ELSEVIER

Chemical Engineering and Processing 35 (1996) 131-139

Optimization
Department of Chemical

of MTBE synthesis in a fixed-bed reactor system

E.M. Elkanzi
Engineering, Faculty of Engineering, UAE University, P.O. Box 17555, Al-Ah, United Arab Emirates

and Petroleum

Received 12 April 1995; accepted 23 August 1995

Abstract A fundamental fixed-bed catalytic reactor model has beendevelopedfor usein selectingalternative operating strategies on a commercialmethyl-t-butyl ether (MTBE) unit. The model is basedon generalchemicalengineering principlesand is tuned to representthe operation of the reactors systemof a given MTBE unit. Constrainedoptimization techniques are usedto determine the optimum operating conditions of the reactors systemthat give the maximum net profit. The model will enablethe user to predict the required bed temperature rises, the required recycle rate for specificsingle-pass conversion and the required heat removal rate in the coolers of an existing unit. For optimization purposes,the model is usedto investigatethe effect on unit profitability when variablessuchasthe conversionper passor the total conversionweremodified. A computer program, MTBEC, wasdevelopedfor solving the model equations.Conversionper passwasvaried from 62.3%to 87.3%in increments of 5%. Based on thesecases, conversionper passhigher than the original designvalue of 72.3%is suggested. The optimum conversionper pass value appearsto be about 75.5% and represents an improvement of about 1.5%on daily net profit for the pricesquoted. These resultsdemonstrate the useof the modelin selecting more economicallyattractive operating targets.The modelcan alsobe used to investigatethe effect of other variablesamenable to optimization, e.g. fresh feed stock quality, feed costsand bed temperature profiles.
Keywords:

MTBE synthesis;Fixed-bed reactor system; Catalytic reactor model; Constrained optimization techniques;Model

equations

1. Introduction

The use of MTBE as a gasoline octane blending component is growing rapidly due to the phase out of tetraethyl lead as an octane boaster. According to most estimates, demand for MTBE could reach 24 million tonne y-i in 1995 [l]. This follows the second phase of reformulated gasoline in 1997 in the USA, plus the potential later in Europe and elsewhere. Moreover, there are some viable alternatives to MTBE, including ethanol, ETBE, TAME and DIPE, and new technologies such as reactive distillation using a solid catalyst where both chemical reaction and fractionation of products can proceed simultaneously are already running. New MTBE plants will come on stream and the existing plants will have to adjust themselves to the current economic situation, The availability and cost of raw materials may become a problem and the existing plants have to improve their efficiency and increase their profitability rather than expand the plant. One
0255-2701/96/$15.00 0 1996 - Elsevier Science S.A. All rightsreserved

way of improving productivity per given reactor volume may be accomplished by optimizing the plant operating conditions [2]. However, the optimization of an existing producing unit is a different type of optimization than that made by the original designer of the unit. The original design is based on a given set of product prices and capital equipment costs with given feed and product specifications. All process equipment are sized and rated to meet the design operation. After a certain period of operation, the economics may change significantly from the original design basis. Certain pieces of equipment, feed and/or product qualtities may become bottlenecks or constraints to the most economic operation. In addition, new catalysts are being developed whose activities and selectivities are better than that used in the original design [3]. As such, a process model is needed to predict optimum operations more economically. In its simplest form this model may be a heuristic model developed by an operator through first-hand observation of the unit. How-

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ever such models cannot be relied upon for accurate quantitative predictions and more rigorous models based on basic chemical engineering principles - material and energy balances,equilibrium thermodynamics and kinetics - are needed to evaluate the subtle economic trade-offs involved in process optimization. The aim of this study is to maximize the profitability of an existing MTBE reactors systemby maximizing an objective function which includes the value of MTBE produced, and the operating and feed costs.The technical basis of a fundamental fixed-bed catalytic reactor model to search for more economically desirable operation of the reactors system is described. Constrained optimization techniques are used to determine the key variables so as to satisfy the objective function while maintaining the reactors temperatures within safe limits.
2. Process description 2.1. Process chemistry

At design conditions the isobutylene selectivity to form these isomers is less than 0.5% [9]. Higher reaction temperatures tend to produce more and should be avoided. Dimethyl ether (DME) can be formed by the interaction of two methanol molecules in the presence of an acid catalyst [9]. H H-C-OH H H + H-C-OH H H H

I I

I I

+H-C-0-C-H+H1O H

I I

I I

(3)

Reaction (3) is not only harmful by itself but the water produced may also react with isobutylene to form t-butyl alcohol (TBA) [9]. CK CH,

H,O + C=CH2 + HO-C-CH3

I CH,

I CH,

(4)

Methyl-t-butyl ether, or MTBE, is the equilibrium product of the reaction of isobutylene (iC,) with methanol in the presenceof an acid catalyst. The main reaction is [4]. H CH, I I + C=CH, $ H-C-0-C-CH, (1) I I I H CH, CH, This reaction is exothermic with 37.7 kJ of heat released for each mole of isobutylene converted, the maximum conversion being determined by a thermodynamic equilibrium value [4-61. The reaction is also extremely selective to isobutylene, i.e. other butenes are not converted [7] other than under conditions of hot spots when linear butenes can react [8]. Under design conditions and using a sulfonated polystyrene resin (e.g. polystyrene/divinylbenzene copolymer), essentially the only hydrocarbon molecule to react is isobutylene. The remaining hydrocarbons in the feed stream are almost entirely inert. However, undesirable side-reactionsmay take place side by side with the main reaction of Eq. (1). The most important side-reaction is the dimerization of isobutylene to a mixture of the isomers 2,4,4trimethyl-1-pentene (TMP-1) and 2,4,4-trimethyl2-pentene (TMP-2). Interaction of two molecules of isobutylene produces the dimer [4], CI-4 CH, CH3 CH, CH, H I H-C-OH I H

Production of TBA is not totally undesirable because its blending octane number is lower than that of MTBE but higher than that of base gasoline. Besides the formation of TBA, water has another harmful effect in that it reduces the acidity of the catalyst and thus lowers its activity and a higher reaction temperature is therefore required. This effect disappears when water is converted into TBA and in fact only a few centimeters at the reactor are affected by water [lo]. At design conditions, the isobutylene selectivity to form TBA is lessthen 0.9% [ll].
2.2. Reaction kinetics

C=CH2 + C=CH, Z+ C=C-C-CH,

I I

I CH,

I CH,

CH, H CH,

(2)

The direct addition of olefins catalyzed by ion-exchange resins to give ethers was investigated by Ancillotti et al. [12]. They confirmed the high reactivity of isobutylene with methanol compared to other olefins. Several investigators [4,5,12- 171have studied the kinetics of the reaction of Eq. (1) both in the liquid and vapor phases, and generally two approaches were followed for the analysis of the kinetic data. In the first approach the reaction is considered as a homogeneous catalytic reaction where the reactants are confined within the gel-like resin. In the second approach, the resin is treated like a solid catalyst and the reaction is considered as a heterogeneouscatalytic reaction. In one study [5], a first-order dependence with respect to isobutene was found together with a -0.25 order dependence with respect to methanol. In another study [12], a power law rate expression with a zero-order dependenceof rate on methanol concentrations of more than 4 mall- was reported. In the same study, a

E.M. Elkauzi 1 Chemical Engineering and Processing 3.5 (1996) 131-139

133

first-order dependence of the rate on the isobutylene concentration with an activation energy of 17 kcal mol- was also reported. In another study 1131, reversible rate expressions with a second-order dependence of the forward reaction and a first-order dependence of the reversible step have been suggested. In the heterogeneous catalytic reaction approach, the kinetic data analysis was based on classical models such as the Langmuir-Hinshelwood-HougenWatson (LHHW) models [4,5,13-171. A typical LHHW model of the reaction is of the form:

Table 1 Normal reactor system operation Parameter LHSV, s- Inlet temp., K AT, K iC, conversion, % based on feed to reactor iC, conversion, % based on fresh feed MTBE selectivity, % Recycle ratio Pressure, bar Catalyst volume, m3 QR>kW QE> kW Products: MTBE, kg/s TMP, kg/s MeOH, kg/s ic,, kg/s Reactor I 2.94 x 1O-3 321 14.2(q) 72.3(X,) Reactor II 7.5 x 10-4 314.7 3.2(%) 55.5(X,)

Pa)
Under industrial conditions the forward reaction goes almost to completion (96% conversion of isobutylene). Moreover, the reported [4] ratio of k,/kl at 60 C is about 0.03 and the corresponding activation energies ratio is about 1.6. Thus the reversible step may be neglected and Eq. (4a) reduces to a first-order dependence on the isobutylene concentration. In fact, the analysis of the kinetic data of Subramanian and Bhatia [13] based on first-order kinetics gives a better fit of the data than the assumed second-order forward step and the reversible first-order one. Based on the above argument and on the results of Ancillotti et al. [12] and on the analysis of industrial data, a heterogeneous rate expression for the first-order dependence on isobutylene concentration with an activation energy of 17.4 kcal mol- will be used in this study. 2.3. The seactor system In the idealized process involving the flow diagram shown schematically in Fig. 1, the reactor system includes the catalytic reactors, coolers and static mixers. The fresh feed enters a static mixer where methanol and isobutylene liquids are blended. The combined fresh feed (FF) then mixes with the first reactors effluent recycle (R*) and passes through a

91(X,) 87.3 2.88 25 29.3 1.3x103 4.16 0.0072 0.25 0.64

96(X,) 91.4 25 29.3 8.5 x 10 4.9 0.01 0.83 0.2

second static mixer where it is thoroughly blended to ensure a homogeneous mixture - in the stoichiometric proportions of both reactants - before entering the first reactor. In industrial practice, a 10% excess to methanol is used in order to reduce mainly isobutylene dimers by product fermentation. The reactors are operated near adiabatic conditions and the reaction produces a significant amount of heat, causing a temperature rise across the catalytic bed. This temperature is controlled by circulating a portion of the first reactors effluent (E*) to the reactor inlet. The circulating pumps take suction from the first reactors outlet and develop enough discharge head to circulate the effluent through the recycle cooler and combine it with the fresh feed. The remaining effluent (EE) is cooled before entering the second reactor where the remaining unconverted isobutylene reacts to form MTBE, as in the first reactor, so that 96% of the isobutylene contained in the fresh feed to the reactors system is converted.

Table 2 Price assumptions Feeds: iC,(mixed butenes) MeOH Products: MTBE Utilities Water cooling (11.1 K rise), m3 Electricity, kWh Power, pumping Fig. 1. Schematic flow diagram for the reactor system. $17.5 per BBL $23.9 per BBL $45.2 per BBL 14 per kg MTBE 2.2 per kg MTBE SO.07 per BHP h-

134 Table 3 Base case economics Product MTBE Feeds: iC4 MeOH Operating costs: Pumping Cooling Other? Total cost Net profit per day Net profit per BBL MTBE Quantity

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Heat balance yields (datum = 298 K):

T

Unit value

S per day

CpidT-

t
i=l

ET s298

C,i dT-

FiA.H~X=

0
(7)

3780.7 BBL d- 2993.4 BBL d- 1290 BBL d-

S45.2 per BBL 170 888

and
$17.5 per BBL $23.9 per BBL 52 385 30 828 2532 7597 34 445 127 787 43 100 11.4

QR= i
i-l

RT
sT

CpidT

(8)

For the second reactor: VI, = EEi and

s
0

x2 dXi
CBri>

(9)

a Others include: operating costs other than reactor system + freight to USA + sales/delivery + fixed costs + import duty + depreciation.

x = 0.96 -X, 2 1 -x, Heat balance yields: n OTTC,,dTTT X ,I

(10)

3. Optimization

model

2 Pi
i=l

3.1. Reactor equations Commercial MTBE synthesis reactors are operated near adiabatic conditions and are approximately plug flow in nature, resulting in temperature and concentration gradients through the catalytic bed. Since temperature and concentration are the key driving forces in the reaction rate expressions, a model which represents the reactor by individual catalyst bed must integrate the reaction rate and its related heat balance along the catalyst bed. Only a model with such detail will enable the user to predict the required bed inlet temperature, the bed temperature rises, the required recycle rate for a specific single pass and overall conversions and the required heat removal rate in the coolers. The detailed reactor model consists of differential material and energy balances over adiabatic fixed-bed reactors. These balances are coupled with physical property and heat-transfer correlations. For the optimal operation of the reactors system, optimization variables such as the recycle ratio and the reactors inlet temperatures are related to the objective function. The details of the balances around the first reactor with reference to the notation in Fig. 1 and to the nomenclature are: xs dXi t; = Fi (5) where

Cpi dTs 298

EEiAHgX2/=

(11)

and QE = i
i=l

EEi

TO Cpi dT
sT

The variables to be determined from these balances are the recycle ratio, RR, second reactor inlet temperature TT,, and heat removal rates, QR and QE, for given values of X,, X0 and To. 3.2. Objective function and constraints Optimization of the MTBE reactors system operation implies the maximization of unit profit. Within the optimization model this is stated as an objective function defined by [2]. Profit = (product value) - (feed costs) -(operating costs) (13)

s
0

Cmyi)

. FF 01 *Cy I>
(6)

(-r,)=k,k,exp Xl =l+RR(l-XI)

The model is to be used to investigate the effect on unit profitability when variables such as conversion per pass, total conversion or feed quality are modified. This leads to optimization of heat removal from the coolers and recycle rates. These, in turn, determine the external heat flux and recycle ratio which maximize the net profit while maintaining the reactors temperature within safe limits. Assuming that the product value, feed costs and those components of the operating cost which are not related to the reactor sysem are constants, the net profit will then only be a function of the reactors system operating costs. These operating costs are effectively determined by the recycle pumping cost

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0.2 / O.l2 d I 2.2 I 2.4 I 2.6 I 2.8 RECYCLE RATIO I 3.0 I 3.2 I 3.4 3.6

Fig. 2. Variation of conversions with recycle ratio.

and external heat removal cost. Both recycle and heat removal costs are functions of conversion. These rates are used, therefore, to represent the reactor system operating costs in the objective function. Thus, there is an optimal reactors system operating conditions for which the optimal operating cost gives a globally maximum profit. The operating cost itself is thus an optimization variable. In general, the optimization of the reactors system operating conditions is therefore a continuous variable optimization within a singleparameter (operating cost) optimization. The objective function of Eq. (13) is subject to the following implicit constraints:
ATI < E, ATzG%

(14) (15)

where E, and % are limits based on the consideration of the reaction kinetics and MTBE selectivity (typical safe values of these limits are shown in Table 1). It is further assumed that the reactor system is operating against no mechanical constraints, i.e. there is additional capacity on the recycle and cooling water pumps. 3.3. Solution methodology Each set of equations [(5)-(7) and (9)-( 1l)] must be solved simultaneously in order to determine the required recycle ratio and cooler heat loads for various values of a single-pass conversion. These equations were written in forms that were appropriate for solution using a finite-difference approach. It was found convenient to consider the reactor as consisting of a series of elements of volume and employing these equa-

tions by incrementing the known volume of the reactor. The difference equations were solved with iterative convergence on the conversion at each increment. Integration is continued until the reactor volume slightly exceeds the design value and the conversion simultaneously matches with the current value. The objective function [Eq. (13)] and constraints [Eqs. (14) and (15)] were evaluated between each evaluation of the recycle ratio and cooler heat loads in order to determine a new search direction. The optimization search was continued until a maximum profit (or minimum operating cost) was determined. A computer program, MTBEC, was developed for solving the model equations. The algorithm for solving MTBEC was coupled with the method for finding a maximum profit. The model has two main modes of operation; it updates the initial design operating conditions and predicts new operating conditions imposed by the current economic situation. In the update mode, commercial unit test run data are input. These data include observed catalyst bed temperature, liquid feed and recycle rates, cooler heat loads, liquid feed, and product qualities and yields. The model calculates both the conversion per pass and total conversion, and updates all other design parameters. In the predict mode the updated parameters are utilized to solve cases after the user defines the problem. Typically the user specifies the feed rates and qualities, total and per pass conversion levels, current feed costs and product value. The model first iterates to find the required bed temperature rises, the recycle rates, the cooler heat loads and the product yields. Additionally, the predict mode calculations are performed until a maximum profit is achieved.

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I )
2.2

I
2.4

I
2.6

I
2.8 RECYCLE

I
3.0 RATIO

I
3.2

I
3.4

I
3.6

I
3.8 d

Fig. 3. Variationof heatremoval rates with recycle ratio.

3.4. Model use example

To provide a specific example of the models use in optimizing an actual unit, an MTBE reactor system was modelled and a predict case was made to investigate changes in some independence process parameters. The schematic of the reactor system was as shown in Fig. 1. In updating, the model was tuned using a test run representing normal (or base case) operation of the reactor system. This operation is shown in Table 1. The unit produces 444 tonne d-l MTBE and the prices to be used in selecting more optimum operations are as shown in Table 2 [ 1, 18,191. The profit for the base case (assuming a Middle East location for the unit) is shown in Table 3. The conversion per pass was varied from 62.3% to 87.3% and Fig. 2 shows the variation of the conversions (X,, X, and X,) with recycle ratio. The model was run to investigate the effect on unit profitability when this

variable was modified. Fig. 3 shows the variation of the heat removal rates with recycle ratio. As part of the reactors operating cost, it can be seen that the minimum heat removal cost would occur at a recycle ratio of about 2.33. However, at this value of the recycle ratio the constraint of Eq. (14) is not satisfied and the calculated temperature rise of 16.7 C exceeds the safe value. When coupled with the cost of the pumping recycle rate, the variation of the reactors operating cost with recycle ratio is as displayed in Fig, 4. From this figure it can be seen that the minimum cost occurs at a recycle ratio of about 2.7, corresponding to a conversion per pass of 75.4% (see Fig. 2). At this value the constraints of Eqs. (14) and (15) are both satisfied as displayed in Fig. 5 which shows the temperature profiles along the reactor length under optimal conditions. At these optimal operating conditions the improvement in daily net profit, for the prices quoted, is about 1.5% higher than the base case conditions.

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108 0 : ": P * 106 E-2 8 105 107

104 103
102 101 100 2
I I I I I I I

2.2

2.4

2.6

2.8 RECYCLE

3.0 RATIO

3.2

3.4

3.6

3.0

4.0

Fig. 4. Variation of operating cost with recycle ratio.

4. Conclusions The optimum operating conditions of an adiabatic reactors system producing MTBE has been evaluated using a one-dimensional homogeneous fixed-bed catalytic reactor model. It has been found that the optimal policy is a function of the recycle ratio and the external heat removal rates. The convergence of the optimization method depends upon the cost of these parameters and has been found to be definite for the prices considered. No generalization appears to be possible, since optimization of other catalytic processes will be admittedly more complicated as compared to the case studied here. However, the observed easy implementation of the model should give the necessary confidence to accept the challenge.

Appendix A: Nomenclature concentration, km01 mm3 specific heat, kJ kmol- K- CP E acivation energy, kJ kmol-l E* reactor I effluent, kmol s-i EE reactor II feed, km01 s-l F reactor I feed, kmol s-r FF fresh feed, km01 s-l AH heat of reaction, kJ kmol- I isobutylene feed rate, kmol s-l k,, kz reaction rate constants frequency factor, ms- ko catalyst deactivation constant = 1 kd A4 methanol feed rate, km01 s-i n reaction order = 1
ci

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300

0.2

0.4 DIMENSIONLESS

AXIAL

0.6 DISTANCE

0.8

LO

Fig. 5. Temperature profiles under optimum conditions.

Q
R* p-l, T, +T V x &

reactor II effluent stream, kmol s-l rate of heat removal, kW recycle rate, kmol s-l recycle ratio rate of reaction, kmol s-l mm3 temperature of first and second reactor, K reactor volume, m3 conversion temperature difference limit, K

Subscripts E effluent component i inlet ii recycle per pass S References

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[2] T.F. Edgar and D.M. Himmelblau, OptimCation of Chemical Processes, McGraw-Hill, New York, 1989. [3] M.R. Ladisch, R.L. Hendrickson, M.A. Brewer and P.J. Westgate, Catalyst-induced yield enhancement in a tubular reactor, Ind. Eng. Chem. Res., 32 (1993) 1888. [4] A. Ali and S. Bhatia, MTBE formation in a catalytic bed reactor-kinetic and modelling study, Chettr. Etrg. J., 44 (1990) 97. [5] F. Colombo, I. Carl, I. Dalloro and P. Delgu, Equilibrium constant for the methyl tert-butyl ether liquid phase synthesis by use of UNIFAC, Ind. Etzg. Chetn. Amdam., 22 (1983) 219. [6] J.F. Izquierdo, F. Cunill, M. Vila, M. Iborra and J. Tejero, Equilibrium constants for methyl tert-butyl ether and ethyl tert-butyl ether liquid phase syntheses using C,olefinic cut, Ind, Eng. Chetn. Res., 33 (1994) 2830. [7] S.A. Nijhuis, F.P.J.A. Kerkhof and A.N.S. Mak, Multiple steady states during reactive distillation of MTBE, Itzd. Eng. Chetn. Res., 32 (1993) 2767. [8] M. Vila, F. Cunill, J.F. Izquierdo, J. Gonzalez and A. Hernandez, The role of by-products formation in methyl tert-butyl ether synthesis catalysed by a macroporous acidic resin, Appl. Cutal,, 117 (1994) L99. [9] F. Lewis and S. Matar, From Hydrocarbons to Petrochemicals, Gulf Publishing Co., 1981, p. 128.

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[lo] F. Cunill, M. Vila, J.F. Izquierdo, M. Iborra and J. Tejero, Effect of water presence on methyl tert-butyl ether and ethyltertbutyl ether liquid-phase syntheses, 6zd. Eng. Chem. Res., 32 (1993) 561. [I I] Hydrocarbon Process., 69 (1990) 128. [12] F. Ancillotti, M.M. Marcelle and E. Pescarollo, J. Catal., 46
(1977) 49.

[13] C. Subramanian and S. Bhatia, Can. J. Chem. Eng., 65 (1987) 613. [14] A. Gicquel and B. Torck, J. Catal., 83 (1983) 9. [15] Kyung-Ho Chang, Geon-Joong Kim and Wha-Seurg Ahn, Ind. Eng. Chem. Res., 31 (1992) 125.

[16] A. Rehfinger and V. Hoffmann, Kinetics of methyl tertiary butyl ether liquid phase synthesis catalysed by ion exchange resin. 1. Intrinsic rate expression in liquid phase activities, Chem, Eng. Sci., 45 (1990) 1605. [17] D. Parra, J. Tejero, F. Cunill, M. Iborra and J.F. Izquierdo, Kinetic study of MTBE liquid-phase synthesis using C,olefinic cut, Chem. Etzg. Sci., 99 (1994) 4563. [18] C.H. Vervalin, Economically feasible MTBE plants highlight period of new growth, Hydrocarbon Process., 69 (1990) 19. [19] W. Ludlow, Methyl tertiary butyl ether production grows dramatically, Oil Gas J., (June 8, 1987) 54.