PROCESS CONTROL Chinese Journal of Chemical Engineering, 20(6) 11131120 (2012)

The Design and Control of Distillation Column with Side Reactors for Chlorobenzene Production*
BO Cuimei ()1,2,**, TANG Jihai ()2, BAI Yangjin ()1, QIAO Xu ()2, DING Lianghui ()2 and ZHANG Shi ()1
1 2

College of Automation and Electrical Engineering, Nanjing University of Technology, Nanjing 210009, China State Key Laboratory of Materials-oriented Chemical Engineering, Nanjing University of Technology, Nanjing 210009, China

Abstract The distillation column with side reactors (SRC) can overcome the temperature/pressure mismatch in the traditional reactive distillation, the column operates at temperature/pressure favorable for vapor-liquid separation, while the reactors operate at temperatures/pressures favorable for reaction kinetics. According to the smooth operation and automatic control problem of the distillation column with side reactors (SRC), the design, simulation calculation and dynamic control of the SCR process for chlorobenzene production are discussed in the paper. Firstly, the mechanism models, the integrated structure optimal design and process simulation systems are established, respectively. And then multivariable control schemes are designed, the controllability of SRC process based on the optimal steady-state integrated structure is explored. The dynamic response performances of closed-loop system against several disturbances are discussed to verify the effectiveness of control schemes for the SRC process. The simulating results show that the control structure using conventional control strategies can effectively overcome feeding disturbances in a specific range. Keywords distillation column with side reactors (SRC), mechanism models, multivariable control schemes, simulation system, chlorobenzene production

INTRODUCTION

Economic and environmental considerations have forced industry to focus on technologies based on process intensification. Reactive distillation has received much attention in the past decade in both industry and academia [1]. It has several advantages in some chemical systems, which may effectively reduce investment and operating costs, increase conversion and selectivity comparing to conventional multi-unit flowsheets with separate reaction and separation sections [2, 3]. There are two different kinds of integrated structure for reactive distillation process: One structure is that reaction and distillation units are integrated in a single column, namely the conventional reactive distillation; while the other is that the reactors are coupled externally with a distillation column, namely the distillation column with side reactors (SRC). For conventional reactive distillation, the temperatures that are good for reaction must match the temperatures that are good for vapor-liquid separation. Therefore, traditional reactive distillation is not effective in many chemical systems because of a mismatch in temperatures [4]. The distillation column with side reactors can not only effectively increase the conversion and selectivity, but also overcome the temperature or pressure mismatch in the traditional reactive distillation [5, 6]. There are several papers in the literature dealing with

the design and dynamic control of traditional reactive distillation. For example, Professor Luyben and his partners gave eight different type control structures (CS1-CS8) [7-9], which were widely used in traditional reactive distillation control system design [10], while the dynamic control of the SRC process was rarely discussed in the recent literature [11, 12]. In this paper, the mechanism model, structural design and dynamic control of the SRC process for benzene chlorination are explored, and the dynamic response performance of closed-loop system against several disturbances are discussed to verify the effectiveness of design for the SRC process. 2 PROCESS DESCRIPTIONS

Chlorobenzene is widely used in dye and pharmaceutical industry to manufacture some organic intermediates such as phenol, aniline, nitro phenol. Chlorobenzene is produced from the reaction of benzene and chlorine. The production is chlorobenzene and the byproduct is dichlorobenzene (mainly o-dichlorobenzene and dichlorobenzene). Reaction equations are as follows:

(1)

Received 2012-05-28, accepted 2012-07-20. * Supported by the National Natural Science Foundation of China (61203020, 21276126), the Natural Science Foundation of Jiangsu Province (BK2011795), Jiangsu Province Higher Education Natural Science Foundation (09KJA530004), and China Postdoctoral Science Foundation (20100471325). ** To whom correspondence should be addressed. E-mail: qct@njut.edu.cn; lj_bcm@163.com

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(2)

By using ferric chloride as a catalyst, the kinetic equation for chlorobenzene is as follows [13]:

r1 =
r2 =

d[C6 H 6 ] = k1[C6 H 6 ][Cl2 ] dt

(3)

d[C6 H 4 Cl2 ] (4) = k2 [C6 H5 Cl][Cl2 ] dt where r1 and r2 are the reaction rate for monochloride and dichloride; k1 and k2 are the reaction rate constants. The ratio of rate constants = k1 / k2 is about 8 at a reaction temperature of 55 C. The physical properties of benzene (C6H6), chlorobenzene (C6H5Cl) and dichlorobenzene (C6H4Cl2) are shown in the Table 1.
Table 1 Material related properties
Chemical formula benzene chlorobenzene dichlorobenzene C6H6 C6H5Cl C6H4Cl2 Boiling point /C 80.1 132.2 180.4 Molar mass /gmol1 78.11 112.56 147

dichlorobenzene move to the column bottom, in which there are two different zones: reaction zone and separation zone. The several trays in the reaction zone are linked with three side reactors, respectively. The continuous chlorine with a certain proportion is introduced to the bottom of three reactors, respectively, while fresh benzene is given to the first reactor connected with the top condenser. The hydrogen chloride generated in the reactions will escape from the condenser of the column. With continuous removal of the desired product chlorobenzene from the reaction zone, a higher selectivity may be achieved.
3 MODELING AND SIMULATING

The SRC process mechanism model contains two parts: MESH equations of the column and chemical kinetic model equations.
3.1 Reaction mechanism model

Each reactor was assumed to be a perfectly adiabatic mixed stirred tank reactor, and in the continuous chlorination reaction system continuous reaction material equilibrium equations with the tray j are as follows Eqs. (5)-(13):

Due to mismatch between reaction temperature and the separation temperature in benzene chlorination process, the SCR integrated structure for chlorobenzene production is designed, and the dynamic control system is researched. The configuration of SRC for chlorobenzene production is shown in Fig. 1. In Fig. 1, the lighter component benzene moves toward the column top and the heavier component chlorobenzene and

( y j ,1 z j ,1 ) FRj = V k1 z j ,1 = FCl (a + b / 2) (5) ( z j ,2 y j ,2 ) FRj = V ( k1 z j ,1 k2 z j ,2 ) = FCl a (6) ( z j ,3 y j ,3 ) FRj = V k2 z j ,3 = FCl b / 2 (7)

2 2 2

where yj,1, yj,2, yj,3, zj,1, zj,2 and zj,3 are the inlet and outlet mole compositions of benzene, chlorobenzene and dichlorobenzene from the reactor which is connected with the j-th tray; FRj is the inlet liquid flow rate to the reactor; FCl2 is chlorine feed flow rate; V is

Figure 1

Configuration of the SRC process for chlorobenzene production

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the volume of the reactor; and a and b are the mole fractions of chlorine used to form chlorobenzene and dichlorobenzene, respectively. Dividing Eq. (7) by Eq. (6) and introducing the rate-constants ratio = k1 / k2 , Eq. (8) can be obtained.
z j ,2 y j ,2 z j ,3 y j ,3 = k1 z j ,1 k2 z j ,2 k2 z j ,3 =

MESH equations include the material balance equations, phase equilibrium equations, the mole fraction of the normalized equation and heat balance equation [14]. MESH equations of tray j are shown as follows:

z j ,1 z j ,2
z j ,3

2a = (8) b

M j ,i = I j FR z j ,i + (1 I j ) L j 1 x j 1,i L j x j ,i + V j +1 y j +1,i V j y j ,i
E j = y j ,i
S xj = xi , j 1
i =1 c

(14) (15) (16)

When the reaction temperature is 55 C, = 8 . zj,1, zj,2 and zj,3 can be evaluated by shifting Eqs. (5-7) as follows: z j ,1 = y j ,1 FCl2 FRj a + y j ,2 z j ,2 = FCl2 FRj a + y j ,2

rj ,i PjS,i P

x j ,i
c

(9) (10)
(11)

S yj = yi , j 1
i =1

z j ,3 = ( FCl2 FRj ) (b / 2) + y j ,3

H j = I j FRj H Rj + I j FHClj H HClj + (1 I j ) L j 1 H Lj 1 L j H Lj + V j +1 H Vj +1 V j H Vj + VGj +1 H VGj +1 VGj H VGj (17) where j = 1, 2, , N means the number of the column tray; i = 1, 2, 3 means benzene, chlorobenzene and dichlorobenzene, respectively. x j ,i and y j ,i are liquid phase and vapor phase molar composition of component i in the tray j ; L j and V j , represent liquid and vapor flow rate of the tray j; H Lj and H Vj are liquid and vapor enthalpies of the tray j; FRj is the flow rate from the reactor into the tray j; z j ,i is the molar composition from the reactor into the tray j; H Rj is the liquid enthalpy from the reactor into the tray j. The product hydrogen chloride get into the distillation column system, and its influence on the vapor-liquid equilibrium is very little. It only affects the pressure and energy balance of the column. FHClj and H HClj represent hydrogen chloride vapor phase flow rate and enthalpy from reactor into tray j; and VGj and H VGj are hydrogen chloride liquid flow rate and enthalpy of tray j.
3.3 Solution and simulation of mechanism model

Substituting zj,1, zj,2, zj,3 described by Eqs. (9) and (10) to Eq. (8), Eqs. (12) and (13) can be obtained.

y j ,1 ( FCl FRj ) (a + b / 2)
2

2a FRj ) a + y j ,2 = b (12) a + b =1 (13) When the reactor feeding conditions are known ( FCl2 , FR, yj,1, yj,2), we calculate the selectivity of the chlorine on the chlorobenzene and dichlorobenzene. The materials mole distribution of the reactor outlet can be calculated by Eqs. (9-11). For liquid phase reactions, the above Eqs. (5-13) can be used to calculate the liquid mole fraction and the distribution rate of material chlorine on product. ( FCl2 FRj ) a + y j ,2
Cl2

F } (

3.2

Column MESH model

The mechanism model of the distillation column can be built as a column with several side streams. The activity coefficients of the liquid phase are calculated using the Wilson model. A schematic diagram of equilibrium tray is shown in Fig. 2.

For the calculation of strong nonlinearity and

(a) Ij = 0 Figure 2

(b) Ij = 1

Column equilibrium schematic of the tray j (Ij is the signs for reactor site, Ij = 1 mean tray j linked with side reactor)

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coupled relation between thermodynamic equilibrium and the kinetic equations of non-ideal system, the solution of mechanism model is more complex. Since the simulating convergence of model is rather difficult, a good initial value to ensure reliable convergence is needed. In this paper, it is firstly assumed that the capacity of the reactor is large enough to promise chlorine to be consumed completely, and the feeding flow rates of chlorine ( FCl2 ) are defined as the independent reaction amount. Therefore, the mechanism model may be equivalent to distillation column simulation problem with multi-stream inlet and outlet. After distillation column calculating convergent, the material properties of the reactor can be obtained, which is connected with the tray j. According to reaction kinetics model, the sizes of reactors are calculated. This solution has greatly improved the convergence speed of the model of the SCR process [15] The SRC simulation process is that the above reactors equations and MESH equations are simultaneously calculated. The algorithm block diagram of the SCR process is shown in Fig. 3. In this paper, NewtonRaphson method with numerical evaluation of the Jacobian matrix is used to the steady-state solution of the MESH equations. In addition, the initial values of V j and L j are generated from the constant molar flow assumption. The initial column composition profile x j ,i is guessed according to the distribution rule of the

components. The initial tray temperature ( T j ) is set to be the boiling point of benzene at the given pressure. The simulation of the SRC process is completed using MATLAB software.
3.4 Simulation results

The optimal steady-state design of the SCR process for Chlorobenzene production are obtain by the economic optimal design procedures based on sequential quadratic programming (SQP) algorithmic in the literature [15, 16]. The optimization structural parameters and operating parameters are as follows: the column tray numbers N = 12 ; the reactors numbers N R = 3 ; the tray numbers between reactors N RS = 1 ; the vapor boilup in column bottom Vn = 30 kmolh1; the fresh feeding flow rates of chlorine FCl2 = 9.95 kmolh1; and the chlorine proportion to three reactors fb(i) = [0.41 0.31 0.28]. In the simulations, the fresh feeding flow rates of benzene are excess to guarantee the complete reaction of chlorine, and thus, the optimal feeding flow rates of benzene is calculated by the reaction terms. Fig. 4 shows the simulating results. Fig. 4 (a) is the composition distribution of liquid material in the bottom column, Fig. 4 (b) is the temperature distribution of the bottom tray; and Fig. 4 (c) is the flow rate distribution of the column bottom.

Figure 3

Algorithm block diagram of the SCR process

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(a) The composition distribution C6H6; C6H4Cl2; C6H5Cl

(b) The temperature distribution

(c) The flow rate distribution liquid; vapour

Figure 4 Simulating results of the steady-state optimal design

Figure 5

Multivariable control schemes of the SRC process for chlorobenzene production

When the feeding flow rates of chlorine is 9.95 kmolh1, the feeding flow rates of benzene calculated by the reaction terms is FB = 9.58 kmolh1. In the simulated results, the purity of chloride production is 0.9683, the purity of benzene is 0.099%, and the selectivity is 0.968/(10.0309) = 99.88%. Comparing the experimental data, i.e., the chlorobenzene in column bottom is about 96% with various kinds of catalysts, the conversion rate of benzene is 99%, and the selectivity of chlorobenzene is about 97%, it

demonstrates that the simulated results are closed to the experimental results. Thus, the simulated results can be used in the guidance of chlorobenzene production.
4 DESIGN AND ANALYSE OF CONTROL SYSTEM

The dynamic control of the SRC process is the significant element during the engineering application

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design of integrated technology [17]. Comparing with the conventional distillation, the dynamic characteristics of the SRC process are more complicated. As a result of the interaction between the reaction and the separation, the SRC process has strong nonlinear, coupling and multi steady-stable characteristics [18]. The above characteristics make the dynamic operation and control for the SRC process become bottleneck problems.
4.1 Design of multivariable control schemes

the effectiveness of this control structure, the disturbances of feed flow rates, the feed composition and the steam calorific value disturbances are applied to the system, respectively.
4.2.1 Change of temperature set-value The temperature set-value Tsp of the column bottom temperature is adjusted respectively 5 C. Fig. 6 shows the dynamic response of the control structure to set-value change. As seen in Fig. 6, the temperature controlled variables track to the new set-value for both positive and negative changes in a short time. The chlorobenzene composition of the product can be settled down smoothly to steady-state values within specification values of 92%-93.5%. 4.2.2 Change of production rate handle To check the effectiveness of this control structure, the 5% step changes of the production rate (the feed flow rate of chlorine FCl2 ) are applied to the system. The feed flow rate of benzene is growing with increasing feed flow rate of chlorine under the ratio control structure. Fig. 7 shows the dynamic response of the control structure to these disturbances. As seen in Fig. 7, the fluctuation range of the temperature is within about 0.5 C range. The chlorobenzene composition of the production is also maintained in the fluctuation range within about 0.2% range. 4.2.3 The 5% impurities in fresh-feed stream The 5% impurities of nitrogen in fresh-feed stream FCl2 are applied to the system. Fig. 8 gives the responses of control structure to 5% impurities of nitrogen in fresh-feed stream FCl2 . The control structure keeps the temperature within range of about 1 C and product purities within 1.5% of their specified values for the 5% feed stream impurity. 4.3 Analysis of the system performance indexes

Based on the above economic optimal design and simulation analysis of the SRC process for chlorobenzene production, the multivariable control schemes are developed with the conventional control strategies as shown in Fig. 5. The control schemes include several control loops, such as the liquid level control loops (LIC-100, LIC-101), the pressure control loop (PIC-100), the feed flow rate control loops (FIC-101, FIC-102), outlet flow rates control loops of the three reactors (FIC-103, FIC104, FIC105), the temperature cascade control loop (TIC-100), etc., which are given in Table 2. For the composition analyzers have higher cost, require more maintenance, and can introduce dead-time into the control loop, the temperature cascade control loop is proposed. The temperature control of column bottom is the main loop (TIC-100), and the control of the steam flow rate is sub-loop (FIC-100), which are shown in Fig. 5.
4.2 The performance analysis of the close-loop control system

The dynamic simulation of the SRC process for chlorobenzene production with the above designed control structures are explored with chemical simulation software HYSYS. Through reasonable setting control system parameters and operating parameters, the closed loop control system of the SRC process can run smooth and attain the expected control goals. To check
Table 2
Control loop LIC-101 LIC-100 PIC-100 FIC-101 FIC-102 FIC-103 FIC-104 FIC-105 FIC-106 FIC-107 FIC-108 cascade control

The performance indexes of the SRC process for

Loop structure description of multivariable control schemes

Manipulated variable flow rates of reflux outlet flow rates emission of HCl feed flow rates of Cl2 feed flow rates of C6H6 outlet flow rates of reaction 1 outlet flow rates of reaction 2 outlet flow rates of reaction 3 inlet flow rate of reaction 1 inlet flow rate of reaction 2 inlet flow rate of reaction 3 steam flow rate of reboiler Control target 50% 50% 101.3 kPa 9.95 kmolh1 9.58 kmolh1 10 kmolh1 24 kmolh1 25 kmolh1 fb(1) fb(2) fb(3) 135 C

Controlled variable liquid level of condenser liquid level of column bottom pressure of column top feed flow rates of Cl2 feed flow rates of C6H6 outlet flow rate of reaction 1 outlet flow rate of reaction 2 outlet flow rate of reaction 3 inlet flow rate of reaction 1 inlet flow rate of reaction 2 inlet flow rate of reaction 3 temperature of column bottom

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(a) Figure 6 Dynamic response under the temperature set value Tsp changes Tsp + 5 C; Tsp 5 C

(b)

(a) Figure 7 Dynamic response under step change (5%) in production rate handle flow +5% ; flow 5%

(b)

(a) Figure 8

(b)

The dynamic response under the 5% impurities in fresh-feed stream Table 3 Analysis of the system performance indexes
Temperature response ts/min 30 75 3.4 3.4 2.87 IAE 76.42 183.66 0.22 0.28 43 e() 0.5 0.3 0.5 0.3 0.12 ts/min 30 75 3.4 3.4 2.87 Composition response IAE 0.04 0.06 0.001 0.001 1.22 e() 0.001 0.002 0.002 0.002 0.015

Disturbance Tsp change production rate handle FCl2 5% impurities in feed stream FCl2

Disturbance amplitude +5 5 +5%

5%
5%

chlorobenzene production, such as the settling time ts, the absolutely integral error IAE and the steady-state error e() are calculated further under the above disturbances conditions. The calculating results are given

in Table 2. Through the analysis of the performance indexes of the control system in Table 3, the recommended multivariate control structure can overcome effectively the above different type disturbances within

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a certain range.
5 CONCLUSIONS

REFERENCES
1 Harwardt, A., Kraemer, K., Rngeler, B., Conceptual design of a butyl-levulinate reactive distillation process by incremental refinement, Chin. J. Chem. Eng., 19 (3), 371-379 (2011). Kaymak, D.B., Luyben, W.L., Optimum design of a column/side reactor process, Ind. Eng. Chem. Res., 46, 5175-5185 (2007). Sundmacher, K., Kienle, A., Reactive distillation: status and future directions, Wiley-VCH, Weiheim, Germany (2003). Kaymak, D.B., Luyben, W.L., Design of distillation columns with external side reactors, Ind. Eng. Chem. Res., 43 (25), 8049-8056 ( 2004). Baur, R., Krishna, R., Distillation column with reactive pump arounds: an alternative to reactive distillation, Chem. Eng. and Process., 43 (3), 435-445 (2004). Radulescu, G., Gangadwala, J., Paraschiv,N., Dynamics of reactive distillation processes with potential liquid phase splitting based on equilibrium stage models, Computers and Chemical Engineering, 33 (3), 590-597 (2009). Al-Arfaj, M.A., Luyben, W.L., Comparison of alternative control structures for an ideal two-product reactive distillation column, Ind. Eng. Chem. Res., 39 (9), 3298-3307 (2000). Al-Arfaj, M.A., Luyben, W.L., Comparative control study of ideal and methy acetate reactive distillation, Chem. Eng. Sci., 57 (24), 5039-5050 (2002). Kaymak, D.B., Luyben, W.L., Comparison of two types of two-temperature control structures for reactive distillation columns, Ind. Eng. Chem. Res., 44 (13), 4625-4640 (2005). Wang, S.J., Yu, C.C., Huang, H.P, Plant-wide design and control of DMC synthesis process via reactive distillation and thermally coupled extractive distillation, Computers and Chemical Engineering, 34 (3), 361-373 (2010). Kaymak, D.B, Luyben, W.L., Dynamic control of a column/sidereactor process, Ind. Eng. Chem. Res., 47 (22), 8704-8712 (2008). Tsai, R.C., Cheng, J.K., Huang, H.P., Yu, C.C., Design and control of the side reactor configuration for production of ethyl acetate, Ind. Eng. Chem. Res. , 47 (23), 9472-9484 (2008). Cui, M.F. Huang, X.Z., Qiao, X., Study on process of chlorination of benzene in the three-phase catalytic-distillation column with vapor diffluence, Journal of Chemical Engineering of Chinese Universities, 18 (6), 696-700 (2004). Ye, J.C., Huang, J.C., Lin, H., Kinetic-thermodynamic analysis of the reactive distillation process of the cyclohexene hydration using the zeolite catalyst, Chin. J. Chem. Eng., 19 (5), 808-814 (2011). Ding, L.H., Tang, J.H., Cui, M.F., Bo, C.M., Qiao, X., Optimum design and analysis based on independent reaction amount for distillation column with side reactors: production of benzyl chloride, Ind. Eng. Chem. Res., 50 (19), 1143-1152 (2011). Bo, C.M., Tang, J.H., Qiao, X., Ding, L.H., Cui, M.F., The optimization method and simulating system of distillation column with side reactors for benzene chloride production, Journal of Shanghai Jiaotong University, 45 (8), 1157-1162 (2011). (in Chinese) Suresh Babu, K., Pavan Kumar, M.V., Kaistha, Nitin, Controllable optimized designs of an ideal reactive distillation system using genetic algorithm, Chem. Eng. Sci, 64, 4929-4942 (2009). Lin, Y.D., Huang, H.P., Yu, C.C., Relay feedback tests for highly nonlinear processes: reactive distillation, Ind. Eng. Chem. Res., 45 (12), 4081-4092 (2006).

The distillation column with side reactors can not only effectively increase the conversion and selectivity, but also can overcome the temperature or pressure mismatch in the traditional reactive distillation. In this paper, the mechanism model, the optimizing design and dynamic control of the SRC process for chlorobenzene production are discussed. The effectiveness of control structure is demonstrated using disturbances in production rate and fresh-feed compositions. The simulating results show that the control structure using conventional control strategies can effectively overcome various disturbances in a specific range. However, owing to the nonlinear and coupling characteristics, the system will probably deviate from the ideal condition and even cause the instability when the disturbance with larger range is added. The dynamic intelligent control methods and the multivariate predictive control will be researched in future work to solve the problems about the on-line optimizing operation and synergy control for the SRC process.
NOMENCLATURE

2 3 4

10

11
FCl2 FRj fb HLj HRj HVj i j k Lj N NR NRS NS r Tj Vj xj,i yj,c yj,i zj,c

chlorine feeding flow rate, kmolh inlet liquid flow rate of reactor, kmolh1 distributed ratio of chlorine to reactor liquid enthalpies of tray j, MJkmol1 liquid enthalpy from the reactor into tray j, MJkmol1 vapor enthalpies of tray j, MJkmol1 number of components number of trays reaction rate constant, h1 liquid flow rate of tray j, kmolh1 number of trays in the column number of the side reactors number of trays between adjacent reactors in the reaction zone number of stripping trays reaction rate, kmolL1h1 column temperature on tray j, K vapor flow rate of tray j, kmolh1 mole compositions of component i in liquid on tray j inlet mole compositions of reactor, kmolL1 mole compositions of component i in vapor on tray j outlet mole compositions of reactor, kmolL1 rate-constants ratio

12

13

14

15

16

17

18