Kinetics of Methyl Tertiary Butyl Ether Synthesis

Catalyzed by Ion Exchange Resin

ADNAN M. AL-JARALLAH, MOHAMMED A. B. SIDDIQUI, and A. K. K. LEE
Department of Chemical Engineering and the Research Instihrte, King Fahd University of Petroleum & Minerals, Dhahran
31261, Saudi Arabia
This paper presents the results of anexperimental investigation of thekinetics of liquid phase reaction between methanol
and isobutene, catalyzed by an acidic ion-exchange resin, to formmethyl tertiary butyl ether (MTBE). A one litre Parr
batch reactor was used. Experiments were carried out at 70, 80, 90 and 100C and at pressures sufficient to maintain
liquid phase at those temperatures. Initial methanol/isobutene mole ratios of 1 .O and 2.0 were used. The catalyst amount
was also varied.
These kinetic data were used to model the reaction kinetics, by non-linear least squares regression technique. The
reaction was found to follow Rideal-Eley kinetics. The values of the rate constants are reported.
On presente dans cet article les rtsultats dune recherche exptrimentale sur la cinttique de reaction en phase liquide
entre lemethanol et Iisobuttne, catalysts par unertsine tchangeuse ions acide, pour former du methyl tertiaire butyl
ether (MIBE). Ona utilist un rtacteur discontinu Parr de 1 litre. Les exptriences ont ttt mentes a des temperatures
de 70, 80, 90 et 100C et ?i des pressions suffisantes pour maintenir la phase liquide a ces temperatures. Des rapports
molaires initiaux mtthanollisobuthe de 1 ,O et 2, O ont ttt utilists. Laquantitt de catalyseur varie tgalement.
Ces donntes de cinttique ont ett utilistes afin de modtliser la cinktique de reaction, par la technique de regression
des moindres carres non linbaire. On a trouvt que lartaction suit la cinttique de Rideal-Eley. Les valeurs des con-
stantes de vitesse sont egalement donntes.
Keywords: methyl tertiary butyl ether synthesis, MTBE kinetics, ion exchange resin catalysis.
ethyl tertiary butyl ether has received attention in
M recent years as an important alternative to lead alkyls
as a gasoline additive to increase the octane number. Unlike
lead alkyl additives which cause air pollution and are toxic,
MTBE is non-toxic and non-polluting according to studies
by Csikos et al. (1976), Torck et al. (1982), and Furey and
King (1980).
MTBE is produced by reacting methanol (MeOH) with
isobutene (i-Bu) in the presence of an acidic catalyst, such
as sulfuric acid, acidic ion-exchange resins, or other acidic
catalysts:
MeOH +i-Bu MTBE . . . . . . . . . . . . . . . . . . .
(1)
The reaction is reversible and exothermic, with a heat of reac-
tion of -37.2 kJ /mol in the liquid phase at 25C.
Since the discovery of the etherification reaction between
alcohols and olefins by Reychler (1907), very little scien-
tific work has been published on the reaction. Only limited
kinetic information on the reaction was published by Evans
and Edlund (1936) and, recently, by Ancillotti et al. (1977
and 1978), Gicquel and Torck (1983), Csikos et al. (1979),
and by Chu and Kuhl(l987). In the two latter investigations,
sulfuric acid and zeolite were used as catalysts respectively,
while in the first three recent studies the ion exchange resin
(Amberlyst 15) was used as catalyst. Actually this is the most
widely used catalyst in industrial productions of MTBE.
Ancillotti et al. (1977) studied this reaction with Amber-
lyst 15 catalyst and reported a zero order dependence of rate
on methanol concentration, for concentrations greater than
4 mol/litre, with negative orders at lower concentrations and
a first order dependence of rate on isobutene concentration
based on analyses of the initial rates of the reaction. The same
authors in 1978 examined the influence of methanol concen-
tration of the activity of Amberlyst 15 resin. Gicquel and
Torck (1983) investigated this reaction and reported that the
reaction follows Langmuir-Hinshelwood kinetics. They
reported relative values of rate and adsorption equilibrium
constants. A lot of information on reaction conditions, con-
versions, and selectivity in MTBE synthesis can be found
in patents. A comprehensive review of MTBE patents,
production technologies and economics is given by Lee and
Al-J arallah (1986).
In this study, rate equations describing the kinetics of the
MTBE synthesis reaction, catalyzed by ion exchange resin,
have been developed and presented with the values of all the
rate constants involved.
Experimental
The liquid phase reaction between methanol and isobutene
was carried out in a standard one liter Parr pressure reactor.
Batchwise experiments were performed. The Parr pressure
reactor was equipped with magnetic stirrer and internal
cooling coil in addition to the necessary accessories such as
inlet valve, sampling valve, pressure gauge, thermowell and
heater jacket.
A measured volume of methanol was introduced into the
reactor and a weighed quantity of the ion-exchange resin
catalyst was added to it. The contents were heated up to the
desired temperature. Pure liquid isobutene was then fed in
and the reactor was pressurised with nitrogen to maintain
liquid phase. The whole mixture was stirred at lo00 r/min.
to eliminate the effect of agitation on mass transfer which
is significant at speed below 600 r/min. The temperature was
maintained at the desired set point by circulation of the
cooling water through the internal cooling coils. The time
of addition of isobutene was taken as the starting time of
the reaction. The reaction was allowed to run and liquid
samples were collected at regular intervals. Details of the
experimental procedure have been described by Siddiqui
(1987).
802 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 66. OCTOBER, 1988
A
o o O
0 0,
60
w
a.
W
4 0 A 0 I
l%
t
I
Q+ 0
F' A
2 - 0
m
0
!!
X 0 2 5 g c o t
A S 2 9 C o t
0
2 0 - .+ A
0
+7 6 9 c o t
+ 0
X x 12 4 g c o t
0 20 0 9 COl
0
0 4 0 80 1 2 0 160 200
TI ME, ml n AMOUNT OF CATALYST, (I
Figure1 - Isobuteneconversion versus timeat methanol/isobu-
tene =2 and 80C for different amounts of catalyst.
Figure2 - Initial rateof isobuteneconversion versus amount of
catalyst at 80C and methanol/isobutene=2.
The ion exchange resin catalyst (Amberlyst 15) was sup-
plied by Rohm& Haas. The resin is a macroreticular nuclear
sulfonated copolymer of styrene and divinylbenzene. The
catalytically active group is the nuclear sulfonic acid. Its ion-
exchange capacity is 4.9 milli-equivalent/g of dry resin.
Analytical
One microlitre of each sample was analysed by a Varian 3700
gas chromatograph (GC). The GC was equipped with a flame
ionisation detector. A 3. 2 m long, 4 mm ID, stainless steel
column, packed with 10% dinonyl pthalate on chromosorb
W-HP, was used. The detector was connected to a CDS 1 1 1
integrator directly giving the area of the different peaks. The
GC was calibrated with pure compounds, and the amount
of each compound present in the product sample was then
determined fromthe respective area counts using this calibra-
tion. Most of the isobutene escaped to the air as the sample
was depressurised; therefore the amount of isobutene was
calculated from the stoichiometry of the reaction while that
of methanol and MTBE was determined by GC analysis.
Diisobutene was not found in product samples, because
of the very low rates of its formation and excess or equi-
molar methanol at the conditions of these experiments.
Ancillotti et al. (1978) showed that at 60C the initial rates
of isobutene dimerization in MTBE synthesis were insigni-
ficant at methanolhobutene molar ratios greater than 0.30.
Results and discussion
KINETIC DATA
The effects of three variables on the kinetics of MTBE syn-
thesis have been investigated. These variables are tempera-
ture (70 to 100"C), amount of catalyst (2.5 to 20.0 g)
corresponding to 1 % - 10% by weight, and initial
methanol/isobutene molar ratio (1 .O and 2.0). For studying
these effects, only the appropriate parameter was varied while
the other two were kept constant.
The first parameter that was tested was the catalyst amount
in order to determine the optimum catalyst amount to use
for studying other parameters. Figure 1 shows the conver-
sion of isobutene vs. time for different catalyst amounts at
a temperature of 80C and an initial reactants ratio of 2.0.
In this figure, the slope of the curve at any time is an indica-
tion of the rate of conversion of isobutene. Figure 2 shows
that the initial rate of isobutene conversion increased as the
amount of solid catalyst increased from 2. 5 gmto 12.4 gm
and was practically the same when the amount was increased
from 12.4 gm to 20.0 gm. At low catalyst amount, the high
concentration of methanol inside the resin reacts with the acid
groups forming solvated protons which become the catalytic
agent. The solvated proton is a less active acid species than
the acid group S03H, therefore the rate is slower according
to Gates and Rodriguez (1973). As the methanol concentra-
tion decreases relative to the amount of catalyst because of
increasing the amount of catalyst (2.5 gm to 12.4 gm), the
mechanism gradually shifts to catalysis by S03H. At a very
large amount of catalyst (20 gm). there are so many S03H
groups that the rate now only depends on the rate of proto-
nation of the isobutene. However, the conversion of isobu-
tene at equilibrium should be independent of the catalyst
amount. The optimum catalyst amount of 12.4 g was used
for testing other parameters.
The reaction was investigated at temperatures of 70, 80,
90, and 100C. A sample graph showing the changing con-
centration of methanol, MTBE and isobutene with time at
one temperature (80C) is given in Figure 3. The initial molar
ratio of methanolhsobutene was 2.0 and the catalyst amount
was 12.4 g in this experiment. This figure shows that the
MTBE product concentration increases monotonically with
time and approaches asymptotically to a final value; this is
a typical behavior of batchwise operations. Since the initial
molar ratio of methanol to isobutene is two, there is always
a considerable amount of methanol in the reaction mixture,
while isobutene decrease to a very low concentration.
Figure 4 shows the conversion of isobutene with time for
THE CANADIAN J OURNAL OF CHEMICAL ENGINEERING, VOLUME 66, OCTOBER, 1988 803
0 METHANOL
A MTBE
0 Il ODUTENE
0 0. 30
,
-
E
i 0. 24
g
L
I-
2 0.18
U
0 U
0.12
0 . 0 8
0 ' ' ' ' ' ' ' 1 ' 1 1 " '
0 40 80 120 180 200 240 280
TI ME, mi n
Figure 3 - Concentration of methanol, isobutene and MTBE
versus time at 80C, methanol/isobutene =2, and 12.4 g catalyst.
different temperatures. From this figure it can be seen that
the initial increase i n isobutene conversion is faster as the
temperature increases. The final conversions were lower at
higher temperatures, since the equilibrium constant of the
synthesis reaction decreases with increase in temperature
because the synthesis reaction is exothermic. Nevertheless,
high isobutene conversion (about 95 9%) has been obtained.
Figure 5 shows the effect of the initial molar ratio of
methanol to isobutene. From this figure it is seen that the
initial rate as well as the final conversion of isobutene is
higher when the ratio is one. Since Amberlyst 15 catalyst
acts through the intermediary sulfonic groups (S03H)
bonded to insoluble macromolecule, these groups provide
for the protonation of isobutene and the reaction proceeds
to form MTBE. The catalytic mechanism occurring in the
presence of this resin depends on the polarity of the reaction
medium, according to Gates and Rodriguez (1973) and
Thornton and Gates (1974). At low alcohol concentrations,
the resin retains a network of hydrogen bonds between the
sulfonic groups alone, or between these groups and the
alcohol, while at high alcohol concentrations the protons are
solvated and the H-bonded network disappears. In the present
study it seems that for the lower alcohol concentration (molar
ratio of methanol to isobutene of 1 .O) the protons were not
solvated and the isobutene can take the proton directly from
the sulfonic group. According to Gates and Rodriguez (1973)
the sulfonic group (S03H) is a more acidic species than the
solvated proton, and this can account for the increased rate
for the lower molar ratio. Nevertheless, excess methanol is
often used to suppress side reactions forming isobutene
dimers.
KINETIC MODEL
The MTBE synthesis reaction can be represented by:
(2)
A +B C ..............................
0 0 0 0
100
+ A ~ : A A
+ + + + +
80
z
0
z
: 80
>
z
8
5
W
z
40
m
s
0
o h
x x
X
0 80 120 180
TIME, mi n
240 300
Figure 4 - Isobutene conversion versus time at rnethanol/isobu-
tene =2 and 12.4 g catalyst for different temperatures.
where, A, B and C denote methanol, isobutene and MTBE
respectively. In general, the forward reaction is order a in
A and order b in B, and the reverse reaction is order c in C.
The rate of surface reaction, r,, is assumed to be the rate
controlling step, as there were no mass transfer limitations.
There are two possible mechanisms by which this surface
reaction takes place:
1) Reaction between adsorbed molecules of both A and
B on adjacent active centers, and
2) Reaction between one adsorbed reactant and the other
reactant in solution.
The first mechanism is the Langmuir-Hinshelwood
mechanism and the second one is the Rideal-Eley mechanism
as discussed in Smith (1981) and Satterfield (1980). In these
references the reaction is assumed to be a simple reaction,
that is, the reaction is first order in all species. The following
rate equations were derived for general orders of reaction
a, b and c. For a Langmuir-Hinshelwood model, the rate
of reaction can be represented by the following equation:
r, =k,KjK;
. . . (3)
1
Cj Ci - C:/K
[ (1 +KACA +KBCB +KCCC)~''
For the case of the Rideal-Eley mechanism, there are two
possibilities in which either one of the two reactants is
adsorbed on the catalyst and then reacts with the other reac-
tant in solution. For the case when the methanol (A) is
adsorbed and reacted with the isobutene (B) in solution, the
final rate equation is:
. . . . . . .
1
Cj C; - CZIK
(1 +KACA +KcCc)a
r, =k, Kj
(4)
804 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 66, OCTOBER, 1988
TABLE 1
Reaction Equilibrium Constant, Rate Constant, and Equilibrium Adsorption Constants for
Eq. (4) with a =1 , b =0.5 and c =1.5
T
("C) K k.s KA KC
70 38.0 0.512 359.8 202.1
80 15.8 1.065 159.8 73.3
90 13.0 2.537 47.6 18.5
100 6. 9 6.080 25.5 7.64
90
0 -
70
OQ
5 0 -
4 0
3 0 -
20
10-
0'
3
- 0 0 O
0
0
0
h
0 A A
A
~
A
-
0
A
-
h
A
-
0 YLTl i Am)LIISOIUTLNL 2 9
~YETl 4ANOLIISODUTLIIC : 2
' I I
30 60 90 110 180
i
Q
ln
K
W
>
z
0
0
Y
W
I-
3
0
m
B
TIME, mln
Figure 5 - Comparison of isobutene conversion versus time at
80C and 5 wt% catalyst for methanol/isobutene ratios of 1 and 2.
For the case when isobutene is adsorbed and reacted with
methanol in solution, the final rate equation is:
. . . . . . .
1
Ci Cj - C:/K
(1 +KBCB +K c C ~ ) ~
r, =k, K j
For a given set of a, b and c the unknown parameters in
Equations (3), (4) and ( 5) are the surface reaction rate cons-
tant, k,, the equilibrium adsorption constants KA, KB and
Kc, and the thermodynamic equilibrium constant, K. This
equilibrium constant can be calculated from experimental
concentration data in which concentration equilibrium has
been reached.
Since
K =K, K, ................................. (6)
K, was calculated from the mole fractions of components
from experimental data and K, was calculated from the
UNIFAC method as described by Colombo et al. (1983).
Thus K values obtained at 70, 80, 90, and 100C are 38.0,
15.8, 13.0, and 6.9, respectively.
In data analysis the experimental concentrations versus
time for methanol, isobutene, and MTBE were fitted to poly-
nomials so that a polynomial i s obtained for each compo-
nent for each temperature. These polynomials were used to
P.? 2.0
I IT x 103, ~ - 1
Figure 6 - Arrhenius plot for k,.
obtain values of concentrations at different times. The poly-
nomial for MTBE was differentiated in order to calculate
the rate of MTBE formation at different times.
Non-linear least square regression analysis was then used
to determine the rate constant and the equilibrium adsorp-
tion constants for integral and half-integral values of the expo-
nents (a, b and c ) ranging from zero to three. The kinetic
data were fitted to different combinations of a, b and c for
all the three possible models above (Equations 3, 4 and 5) .
The criteria for the acceptance of the model were:
1) The estimated rate constant, k, , and the adsorption
equilibrium constants should be positive.
2) A plot of the logarithm of the rate constant, In k, ,
versus 1/T (Arrhenius plot) should be linear with a
negative slope.
3) A plot of the logarithm of each adsorption constant
versus l/T (van't Hoff plot) should be linear with a
positive slope, except when chemisorption is
endothermic, and
4) The goodness of the fit as indicated by the statistical
percentage absolute average deviation.
Regression analysis was carried out for various sets of a,
b and c. Based on the above criteria, rate Equations (3) and
( 5) were rejected. Equation (4) met the above mentioned
criteria and gave the best fit for a =1.0, b =0.5 and c
=1.5. The parameters k, , KA and Kc for Equation (4) at
different temperatures are given in Table 1.
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 66, OCTOBER, 1988 805
r
8. 00 -
5.20 -
a
Y
c
-
4. 40 -
2. 00 L
I I I I
2.eo 2.68 2.70 2.84 e.92 3
Figure 7 - van? Hoff plot for K, .
I
The dependence of the rate constant, k,, on temperature
was determined from the Arrhenius equation,
.......................
k, =k,r,l exp(-EIIRT) (7)
The values of k,, and El were found from the least squares
fit of Equation (7) as shown in Figure 6. Thus:
(8)
k, =1.2 x 1013 exp(-87,900/RT) . . . . . . . . . . . .
The activation energy (87.9 kJ /mol) is similar to the values
in other homogeneous and heterogeneous investigations as
summarized by Gicquel and Torck (1983).
The dependence of the adsorption constants, KA and Kc,
was determined from the vant Hoff equation,
(9)
.................... KA =KAo exp( -AHA/RT)
and
. . . . . . . . . . . . . . . . . . Kc =Kco exp( -A HclRT)
(10)
The values of KA,, Kco, A HA and A Hc were obtained from
the least squares fit of the above two equations as shown in
Figures 7 and 8. Thus:
KA =5.1 x exp(97,500/RT) . . . . . . . . . . . ( 1 1)
and
KC =1.6 X 10-16exp(119,000/RT) . . . . . . . . . . (12)
Conclusion
This investigation showed that in the range of conditions
studied the reaction kinetics for MTBE synthesis can be
represented by a Rideal-Eley model. Methanol is preferen-
tially adsorbed in the ion-exchange resin catalyst. The catalyst
is more active at low methanol/isobutene ratios.
The rate constant increases with increase in temperature.
The reaction has an activation energy of 87.9 kl/mol. The
thermodynamic equilibrium constant and the adsorption
equilibrium constants for methanol and MTBE decrease with
t
2.80 2.68 2.78 2.04 2.92 3.00
i T ,to3, K-
Figure 8 - vant Hoff plot for K,.
increases in temperature.
The heterogeneous catalyzed reaction is a complex reac-
tion. The reaction is first order in methanol, half order in
isobutene and 1.5 order in MTBE.
Acknowledgement
We acknowledge with thanks the financial support of this project
No. AR-6-133 by King Abdul Aziz City for Science and Tech-
nology. We also gratefully acknowledge the support and encourage-
ment by King Fahd University of Petroleum & Minerals, Dhahran,
Saudi Arabia.
Nomenclature
a, b, c =order of reaction of species A, B and C, respectively.
C,
C,
C,
El
AH,
AH,
K
K,
K B
K,
K,
K,
KAo =preexponential factor
kS0 =preexponential factor
K,, =preexponential factor
k S =surface reaction rate constant (forward), (mol/g
rs
R
T =temperature, K
Xi =mole fraction
yi =activity coefficient
References
=bulk concentration of A, mol A/g cat
=bulk concentration of B, mol B/g cat
=bulk concentration of C, mol Clg cat
=activation energy of theforward reaction, J /mol
=heat of adsorption of methanol, J/mol
=heat of adsorption of MTBE, J /mol
=equilibrium constant for the overall reaction
=equilibrium adsorption constant for A, g cat/rnol
=equilibrium adsorption constant for B, g cat/mol
=equilibrium adsorption constant for C, g cat/mol
=mole fraction equilibrium ratio
=ratio of activity coefficients at equilibrium
cat) .5/h
=rate of surface reaction, (mol/g cat)/h
=gas constant, 8.314 J ho1.K
Ancillotti, F., M. M. Mauri and E. Pescarollor, Ion Exchange
Resin catalysed Addition of Alcohols to Olefins, J . Catal. 46,
49-57 (1977).
806 THE CANADIAN J OURNAL OF CHEMICAL ENGINEERING, VOLUME 66. OCTOBER. 1988
Ancillotti, F., M. M. Mauri and E. Pescarollo, Mechanisms in
the Reaction Between Olefins and Alcohols Catalyzed by Ion
Exchange Resins, J . Mol. Catal. 4, 37-48 (1978).
Chu, P., and G. H. Kuhl, Preparation of Methyl tert-Butyl Ether
(MTBE) over Zeolite Catalysts, Ind. Eng. Chem. Res. 26,
Colombo, F., L. Corl, L. Dalloro and P. Delogu, Equilibrium
Constants for the Methyl Tertiary Butyl Ether Liquid Phase Syn-
thesis by Use of UNIFAC, Ind. Eng. Chem. Fund. 22,
Csikos, R., I. Pallay, J . Laky, E. D. Radcsenke, B. A. Englin and
Roberts, J . A. Low-lead Fuel with MTBE and C, Alcohols,
Hydrocarbon Processing, 121-125 (July 1976).
Csikos, R., I. Pallay and J . Laky, Practical Use of Methyl Ter-
tiary Butyl Ether Produced from C, Fraction, Proceedings of
Tenth World Petroleum Congress, Bucharest, 167-175 (1979).
Evans, T. W. and K. R. Edlund, Tertiary Alkyl Ethers, Prepara-
tion and Properties, Ind. Eng. Chem. 28, 1186-1 188 (1936).
Furey, R. L. and J . B. King, Evaporative and Exhaust Emissions
from Cars Fueled with Gasoline Containing Ethanol or Methyl
Tert-Butyl Ether, Paper 800261 presented at the Congress and
Exposition of the Society of Automotive Engineers, Detroit,
Michigan, February (1980).
Gates B. C. and W. Rodriguez, General and Specific Acid Catal-
ysis in Sulfonic Acid Resin, J . Catal. 31, 27-31 (1973).
365-369 (1987).
219-223 (1983).
Gicquel, A. and B. Torck, Synthesis of Methyl Tertiary Butyl
Ether Catalysed by Ion-Exchange Resin. Influence of Methanol
Concentration and Temperature, J . Catal. 83, 9-18 (1983).
Lee, A. and A. Al-J arallah, MTBE Production technologies and
Economics, Chemical Economy and Engineering Review, 18,
9, 25-34 (1986).
Reychler, A., Bull. SOC. Chem. Belg., 21, 71 (1907).
Satterfield, C. N., Heterogeneous Catalysis in Practice,
McGraw-Hill, New York (1980).
Siddiqui, M. A. B.; Kinetics of MTBE Synthesis by Homogeneous
and Heterogeneous Catalysis M. Sc. Thesis, King Fahd
University of Petroleum and Minerals, Dhahran 31261, Saudi
Arabia (1987).
Smith, J . M., Chemical Engineering Kinetics, McGraw-Hill,
New York (1981).
Thornton, R. and B. C. Gates, Catalysis by Matrix-Bound Sul-
fonic Acid groups: Olefin and Paraffin Formation from Butyl
Alcohols, J . Catal. 34, 275-287 (1974).
Torck, B., A. Convers and A. Chauvel, Methanol for Motor Fuel
Via the Ethers Route, Chem. Eng. Prog. 78, (8), 36-45
(August 1982).
Manuscript received November 12, 1987; revised manuscript
received March 4, 1988; accepted for publication April 19, 1988.
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 66, OCTOBER, 1988 807