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ELSEVIER

Chemical Engineering and Processing 35 (1996) 131-139

Optimization

of MTBE synthesis in a fixed-bed reactor system


E.M. Elkanzi

Department

of Chemical

and Petroleum

Engineering,

Faculty

of Engineering,

UAE

University,

P.O.

Box

17555, Al-Ah,

United

Arab

Emirates

Received 12 April 1995; accepted 23 August 1995

Abstract
A fundamental fixed-bed catalytic reactor model has beendevelopedfor usein selectingalternative operating strategieson a
commercialmethyl-t-butyl ether (MTBE) unit. The model is basedon generalchemicalengineeringprinciplesand is tuned to
representthe operation of the reactors systemof a given MTBE unit. Constrainedoptimization techniquesare 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-passconversion 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 incrementsof 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 representsan improvement of about 1.5%on daily net profit for the pricesquoted. These
resultsdemonstratethe useof the modelin selectingmore economicallyattractive operating targets.The modelcan alsobe used
to investigatethe effect of other variablesamenableto 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- ElsevierScience
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-

132

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Elkanzi

/ Chemical

Engineering

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.

and Processing

35 (1996)

131-139

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-C-OH

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,

CH,

CH3

I
CH,

I
CH,

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

CH, H CH,

(2)

(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].

I
CH,

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].

CH,

CH,

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

2.1. Process chemistry

H
I
H-C-OH
I
H

CK
2. Process description

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

I
CH,

(4)

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

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

133

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

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:

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

Table 1
Normal reactor system operation
Parameter

Reactor I

Reactor II

LHSV, s-
Inlet temp., K
AT, K

2.94 x 1O-3
321
14.2(q)

7.5 x 10-4
314.7
3.2(%)

iC, conversion, % based on


feed to reactor

72.3(X,)

55.5(X,)

91(X,)
87.3
2.88
25
29.3
1.3x103

96(X,)
91.4
25
29.3
8.5 x 10

4.16
0.0072
0.25
0.64

4.9
0.01
0.83
0.2

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

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

Fig. 1. Schematic flow diagram for the reactor system.

Feeds:
iC,(mixed butenes)
MeOH

$17.5 per BBL


$23.9 per BBL

Products:
MTBE

$45.2 per BBL

Utilities
Water cooling (11.1 K rise), m3
Electricity, kWh
Power, pumping

14 per kg MTBE
2.2 per kg MTBE
SO.07 per BHP h-

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Table 3
Base case economics

and Processing

35 (1996)

131-139

Heat balance yields (datum = 298 K):


T

Product

Quantity

Unit value

MTBE

3780.7 BBL d-

S45.2 per BBL 170 888

Feeds:
iC4
MeOH

2993.4 BBL d-
1290 BBL d-

$17.5 per BBL


$23.9 per BBL

CpidT-

S per day

ET

C,i dT-

FiA.H~X=

s298

i=l

(7)

and
52 385
30 828

QR= i

Operating costs:
Pumping
Cooling
Other?
Total cost
Net profit per day
Net profit per BBL
MTBE

2532
7597
34 445
127 787
43 100
11.4

CpidT

(8)

sT

For the second reactor:


VI, = EEi

x2 dXi

and

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

3. Optimization

RT

i-l

model

(9)

CBri>

x = 0.96 -X,
2
1 -x,

(10)

Heat balance yields:


n
OTTC,,dT-

,I

2 Pi
i=l

3.1. Reactor equations

TT

Cpi dT-

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)

s
0

where

Cmyi)

(-r,)=k,k,exp

FF
01
Xl

=l+RR(l-XI)

.
*Cy
I>
(6)

EEiAHgX2/=

(11)

s 298

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)

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

E.M.

Elkanzi

/ Chemical

Engineering

and Processing

3.5 (1996)

135

131-139

0.2 /
O.l-

d
2

I
2.2

I
2.4

I
2.6

I
3.0

2.8
RECYCLE

I
3.2

I
3.4

3.6

RATIO

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,

(14)

ATzG%

(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.

136

EM. Elkanzi / Chemical Engineering and Processing 35 (1996) 131-139

2.2

2.4

2.6

2.8

3.0

3.2

3.4

3.6

3.8

RECYCLE

RATIO

Fig. 3. Variationof heatremovalrateswith recycleratio.

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.

EM. Elkanzi / Chemical Engineering and Processing 35 (1996) 131-139

137

108
0
:

107

":
P
* 106
E-2
8 105

104
103
102
101
100
2

2.2

2.4

2.6

2.8

3.0

3.2

3.4

3.6

3.0

RECYCLE

4.0

RATIO

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

EM. Elkanzi 1 Chemical Engineering and Processing 35 (1996) 131-139

138

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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