et al. (2003), the Lang factor for a liquid


The operational cost present value is given by Eq. (37):
processing plant is 4.74.
As mentioned in Section 2.4, the maximum iron concen-  
tration in the treated effluent is 15.0 mg L−1 and, therefore, 1 1
PVop,T = Cop · − T
(37)
the excess iron must be removed. There are several treatment iract iract · (1 + iract )
processes for dissolved iron removal such as precipitation, oxi-
dation, ionic exchange and filtration. The latter is considered, The actual annual interest rate can be given by:
as shown in the case study to be presented in the next section.
The acquisition cost for equipment units depends on sev- (1 + irnom )
iract = −1 (38)
(1 + irinfl )
eral factors such as capacity and construction materials.
Turton et al. (2003) and Peters and Timmerhaus (1981) pro-
For the present value of the depreciation cost, the following
pose the following equation to relate the costs, C1 and C2 , of
expression is used:
two similar equipment units with different capacities, A1 and
A2 :  
1 1
 A ne PVdp,T = Cdp · − T
(39)
C1 iract iract · (1 + iract )
1
= (32)
C2 A2
Therefore, the overall present value is given by:
Sweeting (1997) uses a value of 0.6 for ne for all equipment
units. Eq. (32) is used in this paper in the context of Caq,rt PVTreat,T = PVcp,T + PVop,T + PVdp,T (40)
(rt = 1. . .RT) and Caq,rem that are presented in Eq. (31).
For the Fenton process, the operational costs for the phenol For the optimal synthesis of the Fenton process treatment
contaminated effluent treatment include the acquisition costs unit, the objective function can be expressed by the minimiza-
for the reactants, which are proportional to their flow rates. tion of present value of the overall cost:
Therefore, the expression for the operational costs, Cop , can
be defined as: Z = min PVPlant,T (41)
 RT

Cop = dop · CFe2T · FR-Fe2+ ,rt · SFe2T,R-Fe2+ 4. Case study for Fenton process treatment
rt=1
 4.1. Economical parameters for phenol degradation by
+CH2 O2 · FR-H2 O2,rt · SH2 O2 ,R-H2 O2 (33) the Fenton process

The results for a Fenton reactor network optimal synthesis


The depreciation cost refers to a decrease in the book value
depend on the attributed values for equipment and reactant
of the asset due to its usage and wear. It is an accounting
prices. These prices, however, vary considerably according to
value, and not necessarily cash flow expenditure. The depreci-
the year, plant location, acquired reactants quantities, ven-
ation costs Cdp contemplate the reactors and the iron removal
dors, etc. Obviously, for real effluent treatment problems the
system present in the network:
synthesis can be done with specific values for the parameters,
 RT however, for this work the analysis is done using market ori-
1  entative prices and typical ranges for the parameter values of
Cdp = · ifrt · Caq,rt + iffrt · (Caq,rt + iffl1,rt · Caq,l1
ny the economic evaluation.
rt=1
 For the iron removal system, it is considered that a filtration
unit is installed downstream from the treated effluent stream
+iffl2,rt .Caq,l2 ) + Caq,rem (34) and that it reduces its iron concentration to 15.0 mg L−1 . The
filtration unit has a capacity of processing streams with flow
rates of 0.61 L s−1 and iron content of 10 ppm (31.0 mg L−1 ). Eq.
Eq. (34) relies on a linear depreciation cost (Brealey and (32) is used to scale up a similar iron removal system suited to
Myers, 2003). For this work, the following simplification for the cases studied in this paper. Tables 1 and 2 present average
712 chemical engineering research and design 8 9 ( 2 0 1 1 ) 706–721

5.1. Single Fenton reactor network synthesis


Table 1 – Equipment average orientative prices for a
Fenton process reactor network.
A network of one Fenton reactor necessarily contains the
Equipment Cost (US$) Reference (May 2009)
reactor (if1 = 1) to treat the phenol contaminated effluent.
Fenton reactor 1320 Bailiff Enterprises (2009) Therefore, the resulting model is a NLP (non-linear program-
(9463.5 L or ming) solved with CONOPT (Drud, 1994).
2500 gal)
Fig. 3 shows the optimal solution for a single Fenton
Filtration system 589 Excel Water Technologies (2009)
reactor network superstructure that treats phenol contam-
(10 ppm iron
removal in 6 GPM inated effluent stream with the parameter values listed in
or 0.61 L s−1 ) Tables 3 and 4.
In the case of a higher phenol concentration in the feed
stream, Sphenol,FD = 1.0 × 10−2 mol L−1 , the optimal solution con-
Table 2 – Average orientative prices for reactants of a figuration is presented in Fig. 4. The phenol load, mphenol,FD ,
Fenton process reactor network.
for Fig. 3 case is 1.0 × 10−3 mol s−1 , whereas for Fig. 4 case,
Reactant Cost (US$ mol−1 ) Reference mphenol,FD = 1.0 × 10−2 mol s−1 .
H2 O2 0.003 US Peroxide (2009) US Peroxide (2009) recommends the usage of 5.0 kg of
FeSO4 0.036 The Innovation Group (2009) H2 O2 to treat each kg of phenol by the Fenton process.
The optimal solution in Fig. 3 presents a weight ratio of
4.0 kg H2 O2 /kg phenol, whereas for the optimal solution in
orientative prices of equipment and reactants between 2006 Fig. 4, this ratio is 3.6 kg H2 O2 /kg phenol. The decrease in
and 2009. this ratio comes from the linear dependence between oper-
The studies performed in this work rely on the economic ational costs and reactant consumption. To compensate the
parameters presented in Table 3. Nominal interest and infla- reduction in the reactant to contaminant ratio, the optimal
tion rates were calculated using 2004–2009 average values. solution in Fig. 4 presents a reactor volume to phenol load
According to Eq. (38), the parameters given in Table 3 yield ratio of 5.93 × 104 m3 s mol−1 , whereas for Fig. 3 this ratio is
an actual annual interest rate, iract , of 1.3%. 3.98 × 104 m3 s mol−1 .
Sensitivity analysis was performed for the single reac-
4.2. Effluent parameters for phenol degradation by the tor network varying the values of FFD , Sphenol,FD , dop , T, irreal ,
Fenton process Sarom,max to study the effect of these parameters on the opti-
mal solution. A base case with optimal solution Zb is defined
The network synthesis also depends on the effluent flow rate and Pb represents the base case parameter values as listed
and phenol concentration, as well as the annual operating in Tables 3 and 4. For each performed optimization, only one
time for the treatment plant. Table 4 assigns values of the parameter is varied, whereas the others are kept at their base
effluent parameters for the base case. values. The established range for all parameters was the fol-
The concentrations of reactants in their respective feed lowing:
streams were set to a base value of 1.0 mol L−1 . The overall
amounts that are fed are optimized by calculating the stream
flow rates. Pmin = 0.1 · Pb ≤ P ≤ 10 · Pb = Pmax (42)

5. Fenton reactor network optimal Fig. 5, presented in log–log scale, shows the effect of the
synthesis results variation of P/Pb on the objective function value, Z/Zb . While
Fig. 6, presented in semi-log scale, shows this effect on the
Networks containing one to three Fenton reactors are opti- operational cost ratio, PVop,T /Z (see Eqs. (37) and (40)).
mized for the treatment of phenol contaminated effluents. Figs. 5 and 6 show that the higher the phenol load to be
degraded, i.e. higher values of FFD and/or Sphenol,FD , the higher
the operational costs are in relation to the capital and depreci-
Table 3 – Economic evaluation parameters for Fenton ation costs. Note that operational costs increase linearly with
process reactor network design.
the phenol load, but capital and depreciation costs increase
Parameter Value Reference by a 0.6 factor.
Brazilian nominal interest rate (irnom ) 14.9% Invertia (2009) Although the phenol load to be degraded is the same in the
Annual inflation rate (irinfl ) 13.4% Invertia (2009) case of FFD = 10 L s−1 and Sphenol,FD = 1.0 × 10−3 mol L−1 as well as
Evaluation period (T) 20 years – in the case of FFD = 1 L s−1 and Sphenol,FD = 1.0 × 10−2 mol L−1 , the
value of Z is higher in the former case, which has the higher
overall effluent flow rate. This happens because higher efflu-
Table 4 – Effluent parameters for Fenton process reactor
ent flow rates yield higher hydraulic retention times, hence
network design.
requiring a larger reactor capacity to process the effluent.
Parameter Value For an actual interest rate of 13.5% (iract,max ), it is shown in
−1 Fig. 5 that the value of Z reaches its lowest value, since the dis-
Effluent flow rate (FFD ) 1Ls
Effluent phenol concentration (Sphenol,FD ) 1.0 × 10−3 mol L−1 counted values of operational costs in the latter years decrease
Annual operating time (dop ) 365.25 days year−1 as the actual interest rate increases.
H2 O2 feed stream concentration (SH2 O2 ,R-H2 O2 ) 1.0 mol L−1 As expected, Z increases with T and dop because the treat-
Fe2 SO4 feed stream concentration (SFe2T,R-Fe2T ) 1.0 mol L−1
ment plant operates for a longer time. For minimum values of
Maximum overall concentration of aromatic 0.5 mg L−1
compounds (Sarom,max )
T and dop , the operational cost ratio is reduced to only 30% of
the overall costs.
chemical engineering research and design 8 9 ( 2 0 1 1 ) 706–721 713

Fig. 3 – Optimal solution for a single Fenton reactor network superstructure (FFD = 1 L s−1 and Sphenol,FD = 1.0 × 10−3 mol L−1 ).

Fig. 4 – Optimal solution for a single Fenton reactor network superstructure (FFD = 1 L s−1 and Sphenol,FD = 1.0 × 10−2 mol L−1 ).
1.0E+01

FFD

Sphenol,FD
Sarom,max

irreal
Z / Zb

1.0E+00

T
dop

1.0E-01
1.00E-01 1.00E+00 1.00E+01

P/Pb

Fig. 5 – Objective function value sensitivity analysis ( : value for the EPA standard).
714 chemical engineering research and design 8 9 ( 2 0 1 1 ) 706–721

8.0E-01

FFD
irreal
6.0E-01 Sarom,max
Sphenol,FD
PVop,T / Z

4.0E-01
T
dop

2.0E-01
1.00E-01 1.00E+00 1.00E+01
P/Pb

Fig. 6 – Operational cost ratio sensitivity analysis ( : value for the EPA standard).

In the case of a treatment plant bound by EPA standards taminated effluent treatment with the base case parameter
(Sarom,max = 0.3 mg L−1 ), such as mentioned in Section 2.6, there values.
would be an increase of 15% in the objective function value as The optimal solution presented in Fig. 7 has two reactors in
shown in Figs. 5 and 6. serial configuration, FeSO4 feed streams in both reactors, but
H2 O2 feed stream only in the first reactor.
5.2. Synthesis of multiple Fenton reactor networks The optimal solution shown in Fig. 7 presents a lower con-
sumption of reactants than the one presented for a single
Using GAMS/DICOPT++ (Viswanathan and Grossmann, 1990), Fenton reactor superstructure network shown in Fig. 3. The
optimizations were performed for network superstructure three cost terms decrease with the additional reactor. The
models of two and three Fenton reactors. optimal solution value of a network of two Fenton reactors
Fig. 7 presents, for a network superstructure of two Fenton is 24% lower than that of a single Fenton reactor network
reactors, the optimal solution configuration of a phenol con- superstructure.

Fig. 7 – Optimal solution for a network superstructure with two Fenton reactors (FFD = 1 L s−1 and
Sphenol,FD = 1.0 × 10−3 mol L−1 ).
chemical engineering research and design 8 9 ( 2 0 1 1 ) 706–721 715

Fig. 8 – Optimal solution for a network superstructure with two Fenton reactors (FFD = 1 L s−1 and
Sphenol,FD = 1.0 × 10−2 mol L−1 ).

In the case of a higher phenol concentration in the feed the one shown in Fig. 3; nevertheless, it is only 2.4% lower than
stream, Sphenol,FD = 1.0 × 10−2 mol L−1 , the optimal solution con- the optimal solution with two reactors.
figuration is presented in Fig. 8. In the case of a higher phenol concentration in the feed
In both optimal solutions, the reactors are in serial config- stream, Sphenol,FD = 1.0 × 10−2 mol L−1 , the optimal solution con-
uration. The network shown in Fig. 8 has a FeSO4 feed stream figuration is presented in Fig. 10.
only for the first reactor and H2 O2 feed streams for both reac- In comparison to the optimal solution shown in Fig. 9, the
tors; however, the optimal solution shown in Fig. 7 has H2 O2 one shown in Fig. 10 has also the three reactors in series, but
in the first reactor and FeSO4 in both. the reactants are fed only to the first reactor.
In the optimal solution shown in Fig. 7, the volume of the The optimal solution shown in Fig. 9 has a weight ratio
first reactor is 7.8 times larger than that of the second one; of 2.6 kg H2 O2 /kg phenol, whereas for the optimal solution
however, this ratio decreases to about 1.8 for the optimal solu- shown in Fig. 10, this ratio is of 2.5 kg H2 O2 /kg phenol.
tion shown in Fig. 8. The FeSO4 quantity used in the optimal
solution shown in Fig. 7 is about 1.7 times higher than the one 5.3. Comparison of the optimal solutions for the
used in the optimal solution shown in Fig. 8, however for H2 O2 , Fenton reactor network superstructure
this ratio is about 8.5. The increase in the H2 O2 :FeSO4 ratio can
be explained by the upper bound imposed for the maximum Tables 5–7 present a comparison among optimal solutions for
iron concentration in the treated effluent (CONAMA, 2005). It one to three reactor network superstructures. Case S1 uses
can be noted that the quantity of iron present in the treated the parameter base values, whose solutions were presented
effluent stream is equal to the quantity added to the reactors. in Figs. 3, 7 and 9. Case S2 has the Sphenol,FD value multiplied
The optimal solution shown in Fig. 7 has a weight ratio by 10, whose solutions were presented in Figs. 4, 8 and 10.
of 2.9 kg H2 O2 /kg phenol, whereas for the optimal solution As for Case S3, the value for Sphenol,FD is 20 times higher than
shown in Fig. 8, this ratio is of 2.5 kg H2 O2 /kg phenol. the one used in Case S1. Finally, Case S4 has the same phenol
Fig. 9 presents, for the network superstructure model with concentration presented in S1, but the effluent flow rate, FFD ,
three Fenton reactors, the optimal solution configuration with is multiplied by 10.
the base case parameter values. Table 5 presents the objective function value for Cases
The optimal solution presented in Fig. 9 has three reactors S1–S4 as a function of the number of reactors in the super-
in series, FeSO4 feed stream for all reactors, and H2 O2 fed only structure. For higher values of mphenol,FD , such as Case S3, the
to the first reactor. This optimal solution presents lower values increase in the number of reactors yields a higher decrease
for the three considered costs than the ones presented by the in the value of the objective function than lower values of
optimal solutions of Fig. 3, one Fenton reactor, and Fig. 7, two mphenol,FD , such as Case S1. The impact of adding a reactor to
Fenton reactors. The optimal solution value is 26% lower than the network is higher for one to two reactors than that of two
716 chemical engineering research and design 8 9 ( 2 0 1 1 ) 706–721

Fig. 9 – Optimal solution for a network superstructure with three Fenton reactors (FFD = 1 L s−1 and
Sphenol,FD = 1.0 × 10−3 mol L−1 ).

Table 5 – Comparison among optimal solutions for one, two and three reactor network superstructures.
Case S1 Case S2 Case S3 Case S4
−1
FFD (L s ) 1.0 1.0 1.0 10.0
Sphenol,FD (mol L−1 ) 1.0 × 10−3 1.0 × 10−2 2.0 × 10−2 1.0 × 10−3
mphenol,FD (mol L−1 ) 1.0 × 10−3 1.0 × 10−2 2.0 × 10−2 1.0 × 10−2
Z (RT = 1) US$55,979 US$311,679 US$553,278 US$395,650
Z (RT = 2) US$42,292 US$177,666 US$317,183 US$305,368
Z (RT = 3) US$41,179 US$163,520 US$284,543 US$299,846
Z (RT = 2)/Z (RT = 1) 75.5% 57.0% 57.3% 77.2%
Z (RT = 3)/Z (RT = 1) 73.6% 52.5% 51.4% 75.8%
Z (RT = 3)/Z (RT = 2) 97.4% 92.0% 89.7% 98.2%
PVop,T /Z (RT = 1) 0.59 0.68 0.72 0.66
PVop,T /Z (RT = 2) 0.62 0.76 0.82 0.67
PVop,T /Z (RT = 3) 0.63 0.76 0.83 0.68

Table 6 – Reactor volumes (in m3 ) for one, two and three reactor network superstructures.
Number of Case S1 Case S2 Case S3 Case S4
reactors (RT)

1 V1 = 39.8 V1 = 593 V1 = 1250 V1 = 1000


2 V1 = 12.2 V1 = 55.2 V1 = 72.0 V1 = 373

V2 = 1.56
V 2 = 30.3
V 2 = 51.4
V 2 = 41.1
V = 13.8 V = 85.5 V = 123 V = 414
3 V1 = 9.44 V1 = 29.7 V1 = 31.7 V1 = 351
V2 = 0.602 V2 = 16.1 V2 = 21.5 V2 = 11.9

V3 = 0.444
V 3 = 10.1
V 3 = 20.1
V 3 = 7.81
V = 10.5 V = 55.9 V = 73.3 V = 371
chemical engineering research and design 8 9 ( 2 0 1 1 ) 706–721 717

Fig. 10 – Optimal solution for a network superstructure with three Fenton reactors (FFD = 1 L s−1 and
Sphenol,FD = 1.0 × 10−2 mol L−1 ).

to three reactors. For instance, the objective function value Table 6 shows the optimal reactor volumes for each net-
decreases by 43% in Case S3 when a second reactor is added work. All solutions present a serial configuration for the
to the network and by only 10% with the addition of the third network. Similarly to the present value, results show that the
reactor. The operational cost ratio increases with the num- higher the phenol concentration in the feed stream, the larger
ber of reactors in the network and the phenol load. This ratio is the decrease in the overall volume. For instance, in Case
reaches a maximum for Case S3, for which the phenol con- S1 the network with three reactors presents a decrease of
centration in the feed stream is the highest. In all cases, the 73%, whereas for Case S2 this decrease reaches 91%. Never-
filtration unit cost (not shown) represents less than 10% of the theless, Case S4 also presents a 73% volume decrease from
overall capital costs. the three-reactor to the single reactor network, which leads to

Table 7 – Reactants feed flow rates (in L s−1 ) for one, two and three reactor network superstructures.
Reactant flow rate Case S1 Case S2 Case S3 Case S4

FH2 O2 (RT = 1) FH2 O2 ,1 = 1.10 × 10−2 FH2 O2 ,1 = 1.00 × 10−1 FH2 O2 ,1 = 1.93 × 10−1 FH2 O2 ,1 = 9.55 × 10−2
FFeSO4 (RT = 1) FFeSO4 ,1 = 7.48 × 10−4 FFeSO4 ,1 = 2.34 × 10−3 FFeSO4 ,1 = 4.01 × 10−3 FFeSO4 ,1 = 4.99 × 10−3
FH2 O2 (RT = 2) FH2 O2 ,1 = 7.96 × 10−3 FH2 O2 ,1 = 6.73 × 10−2 FH2 O2 ,1 = 1.27 × 10−1 FH2 O2 ,1 = 7.44 × 10−2
0 −4 −3 0

FH2 O2 ,2 = 0.00 × 10
FH2 O2 ,2 = 7.62 × 10
FH2 O2 ,2 = 5.00 × 10
FH2 O2 ,2 = 0.00 × 10
FH2 O2 ,2 = 7.96 × 10−3 FH2 O2 ,2 = 6.80 × 10−2 FH2 O2 ,2 = 1.32 × 10−1 FH2 O2 ,2 = 7.44 × 10−2
FFeSO4 (RT = 2) FFeSO4 ,1 = 5.46 × 10−4 FFeSO4 ,1 = 1.11 × 10−3 FFeSO4 ,1 = 2.19 × 10−3 FFeSO4 ,1 = 3.27 × 10−3
−4 0 0 −4

FFeSO4 ,2 = 1.09 × 10
FFeSO4 ,2 = 0.00 × 10
FFeSO4 ,2 = 0.00 × 10
FFeSO4 ,2 = 8.69 × 10
FFeSO4 = 6.55 × 10−4 FFeSO4 = 1.11 × 10−3 FFeSO4 = 2.19 × 10−3 FFeSO4 = 4.14 × 10−3
FH2 O2 (RT = 3) FH2 O2 ,1 = 7.14 × 10−3 FH2 O2 ,1 = 6.39 × 10−2 FH2 O2 ,1 = 1.22 × 10−1 FH2 O2 ,1 = 6.93 × 10−2
FH2 O2 ,2 = 0.00 × 100 FH2 O2 ,2 = 0.00 × 100 FH2 O2 ,2 = 1.71 × 10−3 FH2 O2 ,2 = 0.00 × 100
0 0 −4 0

FH2 O2 ,3 = 0.00 × 10
FH2 O2 ,3 = 0.00 × 10
FH2 O2 ,3 = 1.58 × 10
FH2 O2 ,3 = 0.00 × 10
FH2 O2 ,2 = 7.14 × 10−3 FH2 O2 ,2 = 6.39 × 10−2 FH2 O2 ,2 = 1.24 × 10−1 FH2 O2 ,2 = 6.93 × 10−2
FFeSO4 (RT = 3) FFeSO4 ,1 = 5.22 × 10−4 FFeSO4 ,1 = 9.48 × 10−4 FFeSO4 ,1 = 7.48 × 10−4 FFeSO4 ,1 = 3.12 × 10−4
FFeSO4 ,2 = 1.53 × 10−4 FFeSO4 ,2 = 0.00 × 100 FFeSO4 ,2 = 0.00 × 100 FFeSO4 ,2 = 1.10 × 10−3
FFeSO4 ,3 = 3.67 × 10−5
FFeSO4 ,3 = 0.00 × 100
FFeSO4 ,3 = 0.00 × 100
FFeSO4 ,3 = 2.80 × 10−4

FFeSO4 = 7.13 × 10−4 FFeSO4 = 9.48 × 10−4 FFeSO4 = 1.60 × 10−3 FFeSO4 = 4.50 × 10−3
718 chemical engineering research and design 8 9 ( 2 0 1 1 ) 706–721

the conclusion that the flow rate does not influence the rate not included in this study, such as piping and instrumentation,
of decrease. Note that Cases S2 and S4 have the same phenol might nullify the treatment cost reduction incurred by extra
load but the latter requires larger volumes because of the more reactors.
diluted effluent feed stream. The methodology presented in this paper can be extended
For higher phenol concentrations, the FeSO4 feed stream to incorporate other AOP processes to the network superstruc-
is present only for the first reactor. The optimal solution for ture, such as the photo-Fenton process, as well as aerobic and
multiple reactor networks in Cases S2 and S3 present con- anaerobic treatment processes.
figurations with multiple H2 O2 feed streams and/or reactor
volumes with the same order of magnitude in order to avoid Acknowledgement
high concentrations of iron in the treated effluent stream.
For lower phenol concentrations, such as Case S1, the opti- The authors acknowledge financial support from CAPES
mal solutions for multiple reactor networks present multiple (Brazil).
FeSO4 feed stream and a first reactor about 10 times higher
than the downstream reactors. For Case S4, the high feed Appendix A. Mathematical model of phenol
stream flow rate is able to dilute the high quantity of iron degradation by the Fenton process
added to the treatment, hence the multiple FeSO4 feed stream
is present in the optimal solutions for multiple reactor net- A.1. Stoichiometric model
works.
The reactions for the phenol degradation by the Fenton pro-
cess that were developed by Pontes et al. (2010) are given in
6. Conclusion Table A1.

The present paper addressed the optimal synthesis of Fen-


A.2. Kinetic model
ton reactor network superstructures applied to the treatment
of effluents contaminated by phenol. Based on a mechanistic
The reaction rates rn are given by:
model developed for the phenol degradation by the Fenton
process (Pontes et al., 2010), a mixed-integer optimization

rn = kn · Sj j,n ∀n (A1)
model was developed that also includes mass balances of the
j
feed and interconnecting streams.
An objective function was developed to minimize the
The j components consumption/production rates are given
treatment cost by the Fenton process that considers capital,
by:
operation and depreciation costs. Effluent quality constraints
were added as upper bounds for the residual overall aromatic 
compounds and iron concentrations. Since the iron concen- Rj = j,n · rn (A2)
trations in the treated effluents are higher than the ones n

permissible by the environmental agencies, an iron removal


A.3. Flow model
system is included in the capital and depreciation costs.
A case study was defined in the present paper. Sensitivity
For a CSTR (Continuous Stirred-Tank Reactor) model in steady-
analysis was performed for several parameter values to assess
state:
how these parameters influence the optimal solution value as
(A3)FIN · (Sj,IN − Sj ) + Rj · V = 0 ∀ j
well as the operation to overall cost ratio. Higher phenol loads,
as result of high flow rates and phenol concentration of the
feed stream, yield naturally higher optimal solution values, A.4. Model dimensions
for which there is a higher increase in the operational costs in
relation to the capital and depreciation costs. In particular, The variables and equations intrinsic to the Fenton reactor are
the feed flow rate has higher impact than the phenol con- given in Tables A2 and A3. Note that the stand-alone reactor
centration because it requires larger reactors. Lower operation model has only one degree of freedom.
periods for the treatment plant yields lower optimal solution
values and higher capital costs/operational cost ratios. Appendix B. Fenton reactor network
Network superstructures of one to three Fenton reactors superstructure model
were optimized and the results show that increasing the
number of reactors in the network yields lower optimal solu- B.1. Model for a network superstructure of a single
tion values. The addition of a second reactor in the network Fenton reactor
results in a reduction of 24–43% in the optimal solution values.
Moreover, the addition of the second reactor also decreases The variables for the single Fenton reactor network super-
the amount of reactants required to degrade the phenol. For structure are given in Table B1.
multiple reactor network superstructures, lower phenol con- The equations that describe the single Fenton reactor net-
centrations require addition of iron to all reactors, whereas work superstructure are given in Table B2.
optimal solutions for higher phenol concentrations present
the FeSO4 feed stream only to the first reactor; moreover the B.2. Model for a network superstructure of two Fenton
latter require larger reactor volumes that are all fed by H2 O2 . It reactors
is important to note that the cost reduction achieved by adding
a third reactor might not compensate, though, the higher oper- The variables for a network superstructure of two Fenton reac-
ational complexity of the system. Moreover, other capital costs tors are given in Table B3.
chemical engineering research and design 8 9 ( 2 0 1 1 ) 706–721 719

Table A1 – Stoichiometric model for the phenol degradation by the Fenton process.
Reaction kr (L mol−1 s−1 ) Reaction kr (L mol−1 s−1 )

(R1) Fe3+ +H2 O2 → Fe2+ + H+ + HO2 • 1.0 × 10−2 (R25) 1,4-DHCD• + Fe3+ → Fe2+ + Hydroquinone 4.2 × 103
(R2) Fe3+ + HO2 • → Fe2+ + H+ + O2 3.3 × 105 (R26) 1,2-DHCD• + HO• → THB 2.1 × 1010
(R3) Fe3+ + O2 •− → Fe2+ + O2 5.0 × 107 (R27) 1,4-DHCD• + HO• → THB 2.3 × 1010
(R4) Fe2+ + H2 O2 → Fe3+ + HO• + OH− 6.3 × 101 (R28) Catechol + Fe3+  4.4 × 10−1
1,2-Semiquinone• + Fe2+ + H+ 4.6 × 101
(R5) HO• + H2 O2 → HO• + H2 O 3.3 × 107 (R29) Hydroquinone + Fe3+  8.0 × 10−2
1,4-Semiquinone• + Fe2+ + H+ 7.3 × 100
(R6) HO2 • + H2 O2 → HO• + H2 O + O2 5.0 × 10−1 (R30) Catechol + HO• → THCD• 2.1 × 1010
(R7) 2HO2 • → H2 O2 + O2 8.3 × 105 (R31) Hydroquinone + HO• → THCD• 1.5 × 109
(R8) HO2 • + HO• → H2 O + O2 1.0 × 1010 (R32) 1,2-Semiquinone• + Fe2+ + H+  1.0 × 103
1,2-Benzoquinone + Fe3+ 1.1 × 101
(R9) Fe2+ + HO• → Fe3+ + OH− 3.2 × 108 (R33) 1,4-Semiquinone• + Fe2+ + H+  1.0 × 103
1,4-Benzoquinone + Fe3+ 1.1 × 101
(R10) HO2 • ↔ H+ + O2 • − 1.6 × 105 s−1 (R34) THCD• + Fe3+ → THB + Fe2+ + H+ 3.8 × 103
1.0 × 1010
(R11) Fe2+ + HO2 • + H+ → Fe3+ + H2 O2 1.2 × 106 (R35) Fe3+ + THB → Fe3+ + AML 4.0 × 100
(R12) Fe2+ + 2H+ + O2 • − → Fe3+ + H2 O2 1.0 × 107 (R36) 1,2-Benzoquinone + HO• → MA• 4.2 × 108
(R13) 2HO• → H2 O2 4.2 × 109 (R37) 1,4-Benzoquinone + HO• → MA• 1.0 × 109
(R14) HO• + O2 •− → OH− + O2 1.0 × 1010 (R38) THB + HO• → AML 5.8 × 1010
(R15) HO2 • + O2 •− + H+ → H2 O2 + O2 9.7 × 107 (R39) MA + HO• → MA• 5.0 × 108
(R16) SO4 2− + HO• + H+ → H2 O + SO4 • − 1.2 × 106 (R40) AML + HO• → AML• 8.7 × 109
(R17) SO4 •− + OH− → SO4 2− + HO• 1.0 × 107 (R41) AOX + HO• → AOX• 1.4 × 106
(R18) SO4 •− + H2 O2 → H+ + HO2 • + SO4 2− 3.0 × 108 (R42) Fe3+ + MA• → Fe2+ + MA 3.7 × 101
(R19) SO4 •− + HO2 • → H+ + O2 + SO4 2− 6.6 × 102 (R43) Fe3+ + AML• → Fe2+ + AML 3.7 × 101
(R20) SO4 •− + Fe2+ → Fe3+ + SO4 2− 5.0 × 108 (R44) Fe3+ + AOX• → Fe2+ + AOX 3.7 × 101
(R21) SO4 •− + H2 O → H+ + HO• + SO4 2− 6.0 × 109 (R45) MA + HO• → AML + CO2 5.0 × 108
(R22) HO• + Phenol → 1,2-DHCD• 1.0 × 1010 (R46) AML + HO• → AOX + CO2 8.7 × 109
(R23) HO• + Phenol → 1,4-DHCD• 7.7 × 109 (R47) AOX + HO• → CO2 1.4 × 106
(R24) 1,2- DHCD• + Fe3+ → Fe2+ + Catechol 7.0 × 103 (R48) Fe3+ + AOX → Fe(III)-organocomplexes 2.6 × 100

Table A2 – Fenton reactor model variables. Table B2 – Equations for a single Fenton reactor network
superstructure.
Variable Symbol Quantity
Equation Quantity
Reactor volume V 1
Concentration in Sj,1 26 Global mass balance in the reactor 1
the reactor of Mass balances in the mixers and splitters 54
component j SO4 2− concentration in the FeSO4 feed stream 1
Reaction rates rn n =
/ 6, 8 53 Total 56
and 62
Production/ Rj 26
consumption
rates
Total 106

The equations that describe a network superstructure of


two Fenton reactors are given in Table B4.
Table A3 – Fenton reactor model equations.
Equation Quantity
B.3. Model for a network superstructure of multiple
Reaction rates 53
Fenton reactors
Reactor mass balances 26
Production/consumption 26
rates of components The variables for a network superstructure of multiple Fenton
Total 105 reactors are given in Table B5.
The equations that describe a network superstructure of
multiple Fenton reactors are given in Table B6.

Table B1 – Variables for a single Fenton reactor network superstructure.


Variable Symbol Quantity
2+
Superstructure streams flow rates Ff f = FD, R-Fe , R-H2 O2, BP, IN, OT and FN 7
Concentration of component j in stream f Sj,f f = FD, IN and FN 78
FeSO4 concentration in stream R-Fe2T Sj,R-Fe2T j = Fe2T and SO4 T 2
H2 O2 concentration in stream R-H2 O2 SH2 O2 ,R-H2 O2 1
Total 88
720 chemical engineering research and design 8 9 ( 2 0 1 1 ) 706–721

Table B3 – Variables for a network superstructure of two Fenton reactors.


Variable Symbol Quantity

Superstructure streams flow rates Ff f = FD, RFrt , R-Fe2+ ,rt , R-H2 O2,rt, BPrt, Srt−rt , INrt , OTrt, RMrt and FN rt = 1 and 2 18
FeSO4 concentration in streams RFFe2T,rt Sj,R-Fe2T j = Fe2T and SO4 T 2
H2 O2 concentration in streams RFH2 O2,rt SH2 O2 ,R-H2 O2 1
Concentration of component j in stream f Sj,f f = FD, INrt , RMrt , FN 156
TOTAL (RT > 1) 177

Table B4 – Equations for a network superstructure of two Fenton reactors.


Equation Quantity

Global mass balance in the reactors 2


Mass balances in mixers/splitters 136
SO4 2− concentration in FeSO4 feed stream 1
Total (RT > 1) 139

Table B5 – Variables for a network superstructure of multiple Fenton reactors.


Variable Symbol Quantity

Superstructure streams flow rates Ff f = FD, RFrt , R-Fe2+ ,rt , R-H2 O2,rt , BPrt , Srt−rt , INrt , OTrt , RMrt and FN 2 + 6·RT + RT2
rt = 1·RT
FeSO4 concentration in streams RFFe2T,rt Sj,R-Fe2T j = Fe2T and SO4 T 2
H2 O2 concentration in streams RFH2 O2,rt SH2 O2 ,R-H2 O2 1
Concentration of component j in stream f Sj,FD f = FD, INrt , RMrt , FN 52 + 52·RT
rt = 1·RT
Total (RT > 1) 57 + 58·RT + RT2

without constraints. Industrial and Engineering Chemistry


Table B6 – Equations for a network superstructure of
Research 29, 49–58.
multiple Fenton reactors.
Invertia, 2009. Economia – Indicadores.
Equation Quantity http://br.invertia.com/economia/indicadores/indicadores.aspx
(accessed on 01.02.09).
Global mass balance in the reactors RT
Kang, N., Lee, D.S., Yoon, J., 2002. Kinetic modeling of Fenton
Mass balances in mixers/splitters 54·RT + 28
oxidation of phenol and monochlorophenols. Chemosphere
SO4 2− concentration in FeSO4 feed stream 1
47, 915–924.
Total (RT > 1) 29 + 55·RT
Kokossis, A.C., Floudas, C.A., 1990. Optimization of complex
reactor networks. I. Isothermal operation. Chemical
Engineering Science 45 (3), 595–614.
Lakshmanan, A., Biegler, L.T., 1996. Synthesis of optimal
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