ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING Asia-Pac. J. Chem. Eng.

2011; 6: 357368 Published online 17 March 2011 in Wiley Online Library (wileyonlinelibrary.com) DOI:10.1002/apj.569

Special theme research article

Design and control of an ideal reactive divided-wall distillation process

San-Jang Wang,1 * Hsiao-Ping Huang2 and Cheng-Ching Yu2
1 2

Department of Chemical and Material Engineering, Ta Hwa Institute of Technology, Chiunglin, Hsinchu 307, Taiwan Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan

Received 25 September 2010; Revised 3 January 2011; Accepted 31 January 2011

ABSTRACT: Reactive distillation and divided-wall distillation are two promising technologies achieving substantial economical benets from process intensication. In this study, a novel reactive divided-wall distillation process, procuring technical advantages from both reactive distillation and divided-wall distillation, is designed with different degrees of thermal coupling to achieve possible energy saving for an ideal quaternary reaction system with the least favorable relative volatility ranking under excess-reactant design. Simulation results demonstrate that reactive divided-wall distillation can provide better energy efciency than reactive distillation without thermal coupling. Energy efciency increases with the degree of thermal coupling. Proper selection and pairing of controlled and manipulated variables chosen for three control objectives are determined by using steady-state analysis. Temperature control in the reactive distillation column is used to maintain reactant inventory in the process. Product purities are maintained by the temperature control loops in the divided-wall column. Stage temperatures that have modest sensitivity to manipulated variables and have little variations with respect to throughput rate changes are selected as controlled variables. Dynamic tests show that the proposed control scheme can maintain high product purity and stoichiometric balance between the reactant feeds for throughput rate changes. 2011 Curtin University of Technology and John Wiley & Sons, Ltd. KEYWORDS: reactive distillation; divided-wall distillation; thermal coupling; design; control

INTRODUCTION
Distillation is one of the most important separation technologies in the chemical industry. The separation of multicomponent mixtures by continuous distillation has traditionally been accomplished by arranging columns in series. Several alternative congurations exist, most notably the direct sequence and indirect sequence. However, the main disadvantage of distillation is its high energy consumption, and therefore saving energy is an important objective in the distillation design. Thermal coupling between two columns in a sequence has proven to be very successful in providing energy savings of around 30% with respect to the conventional distillation trains.[1 7] These separation sequences evolved into the divided-wall distillation congurations with different degrees of thermal coupling. Compared to conventional distillation, divided-wall distillation offers higher thermodynamic efciency, lower capital investment, lower energy requirement, etc. The options of
*Correspondence to : San-Jang Wang, Department of Chemical and Material Engineering, Ta Hwa Institute of Technology, Chiunglin, Hsinchu 307, Taiwan. E-mail: cewsj@et4.thit.edu.tw
2011 Curtin University of Technology and John Wiley & Sons, Ltd. Curtin University is a trademark of Curtin University of Technology

divided-wall distillation processes can decrease energy consumption because remixing is avoided or reduced, in contrast to conventional distillation sequences.[4,8] Remixing is associated with higher energy consumption because additional energy is required in the next column in order to re-purify the mixture. However, application of divided-wall distillation was limited, mainly because of complexity in design and control of these structures.[9] Reactive distillation is an innovating process which realizes both chemical reaction and separation into a single unit. It increases reaction conversion by removing the product and simplies separation by reacting away azeotropes. The literature up to 1992 was reviewed by Doherty and Buzad[10] and simulation and designs have been reviewed by Taylor and Krishna.[11] Books by Doherty and Malone,[12] Sundmacher and Kienle,[13] and Luyben and Yu[14] present updated summaries. Despite recent progress in reactive distillation, conceptual design of reactive distillation processes and, more importantly, quantitative assessment of the reactive distillation process over conventional reaction/separation process is still lacking. Ideal reactive

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distillation processes[15,16] offer a continuous spectrum in studying the process behavior by stripping away all the non-ideal phase equilibrium and specic reaction rates. The design of ideal reactive distillation has been explored[17 19] and comparison to conventional multiunit recycle processes has been made for specic systems.[15,20] Tung and Yu[21] studied the effects of relative volatility rankings to the stoichiometric design of ideal reactive distillation processes. For quaternary reaction (A + B C + D) systems, all possible relative volatility rankings can be classied into six processes based on the distribution of reactants and products in the relative volatility sequence. The reaction system with the least favorable relative volatility ranking needs the largest total annual cost (TAC). Following the approach of Tung and Yu[21] , Lin[22] explored the question of when and how the excess-reactant design should be used in the design of the ideal reactive distillation processes. Simulation results show that TAC can be substantially reduced by using excess-reactant design for the reaction system with the least favorable relative volatility ranking. Process intensication represents an important trend in chemical engineering and process technology and attracts more and more attention in industry and research communities. Divided-wall distillation and reactive distillation are two promising technologies achieving substantial economical benets from process intensication. In the study, the performance of reactive divided-wall distillation, a technology combining reactive distillation and divided-wall distillation, with different degrees of thermal coupling is investigated for the ideal quaternary reaction system with the least favorable relative volatility ranking under excess-reactant design. We demonstrate that reactive divided-wall distillation can provide better energy efciency than conventional reactive distillation. The process with better energy efciency means that it can provide less energy consumption. Energy efciency increases with the degree of thermal coupling. Finally, the feasibility of temperature control designed by steady-state analysis is investigated for the intensied process with the maximum degree of thermal coupling.

LLK, LK, HK, and HHK are used to denote the components ranging from the lightest boiler to the heaviest boiler. The relative volatilities of the products are adjacent to each other, with two reactants on opposite sides. The two reactants have a maximum boiling-point difference for this type process. This corresponds to the worst case scenario, because two reactants can hardly coexist in the liquid phase. In the reactive zone of the reactive distillation process, the reaction rate of component i on tray j is expressed as: Rj ,i = i Mj (kFj xj ,A xj ,B kBj xj ,C xj ,D ) (2)

where Rj ,i is the reaction rate of component i on the j th tray (mol/s), i is the stoichiometric coefcient which takes a negative value for the reactants, Mj is the kinetic holdup on reactive tray j (mol), and xj ,i is the mole fraction of component i on tray j . The forward and backward specic rate constants described by the Arrhenius law of the rate constants on tray j are kFj = aF e EF /RTj kBj = aB e
EB /RTj

(3) (4)

DESIGN OF REACTIVE DISTILLATION SEQUENCE WITHOUT THERMAL COUPLING

Tung and Yu[21] studied the effects of relative volatility rankings on the design of ideal stoichiometric reactive distillation processes. Simulation results indicate that the type IR reactive distillation gives the most expensive design. The reaction for type IR process is proceeded as follows: A LLK + B HHK C LK + D (1) HK
2011 Curtin University of Technology and John Wiley & Sons, Ltd.

where aF and aB are the pre-exponential factors, EF and EB are the activation energies, and Tj is the absolute temperature on tray j . Tray temperature is computed from the ideal vapor liquid equilibrium, provided with Antonie vapor pressure expression. Kinetic holdup comes from the tray sizing by considering a weir height of 10 cm and the column diameter is determined from the maximum vapor rate by assuming an F -factor of 1. For the case when the reaction occurs in the reboiler and/or the condenser, the maximum kinetic holdup is taken to be 20 times the tray holdup. Kinetic and physical property data are given in Table 1. By considering column pressure as a design variable, Lin[22] followed the approach of Tang and Yu[21] and designed the type IR process with exact stoichiometric feeds by using TAC as an objective function. Figure 1a shows the optimal conguration with minimum TAC under the stoichiometric design. The reactive zones are placed at the opposite ends of the reactive distillation column (RDC) where signicant amounts of LLK and HHK (two reactants) are present. The heavy reactant (HHK) is introduced into the top of the column where a signicant amount of the other reactant (LLK) is present. Similarly, the light reactant (LLK) is fed to the bottom of the column where a signicant amount of HHK is present. The product, mixtures of LK and HK, is withdrawn as a sidestream and is fed to a conventional column for further separation. Poor reactant composition distribution in the reactive zone (e.g. a high concentration of one reactant while a low concentration of the other) can be observed for this type process. To improve the reactant distribution in
Asia-Pac. J. Chem. Eng. 2011; 6: 357368 DOI: 10.1002/apj

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DESIGN AND CONTROL OF REACTIVE DIVIDED-WALL DISTILLATION

359

Table 1. Kinetic and physical properties of the ideal system studied.

Activation energy (cal/mol) Forward (EF ) Backward (EB ) Specic rate constant at 366 K (kmol s1 kmol1 ) Forward (kF ) Backward (kB ) Heat of reaction (cal/mol) Relative volatilities (LLK/LK/HK/HHK) Vapor pressure constantsa (ln P S i = AVP,i BVP,i /T ) AVP BVP
a

12 000 17 000 0.008 0.004 5000 8/4/2/1 LLK LK HK HHK 13.04 12.34 11.65 10.96 3862 3862 3862 3862

P S i is in bar and T is in Kelvin.

the reactive zone, making one of the reactants feed to the RDC in excess is a straightforward approach. The principle for the selection of the excess reactant is to identify the limiting reactant in the reactive zone. The analysis of the composition prole given in the work
A 12.6 mol/s B 12.6 mol/s B 12.6 mol/s

of Tung and Yu[21] revealed that reactant B (HHK) is the limiting reactant in the upper part of the RDC, and reactant A (LLK) is the limiting reactant in the lower part of the RDC. If reactant B is chosen to be in excess, the reactive zone should be placed in the upper section of the RDC, where the concentration of reactant A is higher. If reactant A is made in excess, the reactive zone should be located in the lower section of the RDC, where the other reactant B has high concentration instead. Lin[22] designed these different processes and showed that heavy-reactantexcess gives the least TAC. Figure 1b gives the type IR process designed by Lin[22] under excess-reactant design. It consists of one RDC and two conventional separation columns. The TAC of the excess design is less than half (41%) that of the stoichiometric design. In this section, the nominal process with the minimum total reboiler duty is designed rst and will be compared later with the reactive divided-wall distillation processes with different degrees of thermal coupling. The same pressure of a conventional distillation column as that of an RDC is used for the implementation of thermal coupling between columns. Note that the design and simulation of the ideal reactive distillation in this study

C (95 mol%) RR=2.03 C1 19 NS=29 C2 19 NT=35 NS=14 NT=36 C1 Nrxn=21 C2 19

C (95 mol%) C3 14 NT=26

D (95 mol%)

A 2 mol% B 2 mol% C 48 mol% D 48 mol%

A 12.6 mol/s (a) A 12.6 mol/s B 12.6 mol/s

D (95 mol%)

Recycle B (b) 12.6 mol/s A 4.04 mol% B 0 mol% C 95 mol% D 0.96 mol% RR=2.33

B (95 mol%)

C1 Nrxn=21 37.78 mol/s A 1.35 mol% B 32.98 mol% NS=14 C 32.00 mol% D 33.67 mol%

C2 19 NT=36 25.18 mol/s A 0 mol% B 49.48 mol% C 0.48 mol% D 50.04 mol%

C3 14 NT=26

12.6 mol/s A 0 mol% RR=1.89 B 4.04 mol% C 0.96 mol% D 95 mol%

QR = 255.5 kcal/s Recycle B QR = 268.3 kcal/s QR = 299.0 kcal/s 12.58 mol/s A 0 mol% B 95 mol% C 0 mol% D 5 mol%

(c)

Figure 1. Process congurations for type IR with (a) stoichiometric design, (b) excess design by Lin,[20] and (c) excess

design with the minimum total reboiler duties. This gure is available in colour online at www.apjChemEng.com.
2011 Curtin University of Technology and John Wiley & Sons, Ltd.

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use the rigorous distillation model provided by ChemCad software. Parameters such as physical properties, relative volatilities, chemical equilibrium constant, activation energies, pre-exponential factors, etc. were given in the software for the quaternary system with hypothetical components. The equilibrium-based approach was used for simulation. Figure 1c shows the nominal process for type IR with excess design. In this study, we number stages from the column top, so that the condenser plus reux-drum as a whole is numbered stage 1, as that in the ChemCad software. Reactants A (LLK) and B (HHK), with a ow rate of 12.6 kmol/h, respectively, are fed into a 35-stage RDC (C1 ) at stage 1. The RDC has 21 trays (including a total condenser) in the reaction zone, followed by a stripping section with 14 trays (including a partial reboiler). The column is operated at 8 bar under total reux. The bottom product of column C1 is then fed to a 36-stage conventional distillation column (C2 ) at stage 19. Product C (LK) with purity 95 mol% is produced in the column distillate. The bottom product, mainly consisting of B (HHK) and D (HK), of the column is fed to a 26stage conventional distillation column (C3 ) at stage 14. Product D with purity 95 mol% is obtained from the column overhead and reactant B (with purity 95 mol%) recovered from the column base is recycled back to the column C1 . In the process, there are ve design degrees of freedom: boilup ratios of three columns and reux ratios of columns C2 and C3 . The reux ratio of column C2 and reux and boilup ratios of column C3 are adjusted to satisfy purity specications of C, D, and B, respectively, from three outlet streams. The remaining two design degrees of freedom, boilup ratios of columns C1 and C2 , are used to minimize the total reboiler duty of the process. Figure 1c also shows the stream information and operating conditions of the process with the minimum total reboiler duty (822.8 kcal/s) when the boilup ratios of columns C1 and C2 are 0.980 and 1.680, respectively. The reboiler heat inputs for columns C1 , C2 , and C3 are 268.3, 299.0, and 255.5 kcal/s, respectively.

thermal coupling between two conventional distillation columns (PTC), (2) partial thermal coupling between column C1 and the system with partial thermal coupling (PTC + PTC) (constructed in structure 1), (3) full thermal coupling between two conventional distillation columns (FTC), and (4) partial thermal coupling between column C1 and the system with full thermal coupling (PTC + FTC, PTC + FTC ) (constructed in structure 3). The design of these dividedwall distillation processes and the effect of thermal coupling on energy consumption are discussed in the following.

Partial thermal coupling between two conventional distillation columns

Figure 2a shows the reactive distillation conguration (denoted by PTC) where partial thermal coupling is implemented between two conventional distillation columns. Liquid and vapor are interchanged between columns C2 and C3 . There are several design degrees of freedom in the process. The feed locations of columns C2 and C3 , boilup ratio of column C1 and vapor split ratio (VSR) in column C3 are used as the design degrees of freedom to minimize the total reboiler duty of the process while the reux ratio of column C2 and the reux and boilup ratios of column C3 are used to satisfy three purity specications of C, D, and B, respectively. Figure 2a also shows the stream information and operating conditions of the process with the minimum total reboiler duty (756.7 kcal/s) when boilup ratio of column C1 and VSR in column C3 are 0.915 and 1.586, respectively. The feeds of columns C2 and C3 are located at tray 19 in column C2 and tray 13 in column C3 , respectively. The reboiler heat inputs for columns C1 and C3 are 257.5 and 499.2 kcal/s, respectively. The process shown in Fig. 2a can save 8% total energy consumption than the one without thermal coupling. Figure 2b shows the owsheet of the reactive distillation process with divided-wall structure thermodynamically equivalent to the one in Fig. 2a. A vertical wall is located at the upper section of the divided-wall column (DWC) and extended through the column top.

DESIGN OF REACTIVE DIVIDED-WALL DISTILLATION

In this section, reactive divided-wall distillation with different degrees of thermal coupling is designed for the type IR case with excess design. The number of stages of one RDC and two conventional distillation columns remain unchanged in the study for the processes with and without thermal coupling to investigate the effect of thermal coupling on energy consumption. The same reaction volume and catalyst on every tray in the reactive zone are also used. There are several thermally coupled structures proposed in the study for the process shown in Fig. 1c: (1) partial
2011 Curtin University of Technology and John Wiley & Sons, Ltd.

Partial thermal coupling between column C1 and the system with partial thermal coupling
To reduce energy consumption further, partial thermal coupling is explored between the RDC and the system with partial thermal coupling shown in Fig. 2a. Figure 3a shows the process conguration (denoted by PTC + PTC) with partial thermal coupling twice. Liquid and vapor are interchanged not only between
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A 12.6 mol/s B 12.6 mol/s

DESIGN AND CONTROL OF REACTIVE DIVIDED-WALL DISTILLATION

12.6 mol/s A 4.20 mol% B 0 mol% C 95 mol% D 0.80 mol% RR=2.40 C1 C2 38.77 mol/s A 1.37 mol% B 34.62 mol% C 31.13 mol% D 32.88 mol% 19 NT=36 C3 13 NT=26 RR=1.19

361

12.6 mol/s A 0 mol% B 4.20 mol% C 0.80 mol% D 95 mol%

Nrxn=21

NS=14

QR = 499.2 kcal/s Recycle B QR = 257.5 kcal/s 13.57 mol/s A 0 mol% B 95 mol% C 0 mol% D 5 mol%

(a)

A 12.6 mol/s B 12.6 mol/s 12.6 mol/s A 4.20 mol% B 0 mol% C 95 mol% D 0.80 mol% C1 38.77 mol/s A 1.37 mol% B 34.62 mol% C 31.13 mol% D 32.88 mol% 13.57 mol/s A 0 mol% B 95 mol% C 0 mol% D 5 mol% (b) 12.6 mol/s A 0 mol% B 4.20mol% C 0.80 mol% D 95 mol%

RR=2.40

RR=1.19

Recycle B

QR = 257.5 kcal/s

QR = 499.2 kcal/s

Figure 2. Flowsheet of reactive distillation processes with (a) PTC structure

and (b) corresponding divided-wall structure. This gure is available in colour online at www.apjChemEng.com.

columns C2 and C3 but also between columns C1 and C2 . In the design degrees of freedom of the process, feed locations and VSRs of columns C2 and C3 are used to minimize the total reboiler duty of the process while the reux ratio of column C2 and the reux and boilup ratios of column C3 are used to satisfy three purity specications of C, D, and B, respectively. Figure 3a also shows the stream information and operating conditions of the process with the minimum total reboiler duty (669.5 kcal/s). The feeds of columns C2 and C3 are located at tray 20 in column C2 and tray 13 in column C3 , respectively. The process with this structure can save 18.6% total energy consumption than the one without thermal coupling. Figure 3b shows the owsheet of the reactive divided-wall distillation process thermodynamically equivalent to the one in Fig. 3a. Two vertical walls are inserted in the conguration. They are all located at the upper section of the reactive DWC and extended through the column top.
2011 Curtin University of Technology and John Wiley & Sons, Ltd.

Full thermal coupling between two conventional distillation columns

Figure 4 shows the reactive distillation conguration (denoted by FTC) where a DWC is constructed by implementing full thermal coupling between two conventional distillation columns. A vertical wall is placed at the middle section of the column. There is only one design degree of freedom, boilup ratio, in the RDC. In the design degrees of freedom for the DWC, feed location, sidedraw location, divided-wall location, liquid split ratio (LSR), and VSR are used to minimize the total reboiler duties of the process while reux ratio, sidedraw ow, and boilup ratio are adjusted to satisfy the purity specications of C, D, and B at the DWC distillate, sidedraw, and bottom, respectively. Figure 4 also shows the stream information and operating conditions of the process with the minimum total reboiler duty (754.2 kcal/s) when boilup ratio of column C1 , LSR and VSR in the DWC are 0.96, 3.09, and 1.19, respectively.
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A 12.6 mol/s B 12.6 mol/s 12.6 mol/s A 4.13 mol% B 0 mol% C 95 mol% D 0.87 mol% RR=1.64 C1 Nrxn=21 20 NS=14 NT=36 13 C2

Asia-Pacic Journal of Chemical Engineering

RR=0.99 C3

12.6 mol/s A 0 mol% B 4.13 mol% C 0.87 mol% D 95 mol%

NT=26

QR = 669.5 kcal/s Recycle B 14.15 mol/s A 0 mol% B 95 mol% C 0 mol% D 5 mol%

(a)

A 12.6 mol/s B 12.6mol/s RR=1.64

12.6 mol/s A 4.13 mol% B 0 mol% C 95 mol% D 0.87 mol%

12.6 mol/s A 0 mol% RR=0.99 B 4.13 mol% C 0.87 mol% D 95 mol%

14.15 mol/s A 0 mol% B 95 mol% C 0 mol% D 5 mol% Recycle B (b)

QR = 669.5 kcal/s

Figure 3. Flowsheet of reactive distillation processes with (a) PTC + PTC structure and (b) corresponding divided-wall structure. This gure is available in colour online at www.apjChemEng.com.

The reboiler heat inputs for column C1 and DWC are 274.4 and 479.8 kcal/s, respectively. The process shown in Fig. 4 can save 8.3% total energy consumption than the one without thermal coupling. It can be seen from the gure that the optimal position of the divided wall is located at the column middle when the feed compositions of the DWC for components C, D, and B are near equal. Similar energy efciency is provided by these two processes shown in Figs 2a and 4.

A 12.6 mol/s B 12.6 mol/s 39.48 mol/s A 0.76 mol% B 35.12 mol% C 31.16 mol% D 32.97 mol% 12.6 mol/s A 2.37 mol% B 0.01 mol% RR=4.37 C 95 mol% 5 6 32 D 2.62 mol%
18 43 1

C1
Nrxn=21

NS=14

31 57 58

12.6 mol/s A 0 mol% B 2.37 mol% C 2.63 mol% D 95 mol%

62

Partial thermal coupling between column C1 and the system with full thermal coupling
Figure 4.

Recycle B

QR = 274.4 kcal/s

QR = 479.8 kcal/s

14.28 mol/s A 0 mol% B 95 mol% C 0 mol% D 5 mol%

To further investigate the effect of thermal coupling on energy consumption, partial thermal coupling is
2011 Curtin University of Technology and John Wiley & Sons, Ltd.

Flowsheet of reactive distillation process with FTC structure. This gure is available in colour online at www.apjChemEng.com.
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A 12.6 mol/s B 12.6 mol/s
1

DESIGN AND CONTROL OF REACTIVE DIVIDED-WALL DISTILLATION

363

Table 2. Energy saving of different thermally coupled processes.

12.6 mol/s A 2.79 mol% B 0.02 mol% C 95 mol% D 2.19 mol% 12.6 mol/s A 0 mol% B 2.76 mol% C 2.24 mol% D 95 mol%
62

C1 Nrxn=21

31

RR=3.58

Total reboiler duty (kcal/s) No thermal coupling PTC PTC + PTC FTC PTC + FTC PTC + FTC 822.8 756.7 669.5 754.2 675.6 639.8

Energy saving (%) 0 8.0 18.6 8.3 17.9 22.2

16

42

NS=14

30 56 57

Recycle B (a) A 12.6 mol/s B 12.6 mol/s

QR = 675.6 kcal/s

14.91 mol/s A 0 mol% B 95 mol% C 0 mol% D 5 mol%

RR=3.29 C1 Nrxn=21
9 10 32 16 41

12.61 mol/s A 2.73 mol% B 0 mol% C 95 mol% D 2.27 mol% 12.6 mol/s A 0 mol% B 2.80 mol% C 2.20 mol% D 95 mol%

NS=14

31 53 54 62

Recycle B (b) A 12.6 mol/s B 12.6 mol/s

QR = 639.8 kcal/s

17.15 mol/s A 0 mol% B 95 mol% C 0 mol% D 5 mol%

12.61 mol/s A 2.73 mol% B 0 mol% RR=3.29 C 95 mol% D 2.27 mol% 12.6 mol/s A 0 mol% B 2.80 mol% C 2.20 mol% D 95 mol%

17.15 mol/s A 0 mol% B 95 mol% C 0 mol% D 5 mol% Recycle B (c)

QR = 639.8 kcal/s

Figure 5. Flowsheet of reactive distillation processes with (a) PTC + FTC structure, (b) PTC + FTC structure, and (c) corresponding divided-wall structure of setup (b). This gure is available in colour online at www.apjChemEng.com.

also implemented between the RDC and the DWC of the process shown in Fig. 4. Figure 5a shows the process conguration (denoted by PTC + FTC) with both partial thermal coupling and full thermal coupling. There is no design degree of freedom in the RDC. In the design degrees of freedom of the DWC, feed location, sidedraw location, divided-wall location, LSR, and VSR in the DWC and the vapor split from the DWC to the RDC are used to minimize the total reboiler duties of the process while the reux ratio, sidedraw ow, and boilup ratio of the DWC
2011 Curtin University of Technology and John Wiley & Sons, Ltd.

are adjusted to satisfy the purity specications of C, D, and B at the DWC distillate, sidedraw, and bottoms, respectively. Figure 5a also shows the stream information and operating conditions of the process with the minimum total reboiler duty (675.6 kcal/s) when LSR and VSR of the DWC and VSR from the DWC to the RDC are 4.8, 0.57, and 1.66, respectively. The process with this structure can save 17.9% total energy consumption than the one without thermal coupling. From the processes in Figs 4 and 5a, 9.6% energy consumption can be further reduced by implementing partial thermal coupling between the RDC and the DWC. In addition, similar energy efciency is provided by these two processes shown in Figs 3a and 5a. In the design of DWC for the processes of Figs 4 and 5a, the number of stages of DWC is set to be equal to the sum of the number of stages of the two conventional distillation columns. The number of stages in each side of the DWC is set to be equal to that of the conventional distillation column with less number of stages. However, what is the effect of the dividedwall length on energy consumption when the number of stages of the DWC remains unchanged? Figure 5b shows the process conguration (denoted by PTC + FTC ) with the minimum reboiler duty (639.8 kcal/s) when the length of the divided wall is used as a design degree of freedom. The number of stages in each side of the divided wall is reduced from 26 to 22. LSR and VSR of the DWC and VSR from the DWC to the RDC are 4.8, 0.55, and 1.68, respectively, for the optimal condition with the minimum reboiler duty. Energy saving of 22.2% can be obtained for the process shown in Fig. 5b than the one without thermal coupling. Energy consumption can be further reduced 4.3% by decreasing the length of the divided wall in the process shown in Fig. 5b. Figure 5c shows the conguration of the reactive divided-wall distillation process thermodynamically equivalent to the one in Fig. 5b. Two vertical walls are placed in the conguration. One is located at the upper section of the reactive DWC and extended through the column top while the other is placed at the middle section of the column. Table 2 summarizes the energy saving of different thermally coupled processes. These simulation
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0.2 Temperature deviation (K) Temperature change (K)
Feed A + 0.1% Feed A -0.1%

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1.0

0.1

0.5

0.0

0.0

-0.1

RDC

-0.5

DWC

-0.2

1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 Stage number

-1.0

11 16 21 26 31 36 41 46 51 56 61 Stage number

0.04 Temperature deviation (K) Temperature change (K)

0.02

Reflux flow + 0.1% Reflux flow -0.1%

0.00

-0.02

RDC

-1

DWC

-0.04

1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 Stage number

-2

11 16 21 26 31 36 41 46 51 56 61 Stage number

0.04 Temperature deviation (K)

Side draw flow + 0.3% Side draw flow -0.3%

1.0 Temperature change (K)

0.02

0.5

0.00

0.0

-0.02

RDC

-0.5

DWC

-0.04

1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 Stage number

-1.0

11 16 21 26 31 36 41 46 51 56 61 Stage number

0.04 Temperature deviation (K) Temperature change (K)

Reboiler duty + 0.1% Reboiler duty -0.1%

0.02

0.00

-0.02 RDC -0.04

-1 DWC -2

1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 Stage number

11 16 21 26 31 36 41 46 51 56 61 Stage number

Figure 6.

Stage temperature deviations from nominal values for changes in manipulated variables. This gure is available in colour online at www.apjChemEng.com.

results indicate that energy efciency increases with the degree of thermal coupling. The control strategies of the reactive divided-wall distillation process with the maximum degree of thermal coupling are investigated in the following section.
2011 Curtin University of Technology and John Wiley & Sons, Ltd.

CONTROL OF A REACTIVE DIVIDED-WALL DISTILLATION PROCESS

In an RDC, if the reaction is so fast that the system is in equilibrium, temperature and composition proles
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365

almost remain unchanged whenever there is a change in the production rate. However, for an RDC in the kinetic regime, the desired steady-state temperature or composition prole changes when feed rate changes and product purities are kept at their designed values.[23] Because of changes in the residence times on the catalytic stages, conversion changes. This poses a problem for controller design because the controller set points must be reset for various feed ow rates. In industrial applications, temperature control is usually used instead of composition control. The reason is that most product analyzers, such as gas chromatographs, suffer from large measurement delays and high investment and maintenance cost. To improve the control performance and have a faster mean of measuring the changes occurring in the column during transient conditions, the feasibility of temperature control is investigated in this study for throughput rate changes. There are three keys to controlling such a process: (1) to maintain the correct stoichiometric balance between the reactant feeds, (2) to maintain the product quality, and (3) to account for possible changes in control objective when throughput rate changes. The product purity and stoichiometric balance between the reactant feeds must be maintained when operating a reactive divided-wall distillation process. Feed-ratio control is the simplest way to maintain stoichiometric balance. However, when there is a measurement bias in feed ow rate, the feed-ratio control scheme will not be able to keep the desired feed ratio. To overcome this problem, Al-Arfaj and Luyben[24] suggested that the reactant composition of some column stage be controlled by the reactant feed ow. In this study, an internal composition loop is replaced by an internal temperature loop. The feed ows of reactants A and B are two candidates for the manipulated variable of the internal temperature control. From the open-loop sensitivity analysis, reactant A feed ow is selected as the manipulated variable because internal stage temperature is more sensitive to reactant A feed ow than reactant B feed ow. To more clearly distinguish the original position of the controlled stage temperature chosen by the following steady-state analysis, the structure shown in Fig. 5b is adapted in the control study. There are three product compositions (C at the distillate, D at the side draw, and B at the bottom of the DWC) to be maintained in the reactive dividedwall distillation process. They are maintained by adjusting the reux ow, sidedraw, and reboiler duty of the DWC. Figure 6 gives stage temperature deviations from nominal values for changes in reactant A feed ow in the RDC, reux ow, sidedraw, and reboiler duty in the DWC, respectively. These data can be used to pair the manipulated variables and controlled variables. Figure 7 shows the desired proles of temperature changes for the RDC and DWC when feed rates of reactant A and B are simultaneously increased or decreased by the same amounts, 20%, under product purities kept as their
2011 Curtin University of Technology and John Wiley & Sons, Ltd.

designed values. It indicates that the desired temperature prole changes as the feed rate changes for the RDC in the kinetic regime. It also gives the necessary variations of stage temperatures from the nominal condition under different feed ow rates. Hence, the set points of the temperature control loops must be adjusted as longterm disturbances occur. This causes great difculty in the process operation. However, we were able to nd some suitable candidates of controllable variables which have modest sensitivity to manipulated variables and are almost invariant or have little variations with respect to

(a)

1.0

Temperature change (K)

0.5

Feed flow -20% Feed flow +20%

0.0

-0.5

-1.0

1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 Stage number

(b)

1.0

Temperature change (K)

0.5

0.0

-0.5

-1.0

11

16

21

26 31 36 41 Stage number

46

51

56

61

Figure 7. Desired proles of temperature changes in the (a) RDC and (b) DWC for changes of reactant feed rates under product purities kept as their designed values. This gure is available in colour online at www.apjChemEng.com.

Table 3. Relative gain array analysis between controlled stage temperatures and manipulated variables.

m1 T16 T10 T37 T61

(RDC) (DWC) (DWC) (DWC)

m2 0.000 5.757 4.805 0.048

m3 0.000 0.002 0.006 1.008

m4 0.215 3.881 4.705 0.039

0.785 0.874 1.106 0.017

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Asia-Pacic Journal of Chemical Engineering

PC

TC PC A FC C B LC 10 TC D 16 TC LC

37

TC 61

LC Recycle B

Figure 8. Control scheme of the reactive divided-wall distillation process.

This gure is available in colour online at www.apjChemEng.com.

throughput rate changes. The temperature of stage 16 in the RDC and the temperatures of stages 10, 37, and 61 in the DWC are selected in the study as controlled variables of temperature loops from Figs 6 and 7. Table 3 shows the relative gain array analysis of these controlled stage temperatures and manipulated variables. m1 , m2 , m3 , and m4 represent the reactant A feed ow in the RDC, reux ow, sidedraw ow, and reboiler duty in the DWC, respectively. Hence the control loop pairing is that the temperature at stage 16 in the RDC is controlled by manipulating the reactant A feed ow. The temperatures at stages 10, 61, and 37 in the DWC are controlled by manipulating reux ow, sidedraw ow, and reboiler duty in the DWC, respectively. The temperature loop in the RDC is used to maintain reactant inventory in the process. Product purities are maintained by three temperature loops in the DWC. In the following discussions on control performance, the controllers were tuned using a sequential design approach[25] after the pairing was determined. For each controller, a relay-feedback test[26] is performed to obtain ultimate gain and ultimate frequency. The following equations are used to calculate the tuning parameters of PI controllers: KC = KCU 3 PU TI = 0.5 (5) (6)

where KC and TI represent proportional gain and integral time respectively, and KCU and PU are ultimate gain and ultimate period, respectively. Figure 8
2011 Curtin University of Technology and John Wiley & Sons, Ltd.

shows the scheme of temperature control in the reactive divided-wall distillation process. Four temperature control loops are designed by the above steady-state analysis. In the RDC, column pressure is controlled by manipulating the coolant ow rate. Reux-drum level is maintained by changing the reux ow rate. Reactant B feed is ow controlled. In the DWC, column pressure is controlled by manipulating the coolant ow rate. Reux-drum level and base level are maintained by changing the distillate ow rate and bottom ow rate, respectively. In the dynamic simulation, the diameters of RDC and DWC are designed as 0.3 and 0.45 m, respectively. The dimension of the condenser with horizontal orientation is set to be 2.27 m in diameter and 4.54 m in cylinder length for RDC and 2.41 m in diameter and 4.82 m in cylinder length for DWC. The dimension of the reboiler with vertical orientation is 2.35 m in diameter and 4.70 m in cylinder length for DWC. In the distillation control system, pressure, level, and ow control belong to inventory control maintaining the basic operation of column. Thus in the following discussion, emphasis is placed on the response of the temperature control strategy used to maintain product quality and stoichiometric balance. Figure 9 shows the dynamic responses of controlled stage temperatures, reactant A feed ow, and the corresponding product purities under the temperature control scheme for 20% changes in the reactant B feed ow. The controlled stage temperatures are settled at their corresponding set points. Stoichiometric balance is maintained and three product compositions
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111 Reactant B feed -20% Reactant B feed +20%

DESIGN AND CONTROL OF REACTIVE DIVIDED-WALL DISTILLATION

17 Reactant A feed flow (mol/s)

367

T16(RDC) (C)

109

14

107

11

105

103

10

20 Time (hr)

30

40

10

20 Time (hr)

30

40

117 C composition (mole fraction)

1.000

115 T10(DWC) (C)

0.975

113

0.950

111

0.925

109

10

20 Time (hr)

30

40

0.900

10

20 Time (hr)

30

40

131 D composition (mole fraction)

1.000

130 T37(DWC) (C)

0.975

129

0.950

128

0.925

127

10

20 Time (hr)

30

40

0.900

10

20 Time (hr)

30

40

164 B composition (mole fraction)

1.000

161 T61(DWC) (C)

0.975

158

0.950

155

0.925

152

10

20 Time (hr)

30

40

0.900

10

20 Time (hr)

30

40

Figure 9. Dynamic responses of controlled stage temperatures, reactant A feed ow, and product purities under temperature control for 20% changes in reactant B feed ow.

can almost return to their desired operating values under temperature control.

CONCLUSIONS
Reactive distillation and divided-wall distillation are two successful examples of process intensication. However, they represent different ways of integration. In the study, reactive divided-wall distillation, a
2011 Curtin University of Technology and John Wiley & Sons, Ltd.

technology combining reactive distillation and divided-wall distillation, is performed to further enhance the advantages of both integration ways. Its energysaving potential is investigated for an ideal quaternary reaction system with the least favorable relative volatility ranking under excess design. Different dividedwall structures are constructed by implementing partial or full thermal coupling between columns in the reactive distillation process. The reactive divided-wall distillation process with the maximum degree of thermal
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Asia-Pacic Journal of Chemical Engineering [6] J.A. Vazquez-Castillo, J.A. Venegas-S ancheza, J.G. SegoviaHern andeza, H. Hern andez-Escotoa, S. Hern andeza, C. Guti errez-Antoniob, A. Briones-Ram rezc. Comput. Chem. Eng., 2009; 33, 18411850. [7] R. Premkumar, G.P. Rangaiah. Chem. Eng. Res. Des., 2009; 87, 4760. [8] S. Hern andez, S. Pereira-Pech, A. Jimenez, V. Rico-Ram rez. Can. J. Chem. Eng., 2003; 81, 10871091. [9] G. Dunnebier, C.C. Pantelides. Ind. Eng. Chem. Res., 1999; 38, 162176. [10] M.F. Doherty, G. Buzad. Trans. Inst. Chem. Eng.,, 1992; 70(Part A), 448458. [11] R. Taylor, R. Krishna. Chem. Eng. Sci.,, 2000; 55, 51835229. [12] M.F. Doherty, M.F. Malone. Conceptual Design of Distillation Systems, Hill: New York, 2001. [13] K. Sundmacher, A. Kienle. Reactive Distillation, VCH: Weinheim, 2003. [14] W.L. Luyben, C.C. Yu. Reactive Distillation Design and Control, VCH: New York, 2008. [15] D.B. Kaymak, W.L. Luyben. Ind. Eng. Chem. Res., 2004; 43, 24932507. [16] Y.C. Cheng, C.C. Yu. Chem. Eng. Sci., 2005; 60, 46614677. [17] R.M. Dragomir, M. Jobson. Chem. Eng. Sci., 2005; 60, 50495068. [18] W.R. Hoffmaster, S. Hauan. AIChE J., 2006; 52, 17441753. [19] C.S. Chen, C.C. Yu. Ind. Eng. Chem. Res., 2008; 47, 48304844. [20] D.B. Kaymak, W.L. Luyben, O.J. Smith IV. Ind. Eng. Chem. Res., 2004; 43, 31513162. [21] S.T. Tung, C.C. Yu. AIChE J., 2007; 53, 12781297. [22] L.C. Lin. MS Thesis, National Taiwan University, Taipei, 2007. [23] S.J. Wang, D.S.H. Wong, E.K. Lee. Ind. Eng. Chem. Res., 2003; 42, 51825194. [24] M.A. Al-Arfaj, W.L. Luyben. Ind. Eng. Chem. Res., 2000; 39, 32983307. [25] S.H. Shen, C.C. Yu. AIChE J., 1994; 40, 627646. [26] W.L. Luyben. Ind. Eng. Chem. Res., 1987; 26, 24902495.

coupling is demonstrated to give the best energy efciency. Steady-state analysis is used to select controlled and manipulated variables and determine their pairing. For the process in the kinetic regime, we were able to locate points in the temperature prole that are relatively insensitive to throughput rate changes. Dynamic simulation results show that the temperature control strategy without changing the set points of temperature loops can maintain reactant inventory in the RDC and product purities in the DWC at their desired operating values.

Acknowledgement
This work is supported by the National Science Council of R.O.C. under Grant No. NSC 97-2221-E-233-004MY2.

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Asia-Pac. J. Chem. Eng. 2011; 6: 357368 DOI: 10.1002/apj