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Chemical Engineering Research and Design

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Optimal design of catalytic distillation columns: A case study on synthesis of TAEE

C.A. Gonzlez-Rugerio a, , R. Fuhrmeister b , D. Sudhoff a , J. Pilarczyk c , A. Grak a,d
a
TU Dortmund University, Department of Biochemical and Chemical Engineering, Laboratory of Fluid Separations, Emil-Figge Strasse 70, D-44227 Dortmund, Germany b Danieli Froehling, Scherl Strasse 12, 58540 Meinerzhagen, Germany c Research and Development Centre of Renery Industry S.A., Chemikow 5, 09-411 Plock, Poland d Lodz Technical University, Faculty of Process and Environmental Engineering, Wlczanska 213, 90-924 Lodz, Poland
a b s t r a c t
The design of catalytic distillation (CD) columns is a challenging task because of the superposition of chemical reaction and distillation in one apparatus. In this work, a method to design a cost-optimal CD column for chemical systems with large number of components and chemical reactions is presented. The method is based on the following steps: (1) estimation of the number of theoretical stages and catalyst volume by the decomposition of the CD column into a sequence of chemical reactors and non-reactive distillation columns, (2) estimation of the column diameter and operating conditions using an equilibrium stage model, and (3) design of the column applying an optimisation algorithm and using a rigorous non-equilibrium stage model to represent the CD process. The method is applied to determine the optimal column conguration and operating conditions for the synthesis of tert-amyl ethyl ether from ethanol and isoamylenes. Eight components and four chemical reactions were selected to represent the chemical system in the simulations. 2013 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved. Keywords: Octane enhancer; Tert-amyl ethyl ether; Heuristics; Evolutionary optimisation; Multiple reactions; Etherication
1.
Introduction
Reactive distillation (RD), in which chemical reaction and distillation are integrated into one single apparatus, is a well known example of process intensication. This integration can offer several advantages when compared to sequential reaction-distillation processes, such as reduction of the operating and investment costs, higher product yields and increased catalyst lifetime (Sundmacher and Kienle, 2002; Kenig and Grak, 2007). However, the design of RD columns is
challenging due to the interactions between multicomponent mass and heat transfer, phase equilibrium, hydrodynamics and chemical reaction. Moreover, the complexity to design RD columns increases signicantly for chemical systems with large number of components and chemical reactions. The design of a RD column consists of the estimation of the column dimensions, feed locations and operating conditions which satisfy pre-dened design specications (Ciric and Gu, 1994). In the last years, numerous studies regarding heterogeneously catalysed RD processes, commonly referred as
Abbreviations: 2M1B, 2-methyl-1-butene; 2M2B, 2-methyl-2-butene; 2Mthp, 2-methylpentane; 2M2P, 2-methyl-2-pentene; CD, catalytic distillation; ETBE, ethyl tert butyl ether; EQ, equilibrium stage; EtOH, ethanol; FCC, uid catalytic cracking; IA, Isoamylenes, 2M1B and 2M2B; IUPAC, International Union of Pure and Applied Chemistry; MDE, modied differential evolution; MINLP, Mixed Integer Non Linear Programming; NEQ, nonequilibrium stage; PFR, plug ow reactor; RD, reactive distillation; SRK, SoaveRedlichKwong equation of state; TAEE, tert amyl ethyl ether; TAME, tert amyl methyl ether; THEE, tert-hexyl ethyl ether; UNIFAC, UNIversal Functional Activity Coefcient; VLE, vapourliquid equilibrium. Corresponding author. Tel.: +49 0231 755 6265; fax: +49 0231 755 3035. E-mail addresses: carlos.rugerio@bci.tu-dortmund.de (C.A. Gonzlez-Rugerio), r.fuhrmeister@danieli-froehling.de (R. Fuhrmeister), daniel.sudhoff@bci.tu-dortmund.de (D. Sudhoff), Janusz.pilarczyk@obr.pl (J. Pilarczyk), andrzej.gorak@bci.tu-dortmund.de (A. Grak). Received 4 March 2013; Received in revised form 24 July 2013; Accepted 29 August 2013 0263-8762/$ see front matter 2013 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.cherd.2013.08.030
Please cite this article in press as: Gonzlez-Rugerio, C.A., et al., Optimal design of catalytic distillation columns: A case study on synthesis of TAEE. Chem. Eng. Res. Des. (2013), http://dx.doi.org/10.1016/j.cherd.2013.08.030
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Nomenclature activity of component i (mol mol1 ) annualising factor (year1 ) column diameter (m) distillate to feed ratio (mol mol1 ) nominal diameter (mm) activation energy of reaction i (kJ mol1 ) catalytic section height (m) separation section height (m) height equivalent to a theoretical plate (m) adsorption equilibrium constant chemical equilibrium constant for reaction i pre-exponential factor for the Arrhenius equation (mol kg1 s1 ) ki reaction rate constant for reaction i (mol kg1 s1 ) mass ow rate of TAEE (tonne year1 ) mTAEE nexcess maximal alcohol excess in the feed to the CD alcohol,feed column (mol/s) stoichiometry nalcohol,feed stoichiometric alcohol molar ow rate (mol/s) ncomponents number of components molar ow rate of species i (mol/s) ni molar ow rate of unreacted and inert species ni,feed in the column feed (mol/s) nreactions number of reactions ri reaction rate (mol kg1 s1 ) annual operation time (8000 h year1 ) toper temperature (K) T Tb boiling temperature (K) total investment cost (euro) TIC TOC total operating cost (euro year1 ) V Vapour mass ow rate (kg s1 ) molar fraction of component i in liquid phase xi (mol mol1 ) aze molar fraction of component i at the azeotrope xi (mol mol1 ) density of the vapour phase (kg m3 ) v ai ann ai D/F DN Ei hcat hsep HETP KEtOH Ki k0i
catalytic distillation (CD), have been published. In particular, different methods to design CD columns are available in the open literature. Graphical, heuristic and optimisation based approaches can be considered as the main design categories (Almeida-Rivera et al., 2004). Graphical methods are useful tools for feasibility analysis and screening of the process variants but these methods can only handle a limited number of degrees of freedom (ncomponents nreactions 3). Two conceptual developments that have contributed to extend the application of graphical methods are transformed composition variables (Barbosa and Doherty, 1988) and the element concept (Prez-Cisneros et al., 1997). The main advantage of these two approaches is that the dimensionality of the chemical system is reduced because the number of transformed variables or elements is lower than the number of actual components. To date, several graphical methods are available in literature based on either transformed variables (e.g. Carrera-Rodriguez et al., 2011) or elements (e.g. Jantharasuk et al., 2011). Recently, Avami et al. (2012) presented the feed angle method, which is based on pinch point analysis rather than visual inspection, and thus it seems to be promising to handle chemical systems with multiple components and reactions. Nevertheless, all the
aforementioned methods yield only rough CD column designs which must be improved with subsequent rigorous simulations because the geometric characteristics of the column internals are not considered, which play a key role in actual mass and heat transfer across the vapourliquid interface. Moreover, thermodynamic and chemical equilibrium are usually assumed and economic issues are not directly addressed. In addition to graphical methods, Subawalla and Fair (1999) presented an iterative method based on heuristic rules. This method overcomes some of the limitations of graphical approaches by considering the column internals and enabling the CD column economics to be easily added to the procedure. Moreover, the method can be applied to chemical systems with several components and multiple reactions. However, this method does not guarantee the optimal column because as pointed out by Li et al. (2012), no effective heuristics rules are available that can ensure optimal integration between chemical reaction and distillation. Algorithmic optimisation methods overcome the drawbacks of graphical and heuristic methods. A suitable objective function for the optimisation algorithms is the annual operating and the annualised investment costs. The constraints are given by the mass and energy conservation laws and product qualities (Ciric and Gu, 1994). Mixed Integer Non Linear Programming (MINLP)-based methods have been widely used due to the nonlinearity of the CD model equations and the discrete and continuous variables that have to be optimised (Ciric and Gu, 1994; Stichlmair and Frey, 2001; Gangadwala and Kienle, 2007; to mention a few). Recently, optimisation methods based on random search (e.g. simulated annealing-based, differential strategies and memetic algorithm) have been applied to design CD columns (Cardoso et al., 2000; Lima et al., 2006; Babu and Khan, 2007; Urselmann et al., 2011; among others). These methods have several advantages, such as their easy implementation and their ability to escape of local optimums, but they may require a large number of iterations, leading to high computational effort. To apply the optimisation algorithm, the search space of the optimisation variables must be previously specied. However, the selection of the search space is not trivial (Urselmann et al., 2011; Avami et al., 2012). Most of the optimisation algorithms published for the design of CD columns are based on several assumptions (e.g., constant enthalpy of vapourisation, constant molar overow) that may not realistically represent the phenomena occurring in a CD column (Damartzis and Seferlis, 2010). Although the limitations of equilibrium stage (EQ) models have been identied (Baur and Krishna, 2002), only a few publications presented the design of CD columns using rigorous nonequilibrium stage (NEQ) models (see, e.g., Gmez et al., 2006; Dalaouti and Seferlis, 2006; Damartzis and Seferlis, 2010). The fundamentals of both EQ and NEQ models are discussed in Section 4.3.1. In this work, a method to design a cost-optimal CD column is presented. In the rst two steps of the method, heuristic rules and simple mathematical models, e.g., short cut methods for non-reactive distillation columns, are applied to determine the CD column conguration and operating conditions. Results obtained in these steps are used as starting values for the optimisation algorithm using a steady state NEQ model. The method can be applied to design CD columns for chemical systems involving a large number of components and reactions for any kind of the modelling approach used for CD processes. Moreover, because a NEQ model is used in the nal step of the design method, the geometric characteristics
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of the column internals are taken into account. The method is applied to design a CD column for the synthesis of tert-amyl ethyl ether (TAEE) from ethanol (EtOH) and isoamylenes (IA). The synthesis of TAEE has not been extensively analysed in the open literature and to our knowledge, no CD column design has been published for this reaction system yet.
Table 1 Reaction rate equations for the synthesis of TAEE and THEE (Linnekoski et al., 1997; Zhang and Datta, 1995). Reaction
1 2 3
Reaction rate equation (mol kg1 s1 )

r1 = r2 = r3 = r4 =
k1 (a2M1B aEtOH aTAEE /K1 ) (1+KEtOH aEtOH )2 k2 (a2M2B aEtOH aTAEE /K2 ) (1+KEtOH aEtOH )2 k3 (a2M1B a2M2B /K3 ) 1+KEtOH aEtOH k4 (a2M2P aEtOH aTHEE /K4 ) 2 (1+K a ) EtOH EtOH
2.
Chemical system
TAEE is produced by the heterogeneously catalysed, exothermic and chemical equilibrium limited reactions between EtOH and the two IA, 2-methyl-1-butene (2M1B) and 2-methyl-2butene (2M2B), according to the chemical Eqs. (1) and (2) (Linnekoski et al., 1997). The isomerisation between 2M1B and 2M2B is an additional chemical equilibrium limited reaction (Eq. (3)).
Table 2 Normal boiling points (Aspen Properties PlusTM ). Abbreviation

Isopentane 2M1B 2M2B 2Mthp 2M2P EtOH TAEE THEE
IUPAC name
2-Methylbutane 2-Methyl but-1-ene 2-Methyl but-2-ene 2-Methylpentane 2-Methyl pent-2-ene Ethanol 2-Ethoxy-2-methylbutane 2-Ethoxy-2-methylpentane
Tb (K)
300.6 303.9 311.2 333.4 340.1 351.1 374.2 417.1
+
2M1B
OH
EtOH
TAEE
O
(1)
+
2M2B
OH
EtOH
TAEE
(2)
2M1B
2M2B
(3)
equation for Amberlyst 15 W was assumed to be valid for Amberlyst 16 W as well. Reaction rate equations are shown in Table 1 and kinetic parameters are given in the Appendix (Tables A.2 and A.3). The chemical equilibrium limits the IA conversion to 39% at 333 K and at stoichiometric quantities of IA and EtOH. In practice, an EtOH excess is used to increase the equilibrium conversion.
To produce TAEE at a commercial scale, the light gasoline fraction from uid catalytic cracking (FCC gasoline) is used as the IA feedstock. The FCC gasoline consists of approximately 20 mole% of IA, 5 mole % of C6 reactive olens and the remaining components are nonreactive hydrocarbons (mainly C5 and C6 fractions). In this work, inert hydrocarbons are represented by the components with the highest concentration in the FCC gasoline; C5 fraction by isopentane, C6 fraction by 2-methylpentane (2Mthp) and C6 reactive olens are represented by 2-methyl-2-pentene (2M2P). In addition to the main reactions given by Eqs. (1)(3), several side reactions may take place, e.g., the formation of tert-hexyl ethyl ether (THEE) from C6 reactive olens and EtOH as well as the dimerisation of both IA. Nevertheless, dimerisation reactions are minimised if an EtOH/IA molar ratio greater than one in the catalytic section is ensured (Gonzlez-Rugerio et al., 2012), and thus only the formation of THEE is considered (Eq. (4)).
2.2.
Thermodynamics
Activity coefcients in the liquid phase were calculated using the UNIFAC model while fugacity coefcients were estimated by the SoaveRedlichKwong (SRK) equation of state. The UNIFAC-SRK model predicts VLE experimental data, if available in literature, (Everson and Jansen, 2001; Arce et al., 2005) with an accuracy of 1.3%. Table 2 shows the component names and their normal boiling points. Six homogeneous azeotropes are predicted by the UNIFAC model at 4 bar (Table 3).
3.
Chemical process description
+
2M2P
2.1.
OH
EtOH
Reaction kinetics
THEE
The FCC gasoline is mixed with EtOH and fed to a prereactor, in which chemical equilibrium is reached (Fig. 1). The outlet stream from the prereactor already containing TAEE and THEE is subsequently fed into the CD column. Isopentane and IA are low boiling point components (Table 2) and are obtained in the distillate, while TAEE is the bottom product of the CD column. Unreacted EtOH is recovered in the distillate stream
(4) Table 3 Azeotropes predicted by the UNIFAC model at 4 bar (Aspen Properties PlusTM ). Component 1
EtOH EtOH EtOH EtOH EtOH EtOH
The reaction kinetics of TAEE synthesis on the catalyst Amberlyst 16 W and based on the LangmuirHinshelwood model obtained by Linnekoski et al. (1997) were used in the CD model. The reaction kinetics published by Zhang and Datta (1995) of THEE synthesis on Amberlyst 15 W were applied. Because the physical properties of these catalysts are rather similar (Table A.1 in Appendix), the published reaction rate
Component 2
Isopentane 2M1B 2M2B 2Mthp 2M2P TAEE
x1 (mol mol1 )
0.1320 0.1293 0.1859 0.3687 0.4385 0.8252
Tb (K)
344.3 348.3 354.5 368.1 373.3 389.5
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locations and operating conditions (Fig. 1) that satisfy the design specications.
4.
Design method
The method proposed to design a cost-optimal CD column consists of the following steps (Fig. 2):
Fig. 1 Process ow diagram for TAEE synthesis from EtOH and IA.
due to the minimal boiling point azeotrope between EtOH and isopentane (Table 3). Upstream of the CD column, a prereactor was assumed, which is operated at high pressure (8 bar) to ensure that only the liquid phase is present and at 340 K. An EtOH excess of 20% with respect to the stoichiometric amount for the main reactions was used to increase the equilibrium conversion. Under these conditions, the IA conversion in the prereactor is 47.2% (Eq. (5)) and the selectivity of EtOH towards TAEE is 89% (Eq. (6)). Table 4 shows the inlet and outlet molar ow rates of each stream in the prereactor. This calculation xes the composition of the feed stream to the CD column. In this contribution, only the design of the optimal CD column is carried out. ninlet noutlet i i ninlet i
conversion of componenti =
(5)
selectivityEtOH
TAEE
inlet noutlet TAEE nTAEE outlet ninlet EtOH nEtOH
(6)
3.1.
Design specications
As design specications, a production capacity of 150 ktone year1 (45 mol/s at 8000 h year1 ) of TAEE in the prereactor CD column system is set as the target. A high TAEE purity is not required in this chemical process, but due to environmental regulations, the maximum content of IA in the bottom stream of the column has been restricted (Cruz et al., 2007). A minimum IA conversion of 90% (based on the feed to the CD column), a maximum TAEE concentration of 0.01 mole % in the distillate and a maximum concentration of IA and EtOH in the bottom product of the column of 1 mole % are dened as targets. The proper hydrodynamic conditions within the column are considered by ensuring that the column is operated at the liquid load of 80% of the ooding point of catalytic packing and in the range 6580% for the non-catalytic packing.
3.2.
Problem denition
Once the chemical system was set and the design specications dened, the design problem can be stated as follows (Ciric and Gu, 1994): determine the height of the separation (hsep ) and catalytic (hcat ) sections, column diameter (d), feed
Step 1: Sequential initialisation The aim of this step is to determine the number of theoretical stages for the separation sections and the catalyst volume to be used in the CD column. For this purpose, chemical reaction and distillation are decoupled (Fig. 3), i.e., the CD column is decomposed by a sequence of reactors and non-reactive distillation columns. As a consequence, already available short cut approaches for non-reactive distillation columns and simple mathematical models for ideal chemical reactors can be applied. The decomposition of the CD column has been previously performed by Subawalla and Fair (1999) and Pilarczyk et al. (2005), among others. Subawalla and Fair (1999) simulated on the one hand a non-reactive distillation column to determine the number of theoretical stages while on the other hand they used a series of chemical reactors to estimate the catalyst amount. Later, the catalytic section of the CD column is placed by checking the concentration proles of the reactants in the non-reactive column, i.e., the catalytic zone is located in the stages with the highest reactant concentration. Afterwards, by successive iterations the number of stages in each section of the column and the operating conditions are corrected. In the method proposed here, the catalytic zone is placed in the column as shown in Fig. 3 and no additional iterations are carried out because an optimisation algorithm is applied in the nal step of the method. In addition to the number of stages and catalyst volume, the molar reactant ratio in the column feed is also calculated as shown by Sneesby et al. (1997). Moreover, heuristic rules are used to identify the feed location. Note that this step does not consider the geometric characteristics of the column internals. The decomposition of the CD column used in this step yields information about the column structure, but neither the operating conditions nor the column diameter can be determined. Step 2: Simultaneous initialisation In this step, the column diameter, the height of the column and the operating conditions are estimated. With this aim, chemical reaction and distillation are coupled, and a steady state EQ model is used to describe the CD process. First, the number of theoretical stages determined in step 1 is used to calculate the column diameter by applying a simple EQ model in which the reactions are not taken into account. Once the diameter is estimated, the column height can be calculated. Later, the reaction rate equations are included in the EQ model, and the search direction of the operating conditions to be used during the optimisation is identied. Step 3: Detailed optimisation Finally, an optimisation algorithm is applied to design the CD column using an NEQ model and considering investment and operating costs as the objective function. The column dimensions and operating conditions obtained in the previous step are used as starting values during the optimisation. The following sections describe each step of the method
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Fig. 2 Structure of the design method proposed in this work.
in detail and in Section 4.4, points which deserve special attention to apply the method to other chemical systems are discussed.
4.1. 4.1.1.
Step 1: Sequential initialisation Feed location
The feed location depends not only on the volatilities of reactants and products but also on the purities of the reactants and the formation of azeotropes. Based on the relative volatilities of the components, the following heuristics rules are available to determine the feed location (Bessling et al., 1997): Heuristic 1. If the reactants are the most volatile components in the chemical system, the feed location must be close to the bottom of the reaction zone, otherwise the feed location must be close to the top of the catalytic section (Cheng and Yu, 2005).
Heuristic 2. If the relative volatility of the reactants differs signicantly (AB 4; Barnicki et al., 2006) then two feeds are necessary, one close to the bottom and another close to the top of the catalytic zone. While based on the reactants purity (Subawalla and Fair, 1999): Heuristic 3. If a feed containing the product is used and the concentration of the product in the feed is close to its concentration at chemical equilibrium with the reactants (within approximately 20%), then the feed should be located in the separation zones to remove the products that enter the column before they reach the reaction section to prevent product decomposition. Heuristic 4. In some chemical systems, the formation of azeotropes will also inuence the feed location. For example, although EtOH is an intermediate boiling point component in the TAEE synthesis, the minimal boiling point azeotrope formed between EtOH and isopentane leads EtOH to behave like a minimal boiling point component. Therefore, if pure
Table 4 Feed and product molar ow rates in the prereactor. Component

Molar ow rates (mol/s) Isopentane 2M1B 2M2B 2Mthp 2M2P EtOH TAEE THEE Total mole ow (mol/s)
FCC stream
EtOH feed to the prereactor

0.00 0.00 0.00 0.00 0.00 57.60 0.00 0.00 57.60
Prereactor outlet stream

100.8 2.24 23.11 79.20 9.17 32.12 22.64 2.83 272.11
100.8 16.45 31.55 79.20 12.00 0.00 0.00 0.00 240.00
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column are modelled as non-reactive distillation columns. The number of theoretical stages for the separation sections is calculated with the FenskeUnderwood equation (Fenske, 1932; Underwood, 1948), in which light and heavy key components must be selected as well as their percentage of recovery. The selection of the key components depends on the desired separation (see details in Section 5.1). To estimate the catalyst volume, the reactive zone is represented by a system of ideal reactors and ash separators in series (Subawalla and Fair, 1999; Pilarczyk et al., 2005). In this step, the number of reactors is increased until the target conversion is reached. The catalyst volume in the reactors is varied such that chemical equilibrium is achieved in each reactor. Afterwards, the total volume of catalyst in the reactors is used as the actual catalyst volume in the CD column. If pure reactants are used, the process conguration should be started with the chemical reactors followed by a single non-reactive distillation column to represent the separation sections of the CD column as shown in Fig. 3b. In the distillation column, the number of stages obtained with the FenskeUnderwood equation between the top and the feed can be used as equivalent to the number of stages in the rectifying section of the CD column. Similarly, the number of stages between the feed and the bottom of the distillation column can be used as representative of the stripping section of the CD column. Although this step considers three sections of the column (rectifying, reactive and stripping), it is possible that not all of these sections are necessary, e.g., the rectifying section may not be needed. However, the three sections of the CD column should be considered here, and the third step of the method will determine whether they are indeed required.
4.1.3. Calculation of the molar reactant excess in the column feed

The molar reactant ratio has to be estimated considering the reaction stoichiometry and the composition of the reactants in the azeotropes (Sneesby et al., 1997). The stoichiometric reactant amount is calculated by taking into account the product yield, target conversion and reaction stoichiometry. However, an excess of alcohol is benecial for the production of highoctane gasoline components, such as tert-amyl methyl ether (TAME) and TAEE, by CD because of the following reasons: (1) side reactions, such as IA dimerisation, are suppressed if alcohol is in excess (Rihko et al., 1994), (2) the IA conversion will increase if the alcohol/IA ratio increases (Sneesby et al., 1997) and (3) Sundmacher and Hoffmann (1994) demonstrated that interfacial mass transfer rates can be higher than reaction rates and therefore less reactant is available in the liquid phase for reaction. This behaviour results from the minimal boiling point azeotropes formed by the alcohol and the inert components, which can take the reactant away from the liquid phase, decreasing the alcohol/IA ratio (Subawalla and Fair, 1999). However, if the excess of alcohol is too large, alcohol will also be obtained in the bottom stream of the CD column, decreasing the product purity (Hickey and Adams, 1994). Therefore, an optimal reactant excess exists and must be determined. A rst approximation of the optimal alcohol molar ow rate (nexcess ) can be made using the molar ow alcohol,feed rates of inert components and non-reacted species (ni,feed ) in the column feed as well as the azeotropic composition between these components (xiaze ) and the alcohol at different pressures as shown in Eq. (7). This equation was obtained by analysing several case studies on the production of tertiary
Fig. 3 Decomposition of the CD column into a sequence of chemical reactors and non-reactive distillation columns. (a) Case when a prereacted/impure feed is used, (b) case when pure reactants are used. EtOH is used, it should be fed at the bottom of the reactive section.
4.1.2. Estimation of the number of theoretical stages for the separation sections and catalyst volume
To estimate the number of theoretical stages for the separation sections and the catalyst volume, the CD column is decomposed by a sequence of chemical reactors and non-reactive distillation columns as shown in Fig. 3. Two different situations can occur depending on whether a prereacted/impure feed or pure reactants are used. Fig. 3a shows the process conguration for the case in which a prereacted/impure feed is used. In this case, as mentioned in Section 4.1.1, the feed should be located in the separation zones. Stripping and rectifying sections of the CD
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Table 5 Properties of KATAPAK SP11 (*Brunazzi and Viva, 2006; **Buchaly et al., 2007; Behrens, 2006). Packing characteristics
Specic geometric area (m /m ) Catalyst volume fraction HETP value (m) Maximum vapour load (Pa0.5 ), F-factor
2 3
DN 50
199* 0.23** 0.5**
DN 450
300 0.46 0.5 1.2
Fig. 4 Representation of step 2 of the design method. ethers (Sneesby et al., 1997; Subawalla and Fair, 1999). nexcess nalcohol, feed + alcohol, feed
i=1 stoichiometry nunreacted
ni,feed
1 1 xiaze
i (7)
= unreacted and inert species
Finally, if nexcess > nactual , where nactual is the alcohol,feed alcohol,feed alcohol,feed molar ow rate entering the column, more alcohol should be fed to the CD column. Otherwise, the molar ow rate of alcohol in the prereactor feed (Fig. 1) should be decreased.
4.2.
Step 2: Simultaneous initialisation
The objective of this step is to determine the column diameter, the height of the column and the operating conditions. Before the column diameter is calculated, the geometric properties of the selected catalytic packing are discussed because the column diameter strongly depends on the packing characteristics. Fig. 4 presents a schematic representation of the variables estimated in step 1 and their relationships with the variables calculated in step 2.
i.e., Katapak SP11 and Mellapak 750Y . As catalyst, the sulfonic acid ion-exchange resin Amberlyst 16 W, which is thermal stable up to 400 K was chosen. Because the void fractions of Katapak SP11 and Mellapak 750Y are signicantly different, the suitability of the non-catalytic packing must be veried in the nal design because the CD column must operate close to the optimal hydrodynamics of each packing. The lack of information in the open literature about the scale-up from lab/pilot to industrial scale columns is one of the major problems in the design of CD columns. Hoffmann et al. (2004) showed that the geometric properties, such as the catalyst volume fraction, specic surface area and void fraction of the catalytic packing MULTIPAK , change with the diameter of the column. However, these authors also showed that these geometric properties did not change signicantly for column diameters larger than 400 mm. Information about the maximum capacity and the separation efciency of KATAPAK-SP11 is available in the open literature (Brunazzi and Viva, 2006; Behrens, 2006; Buchaly et al., 2007). Table 5 shows a comparison between the specic geometric area and the catalyst volume fraction of this catalytic packing for two different column diameters (50 and 450 mm nominal diameters, DN). The use of the geometric properties of the catalytic packing obtained with a DN 50 column will provide poor CD column designs. In this work, the experimental measurements (Table 5) determined by Behrens (2006) are used. This author carried out experiments in a column with a diameter of 450 mm, and therefore his experimental data can be considered as representative of an industrial scale column. Correlations published by Hoffmann (2005) and by Rocha et al. (1993, 1996) were applied for the description of the mass transfer and hydrodynamics in Katapak SP11 and Mellapak 750Y , respectively. Moreover, based on the fact that the catalytic particles could not be fully wetted particularly in industrial columns due to liquid mal-distribution problems (Beckmann et al., 2002; Baur and Krishna, 2002), it was assumed that only 80% of the packing area is wetted (Brunazzi E., personal communication, September, 2010).
4.2.2.
Estimation of the column diameter
4.2.1.
Column internals
The selection of proper column internals is one important factor in the design of a CD column. In this study, the column internals used previously during the experimental investigation of the TAEE synthesis in a CD column published by Gonzlez-Rugerio et al. (2012) are applied for column design,
The column diameter (d) is a function of the vapour ow rate (V) within the column and mixture properties (i.e., vapour density, v ), and thus V and v must rst be estimated. To determine the ow rates and the mixture properties, a simulation with the EQ model is performed. The number of theoretical stages for the separation sections estimated in Section 4.1.2 is used in this simulation and the operating conditions are calculated based on the design specications or arbitrarily specied. Specically, an initial guess of the reux ratio and operating pressure is given but the maximal operating temperature of the catalyst is taking into account. Afterwards, the column diameter is calculated using Eq. (8), in which V and v
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are estimated using the non-catalytic packing but the F-factor corresponds to the catalytic packing. d=2 V F-factor
1/2
v)
1/4
(8)
4.2.3.
Calculation of the column height
Once the column diameter is known, the height of the catalytic section (hcat ) is obtained according to Eq. (9) (Baur and Krishna, 2002) using the previously obtained catalyst volume (see Section 4.1.2) and the catalyst volume fraction. The height of the separation sections can be calculated with the number of theoretical stages obtained in Section 4.1.2 and the HETP value of the noncatalytic packing. In this step, the HETP value is assumed to be constant. hcat = 4(catalyst volume) . d2 (catalyst volume fraction) (9)
4.2.4.
Estimation of the operating conditions
Finally, the entire CD column (including three sections) is used to determine the search direction of the operating conditions to be used during the optimisation. Here, reux ratio and pressure are varied to determine the direction in which the IA conversion increases. As base for this calculation, an EQ model is applied, in which the reaction kinetics are included. At this point, a column which does not necessarily meet the design specications is obtained (infeasible column design) but it is taken as starting point for the application of the third step of the proposed method.
ability to escape from local minimums (Babu and Angira, 2006). When compared to gradient based optimisation methods, the MDE has the main advantage of not being inuenced by the starting points chosen for the optimisation because the objective function is evaluated simultaneously in several starting points. However, it is due to this reason than the MDE is slower than gradient based methods (Leboreiro and Acevedo, 2004). In essence, the MDE is based on natural evolution, adopting some biological processes, such as mutation, recombination and selection. The objective function, the constraints and the search space of the optimisation variables must be specied for the MDE algorithm, as well as additional parameters, such as the maximal number of iterations. Moreover, the number of vectors whose components are the optimisation variables must be established. The magnitudes of these components are generated randomly by the MDE within the search space and the objective function is calculated for each vector. The algorithm continues with the combination of the vectors through the execution of stochastic operators (recombination and mutation). After a subsequent calculation of the objective function, selection takes place and only the vectors with the best values of the objective function are kept. This procedure is repeated until either no better option is found (tolerances are satised) or the maximum number of iterations is reached.
4.3.2.1. Objective function. Costs are the most important criteria for the evaluation of a chemical process. In this study, the sum of the annualised investment and the annual operating costs per tonne of TAEE is used as the objective function f. TOC + ann TIC toper mTAEE
4.3.
Step 3: Detailed optimisation
f = min
(10)
The optimal CD column is designed using an optimisation algorithm and an NEQ model. The objective function selected in this study is the production cost per tonne of TAEE. Reux ratio, EtOH molar ow rate and the column dimensions are chosen as decision variables for the optimisation.
Subject to: g(x) = 0 h(x)0 x Here, TIC is the total investment cost, TOC is the total operating cost, ann is the annualising factor (Ciric and Gu, 1994), toper is the annual operation time and mTAEE is the TAEE production. To estimate the TIC of the column, the costs of the shell material and the packing are considered. For the condenser and reboiler, the investment costs are based on the heat exchanger type and material as well as the operating pressure. The TIC is estimated using correlations set up by Douglas (1988), in which the economic factors were updated to the year 2008. Additional economic factors are used to take the peripheries into account according to Hirschberg (1999). The TOC is determined considering the consumption of steam and cooling water in reboiler and condenser, respectively. The constraints of the optimisation problem are given by Eq. (11), in which g(x) represents the CD process model equations, i.e. mass and energy balances, equilibrium relations and summation conditions. The system of non-linear algebraic equations consists of 5ncomponents + 1 equations per segment after the discretisation of the column height in axial direction (Krishnamurty and Taylor, 1985). For the TAEE synthesis, 130 segments were used and thus, 5330 equations were solved. h(x) are the design specications, such as product impurity, IA conversion, and maximal F-factor; and x is the vector of optimisation variables. (11)
4.3.1.
CD process modelling
In the literature several mathematical models to represent the phenomena occurring in a CD process have been presented (Taylor and Krishna, 2000; Noeres et al., 2003; Klker et al., 2005). These models can be primarily classied as either EQ or NEQ models. In the EQ model, it is assumed that both bulk phases are perfectly mixed and that the streams leaving each stage are at thermodynamic equilibrium. In contrast to the EQ model, in the NEQ model it is assumed that thermodynamic equilibrium occurs only at the vapourliquid interface and actual multicomponent mass and heat transfer rates across the vapourliquid interface are accounted for. Within the scope of this work, a steady state NEQ model is applied during the optimisation step. Mass transfer and hydrodynamics related model parameters are estimated by empirical packing-type specic correlations. The heterogeneously catalysed reaction is described by a pseudohomogeneous approach, in which mass transfer resistance between the liquid phase and the solid catalyst is neglected. More details about the applied NEQ model can be found in the supplementary information of this paper.
4.3.2.
Optimisation algorithm
The modied differential evolution (MDE) algorithm (Babu and Angira, 2006) is used as the optimisation method in this work. This optimisation algorithm is easy to implement and has the
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4.4.
Scope of the design method
Before the method is applied to design a CD column for the synthesis of TAEE, some general remarks about the design of CD columns are rstly given in this section. Later on, points which deserve special attention to apply the design method to other chemical systems are discussed.
Table 6 Number of theoretical stages and catalyst volume estimated with the sequential reaction-distillation process. Section
Rectifying section Catalyst volume (m3 ) Stripping section
Number of theoretical stages or volume

12 48 37
1) A fundamental requirement to design CD columns are accurate vapourliquid equilibrium data and reaction kinetics. The latter must be measured at the operating temperature expected in the column. 2) The application of NEQ models is only recommended if accurate correlations to describe the mass transfer and hydrodynamic behaviour within the packing are available. Otherwise, the EQ model should be used during the optimisation. 3) One of the main problems during the design of the CD column is the scale-up. While a large number of mass transfer and hydrodynamic correlations are available, which were measured at lab scale, relatively few information has been published for pilot scale columns. This is particularly important when the geometrical properties of the packing differ signicantly with the column diameter. More research in this area will help to solve this problem.
5.
Application example
In this section, the method is applied step by step to design a cost-optimal CD column for the synthesis of TAEE from EtOH and IA.
5.1. 5.1.1.
Step 1: Sequential initialisation Identication of the feed location
The feed stream to the CD column contains the reactants (IA) and the product (TAEE), which are some of the lightest and the heaviest component, respectively. Therefore, the feed was located in the stripping section not only to ensure a high IA concentration but also to avoid TAEE decomposition in the catalytic section.
The steps of the design method proposed in this paper, which should be done with caution are discussed in the following.
5.1.2. Estimation of the number of theoretical stages for the separation sections and catalyst volume
Once the feed location was identied, the number of theoretical stages and catalyst volume were estimated using the process conguration shown in Fig. 3a. In the rst non-reactive distillation column (stripping section), the Fenske equation was used and 2M2B and 2Mthp were selected as the light and heavy key components, respectively. The selection of the key components depends on the separation requirements. For example, as the stripping section must prevent the presence of impurities in the bottom stream of the CD column, 2M2B was selected as the key light component and 2Mthp was chosen as the key heavy component to prevent this component leaves the column in the distillate stream. Subsequently, the distillate stream of the stripping section containing the reactants was fed to the rst reactor (catalytic section). Four isothermal PFRs operating at 340 K, with a total catalyst volume of 48 m3 were necessary to reach an IA conversion of 90%. Finally, the efuent stream of the last reactor was fed to the second non-reactive distillation column, which represents the rectifying section. Here, the Fenske equation was applied again, choosing 2M2B and TAEE as light and heavy key components, respectively. In Table 6 the estimations of the number of theoretical stages and catalyst volume are shown.
1) Heuristic rules are a valuable approach to determine good estimations of the feed location and column conguration. However, to apply the heuristic rules, a deep analysis of the physical and chemical properties of the chemical system is required. The volatilities between reactants and products, formation of azeotropes and purity of the feed stream will have a crucial inuence in the column feed location, the proper column conguration and the reactant molar ratio in the column feed. Each chemical system has its own characteristic and therefore, the application of the heuristic rules presented in this paper must be done with caution. Particularly, the heuristic rule number four can only be applied for chemical systems in which a minimal boiling point azeotrope containing the reactant is formed. Special attention should be paid to the azeotropes present in the chemical system. 2) For chemical systems non-limited by the chemical equilibrium, the molar reactant ratio in the column feed should not be calculated using Eq. (7). The analysis of the physical and chemical properties of the chemical system will help to determine the excess of reactant, if needed. 3) The MDE algorithm has shown the ability to escape from local optimums, however, it requires a large number of evaluations of the objective function. Gradient based optimisation methods are faster but the nal solution is inuenced by the starting point. 4) Finally, it should be pointed out that steps one and two of the method do not guarantee to reach an optimal column, even if a feasible design is obtained. To tackle this situation, an optimisation algorithm is used in the third step of the method.
Table 7 Molar EtOH ow rates estimated using the reaction stoichiometry and azeotropic composition. At 4 bar
EtOH for reaction in the CD column EtOH IA azeotrope EtOH isopentane azeotrope Total EtOH in the outlet of the reactor Second feed (pure EtOH) 23.57 1.78 15.36 40.71 32.12 8.59
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Fig. 5 Operating and investment costs for the optimal column.
Table 8 IA conversion for different pressures and reux ratios. IA conversion (%) 2
Pressure (bar) 3.8 4.0 4.2 34.4 32.9 31.6
Reux ratio 2.5

43.4 41.6 39.9
Table 10 Comparison between the starting values calculated with the rst two steps of the method and the optimal column structure and operating conditions. Starting values
Operating conditions Reux ratio EtOH mole ow (mol/s) Reboiler heat duty (MW) IA conversion Column dimensions (m) Rectifying section height Reactive section height Stripping section height Diameter 3 8.59 11.7 67.0%
3
68.2 67.0 65.6
Optimal column
3.52 6.44 13.3 90.4%
5.1.3. Calculation of the molar reactant ratio in the column feed

The EtOH molar ow rate to the CD column was estimated using Eq. (7). In Table 7 the ow rates calculated at 4 bar are shown. The results presented in Table 7 enable the following conclusions to be drawn: if the column operates at 4 bar, then the required EtOH ow rate (40.71 mol/s) is higher than the actual efuent EtOH ow rate from the prereactor (32.12 mol/s). Therefore, it is necessary to increase the EtOH ow rate to the CD column. The additional EtOH molar ow rate was added to the column by a second feed located just below the reactive section (Fig. 1) due to the minimal boiling point azeotrope formed between EtOH and isopentane.
2.4 10.8 7.4 3.5
0.9 7.2 5.6 3.7
5.2.2. Calculation of the column height and the operating conditions

The height of the catalytic zone was calculated using Eq. (9), while the height of the non-catalytic sections with the equilibrium stages shown in Table 6 and the HETP of Mellapak 750Y . A sensitivity analysis was carried out for this column conguration using the EQ model including the reaction kinetics. The simulations with this model gave the results shown in Table 8. Note that increasing the reux ratio and decreasing the pressure increase the IA conversion. However, decreasing the pressure increases the impurities in the bottom stream and the diameter of the column (Baur and Krishna, 2002). Therefore, a pressure of 4 bar was chosen during the optimisation, which might meet all design specications. Although the pressure was xed during the optimisation, the algorithm can include the pressure as an optimisation variable with the consequence of increasing the computing time and decreasing the convergence rate of the CD model. Based on the results presented in Table 8, a reux ratio of 3 was used a starting value during the optimisation. Additionally, the column diameter and height of the catalytic zone were updated considering a reux ratio of 3.
5.2. 5.2.1.
Step 2: Simultaneous initialisation Estimation of the column diameter
The column diameter was estimated using the number of theoretical stages of the non-catalytic sections shown in Table 6. Here, the EQ model was applied to estimate the ow rates within the column. To apply the EQ model, the packing and the operating conditions had to be specied. The distillate-tofeed ratio (0.42 kmol/kmol) was calculated based on the feed composition, the desired conversion and the maximal content of impurities in the bottom stream of the column and it is xed during the optimisation. Reux ratio and pressure were selected at 2 and 4 bar, respectively. This simulation gave a column diameter of 3.1 m.
Table 9 Comparison of the best three CD columns found by the MDE algorithm. Optimisation variable
Reux ratio EtOH mole ow (mol/s) Rectifying section height (m) Reactive section height (m) Stripping section height (m) TAEE production cost (euro/tonne)
Column 1 (best solution)

3.52 6.44 0.9 7.2 5.6 18.38
Column 2
3.52 6.38 1.2 7.4 6.0 18.61
Column 3
3.5 6.42 2.2 7.0 5.7 18.75
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Fig. 6 Sketch of the optimal column for the TAEE synthesis.
5.3.
Step 3: Detailed optimisation
Finally, the column structure and operating conditions obtained in the last step of the method were taken as starting values for the optimisation algorithm using an NEQ model. The height of each column section, the reux ratio and the EtOH molar ow rate in the column feed were selected as
optimisation variables (Fig. 1). Table A.4 in Appendix provides the limits of the optimisation variables used in the MDE algorithm. Based on the optimisation results, the percentage of ooding of the non-catalytic sections (both lled with Mellapak 750Y ) was veried. The second stripping section (between the FCC feed and the bottom of the column) was operating close to 100% of the maximal vapour load while the rectifying and the rst stripping section in the range of 6580% of the ooding point. Therefore, another structured non-catalytic packing with a higher capacity than Mellapak 750Y was used for the second stripping section: Sulzer BXTM . After this modication, the optimisation algorithm was applied again. Afterwards, the percentage of ooding of the noncatalytic sections was calculated again and the separation sections were operating between the 65 and 80% of the maximal vapour load. At the end of the optimisation different columns with slightly higher values of the objective function that the one associated with the optimal column were found. In Table 9 a comparison of the best three columns found by the MDE algorithm is presented. Note that the cost associated with columns 2 and 3 is only 1.25% and 2% higher than the one of the optimal column. From the technical point of view, the three columns meet the design specications. However, this does not mean that any feasible design (e.g., the column obtained with simulation studies) has a low cost. In Fig. 5 the distribution of the total cost for the best solution obtained with the MDE are presented. The best solution found by the MDE algorithm has a total cost of 18.38 euro/tonne TAEE. With the optimal column, an IA conversion of 90.4% (based on the inlet to the column) and a TAEE purity of 32.9% can be achieved. Table 10 shows the optimal column structure and operating conditions and compares the optimal values with the
Fig. 7 Composition (top) and temperature (bottom) proles of the liquid phase for the best solution obtained with the MDE.
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Fig. 8 Reaction rate for the TAEE synthesis (left) and liquid and vapour molar ow rates (right) along the column height. Table 11 Molar ow rates in the optimal column. Component
Molar ow rates (mol/s) Isopentane 2M1B 2M2B 2Mthp 2M2P EtOH TAEE THEE Total mole ow (mol/s)
Mixture feed
100.80 2.24 23.11 79.20 9.17 32.12 22.64 2.83 272.11
EtOH Distillate
Bottom
0.0 0.0 0.0 0.0 0.0 6.44 0.0 0.0 6.44
100.34 0.20 0.95 0.0 0.0 15.5 0.0 0.0 116.99
0.45 0.01 1.27 79.20 9.02 0.0 45.56 2.98 138.49
of the column, the temperature increases due to the high concentration of heavy components. The reaction rate is shown in Fig. 8 (left). A maximum in the reactive zone appeared, which is an indication that the column is operating at the optimal conditions. In Fig. 8 (right) the liquid and vapour molar ow rates are shown. A high vapour ow occurs in the reactive section due to the reduced void fraction of the catalytic packing.
7.
Conclusions
starting values obtained with the rst two steps of the method. A sketch of this column is shown in Fig. 6. Note that the starting values are a reasonable starting point for the application of the optimisation algorithm. As expected, the nal column diameter is larger than the estimation based on the noncatalytic packing, because Sulzer BXTM has a higher void fraction than KATAPAK SP11 . The analysis of the optimal column is presented in Section 6.
6.
Optimisation results and discussion
In this work, a method to design a cost-optimal CD column for chemical systems with large number of components and chemical reactions is presented. The complexity of the mathematical models involved in the method is increased step by step. In the rst step of the method, the decomposition of the CD column into a sequence of chemical reactors and non-reactive distillation columns is performed to determine the column structure and the catalyst volume. Later on, an equilibrium stage model is applied to estimate the column diameter and operating conditions. These two steps provide starting values for the next step, in which an optimisation algorithm is applied using a rigorous non-equilibrium stage model for column simulation.
In Table 11, the molar ow rates in each stream of the optimal CD column are shown. Figs. 7 and 8 show the composition and temperature proles, reaction rate and liquid and vapour molar ow rates along the column height. Based on these gures several conclusions can be drawn: EtOH and isopentane are withdrawn at the top of the column, almost reaching the azeotropic composition (Fig. 7, top). A short rectifying section is sufcient to prevent TAEE loss in the distillate stream. The rst stripping section separates the TAEE that enters the column while the second stripping section is responsible for the separation between EtOH and IA from TAEE. The feed is located in the stripping section to prevent TAEE decomposition in the reactive zone. As a result, the formation of THEE is negligible because 2M2P tends to move towards the bottom of the column (Fig. 7, top). The average temperature in the reactive zone is 348.8 K, and an increase of 8.3 K occurs from the top to the bottom of this section (Fig. 7, bottom). This temperature avoids problems with the thermal stability of the catalyst. At the bottom
Table A1 Physical properties of catalysts (Rohm & Haas). Amberlyst 16W

Concentration of active sites (eq/l) Surface area (m2 /g) Average pore diameter (nm) Shipping weight (g/l) Moisture holding capacity (%) 1.7 30 25 780 5258
Amberlyst 15W
1.7 53 30 770 5257
Table A2 Pre-exponential factors and activation energies for the Arrhenius equation (Linnekoski et al., 1997; Zhang and Datta, 1995). Reaction
1 2 3 4
k0i (mol kg1 s1 )

7.82 E11 1.72 E14 4.66 E10 1.42 E15
Ei (kJ mol1 )
76.8 95.9 72.9 108.7
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Table A3 Coefcients for the calculation of the chemical equilibrium constant (Kitchaiya and Datta, 1995). ln Ki = Ai + Bi T1 + Ci ln + Di T + Ei T2 + Fi T3 , K3 = K1 K2 1 . Reaction
1 2 4
Ai
22.809 26.779 84.431
Bi
3136.3 2078.6 6870.67
Ci
5.8227 6.5925 13.032
Di
0.0179 0.0231 0.0378
Ei
6.395 E6 1.126 E5 3.3181 E5
Fi
1.672 E8 1.414 E8 3.260 E8
Table A4 Limits of the optimisation variables used in the MDE algorithm. Variable
Reux ratio Rectifying section height Catalytic section height First stripping section height Second stripping section height EtOH molar ow rate fed to the CD column
Lower limit
2 0.5 6.0 0.5 1.0 5.0
Upper limit
4 2.5 12.0 3.0 6.0 10.0
The method was applied to design a CD column for the synthesis of TAEE from EtOH and IA. No column design for this reaction system could be found in the open literature before. The results presented in this contribution show the feasibility of producing TAEE applying a CD column with an IA conversion higher than 90%. However, due to the high concentration of heavy inert components in the column feed, the TAEE purity is approximately 33 mole%.
Supplementary information
Equations to represent the catalytic distillation process using a non-equilibrium stage model.
Acknowledgement
C. A. Gonzlez-Rugerio is thankful to CONACyT-DAAD for the nancial assistance during the course of this work.
Appendix A.
The adsorption equilibrium constant for EtOH is given by KEtOH = 2.75 for the THEE synthesis and by KEtOH = 3.75E 3 exp( 2369.5/T) for the TAEE synthesis (see Tables A1A4).
Appendix B. Supplementary data

Supplementary material related to this article can be found, in the online version, at doi:10.1016/j.cherd.2013.08.030.
References
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CHERD-1363; No.

Contents lists available at ScienceDirect

Chemical Engineering Research and Design

Optimal design of catalytic distillation columns: A case study on synthesis of TAEE

CHERD-1363; No. of Pages 14

CHERD-1363; No. of Pages 14

Reaction rate equation (mol kg1 s1 )

Table 2 Normal boiling points (Aspen Properties PlusTM ). Abbreviation

Chemical process description

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inlet noutlet TAEE nTAEE outlet ninlet EtOH nEtOH

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Fig. 2 Structure of the design method proposed in this work.

Step 1: Sequential initialisation Feed location

Table 4 Feed and product molar ow rates in the prereactor. Component

EtOH feed to the prereactor

Prereactor outlet stream

100.8 16.45 31.55 79.20 12.00 0.00 0.00 0.00 240.00

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4.1.3. Calculation of the molar reactant excess in the column feed

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= unreacted and inert species

Step 2: Simultaneous initialisation

Estimation of the column diameter

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Calculation of the column height

Estimation of the operating conditions

Step 3: Detailed optimisation

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Scope of the design method

Number of theoretical stages or volume

Step 1: Sequential initialisation Identication of the feed location

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Fig. 5 Operating and investment costs for the optimal column.

Reux ratio 2.5

5.1.3. Calculation of the molar reactant ratio in the column feed

2.4 10.8 7.4 3.5

0.9 7.2 5.6 3.7

5.2.2. Calculation of the column height and the operating conditions

Step 2: Simultaneous initialisation Estimation of the column diameter

Column 1 (best solution)

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Fig. 6 Sketch of the optimal column for the TAEE synthesis.

Step 3: Detailed optimisation

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0.0 0.0 0.0 0.0 0.0 6.44 0.0 0.0 6.44

100.34 0.20 0.95 0.0 0.0 15.5 0.0 0.0 116.99

0.45 0.01 1.27 79.20 9.02 0.0 45.56 2.98 138.49

Optimisation results and discussion

Table A1 Physical properties of catalysts (Rohm & Haas). Amberlyst 16W

k0i (mol kg1 s1 )

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Appendix B. Supplementary data

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