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Production of MTBE Using Reactive Distillation

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Conference Paper January 2009

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 Proceedings of the Third International Conference on Modeling, Simulation and Applied Optimization
Sharjah,U.A.E January 20-22 2009

PRODUCTION OF MTBE USING REACTIVE DISTILLATION TECHNOLOGY

Fahad S. Al-Harthi Ibrahim S. Al-Mutaz Ahmed E. Abasaeed*

SABIC Industrial Complex for Chem. Eng. Dept. Chem. Eng. Dept.
R&T, King Saud University, King Saud University,
POB 42503, Riyadh 11551, POB 800, Riyadh 11421, Saudi POB 800, Riyadh 11421, Saudi
Saudi Arabia Arabia Arabia
alharthifs@sabic.com almutaz@ksu.edu.sa abasaeed@ksu.edu.sa
* Corresponding author

reduced recycle costs.

ABSTRACT
Methyl tertiary butyl ether (MTBE) is a valuable gasolines octane
number booster. A process utilizing reactive distillation (RD) for
producing is simulated by PRO-II software. An optimization
exercise has been carried out for the main parameters. Feed ratio,
feed location, reaction zone and reflux are among the parameters
that have significant effect of the performance of the RD unit.
1. INTRODUCTION
Oxygenates are hydrocarbons that contain one or more oxygen
atoms. The primary oxygenates are alcohols and ethers, including:
fuel ethanol, methyl tertiary butyl ether (MTBE), ethyl tertiary
butyl ether (ETBE), and tertiary amyl methyl ether (TAME). Of
all the oxygenates, MTBE is attractive for a variety of technical
reasons. It has a low vapor pressure. It can be blended with other
fuels without phase separation. MTBE is primarily used in
gasoline blending to boost the octane number of the fuel resulting
in improved hydrocarbon combustion efficiency [1].
improved product selectivity.
over-coming limitations imposed by equilibrium
(reversible reaction).
heat integration benefits
avoidance of hot spots and runaway reactions.
The major constraints of reactive distillation are [5]:
close relative volatilities of components
residence time requirements (avoid long reaction times)
mismatch of process conditions (reaction and
distillation)
scale up and large flow rates (liquid distribution
problems)

MTBE is produced via direct addition of methanol to isobutylene

(IBTE) using sulphonated ion exchange resin as catalysts
according to the following chemical reaction equation:

CH 3OH + (CH 3 ) 2C = CH 2 (CH 3 )3C O CH 3

The conventional process for production of MTBE is composed of

a reactor followed by a train of distillation columns as shown in
Fig. 1a [2]. On the other hand, reactive distillation (RD) provides
Figure 1. (a) conventional and (b) reactive distillation process
a process in which simultaneous chemical reaction and vapor-
liquid phase separation take place in the presence of a
Many models for reactive distillation columns are available in the
heterogeneous catalyst (Fig. 1b). This represents an exciting
literature. Generally speaking, these model can be classified as:
alternative to traditional liquid phase chemical reaction
Steady state equilibrium stage with or without stage efficiency;
processing.
Dynamic equilibrium stage with or without stage efficiency;
Steady state non-equilibrium stage; Dynamic non-equilibrium
1.1 Reactive Distillation
stage and Steady state non-equilibrium cell models [3-17]. All
these models utilize the so-called MESH equations where the
Reactive distillation has many advantages [3-4], such as:
letters stand for: M=Material balance equations; E=Equilibrium
simplification of the separation system can lead to equations; S=Summation equations or composition constraints and
significant capital savings. H=Heat or energy balance equations.
improved conversion of reactant approaching 100%.

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 Proceedings of the Third International Conference on Modeling, Simulation and Applied Optimization
Sharjah,U.A.E January 20-22 2009

In this contribution, reactive distillation process for the production
of MTBE from methanol and isobutene will be presented. PRO-II
software was used to simulate the process. User Added
Subroutines (UAS) were used to enhance the performance and
accuracy of the analysis. Mainly, binary interaction parameters for
evaluation of equilibrium parameters and a recently obtained
kinetic expression [18] were embedded into the program. The
effects of some key parameters will be presented.
2. THE PROCESS AND MODEL
Below is a brief description of the process and the main reactive
distillation model equations. More details regarding operating
conditions, sizes of equipment and elaborate discussions can be
found in [19] due to space limitation.
2.1 The Process
The process flow sheet for MTBE production [19], which was
simulated with PRO-II, is shown in Fig. (2). The salient features
of the flow sheet are: a pre-reactor (RX-1) in which 90-93% of
isobutylene is converted; a reactive distillation unit (T-1) in which
isobutylene conversion over 99% is achieved and MTBE is
recovered (>99.5% purity); a methanol recovery section (T-2) by
washing with water to remove C4s components; and a methanol-
water (T-3) separator to recover and recycle unreacted methanol.
Although the whole process flow sheet was simulated, the
emphasis below is on the reactive distillation unit (T-1).

Figure 2. Flow sheet of the simulated MTBE Plant

Table 1. Binary Interaction Parameters for SRKM_VLE

Comp I NC4 1BUT BTC2 BTT2 IBTE MEOH TBA MTBE

n-butane 1-butene Cis2-butene Trans2-butene Isobutylene Methanol Tert-Butanol
Comp j TBA MEOH MEOH MEOH MEOH TBA H20 DIB
kija 0.0469 0.136 0.136 0.136 0.13553 -0.07397 -0.145 0.05785
kjia 0.1260 -0.0323 -0.0323 -0.0323 -0.0322 -0.05522 -0.253 -0.0093
kijb 0.0 0.0 0.0 0.0 0.0 0.0 0.0 -10.144
kjib 0.0 0.0 0.0 0.0 0.0 0.0 0.0 6.17

2.2 The Model
PRO-II Software utilizes Chemdist Algorithm, but it requires
knowledge of material and energy balance equations as well as
thermodynamics and reactions kinetics. The major assumptions
employed in this simulation include: steady state operation;
pseudo-homogeneous model for reactor; pressure drop along the
reactor is 69 kPa; physical properties are temperature dependent;

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 Proceedings of the Third International Conference on Modeling, Simulation and Applied Optimization
Sharjah,U.A.E January 20-22 2009

and the PRO-II build-in modified Soave-Redlich-Kowng, SRKM, The optimization exercise carried out through process simulation
is used for calculation of vapor liquid equilibrium, VLE. To revealed the optimum values (i.e., to obtain over 99.2%
enhance the equilibrium calculations, binary interaction conversion of isobutylene and over 99.7% MTBE purity) for the
parameters are supplied (see Table 1) using the User Added above parameters are: methanol to isobutylene feed ratio of 1; a
Subroutine (UAS) feature in PRO-II. UAS are, also, used to reflux ratio of 1.1, a total trays number of 30; a feed position tray
supply the kinetics equation based on that of Al-Jarallah, et al. number 15 and a reaction zone between trays number 11 to 13.
[18] as shown in Equation (1). The above values can clearly be seen from Figs (4) and (5) for
feed location and ratio respectively to be the optimum values
C C 0.5 C 1.5 / k (other parameters are assigned the values above). It is clear from
rs = k s k A A B C
1.5
(1)
Fig. (4) that introducing the feed below the reaction zone (trays

(1 + K C
A A + K BC B )
11-13) will have negative effects on both conversion and purity.
As can be seen from Fig. (5) a methanol to isobutylene feed ratio
of 1 gives the optimum value for conversion and the highest value
The basic MESH equations are given by Equs. (2-5): for purity. From reaction stoichiometry , lower ratios (<1) will
result in excess isobutylene, thus lower conversion.
Lk +1 Xk +1,i +Vk 1Yk 1,i (Lk + SLk ) Xk ,i
M: r Conversion (%) MTBE Purity (wt%)
(2)
(Vk + SVk )Yk,i + Fk Zk ,i Rjk ,i = 0
j =1 100

99
E: Yk,i = k,i K k,i X k,i (3)
98
S: X k ,i = 1 = Yk ,i
i i
(4) 97

96

Lk +1 hk +1 + Vk 1 H k 1 ( Lk + SLk ) hk 95
H: r
(Vk + SV k ) H k + Fk h fk Qk + R jk H jk = 0
(5) 94

j =1
6 8 10 12 14 16 18
Feed Tray #
3. RESULTS AND DISCUSSION

Although PRO-II was used to solve the entire flow sheet, the Figure 4. Effect of feed location on conversion and purity
results presented here emphasize the reactive distillation column,.
The main operating parameters that have significant effect on the
performance of the reactive distillation column were determined Conversion (%) MTBE Purity (wt%)
to include: methanol to isobutylene feed ratio; the reflux ratio,
number of total trays; the position of feed tray and the reaction 100
zone.
96
Figure (3) shows the temperature profile inside the reactive
distillation column with tray 1 being the condenser.
92

140 88

120 84
Temperature, C

0.85 0.9 0.95 1 1.05 1.1

100
MeOH/IBTE ratio

80

60 Figure 5. Effect of feed ratio on conversion and selectivity

40 4. CONCLUSIONS
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29
Reactive distillation provides a viable technology for the
Tray # production of MTBE with extremely highly isobutylene
conversion and MTBE purity. The optimum values of the main
Figure 3. Temperature profiles along the RD column parameters for 99.2% conversion of isobutylene and 99.7%

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 Proceedings of the Third International Conference on Modeling, Simulation and Applied Optimization
Sharjah,U.A.E January 20-22 2009
MTBE purity were determined to be: methanol to isobutylene feed
ratio of 1; the reflux ratio is 1.1, number of total trays is 30; the
feed is introduced at tray number 15 and the reaction zone is
confined to trays number 11 to 13.
5. NOMENCLATURE
(Lk+SLk) = molar liquid flow rate leaving stage k.
(Vk+SVk) = molar vapor flow rate leaving stage k.
R jk,i = rates of component i due to reaction j on stage k.
CA = IBTE concentration in mole/l
CB = MEOH concentration in mole/l
CC = MTBE concentration in mole/l
Fk= feed flow rate to stage k.
Hj,k = heat of reaction in stage k.
h k = molar enthalpy of liquid phase in stage k.
HK = molar enthalpy of vapor phase in stage k.
K = equilibrium constant
KA = equilibrium adsorption constant = 5.1x10 -13 exp(97500/RT)
in g catalyst/gmole
KC = equilibrium adsorption constant = 1.6x10-16 exp(119000/RT)
in g catalyst/gmole
Kk,i = vapor-liquid equilibrium constant.
Ks = surface reaction rate constant= 1.2x10 13 exp(-87900/RT) in
(gmole/g catalyst)
Qk = heat duty in stage k.
Xk,j:= mole fraction of liquid phase for species i in stage k.
Yk,I = mole fraction of vapor phase for species i leaving stage k
k,i = activity coefficient of component i in stage k.
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