Ind. Eng. Chem. Res.

1994,33, 581-591
Kinetics of the Liquid-Phase Synthesis of Ethyl tert-Butyl Ether
(ETBE)
Introduction
581
Carles Fit6, Montserrat Iborra, Javier Tejero,. Jose F. Izquierdo, and Fidel Cunill
Chemical Engineering Department, Faculty of Chemistry, University of Barcelona,
Martt i FranquBs, 1, 08028-Barcelona, Spain
The liquid-phase addition of ethanol to isobutene to give ethyl tert-butyl ether (ETBE) on the ion
exchange resin Lewatit K2631 has been studied. Rate data were obtained free of mass transfer
influence in a continuous differential reactor operated at 1.6 MPa and 40-90 "C, measuring steady-
state conversions <l o% for ethanol-isobutene and ethanol-isobutene-ETBE feeds. The reaction
is highly temperature-sensitive. Isobutene has an enhancing effect on the rate whereas ethanol has
an inhibitor one. Besides, low ETBE concentrations enhance the reaction but as chemical equilibrium
is approached the ether shows an inhibitor effect, as expected. As alcohol-olefin-ether mixtures
behave nonideally, kinetic analysis has been performed by using the UNIFAC liquid-phase activities
of isobutene, ethanol, and ETBE. The best kinetic model stems from an Eley-Rideal mechanism
in which the ethanol, adsorbed on one center, reacts with the isobutene from solution to give the
ether adsorbed on one center. Surface reaction is the rate-limiting step. Two additional centers
take part in this step.
The use of oxygenated fuels has allowed lead to be
phased out from gasolines and has been proposed as a
means for reducing carbon monoxide and reactive evap-
orative and exhaust emissions. The Clean Air Amend-
ments of 1990 have increased the severity of the emissions
limits of vehicles and require the manufacture of refor-
mulated gasolines (Peeples, 1991; Potter, 1991). Although
reformulated gasoline specifications will not take effect
until 1995, gasolines must already contain 2.7 wt % oxygen
during the winter in the CO nonattainment areas of US.
Moreover, to reduce volatile organic compounds (VOC)
emissions, the maximum blending Reid vapor pressure
(bRvp) of all US gasoline is set at 9.0 psi. In Europe,
unleaded gasoline has developed slowly and only because
of tax incentives. However, under pressure from envi-
ronmentalists, European gasoline is almost sure to be
reformulated by the year 2000. As a result, oxygenates
demand will increase enormously in the coming years.
Of all the oxygenates, tertiary ethers are preferred by
refiners to lighter alcohols, among other reasons, because
of their lower bRvp and lower vaporization latent heats
and their full fungibility in the petroleum refining and
distribution systems. Currently, the most common ether
is methyl tert-butyl ether (MTBE) because low methanol
prices make MTBE a more atractive option than ethyl
tert-butyl ether (ETBE) (Anderson, 1988). Nevertheless,
some of the US states and a few of the European
Community countries are planning to use ETBE produced
from bioethanol as an alternative to MTBE (Oxy-Fuels
News, 1992a,b). In the US, it is thought that ETBE
economics will become more attractive in 1995 when
Federal reformulated gasoline specifications will encourage
lower bRvp oxygenates such as ETBE. Furthermore, a
cost-competitive process for obtaining bioethanol from
cellulosic biomass appears possible by 2000 (Lynd et al.,
1991). On the other hand MTBE plants can easily be
revamped into ETBE. So, it seems that MTBE producers
are mainly interested in the flexibility of MTBE/ETBE
plants (Anderson, 1988; Forestiere et al., 1991). Another
factor that could reduce ethanol cost is the possibility of
using azeotropic ethanol (96.5 wt %) (Bakas et al., 1990;
Cunill et al., 1993) or subazeotropic ethanol (80-85 wt % )
0888-5885/94/2633-0581$04.50/0
(J ayadeokar and Sharma, 1992) as a raw material for ETBE
production.
Besides the fact that ETBE has a lower bRvp (4 psi)
than MTBE (8-10 psi), which would allow ETBE to be
successfully used to obtain gasoline with bRvp less than
7.8 psi in some US locations during the summertime, ETBE
has an slightly higher blending octane number. Moreover,
ETBE is produced from renewable ethanol, while MTBE
is obtained from methanol derived from natural gas. That
means ETBE would reduce the dependence on methanol
and oil importations and create additional markets for
grain products and agricultural wastes. Of course, the
ETBE option is clearer in countries like India, where
ethanol is considerably cheaper than methanol (J ay-
adeokar and Sharma, 1992).
From a standard pollutants emissions standpoint, ETBE
parallels MTBE, showing a sizeable reduction in CO, a
smaller reduction in unburned hydrocarbons, and a
nonsignificant effect on NO, (Corbett, 1991; Wise, 1992;
Davis, 1992). As for toxic emissions, however, both ethers
increase aldehyde emissions. To sum up, looking at the
emissions data as a whole, the effect of using oxygenates
is positive.
In spite of the increasing interest in ETBE, there is only
limited information about the product, which is mostly
devoted to its behavior as gasoline component (Kaitale et
al., 1987; Iborra, et al., 1988; ARCO, 1989; Furey and Perry,
1990; Forestiere et al., 1991). Much more scarce is the
information available on reaction catalysts (Evans and
Edlund, 1936; Macho et al., 1982; Tau and Davis, 1989),
thermodynamics of ETBE synthesis (Rock, 1992; Vila et
al., 19931, and kinetics (Ancillotti et al., 1977; Kaitale et
al., 1988; J ayadeokar and Sharma, 1992). In this work, a
kinetic study of the reaction for obtaining .ETBE by
addition of ethanol to isobutene has been carried out. As
the alcohol-C4 hydrocarbon-ether system is highly com-
plex (Ancillotti et al., 1977), pure isobutene was used
instead of Cqcuts in order to gain a clear insight into the
influence of reactant concentration on the reaction rate.
Experimental Section
Materials. Ethanol HPLC (<0.2 5% water, 99.5 76 pure)
was supplied by Romil Chemicals Ltd. (Shepshed, U.K.)
0 1994 American Chemical Society
582
Table 1. Physical Properties of Lewatit K2631
Ind. Eng. Chem. Res., Vol. 33, No. 3, 1994
skeleton
structure
active group
nominal crosslinking degree, %
moisture,' max %
mean bead diameter,b mm
uniformity coefficient,b
porosity, vol/vol %
mean porous diameter, 8,
surface area: mz-g-1
exchange capacity: meqg-1
temperature operation, max. O C
styrene-divinylbenzene
macroporous
sulfonic
18
58-60
0.73
1.5
25
650
36
4.83
120
a Determined by Karl Fischer titration. b Determined in our
laboratory by sieving. c Determined by the method of Fisher and
Kunin (1955). Determined by the BET method.
and was dried to less than 0.05 7% water over 3-A molecular
sieves (Fluka, Buchs, Switzerland). Isobutene (99 ' % pure)
was obtained from Carburos Metllicos (Barcelona, Spain)
and used without further purification. ETBE was pre-
pared from ethanol and isobutene and was purified by
extracting the alcohol with water and distillation up to
99% pure (GC). The catalyst was the ion-exchange resin
Lewatit K2631, before SPC 118, from Bayer AG (Le-
verkusen, Germany). Its physical properties are given in
Table 1.
Apparatus. Figure 1 shows the continuous upflow
packed-bed microreactor (15-cm length; 4.4-mm i.d.1 191
where the reaction was studied. The setup was made from
stainless steel.
Ethanol, or ethanol-ETBE mixtures, stored over 3-.A
molecular sieves was fed from an atmospheric tank [l]
placed 2 m over the pump suction valve to ensure a reliable
pump operation. For the same reason, the isobutene was
fed from a pressurized bottle [21, thus avoiding vapor-
ization during the suction. Plugging of the pump suction
valves was avoided by placing 2-pm filters [31 in the pump
suction lines.
A positive displacement pump, Minipump (Dosapro,
Pont-Saint-Pierre, France), duplex-type 141, accuracy f
I ,,pa]
.
0.3% flow rate at pressures over 0.7 MPa, dosed inde-
pendently with ethanol, or ethanol-ETBE blends, and
isobutene, to the reactor. Each feeding line was equipped
with a pulsation damper 151to supply an almost constant
flow, a safety valve 161to release an excessive buildup of
pressure caused by incorrect operation, and a check valve
171to prevent liquid contamination owing to a pump
failure. The damper consisted of a 150 cm3 cylinder with
a membrane (viton for isobutylene, and poly(ethy1ene-
propylene) for ethanol) for sealing the gas against theliquid
side. The damper operating pressure was adjusted before
the experiments with compressed nitrogen to 70% of the
operating pressure.
Before the feed was brought in the reactor, it was
homogenized in a mixer (3/8 in. 0.d.; 18-cm length) [81
packed with 1-mm Pyrex spheres, and preheated in a
preheater coil [lo]. The reactor temperature was con-
trolled by immersing the reactor in a thermostatic bath
[l l l , thereby ensuring a temperature constancy of 10.1
K. Temperature readings of the reacting mixture were
made with three NiCr/NiAl thermocouples (accuracy h0.5
K) placed at 2.5, 7.5, and 12.5 cm from the reactor inlet.
The catalyst bed was placed between two 10-ym stainless
steel frits. Two sampling valves Valco 4-CL4WE [121
allowed to take samples from the reactor inlet and outlet
streams to analyze. To avoid plugging of the sampling
valves 2-pm filters 131were placed in both streams. The
reactor operating pressure (about 1.6 MPa) was controlled
by a BP-3 back-pressure regulator (GO Inc., Whittier, CA)
U31.
Analysis. The sampling valves injected 0.2 pL into an
HP 5890A GLC apparatus equipped with TCD. A 6 m X
3.2 mm 0.d. GLC column packed with Chromosorb 101
(80/100 mesh) separated ETBE, ethanol, isobutene, water,
and possible reaction byproducts (diisobutene, diethyl
ether, and tert-butyl alcohol). The column was temper-
ature programmed with a 4-min initial hold at 130 OC
followed by a 25 OC/min ramp up to 200 "C and held for
7,
2M Pa
Figure 1. Experimental setup. Key: 1, atmospheric tank; 2, pressurized bottle; 3, 2-pmfilter; 4, pump; 5, pressure damper; 6, safety valve;
7, checkvalve; 8, mixer; 9, reactor; 10, thermostatic bath; 11, preheater coil; 12, sampling valve; 13, back-pressure regulator; 14, gas chromatograph.
l 8
'r
a 2 M P a
Table 2. Operating Conditions
6 -
4 -
2 -
Ind. Eng. Chem. Res., Vol. 33, No. 3, 1994 583
r (mol/Q h)
catalyst particle size, mm
catalyst mass (dry), g
inert particle size, mm
dilution ratio, (vol of diluent/
vol of catalyst)
temperature, O C
pressure, MPa
LHSV, h-l
total flow rate, mol-h-l
r(I /Et)
isobutene concentration, mo1.L-1
ethanol concentration, mo1.L-l
ETBE concentration, mo1.L-l
isobutene conversion, %
xo.10
0.03-0.5
0.1 <d, <0.16
2-9
40-90
1.6
>60
2-3.1
0.5-2
1.86-7.45
2.11-9.24
1.69-4.11
<lo
12 min. The carrier gas (helium, 99.998% pure (SEO,
Barcelona, Spain)) flow rate was 30 cm3/min.
Procedure. The catalyst was crushed and sieved, then
dried at 110 "C for more than 14 h, and stored in a
desiccator over concentrated sulfuric acid (98 wt % ). The
water content in the resin, measured by Karl Fischer
titration, was less than 2.9 wt % .
Catalyst samples (d, <0.10 mm) were diluted in quartz
(0.1 <d, <0.16 mm) to obtain an isothermal bed and a
good contact pattern between reactants and catalyst,
avoiding back-mixing and channeling. The remaining
reactor volume was filled up with quartz of the same size
to avoid bed expansion. Before the experiment, the
catalyst bed (5-14-cm length) was preheated in the reactor
at the operating temperature in the presence of an ethanol
stream of 70 cm3.h-l for 30 min, to ensure that an ethanol
amount greater than 10 times the reactor volume was
passed through it. As a result, water content in the resin
was reduced to less than 1.6 wt % according to Fit6 et al.
(1992).
The experiments were carried out in the liquid phase
far from limitation by chemical equilibrium at the oper-
ating conditions given in Table 2. Steady-state conversions
lower than 10 % were measured for ethanol-isobutene,
and ethanol-isobutene-ETBE feeds. When the reactor
behaved differentially, the temperature radial and axial
gradients were lower than 1 "C, and byproducts were not
detected in the reactor effluent. Moreover, according to
the dilution criterion of van de Bleck et al. (1969), observed
rates deviated less than 5 % from isothermal intrinsic ones.
As a result, with consideration of reaction stoichiometry,
the reaction rate was computed from isobutene conversion
by the relationship
In each kinetic run, reactants flow rates were maintained
for 3-4 h, and repeated analyses of reactor inlet and outlet
streams were made to assure that the steady state was
reached. Reported rates are accurate to within &5%.
Afterward, new experimental conditions were tested. Since
the activity level of resins drops irreversibly on changing
feed polarity, the catalyst activity level was controlled by
repeating the first run in the series. The catalyst was
replaced by a fresh one after two or three runs.
Results and Discussion
Preliminary experiments were made at the highest
temperature explored (89.7 "C) to assure that rate data
were generated free of mass transport processes. Blank
runs performed with the reactor packed with quartz
showed that the reaction does not occur in the absence of
0 10 20 30 40 50 60 70 80 90 100 110 120 130
LHSV (l/h)
r (mol /h.a)
e -
r ( l / Et ) - 1.04
I
0 2 4 6 8 IO 12 14 16 18 20 22 24
l/dp (l/mm)
Figure 2. Influence of mass transport on the rate at 89.7 O C : (A)
external mass transport influence (r(I/Et) =1.04; 0.08 <d, <0.1
mm; WHSV =2255 h-1); (B) internal mass transport influence (series
1: r(1IEt) =1.04; 89.7 O C ; LHSV =118 h-1; WHSV 2255 h-1. series
2: r(I/Et) =2.91; LHSV =82 h-l; WHSV =3860 h-1). The shaded
area points out the limits of the experimental error.
catalyst. Runs carried out by maintaining feed compo-
sition and WIF ratio, but using different catalyst mass,
stated the absence of external mass transport effects at
the operating conditions given in Table 2. As Figure 2A
shows, reaction rate does not depend on flow rate for LHSV
1 60 h-l (u 1 2.5 X ms-l). At LHSV <60 h-l data
show a first-order relationship between rate and the LHSV,
disclosing that external mass transfer is the rate-limiting
step.
Internal mass transfer influence on the rate was studied
by performing experiments where, at the same flow rate
and feed composition, catalyst samples of different particle
size were used. Data show that the medium polarity
determines the largest particle size working in a kinetic
regime. As can be seen in Figure 2B, rates were unchanged,
within the limits of the experimental error, for particles
smaller than 0.25 mm at r(I /Et) =1.04 and for particles
smaller than 0.10 mm at r(1IEt) =2.91. This behavior can
be explained because the ethanol permeates easily, and as
a result, the resin swells to a large extent in the presence
of a large amount of the alcohol. On the contrary, when
isobutene is in excess the resin hardly swells at all. Figure
2B also shows that at r(I /Et) 2.91 the rate increases for a
584
Table 3. Experimental Conditions and Obtained Rates for ETBE Synthesis
Ind. Eng. Chem. Res., Vol. 33, No. 3, 1994
T, OC r(I/Et) CI, mol/L CE~ , mol/L CE, mol/L 71 YEt YE a1 aEt UE r, mol/h.g
89.7 0.40
0.50
0.55
0.60
0.80
1.04
1.19
1.39
1.59
1.79
1.99
2.91
0.87
0.44
1.17
1.08
0.54
1.82
79.5 0.50
0.56
0.62
0.70
0.80
1.00
1.19
1.39
1.59
1.79
1.99
2.06
0.85
0.43
1.71
1.08
0.54
1.82
59.5 0.50
0.55
0.62
0.71
1.00
1.19
1.39
1.51
1.65
1.79
1.99
0.87
0.44
1.74
1.08
0.54
1.82
39.4 0.83
1.00
1.19
1.39
1.59
1.79
1.99
3.68
4.17
4.38
4.57
5.21
5.76
6.04
6.34
6.58
6.76
6.93
7.45
2.74
1.86
3.39
4.12
3.04
5.10
4.25
4.48
4.76
5.03
5.31
5.80
6.17
6.47
6.72
6.92
7.10
7.15
2.92
2.04
4.20
4.32
3.02
5.39
4.41
4.66
4.94
5.26
6.04
6.44
6.75
6.92
7.09
7.23
7.41
2.48
2.07
4.01
4.47
3.27
5.62
5.84
6.28
6.70
7.04
7.34
7.54
7.74
9.24
8.37
8.00
7.66
6.53
5.56
5.06
4.55
4.12
3.77
3.48
2.56
3.07
3.78
2.65
3.63
4.72
2.56
8.53
8.12
7.65
7.19
6.66
5.82
5.17
4.65
4.22
3.86
3.56
3.47
3.13
3.83
2.14
3.74
4.91
2.71
8.85
8.42
7.94
7.39
6.06
5.39
4.85
4.58
4.29
4.03
3.72
2.57
3.28
2.11
3.97
5.05
2.86
7.04
6.30
5.61
5.05
4.59
4.21
3.88
3.33
3.68
3.02
2.04
2.39
1.77
3.30
3.65
2.77
1.99
2.46
1.63
4.11
4.11
3.19
2.05
2.47
1.69
sample with 0.16 <d, <0.25 mm. This rise in rate may
be caused by the presence of simultaneous intraparticle
heat and mass transfer resistances. A similar fact was
reported by Rehfinger and Hoffmann (1992), who com-
puted a temperature intraparticle gradient higher than
0.5 K in the ion-exchange-catalyzed addition of methanol
to isobutene in the liquid phase.
Kinetic experiments were carried out at the average
temperatures 89.7, 79.5, 59.5, and 39.4 O C . The r(I/Et)
range explored was 0.4-2.9 at 89.7 O C , and 0.5-2.0 at the
other temperatures. At each temperature three experi-
mental series were performed. In the first one pure ethanol
was fed, and in the other two ethanol containing 29 and
2.26
2.07
1.99
1.93
1.72
1.56
1.48
1.41
1.35
1.31
1.27
1.16
1.28
1.39
1.22
1.33
1.51
1.19
2.10
2.02
1.92
1.83
1.74
1.60
1.50
1.42
1.36
1.32
1.28
1.27
1.29
1.40
1.16
1.35
1.54
1.21
2.16
2.07
1.97
1.87
1.63
1.53
1.45
1.41
1.37
1.34
1.30
1.21
1.34
1.16
1.38
1.56
1.23
1.80
1.67
1.56
1.48
1.41
1.36
1.32
1.11
1.15
1.17
1.20
1.30
1.42
1.50
1.60
1.71
1.81
1.94
2.34
1.82
1.59
2.00
1.72
1.46
2.16
1.15
1.18
1.21
1.25
1.30
1.40
1.51
1.61
1.72
1.82
1.92
1.96
1.84
1.61
2.35
1.73
1.45
2.15
1.16
1.19
1.22
1.26
1.42
1.53
1.64
1.70
1.78
1.86
1.96
2.08
1.80
2.46
1.74
1.48
2.19
1.34
1.43
1.54
1.66
1.77
1.89
2.00
1.15
1.24
1.10
1.17
1.31
1.07
1.15
1.24
1.06
1.18
1.33
1.07
1.14
1.19
1.07
1.20
1.35
1.08
0.643
0.688
0.705
0.721
0.763
0.793
0.807
0.820
0.830
0.838
0.844
0.867
0.384
0.278
0.457
0.561
0.451
0.646
0.698
0.717
0.737
0.755
0.772
0.798
0.815
0.827
0.836
0.844
0.850
0.852
0.403
0.300
0.535
0.579
0.446
0.670
0.719
0.738
0.757
0.777
0.815
0.831
0.842
0.848
0.853
0.858
0.863
0.327
0.293
0.499
0.589
0.473
0.679
0.817
0.835
0.851
0.859
0.867
0.872
0.877
0.793
0.769
0.759
0.750
0.721
0.696
0.683
0.670
0.657
0.647
0.647
0.598
0.610
0.646
0.585
0.638
0.679
0.585
0.770
0.760
0.748
0.736
0.724
0.703
0.687
0.674
0.663
0.653
0.643
0.640
0.617
0.649
0.552
0.645
0.686
0.599
0.773
0.763
0.752
0.739
0.710
0.695
0.683
0.677
0.671
0.664
0.656
0.582
0.625
0.558
0.658
0.691
0.616
0.731
0.716
0.703
0.693
0.684
0.676
0.670
0.418
0.488
0.367
0.244
0.308
0.200
0.407
0.474
0.321
0.233
0.316
0.179
0.510
0.516
0.367
0.235
0.308
0.180
1.46
1.56
2.07
2.17
3.20
3.32
3.27
3.50
3.62
4.20
4.57
4.73
0.905
0.587
1.15
2.42
2.09
3.12
0.797
0.848
0.839
1.11
1.19
1.10
1.27
1.30
1.49
1.47
1.42
1.60
0.580
0.405
0.808
1.26
1.25
1.45
0.141
0.149
0.175
0.175
0.211
0.254
0.263
0.297
0.287
0.298
0.317
0.416
0.333
0.269
0.244
0.244
0.301
0.030
0.026
0.032
0.033
0.032
0.034
0.035
46 mol 76 ETBE, respectively, was fed. Series in the
presence of ETBE were not carried out at 39.4 O C because
an excessive buildup of pressure was produced caused by
the swelling of catalyst, since the catalyst mass used was
very high in order to get reasonable rates at that low
temperature.
Great care was taken over controlling the presence of
water in the system because of its inhibitor effect on the
rate (Buttersack, 1988, Tejero et al., 1988; Cunill et al.,
1989; Cunill et al., 1993). Besides, water seriously affects
the catalytic activity level of the resin since ita presence
changes the medium polarity and, as a result, the catalyst
structure. So, to keep the level of water in a minimum
Ind. Eng. Chem. Res., Vol. 33, No. 3, 1994 585
7 ( mel , hg)
1 5 .
0 0 5 I I5 2 2 5 3 0 0 5 I 15 2 2 5 3 0 0 5 I I 5 2 2 5 3
r( l / El ) r( l / El ) r( l / El )
Figure 3. Rate vs r(I/Et): (A) experiments carried out without ETBE in the feed [XEt =01; (B) experiments with XEt =29% in the feed;
(C) experiments with XEt =46% in the feed. The solid line is the fit to data given by model 5.2: (0) 89.7 "C; (A) 79.5 OC; (*) 59.5 "c; (0)
39.4 "C.
0 2 I b 8 10
c I (mol/l)
Figure 4. ETBE synthesis at 79.5 " C: (A) rate vs isobutene concentration; (B) rate vs ethanol concentration: (C) rate vs ETBE concentration.
The solid line is the fit to data given by model 5.2: ( 0) X E ~ =0; (*) XEt =29%; (A) Xp =46%.
was of the main importance to measure coherent rates
within the limits of the experimental error. Ethanol is
highly hygroscopic and it is difficult to preserve it
anhydrous, so that water was held into a very low level,
by drying the alcohol over 3-w molecular sieves (Carton
et al., 1987), and finally by percolating the ethanol through
the bed (Fit6 et al., 1992). Once the steady state was
reached, water adsorbed in the catalyst was at equilibrium
with the water in the feed. As this was <0.03 wt %, we
can expect that the amount of water adsorbed in the resin
was also very low, and weassumed that its effect on the
rate is negligible.
Table 3 shows the experimental conditions and the
obtained rates upon a dry catalyst mass basis (see also
Figure 3). In line with Benson (1960) weshould expect
to find the bimolecular reactions in solution about 5 times
faster than in the gas phase. Despite of Benson refered
to homogeneous reactions, such a trend could be expected
for heterogeneous catalytic reactions. In this way, mea-
sured rates are more than 25 times faster than those
obtained for the gas-phase addition of ethanol to isobutene
on Lewatit SPC 118 (Iborra et al., 1990). On the other
hand, Ancillotti et al. (1977) showed in a previous work
that liquid-phase syntheses of MTBE and ETBE had
similar rates. However, they used industrial samples of
Amberlyst 15 as a catalyst and their results are probably
influenced by diffusion processes. Measured rates are
higher than those reported by Ancillotti et al. (1977) by
30%, and it deserves to be shown up that our data are
similar to those reported by Rehfinger and Hoffmann
(1990) for MTBE synthesis, a work in which the presence
of mass transport effects can be discarded. From rate
data wecan draw the following conclusions:
1. Reaction rate increases with r(I /Et), in line with the
behavior of isobutenemethanol and isobutene-n-butanol
systems at olefin/alcohol molar ratios of about 1:1 (An-
cillotti et al., 1977).
2. Ethanol inhibits the reaction, whereas isobutene
enhances it. As Figure 4 (parts A and B) shows, reaction
rate decreases on increasing ethanol concentration, but it
increases with that of isobutene. The same trend has been
observed at the other temperatures.
3. In each series, reaction rate decreases on increasing
ETBE concentration (Figure 4C). However, at 89.7 "C,
rates in the presence of ether are lower than those obtained
in the absence of ETBE. At 79.5 "C, the curve with lower
ETBE content shows rates similar to those obtained for
the reaction free of ether. Finally, at 59.5 "C, both curves
in the presence of ether show higher rates than the curve
obtained in the absence of ether. The presence of ETBE
increases the rate of decomposition of the ether, at the
same time as ethanol and isobutene concentrations in the
feed decrease. These factors explain the decrease in the
net reaction rate observed in each series. On the other
hand, it is possible that the rate has a maximum which
shifts to lower ethanol and isobutene concentrations with
decreasing temperatureg.
4. Temperature highly influences the rate. It decreases
by 2.5 times when temperature decreases 10 "C.
I t is well known that alcohol-olefin liquid mixtures
behave nonideally (Colombo et al., 1983; Gicquel and
Torck, 1983; Rehfinger and Hoffmann, 1990; Izquierdo et
al., 1992; Vila et al., 1993). As a consequence, the analysis
of the ethanol-isobutene-ETBE system should be made
as a function of activities rather than concentrations of
involved substances. The activity of component i is related
586 Ind. Eng. Chem. Res., Vol. 33, No. 3, 1994
to its molar fraction in the mixture by means of
ai =xiyi
where the activity coefficients Ti depend on temperature
and composition (yi =1 when Ti =1). Estimates of activity
coefficients were made through the UNIFAC predictive
method (Reid et al., 1987). The parameters needed for
the use of UNIFAC, i.e. group volumes, group surface areas,
and group interaction parameters, were taken from the
tables published by Fredeslund et al. (19771, Skjold-
J orgensen et al. (19791, Almeida et al. (1983), and Tiegs
et al. (1987). As can be seen in Table 3, ethanol, isobutene,
and ETBE activity coefficients are clearly >l . The
estimates for isobutene and ethanol quite agree with
calculated and experimental values for the isobutene-
methanol system (Colombo et al., 1983). As expected,
activity coefficients rise with decreasing molar fractions,
and the ether behaves more ideally than the alcohol and
olefin. I t is worth noting the stronger dependence of rate
on activities than on concentrations, within the range
within the range explored, as Figures 4 and 5 show, which
emphasizes the nonideal behavior of the mixtures.
Prior to formulating kinetic models for the reaction,
the response surface of the rate as a function Of ai, aEt, and
UE was analyzed. Analysis of the response surface allows
us to outline the main features of kinetic models that best
fit rate data, which spares substantial effort in their
formulation and fit. Thus, following the surface response
methodology (Tejero et al., 1989; Iborra et al., 1992), a
polynomial as a function of UI , aEt, and U E was fitted to
data, at each temperature, by a multivariable least squares
method. Table 4 shows the lower order polynomial, whose
fit is significant. Statistical analysis of the terms of
polynomials leads us to outline the following three points.
1. Since a second-order polynomial fits data in a
statistically significant fashion, models to test should be
at the very least of second order.
2. As CI, CEt, and CE are not independent variables
because no diluents were added in the feed, UI , UEt and UE
are reciprocally dependent. As a result, all the terms of
the polynomials have a similar statistical significance (in
fact, some interactive terms are actually more significant
than terms in which a single activity appears), and it is
difficult to analyze the influence of activities on the rate.
3. The influence of UI , UEt and UE terms on the rate
changes with temperature. At 89.7 "C, the order of
significance is UI >aEt >UE; at 79.5 "C, UI >UE >aEt; at
59.5 "C, aEt >UE >UI ; and at 39.5 "C, aEt >ar. Moreover,
at some temperatures second-order terms appear more
significant than first-order ones. As a consequence, in
order to analyze the influence of UI , UEt, and QE on r, the
terms ai and ai2 were considered jointly. Thus, at 89.5 "C,
a1 enhances the reaction rate whereas aEt and UE highly
inhibit it. At 79.5 and 59.5 "C, a1 enhances the reaction
rate, UEt inhibits the reaction except for low ethanol
activities, and U E enhances the reaction for low ETBE
activities, but inhibits it for high activities (close to
chemical equilibrium). Finally, at 39.4 "C, a1 enhances
the reaction rate, and UEt inhibits it except for low ethanol
activities.
I t has been firmly stated that several sulfonic groups
take part in the rate-limiting step of ion-exchanger-
catalyzed reactions. In this way, Wesley and Gates (1974)
reported that up to seven active centers could take part
to stabilize the reaction intermediate in benzene propyl-
ation. Ancillotti et al. (1977) pointed out a third-order
dependence of the rate for obtaining MTBE on the
concentration of sulfonic groups for isobutene-methanol
equimolar mixtures and a fourth-order one when isobutene
is in excess. However, Rehfinger and Hoffmann (1990)
reported a second-order dependence. Discrepancy is Iikely
due to the concentration range explored. Likewise, gas-
phase addition of methanol to isobutene to give MTBE
shows a third-order dependence (Tejero et al., 1989),
whereas ethanol addition to give ETBE shows a fourth-
order one (Iborra et al., 1990).
On the other hand, whereas ethanol adsorption on the
resin is beyond all doubt, isobutene adsorption has not
been considered in the open literature, emphasizing ita
very low adsorption equilibrium constant. In fact, MTBE
synthesis has been frequently described in terms of an
Eley-Rideal (ER) mechanism in which isobutene from
solution reacts with the methanol adsorbed on the resin
(Gicquel and Torck, 1983). One might reasonably regard
this picture as an oversimplification useful to explain the
behavior of the olefin-alcohol mixtures when alcohol is in
excess. However, it is difficult to explain diisobutene
Ind. Eng. Chem. Res., Vol. 33, No. 3, 1994 587
Table 6. Equation Type Tested for Liquid-Phase Synthesis of ETBE (k+ =k&& for a LHHW Mechanism and k& for a
ER Mechanism)
model type mechanism type equation observations
1 LHHW temverature-devendence of KEtiscoherent
k*(aIaEt - a$K) temperature-dependence of KEt is coherent
KI <0 at 89.7 and 79.5 O C
r =
2 LHHW, ER
(1 +KEtaEt +KEaE)"
3 LHHW k*(aIaEt - adK) temperature-dependence of KEI is coherent
KE <0 at 59.5 O C
r =
(1 +KIaI +KEtaEt)"
formation as byproduct without acknowledging that
isobutene adsorption takes place, even if weakly.
From an eclectic standpoint, and considering the
features of the surface response outlined above, wecan
assume that the best kinetic model for the reaction could
stem from the Langmuir-Hinshelwood-Hougen-Watson
(LHHW) mechanism
Et +a + Et*u
I +a+I . a
Et-a +1.a+(n - 2)a + E.a +( n - 1)a
E*a + E +u
in which the adsorbed ethanol and isobutene react to yield
ETBE or, otherwise, from the following ER mechanism
in which isobutene from solution reacts with the adsorbed
ethanol.
Et +a + Et-a
Et-a +I +( n - 1)a =,E-a +(n - 1)a
E.u+E +
One or more supplementary active sites take part in the
surface reaction step, in both mechanisms. Considering
this step as the rate-determining one, the basic LHHW
and ER kinetic models would be, respectively, as follows:
kKEt( aIaEt - 2)
r =
Such models, with n 2 2, fulfil the response surface
features indicated above. The enhancing effect of
isobutene on the rate, would be because isobutene influ-
ences mainly the driving force of eqs 1 and 2. The inhibitor
effect of ethanol, except for low activities, would be because
ethanol influences mainly the adsorption term and, at low
activities (low values for the adsorption term), the driving
force. The fact that ETBE enhances the rate at low
activities, whereas it inhibits the reaction at high activities,
temperature-dependence of KEt is not coherent
convergency is difficult for n >2
KEt <0 for n even
temperature-dependence of k* is coherent
could be explained because the presence of ETBE involves
a decrease in a1 and aEt, so that a simultaneous decrease
in the driving force and in the adsorption term is seen. At
low UE the decrease in the adsorption term is higher, and
an increase in reaction rate is observed. When ether
concentration is high, and therefore aE, the decrease in
the driving force is higher, and as a result, reaction rate
decreases. Finally, these models with n 1 2 can describe
appropriately the presence of a maximum in rate, at least
relative to aEt.
Models of the type indicated in Table 5 were fit to data
by using the nonlinear least-squares method of Box-
Kanemasu (Beck and Arnold, 1977), with n ranging from
2 to 7. The thermodynamic equilibrium constant for the
reaction, K, was estimated by means of (Vila et al., 1993)
In K =1140 - 14580T' - 232.9(1n 2 ' ) +1.087T-
(1.114 X 10-3)p +(5.538 X lO-')P
The sum of the squares of lack of fit for model type 1
worsened on increasing n. The adsorption parameter for
ethanol was always positive, and its temperature-depen-
dence was coherent. However, negative adsorption pa-
rameters for isobutene at 89.7 and 79.5 "C and for ETBE
at 59.5 "C were found. This fact could be due to the nature
of the experimental design. As mentioned above, activities
of compounds were reciprocally dependent, and as a result,
correlation between parameters was too high (~1). I t is
worth noting that there was no possibility to obtain data
close to chemical equilibrium, due to the very low rates,
which would have allowed us to obtain adsorption pa-
rameters with physicochemical meaning on enlarging the
range of activities explored. Model types 2 and 3 had
higher sums of squares of lack of fit than model type 1,
as could be expected, but show the same trends. As a
result, the influence of ethanol on the adsorption term is
much higher than those of isobutene and ETBE, in
agreement with their decreasing order in polarity.
As rates were measured free of control by diffusion, it
is likely that all the accesible sites were attached to
reactants. Ethanol permeates more easily than isobutene
and ETBE. So, most of the active centers were occupied
by the alcohol, the fraction of free sites being negligible.
That is why it was striking that negative adsorption
parameters for ethanol were found at 79.5 and 59.5 "C for
model type 4. This incoherence can be only due to
mathematical problems in the fit. Therefore, model type
5 was tested with the aim of finding a model with a
588 Ind. Eng. Chem. Res., Vol. 33, No. 3, 1994
Table 6. Kinetic Models of Type 5 Tested for ETBE
Liauid-Phase Synthesis
r calc (mol1h.g)
102k',
model equation T, "C mol/h.g s d 2
5.1
5.2
5.3
5.4
5.5
5.6
89.7
79.5
59.5
39.4
89.7
79.5
59.5
39.4
89.7
79.5
59.5
39.4
89.7
79.5
59.5
39.4
89.7
79.5
59.5
39.4
89.7
79.5
59.5
39.4
temperature-dependence coherent.
289
110
2.34
2.58
194
74.3
1.62
1.79
127
49.2
11.0
1.24
82.1
31.9
7.33
0.855
52.1
20.2
4.79
0.589
32.5
12.4
3.07
0.405
5.990
0.910
0.188
2.20 x 10-5
3.49
0.829
0.154
1.91 x 106
4.43
1.13
0.130
2.71 X 10-5
7.16
1.84
0.119
4.55 x 10-8
11.8
2.94
0.125
7.35 x 10-5
18.2
4.38
0.148
1.11 x lo"'
I t converges easily,
because there is only an adjustable parameter, the apparent
rate coefficient k', which is the product of the following
constants for the LHHW and the ER mechanism, re-
spectively:
(3) k' =k*KE;n =k K I K Et -(n - l)
k' =k*KE;n =k K Et -(n - l)
(4)
As Table 6 shows, at 89.7,79.5, and 39.4 O C the sum of
squares of lack of fit has a minimum for model 5.2 (three
active centers in the surface reaction step), whereas at
59.5 OC, model 5.4 (five centers in this step) has the
minimum sum of squares. As it is not likely that the
mechanism changes at an intermediate temperature of
the range explored, weassume that model 5.2 is the best.
Besides, as Figure 6 shows, residuals corresponding to 79.5
"C are random. The residuals of the rest of temperatures
have a similar trend.
Figure 7 shows the dependence of k' with temperature.
The fit of the Arrhenius law to k'values gives the expression
k' =4.7 X 10" exp - -
( 'OF ),
(5)
Model 5.2 can be regarded as a coherent temperature-
dependence one. But it remains to be seen whether it is
able to predict the behavior of an integral reactor. In an
earlier work (Cunill et al., 1993) an experiment performed
in a batch reactor at 40.5 "C and r(I/Et) =0.76 was
reported. An isobutene conversion of about 82% was
achieved on an industrial sample of Lewatit K 2631 in a
200 min run. As Figure 8 shows, conversions computed
from model 5.2 are lower only by 5%, in good agreement
with data within the limits of the experimental error, seeing
that the presence of concentration and temperature
gradients can be neglected in line with the modified Weisz-
Prater criteria for testing intraparticle transport limita-
tions (Mears, 1971; Rase, 1977). The discrepancy can be
due to some inaccuracy of the model because of the
1.6 -
1.4 -
1.2
-
1 -
0.8
-
0.6 -
0. 4 -
I
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8
r (mol/h.g)
Figure 6. Residuals of model 5.2 at 79.5 OC.
in k'
1 1
2.5 2.7 2.9 3.1 3.3 3.5
(1/~)*103 ( K- l
Figure 7. Temperature dependence of k'.
impossibility of measuring reliable rate data in the
differential reactor at conversions >60%, and also to the
fact that integral run was performed in a different setup,
and with a different procedure.
From eq 5, an apparent activation energy of 86.1 kJ/
mol was obtained. This value is itself rather high, in line
with the high temperature-sensitivity of the reaction. As
can be seen in Table 7, this value is higher than those of
Ancillotti et al. (1977) and Kaitale et al. (1988). These
used industrial samples of catalyst, so that their results
are probably influenced to some degree by mass transport
limitations. On the other hand, comparing with the
apparent activation energy of MTBE synthesis (Table 8),
one can observe that the E'value is similar to that reported
by Rehfinger and Hoffmann (19901, a work in which the
presence of mass transport effects can be discarded.
Ind. Eng. Chem. Res., Vol. 33, No. 3, 1994 589
Table 7. ADDarent Activation Enerav for ETBE Synthesis and ComDarison with Literature Data
~~ ~
reference E', kJ -mol-l catalyst observations
this work 86.1 K 2631 d, <0.10 mm
Ancillotti et al. (1977) 73.8 Amberlyst 15 industrial samples
Kaitale et al. (1988) 49.6 Dowex M-32 industrial samples (0.4 <d, <1.2 mm)
Table 8. Activation Energy for MTBE Synthesis
catalyst E', kJ.mol-1 E, kJ.mol-1 reference
p-toluenesulfonic acid
sulfuric acid
methyl sulfuric acid
Amberlyst 15 77.7
92.4
X I experimental
0 0,l 0.2 0.3 0, 4 0,5 0.6 0.7 0.8 0.9 1
XI model
Figure 8. Experimental conversion against time in a batch reactor
(r(I/Et) =0.76; 40.5 OC; 500 rpm; catalyst mass 10 g; reactor volume
260 cm3) and predicted values by model 5.2.
Table 9. Vaporization and Gas-Phase Adsorption
Enthalpies for Isobutene and Ethanol
A" a ( P. ) O, AH"o,
' compound kJ mol-' kJ mol-' reference
ethanol -44.0 Kabel and J ohanson (1962)
isobutene -72.6 Iborra et al. (1990)
40.6 Gallant (1968)
18.8 Gallant (1968)
The activation energy, E, can be computed from E' and
the liquid-phase adsorption enthalpies of isobutene and
ethanol. From eqs 3 and 4, the following expressions can
be found for the LHHW and the ER mechanism, respec-
tively:
E =E' - +(n - l).AHoa,E, (6)
(7)
As liquid-phase adsorption enthalpies for isobutene and
ethanol were not found in the literature, these quantities
were computed from the values of Table 9 by means of
Gas-phase adsorption enthalpy of ethanol was deduced
from chemisorption data of Kabel and J ohanson (1962).
E =E' +(n - l).AHoa,,,
moa, i ( l ) =mo a , i ( g ) +mov,i
101.5
104.1
91.2
85.7
104.6
91.2
71.1
82.0
82.4
Evans and Halpern (1952)
Ancillotti et al. (1977)
Gicquel and Torck (1983)
Csikos et al. (1980)
Al-J arallah et al. (1988)
Gicquel and Torck (1983)
Ancilotti et al. (1977)
Gicquel and Tork (1983)
Rehfinger and Hoffmann (1990)
Isobutene chemisorption data were not found in literature,
so that adsorption enthalpy for isobutene was obtained
from gas-phase synthesis of ETBE kinetic data (Iborra et
al., 1990). Despite the fact that the liquid-phase adsorption
enthalpy for isobutene is less reliable than that of ethanol,
it is useful to obtain the order of magnitude of activation
energy for liquid-phase ETBE synthesis.
An activation energy of 133 kJ /mol was obtained from
equation 6 assuming that the reaction follows a LHHW
mechanism, whereas a value of 79.3 kJ /mol was obtained
from eq 7 assuming that the reaction follows an ER
mechanism. As true activation energy values were not
found in the literature, there has not been able to check
the obtained values. However, it is useful to compare these
values with those of MTBE synthesis. As Table 8 shows,
the first value is higher than those of homogeneous MTBE
synthesis, whereas the second are only a bit smaller. In
spite of the fact that it is about different reactions, the
value of 133 kJ /mol seems unlikely. So, wecan conclude
that the most probable mechanism for the reaction would
be an ER one, in which isobutene from solution reacts
with adsorbed ethanol. However, from an eclectic stand-
point it must be recognized that despite the fact that ETBE
synthesis occurs mainly through an ER mechanism under
the experimental conditions, the contribution of an LHHW
mechanism might gain importance on increasing r(I/Et).
Conclusions
The liquid-phase addition of ethanol to isobutene to
give ethyl tert-butyl ether (ETBE) has been studied on
the ion exchange resin Lewatit K2631 at 1.6 MPa and
40-90 OC. Rate data show that the reaction is highly
temperature sensitive, and isobutene has an enhancing
effect on the rate whereas ethanol has an inhibitor one.
Low ETBE concentrations enhance the reaction but as
chemical equilibrium is approached the ether shows an
inhibitor effect, as expected. Alcohol-olefin-ether mix-
tures behave nonideally. So, kinetic analysis has been
carried out by means of the UNIFAC liquid-phase activities
of isobutene, ethanol, and ETBE. The best kinetic model
could be deduced from a ER mechanism and also from a
LHHW one. In the ER mechanism, isobutene from
solution reacts with the ethanol, adsorbed on one center,
to give the ether adsorbed on one center. In the LHHW
mechanism, the ethanol and isobutene, each one adsorbed
on one center, react to give the ether adsorbed on one
center. The rate-determining step of both mechanisms is
the surface reaction, and up to three active centers take
part in this step. From the activation energy values it can
be concluded that the most probable mechanism is the
Eley-Rideal one.
590 Ind. Eng. Chem. Res., Vol. 33, No. 3, 1994
Acknowledgment
The authors wish to express thanks for financial support
to CAICYT, Spain (Project PB87-0509) and to the refining
company Repsol Petroleo S.A.
Nomenclature
ai =activity of compound i, dimensionless.
ci =concentration of compound i, mo1.L-1
d, =particle diameter, mm
E =ethyl tert-butyl ether
E =activation energy, kJmmol-1
E' =apparent activation energy, kJ-mol-'
Et =ethanol
F =total molar flow rate, mo1.h-1
Fi =molar flow rate of compound i, mo1.h-1
I =isobutene
k =rate coefficient, mol.(h.g)-l
k' =apparent rate coefficient, mol.(h.g)-l
k' =apparent rate coefficient, mol.(h.g)-l
K =thermodynamic equilibrium constant for the reaction,
Ki =adsorption equilibrium constant of compound i, di-
n =number of active centers that take part in the surface
r =intensive reaction rate, mol.(h.g)-l
r(I/Et) =isobutene/ethanol molar ratio in the feed
Sd* =sum of squares of lack of fit
T =temperature, K
u =superficial velocity based upon cross-sectional area of
W =catalyst mass, g
Xi =degree of conversion of reactant i, dimensionless
xi =molar fraction of substance i, dimensionless
yi =activity coefficient of compound i, dimensionless
AXi =degree of conversion change of reactant i, dimensionless
AHoa,i =adsorption enthalpy of compound i, kJ.mol-l
AHov,i =vaporization latent heat of compound i, kJ-mol-1
u =active center
Subscripts
a =adsorption
E =ethyl tert-butyl ether
Et =ethanol
g =gas phase
I =isobutene
i =inlet
1 =liquid phase
o =outlet
v =vaporization
Abbreviations
dimensionless
mensionless
reaction step
empty reactor, m d
bRvp =blending Reid vapor pressure
ER =Eley-Rideal
ETBE =ethyl tert-butyl ether
LHHW =Langmuir-Hinshelwood-Hougen-Watson
LHSV =liquid hourly space velocity, h-1
MTBE =methyl tert-butyl ether
VOC =volatile organic compounds
WHSV =weight hourly space velocity, h-1
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Received f or review April 20, 1993
Revised manuscript received October 4, 1993
Accepted November 7, 1993'
Abstract published in Advance ACS Abstracts, J anuary 15,
1994.