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phenol degradation

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

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

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:

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

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:

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}

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)

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 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

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)

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.

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

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

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.

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

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

Equation Quantity

Mass balances in mixers/splitters 136

SO4 2− concentration in FeSO4 feed stream 1

Total (RT > 1) 139

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

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.

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