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Fuel Processing Technology 92 (2011) 17251732

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Fuel Processing Technology


j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / f u p r o c

Hybrid modeling of ethylene to ethylene oxide heterogeneous reactor


G. Zahedi a,, A. Lohi b, K.A. Mahdi c
a b c

Process Systems Engineering Centre (PROSPECT), Faculty of Chemical Engineering, Universiti Teknologi Malaysia, UTM Skudai, 81310 Johor Bahru, Johor, Malaysia Department of Chemical Engineering, University of Ryerson, Toronto, Ont. M5B 2K3, Canada Department of Chemical engineering, University of Kuwait, Safat 13060, Kuwait

a r t i c l e

i n f o

a b s t r a c t
In this research a dynamic grey box model (GBM) of ethylene oxide (EO) xed bed reactor has been presented. In the rst step of the study, kinetic model of the existing reactions was obtained using articial neural network (ANN) approach. In order to build the ANN model industrial data of a typical EO reactor were employed. Time, C2H4, C2H4O, CO2, H2O and O2 mole fractions were network inputs and the multiplication of reaction rate and catalyst deactivation (r * a)was ANN output. From 164 data, 109 data were employed to train ANN. After employing different training algorithms, it was found that, the radial basis function network (RBFN) training algorithm provides the best estimations of the data. This best obtained network was tested against fty ve unseen data. The network estimations were close to unseen data which conrmed generalization capability of the obtained network. In the next step of study, (r * a) was estimated with ANN and then the hybrid model of the reactor was solved. Simulation results were compared with EO mechanistic model and also with plant industrial data. It was found that GBM is 8.437 times more accurate than the mechanistic model. 2011 Elsevier B.V. All rights reserved.

Article history: Received 2 August 2010 Received in revised form 7 April 2011 Accepted 12 April 2011 Available online 4 May 2011 Keywords: Simulation Ethylene oxide reactor Grey box modeling Neural network Dynamic modeling

1. Introduction Ethylene oxide (EO) has many applications like in disinfection, sterilization of surgical equipments, fumigation and cosmetic [1-3]. Several studies have been carried out on EO reactor modeling [4-11]. The EO epoxidation was optimized by Zhu [6]. Baratti et al. proposed strategies to optimize the reactor performance [7]. Bingchen et al. modeled the EO synthesis in a slurry reactor with silver catalyst. They found that a slurry reactor has higher selectivity than a gassolid xed bed catalytic reactor [8]. Modeling of the transient kinetics of ethylene oxidation by oxygen over a commercial catalyst was performed by Harmsen et al. [9]. The simulation of EO reactor in order to nd the optimum temperature was performed by Hwang and Smith [10, 11]. Zhou and Yuan studied optimization of EO reactor [5]. Recently Zahedi et al. investigated the effect of operating conditions on an industrial EO reactor performance using a mechanistic (white box) model. The model was validated with plant industrial data [12]. Dynamic modeling and optimization of an industrial EO multitubular reactor in the presence of silver-based catalyst and ethylene dichloride as a moderator was investigated by Aryana et al. [13]. They simultaneously solved a set of nonlinear equations; kinetic heat mass transfer equations and catalyst deactivation. Their model was in good agreement with plant data. They also investigated the effect of operating parameters on reactor performance and optimized the
Corresponding author. Tel.:+60 07 5535583; fax: + 60 07 5581463. E-mail address: grzahedi@fkkksa.utm.my (G. Zahedi). 0378-3820/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.fuproc.2011.04.022

performance of ethylene oxide reactor to maximize EO yield and selectivity [13]. Hybrid modeling of EO reactor has not been a subject of any research based on our literature survey. In order to provide a realistic model of industrial EO reactor, accurate knowledge of reaction kinetics is desirable. In spite of applying some reactions for many years, their reaction mechanisms are not still understood. Sometimes many reactions and intermediates play signicant roles in reaction systems and also kinetic modeling is related to some state variables which are not measurable using conventional methods [14, 15]. In this case as elementary reaction kinetics vary with reaction conditions, applying global reaction rates for a reaction network is impossible. According to these facts and due to the lack of precise kinetic models, using some alternative models like articial neural network (ANN) instead of mathematical reaction rates is useful [14, 15]. Generally, there are three main procedures for process modeling; white box, black box and grey box modeling [16]. White box, rst principle model (FPM) or deterministic model is used when complete information of the process is accessible and the whole governing equations of the system are solvable using analytical or numerical techniques. The governing equations are mass, energy and momentum balances and empirical equations from thermodynamics and kinetics [17, 18]. The commercial simulators for simulation of oil rening units use FPMs [19]. If the governing equations are not available, cannot be solved or need long computational time; the process simulation can be carried out using pure ANN. This type of modeling which uses only input and output data is called black box modeling [17, 18].

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Abbreviations Ac A1 Ao a av CPg CPs Ct D D0 Deq Di Dn Do dp Ed Ed0 Ft Hf,i H298 Hf hi ho Kw Kd Kgi L m N R ri T Ts Tshell t Ushell yi yi0 yis z cross sectional area of reactor (m2) inner area of each tube (m2) outside area of each tube (m2) activity of catalyst specic surface area of catalyst pellet (m2/m2) specic heat of the gas at constant pressure (J/mol) specic heat of the solid at constant pressure (J/mol) total concentration of gas ow (mol/m3) active surface of catalyst initial active surface of catalyst active surface at innite time tube inside diameter (m) parameter of Eqs. (4) and (5) tube outside diameter (m) particle diameter (m) activation energy used in the deactivation model (J/ mol) constant of activation energy used in the deactivation model (J/mol) total molar ow per tube (mol/s) enthalpy of formation of component i (J/mol) enthalpy of reaction at 298 K (J/mol) gas-solid heat transfer coefcient (W/m2K) heat transfer coefcient between uid phase and reactor wall (W/m2K) heat transfer coefcient between coolant stream and reactor wall (W/m2K) conductivity of the reactor wall (Wm/K) the constant parameter of the deactivation model (1/ s) mass transfer coefcient for component i (m/s) length of reactor (m) sintering order of catalyst number of components used in the model (N = 5) universal gas constant (J/molK) reaction rate of component i (mol/molkg s) bulk gas phase temperature (K) temperature of solid phase (K) temperature of coolant stream (K) time (s) overall heat transfer coefcient between coolant and process streams (W/m2K) mole fraction of component i in the uid phase (mol/ mol) mole fraction of component i in the uid phase at the inlet of bed (mol/mol) mole fraction of component i in the solid phase (mol/ mol) axial reactor coordinate (m)

ANN and FPM models have their own advantages and disadvantages [19]. In FPM the model development may be very complex, and time consuming. Usually in FPM complex partial differential equations or complex algebraic equations appear which should be solved analytically or numerically. ANNs need large number of training sets and have limited and weak extrapolation capacity [20]. ANN or black box model is built based on the specic process data, so it cannot be used for non-identical processes [19]. Hybrid or grey box model (GBM) is a combination of white box and black box models which can overcome pitfalls of both white box and black box models. The combination of the mathematical model with ANN can be performed by consecutive or parallel methods [17, 18]. GBM inherits the advantages of both techniques (ANN and FPM) simultaneously and renders their limitations [20]. GBM has extrapolation capacity where ANNs fail in this case and usually is more accurate than FPMs [15]. The applications of hybrid model as a proper technique to simulate kinetic models have been reported in many studies, [15, 21-25]. Nandi et al. used hybrid ANN and genetic algorithm (GA) approach to model and optimize benzene hydroxylation reactor [26]. An ANN hybrid model was used by Bollas et al. to scale up a uid catalytic cracking unit. They found that the hybrid model is able to provide reliable data for scale up purposes rather than FP model [27]. ANN hybrid model of the hydrodesulphurization reactor was developed by Bellos et al. [28] in 2005. An ANN was used to evaluate the kinetic parameters from industrial data. The results conrmed the model capability to predict the reactor yield and catalyst deactivation [28]. Zahedi et al. studied hydrogenation of CO2 to methanol by building a grey box model of the reactor. FPM was employed to calculate the output temperature of reactor while outlet mole fractions were calculated by ANN [15]. Bhutani et al. studied hybrid modeling of an industrial hydrockracker unit [29]. They optimized the reactor using GA. To the best of our knowledge, the dynamic grey box modeling of EO reactor has not been investigated in the literatures. The representative diagram of the utilized White Box, Black Box and their integration as a Grey Box model in our research are depicted in Fig. 1. At the rst step of the study an ANN model was trained to learn the kinetic of industrial reaction (r * a). The output of ANN is introduced to the FPF. In the next step of the research hybrid model of EO reactor was validated with plant data. Finally, the proposed grey box model was compared with our previously build FP model [20].

2. Process description EO is an important chemical which is produced by selective oxidation of ethylene over the supported silver catalyst in a xed bed multi-tubular reactor at temperatures of 180 C240 C and pressure of 2.1 MPa respectively [2, 8]. Conversion of ethylene to EO is an important catalytic reaction in petrochemical complexes. Fig. 2 depicts a typical EO reactor. The most popular reactor for this process is a vertical reactor resembling shell and tube heat exchanger [4]. Tubes are packed with silver catalyst [30]. Boiling water which is used as a coolant owed inside the shell [8]. The released heat of reaction is absorbed by the boiling water in the shell side. Water temperature is 230 C and the reactor temperature is controlled by the boiling water pressure [30]. In EO production plant, EO is produced in four parallel reactors. The produced EO is a feed for other units including: ethylene glycol, ethanol amine, and ethoxylate. The annual production of this typical unit is 12,000 tones. 1000 tones/annum pure EO is used in domestic. Tables 1 and 2 represent feed and the reactor specications respectively [30].

Greek letters s void fraction of catalytic bed (m3/m3) kinematic viscosity (m2/s) B density of catalytic bed (kg/m3)

ANN models only use inputoutput data of a system without requiring the process details and knowledge of systems. Usually, they are faster that FPMs. These specications make ANNs popular for modeling, control and optimization purposes [19].

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Black Box model ANN


Input

White Box model


Mass Balance EO Mathematical Model Energy Balance

Grey Box model


Mass Balance EO Mathematical Model

ANN
Input

Energy Balance

Fig. 1. Diagram representing the white box, black box and their integration in a grey box model.

2.1. Kinetics The following parallel reactions occur in the EO reactor [32]: C2 H4 + 0:5O2 C2 H4 O C2 H4 + 3O2 2CO2 + 2H2 O
Ag Ag

H1 = 105:39 KJ = mol H2 = 1321:73 KJ = mol

1 2

The synthesis process of EO is a parallel reaction system. Conversion ratio of ethylene is about 1012% with EO selectivity of 78 82% [4, 8]. In EO production process, the selective oxidation, epoxidation, occurs between adsorbed oxygen and adsorbed ethylene (reaction (1)) and a combustion reaction (reaction (2)) takes place to convert ethylene to water and carbon dioxide as a side reaction. Due to the high reactivity of EO another combustion reaction (3) may take place

H1 and H2 are the heat of reactions.


Table 1 Typical EO reactor feed inlet conditions [30]. Feed compositions C2H4 O2 CO2 H2O C2H4O CH4 (ballast gas [31]) N2 Total molar ow rate per tube (mol/s) Inlet temperature (K) Pressure (bar) Value (mol%) 25.00 8.00 7.00 0.25 0.01 47.03 0.24 0.89 463 21.7

Boiling Water
Steam Drum

Table 2 Typical EO reactor specications [30].

EO

Quantity s (kg/m ) dp(m) Cps (J/kg.K) Number of tube Length of reactor (m)
3

Value 890 7.74 10 3 1000 5523 8.7

Et and O2
Fig. 2. A schematic sketch of a typical ethylene oxide reactor.

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Et and O2

Axial element

energy balances which are coupled with thermodynamic correlations (Fig. 3). 3.1.1. Mass balance The governing equation in term of component mass balances in solid phase, Eq. (7), and uid phase, Eq. (8), can be expressed as: s Ct dyis = kgi yi yis + ri B a dt i = 1; 2; ; N1 i = 1; 2; ; N1 7 8

Cooling Water

Cooling Water

B Ct
EO, CO2 and H2O
Fig. 3. An axial element for mass and energy balances in both gas and solid phases.

dyi F y = t i + av Ct kgi yis yi dt Ac z

to convert EO to water and carbon dioxide, so the reaction must be stopped after producing EO [2]:
Ag 1 C2 H4 O + 2 O2 2CO2 + 2H2 O 2

where S and B are the void faction of catalyst and bed, respectively, Ct total concentration of gas ow, yi and yis are the mole fractions of component i in gas and solid phases, respectively. t, z, Ac and Ft are time, axial reactor coordinate, cross sectional area of each tube and total molar ow rate of each tube in the reactor. B is the density of catalytic bed. ri and kgi are rate of reaction and mass transfer coefcient of component i between gas phase and solid phase. a is the catalyst deactivation and av is specic surface area of catalyst pellet. N is the number of components. The reaction components in this process are C2H4, C2H4O, CO2, H2O and O2. The relevant boundary and initial conditions are: at z = 0 yi = yi0 at t = 0 yi = yi ; yis = yis and a = 1
ss ss ss ss

Silver is process catalyst because of its effectiveness in oxygen adsorption. Based on different proposed mechanisms different results are obtained for EO production which do not match with real observations. In this case ANN can be employed to render this problem [32-34]. The corresponding rate equations are as follows [32]:
0:75 exp10:308358:5 = T PET PO 2

9 10

yi and yis are the steady state mole factions of component i in uid and solid phase. 3.1.2. Energy balance The energy balance of solid and uid phases are expressed in Eqs. (11) and (12), respectively as follows: B Cps   N dTs = av hf T Ts + B a ri Hf ;i dt i=1 T F T Di U T T = t + av hf Ts T + Ac z Ac shell shell t 11

rE O =

1 + Dn exp12:549835:2 = T PET PO2 1 + Dn

rC O 2 =

rEO and rCO2 are the reaction rate of EO and CO2, while PET and PO2 are the pressure of EO and O2 respectively. Dn is calculated as the following: Dn = 1 + exp9612:8 = T 21:68PCO2 + exp16129:2 = T 34:58 PO2 PH2 O
0:5

B Ct Cpg

12

Ushell is the overall heat transfer coefcient between coolant and process streams (gas phase) which can be calculated as the following: Ai ln   Do A 1 Di + i Ao ho 2 LKw

3. Grey box modeling of ethylene oxide reactor 3.1. FP (white box) modeling In this study the one-dimensional heterogeneous model is presented. The main structure of this model is a combination of mass and

1 1 = + Ushell hi

13

The boundary condition for energy equations is: at z = 0 T = T0 14

Artificial Neural Network

Energy and mass equations

Fig. 4. Schematic of grey box model of ethylene oxide reactor.

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Fig. 5. (a) Mean square error, (b) linear regression between industrial unseen data and ANN results for ethylene oxide, (c) ethylene, (d) oxygen, (e) water, (f) carbon dioxide.

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0.03 0.025
First Principle Grey Box

Table 3 Comparison of ethylene oxide mole percent among plant data [30] and simulation results of white box and grey box models. Time (day) plant data 2.020 2.016 2.013 2.000 2.000 Grey box results 2.16 2.11 2.08 2.05 2.01 MSE = 0.71% White box results 2.47 2.21 2.18 2.14 2.11 MSE = 5.99%

EO mole fraction

0.02 0.015 0.01 0.005

0 25 50 75 100

3.2. ANN modeling


0 0 5 10 15 20 25 30 35

Bed height (grid point)


Fig. 6. Comparison of EO mole fraction between dynamic simulation results of rst principle model (white box) and grey box after 25 days of operation versus bed grid points.

The initial conditions of energy equations are: at t = 0T = T ; Ts = Ts


ss ss

15

3.1.3. Catalyst deactivation Catalyst deactivation is one of the most challenging problems in catalytic reactors. Sintering, poisoning and wearing are three main factors affecting catalyst activity, while sintering is the main reason of Ag catalyst deactivation Ag [35, 36]. This process decreases the catalyst active sites. Decreasing of catalyst active sites is usually expressed by the generalized power law expression as the following [37]:   Deq m dD = D0 D = kd dt D0 D0 16

In the present study the r * a for all components (C2H4, C2H4O, CO2, H2O and O2) was found using ANN. For training of ANN, various architectures of multi layer perceptron and radial basis function network (RBFN) were used to predict industrial (r * a). RBFNs are most popular feed forward neural networks due to the good approximation and fast training [38]. Radial basis networks require more neurons than standard feed forward back propagation networks, but often they can be designed faster than standard feed forward networks [39-42]. Time, C2H4, C2H4O, CO2, H2O and O2 mole fractions are ANN inputs while (r * a) is ANN output. 2 3 of the data set (totally 164 data) were selected to train the ANN and the remaining 1 3 data were used to check generalization of the trained ANN model. 4. Grey box model In this section the FPM was compared to grey box model. Fig. 4 shows a schematic of the proposed grey box modeling of EO reactor. Using this hybrid model the outlet mole fractions of all components were calculated as a function of time. 5. Results and discussion Fig. 5a shows the mean square error (MSE) of the trained ANN. The linear regression between the ANN results and unseen industrial data are shown in Fig. 5bf. As depicted in these gures, the best obtained ANN has good agreement with experimental data. In order to validate the proposed GBM, the results of white box model were compared with GBM after 25 and 50 operating days (Figs. 6 and 7). The mole fraction of EO is an important parameter for validation of model which reects the reactor performance. In these gures the mole fraction of EO is compared during different operating times. As shown in these gures, the FPM and grey box simulation results are close to each other. Table 3 compares EO mole fraction from grey box with white box modeling and plant data. According to this table the MSE between grey box model and plant data is 0.71% while MSE between white box
Grey box
22.28%

where D0 is the initial active surface; Deq is an active surface at innite time; m is sintering order, which usually equals to two and kd is the sintering rate constant and is a function of temperature, as: kd = kd0 e
Ed = RT

17

More details on FPM and its validation can be found in our previous work [12].
0.03 0.025
First Principle Grey Box

EO mole fraction

0.02 0.015 0.01 0.005


6.93%

White box
22.28%

9.62% 4.66%

8.30% 5.50% 3.33% 2.50% 0.50%

0 0 5 10 15 20 25 30 35 0
Fig. 7. Comparison of ethylene oxide mole fraction between dynamic simulation results of rst principle model (white box) and grey box after 50 days of operation versus bed grid points.

Bed height (grid point)


25 50 75

100

Fig. 8. Relative error percentage between grey box and white box results versus operational days.

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0.025
day 25 day 50 day 75 day 100

0.085
day 25 day 50 day 75 day 100

0.02

0.08

Oxygen mole fraction

EO mole fraction

0.015

0.075

0.01

0.07

0.005

0.065

10

15

20

25

30

35

0.06

10

15

20

25

30

35

Bed height (grid point)


Fig. 9. Ethylene oxide mole fraction versus length of reactor after 25, 50, 75 and 100 operational days.

Bed height (grid point)


Fig. 11. Oxygen mole fraction versus length of reactor after 25, 50, 75 and 100 operational days.

model predictions and plant data is 5.99%. In this case, the grey box model is 8.437 times or 843.7% more accurate than FPM. Relative error between grey box and FPM for 0, 25, 50, 75 and 100 operational days were shown in Fig. 8. According to Fig. 8, the hybrid modeling predictions are more accurate than the mechanistic model. The mole fraction of EO, ethylene and oxygen after 25, 50, 75 and 100 operating days were demonstrated versus bed grid points (bed height) in Figs. 9, 10 and 11, respectively. According to Fig. 9, by the passage of time the desired product (EO) is decreased. As EO is a desired product, it increases by along the rector bed. According to Figs. 10 and 11 the ethylene and oxygen contents are decreased along the reactor bed. The ethylene and oxygen content increase as time passes because of the catalyst deactivation. Catalyst deactivation results in decreasing the consumption of ethylene and oxygen. In this case, the maximum amounts of these two feeds are expected in the nal operating day. According to the foregoing results, the GBM is more capable for simulation of EO reactor than white box model.

5. Conclusion In this paper, conversion of ethylene to ethylene oxide using grey box modeling technique has been studied. The grey box model applies both the ANN (black box) model and rst principle (white box) model. In order to validate the proposed grey box model, its estimation capacity was compared with industrial plant data. It was found that the performance of grey box model is 8.437 times more than the white box model. It was found that grey box models have: - Good accuracy, which is robust for noisy data - Short response time, compared to white box models. - The extrapolation ability, which black box models provide poor results in this case. References
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0.25 0.248 0.246


day 25 day 50 day 75 day 100

Ethylene mole fraction

0.244 0.242 0.24 0.238 0.236 0.234 0.232 0.23 0 5 10 15 20 25 30 35

Bed height (grid point)


Fig. 10. Ethylene mole fraction versus length of reactor after 25, 50, 75 and 100 operational days.

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