4452 Ind. Eng. Chem. Res.

1997, 36, 4452-4458

Liquid-Phase Etherification/Dimerization of Isobutene over Sulfonic

Acid Resins
Marco Di Girolamo, Massimo Lami, Mario Marchionna, Ermanno Pescarollo,
Lorenzo Tagliabue,* and Francesco Ancillotti
Snamprogetti Research Laboratories, Via Maritano 26, 20097 S. Donato Milanese, Italy

Simultaneous isobutene etherification/dimerization reactions have been studied in the liquid

phase using macroporous sulfonic acid resins. It has been found that, in the presence of
methanol, oligomerization to species heavier than dimers may be greatly reduced with respect
to data reported in the literature for isobutene dimerization. Products of the described synthesis
are MTBE and a mixture of branched C8 hydrocarbons having excellent properties for gasoline
blending. These two products may be obtained in a wide range of relative ratios. The influence
of methanol (i.e., methanol/isobutene molar ratio), feedstock type, and reactor design on product
composition and byproducts formation is discussed.

Introduction (Rehfinger and Hoffmann, 1990; Izquierdo et al., 1993;

In order to face serious environmental concerns, it is
generally accepted (Unzelman, 1997) that the worldwide
trend for gasoline formulation will be toward lower
evaporative emissions and a more complete combustion
by means of (a) an important and expanding role of
oxygenates and branched saturated hydrocarbons (such
as those found in alkylate) as gasoline components and
(b) a reduction of gasoline volatility and of aromatics,
lighter olefins, and sulfur contents.
Besides tert-alkyl ethers (MTBE, ETBE, TAME, etc.),
branched saturated hydrocarbons represent the other
most important class of compounds for the gasoline
reformulation. They can be made by alkylation and by
olefins dimerization. Alkylate is particularly suitable
for its high octane number, low volatility, and absence
of sulfur and aromatics.
Alkylation is a well-established process; however, a
number of environmental concerns will cause increasing
troubles for new plants based on the present technolo-
gies: HF should be ruled out for installations in
populated areas due to its extreme toxicity, while H2-
SO4 is highly corrosive and produces great amounts of
acid muds which are difficult to dispose of. Alternative
processes with solid acid catalysts are being developed,
but their commercial applicability still has to be proved
(Rao and Vatcha, 1996).
This work describes an effective way to perform the
combined production of MTBE and highly branched C8
hydrocarbons through the simultaneous dimerization/
etherification of isobutene.
2,4,4-Trimethyl-1-pentene and 2,4,4-trimethyl-2-pen-
tene (RON ) 100; MON ) 89) are mainly obtained
among C8 species. Since they can be easily hydroge-
nated to 2,4,4-trimethylpentane (isooctane), which is the
reference compound for rating the gasoline antiknock
properties (RON ) 100; MON ) 100), the quality for
gasoline blending of these low-volatile olefins can be
further improved.
It is well-known that isobutene dimerization may be
carried out in the liquid phase with acid catalysts, but,
so far, this reaction has found only a few industrial
applications (Scharfe, 1973) because of its high exother-
micity, which makes control of the oligomerization
reactions very difficult. Diisobutenes formation as
byproducts in the MTBE synthesis has been more often
described due to its interest for industrial applications
S0888-5885(97)00093-6 CCC: $14.00
Vila et al., 1994; Miracca et al., 1996).
Now, we have found that by feeding methanol to-
gether with isobutene (methanol/isobutene ) 0.2-0.6
mol/mol) a thorough control of this fast and highly
exothermic reaction is achieved, resulting in a formation
of trimers and tetramers much lower than previously
reported for this synthesis (Haag, 1967; Scharfe, 1973).
Since methanol is fed to the system, some MTBE is
formed; however, in this case, the optimal methanol/
isobutene molar ratio is sensibly lower than the sto-
ichiometric one used in the MTBE synthesis. If needed,
the produced MTBE may be easily separated from the
oligomers mixture. As in the MTBE synthesis, every
C4 feedstock containing isobutene (from FCC units,
steam-cracking, isobutane dehydrogenation units, etc.)
can be conveniently exploited.
This paper addresses a number of factors influencing
the joint production of MTBE and isobutene oligomers.
The effects on products and byproducts formation of
methanol/isobutene molar ratio, resin type, and feed-
stock composition are discussed, referring to results
obtained both on a pilot plant and in a bench-scale
reactor. Finally, in order to assess the importance of a
proper reactor configuration, results from runs where
the pilot reactor was operated with heat transfer are
compared with ones obtained in adiabatic operations.
Experimental Section
Analytical Methods. The products have been ana-
lyzed with a Hewlett-Packard gas chromatograph Model
5890 Series II equipped with a flame ionization detector
(FID) and a constant-volume valve for samples injection.
Using this injection system, internal standards are not
necessary and the analysis is extremely accurate (stan-
dard deviation < 0.1%). For a better resolution two
analytical procedures have been used. Reaction prod-
ucts were resolved by a WCOT fused-silica capillary
column CPSIL 19 CB (50 m × 0.25 mm) with a method
allowing the complete separation of C4, dimethyl ether
(DME), methanol, tert-butyl alcohol (TBA), methyl tert-
butyl ether (MTBE), and C8, C12, and C16 hydrocarbons.
The column temperature was held at 40 °C for 6 min
followed by a 6 °C/min ramp up to 90 °C and by a second
ramp at 8 °C/min up to 180 °C; the final temperature
was held for 15 min.
C4’s separation was performed with an alumina-
coated KOH fused-silica capillary column (50 m × 0.25
© 1997 American Chemical Society
 Ind. Eng. Chem. Res., Vol. 36, No. 11, 1997 4453

Figure 1. Pilot-plant scheme.

Table 1. Physical Properties of Catalysts Employed in through a valve directly into 40 cm3 stainless steel
This Study bottles. Sampling bottles were pressurized and con-
Amberlyst 15 Amberlyst 35 nected to the gas chromatograph for the analysis.
acidity, mequiv H+/g (dry) 4.75 5.23 The reaction temperature was controlled by circulat-
moisture content, % 53.1 55.4 ing water at 40 °C from a thermostatic bath to the
apparent density, g/cm3 0.77 0.82 reactor jacket. This arrangement resulted in peaks of
surface area, m2/g 45 44 70-110 °C, depending on the methanol/isobutene molar
particle size (95% vol.) (mm) 0.63-1.25 0.63-1.25
porosity, cm3/g 0.30 0.35
ratio, isobutene concentration, and LHSV used, located
near the reactor inlet and in a lower temperature
Table 2. Isobutene Dimerization and Product plateau near the outlet zone. A backpressure regulator
Composition held the whole system at 15 bar in order to maintain
a b c the reactants in the liquid phase over all the investi-
gated temperature range.
isobutene conversion (%) 85.6 58 up to 99%
product composition (%) Further experimentation was carried out on the pilot
C8 54.2 52 58.0 plant whose scheme is presented in Figure 1. Methanol
C12 40 40 38.3 and C4 hydrocarbons taken as side streams in the
C16 5.8 8 3.7 ECOFUEL’s MTBE plant (Ravenna, Italy) are homog-
a MeOH ) 0, isobutene 53% by weight, Amberlyst 15, T
max ) enized in a static mixer and fed to the reactor with liquid
98 °C, Twater ) 40 °C, LHSV ) 5.5 h-1 (this work). b MeOH ) 0, hourly space velocities of 3-9 h-1. The reactor is a 6
isobutene ) 30% by weight, Amberlyst 15, temperature ) 60 °C, m × 1 in. i.d. stainless steel tube, packed with 2 L of
LHSV ) 1 h-1 (Haag, 1967). c MeOH ) 0, isobutene ) 45.4% by
weight, catalyst ) acid slurry, temperature = 100 °C (Scharfe,
Amberlyst 35 and provided with a jacket for water
1973). cooling. Reaction is monitored by 12 thermocouples
(RT 01-RT 12). Twelve valves located in correspon-
mm) at 110 °C. Before the analysis, every sample was dence with the thermocouples allow samples collection.
washed with water in order to remove methanol and Temperatures of reactants and cooling water are set by
MTBE, which are very harmful for this particular two heat exchangers (E1-C, E2-C). Data acquisition and
column. remote control are performed through the SCADA
(Supervisory Control Alarm and Data Acquisition)
Equipment. Preliminary catalytic tests have been
software FIX DMACS version 5.5 (Intellution Co.).
carried out on a laboratory scale with a downflow
tubular reactor (36 × 1.4 i.d. cm) packed with measured Catalysts. Commercial samples of Amberlyst 15 and
amounts of catalyst (20 cm3) and provided with a Amberlyst 35 (Rohm and Haas Co.) have been used as
thermocouple sliding inside a sheath to measure tem- catalysts. Both resins are macroporous styrene-divi-
perature profiles. nylbenzene copolymers with sulfonic groups as the
Reactants were introduced in the reactor with a functional structure. Their physical properties are
HPLC pump at liquid hourly space velocities (LHSV) reported in Table 1.
in the range 3-9 h-1. The reactor effluent was collected In order to avoid the loss of sulfonic groups, reaction
in a cooled vessel; samples were withdrawn every hour temperatures above 120 °C have been carefully avoided.
4454 Ind. Eng. Chem. Res., Vol. 36, No. 11, 1997

Figure 2. Isobutene dimerization and codimerizations. Main reactions.

Table 3. Effect of Methanol/Isobutene Molar Ratio on Table 4. Compositions (% by Weight) of Typical C4

Selectivity and Product Compositiona Streams
0.2 0.4 0.6 steam isobutane
isobutene (% by weight) 46 50 48 cracking FCC dehydrogenation
reaction temp (max) 74 73 72 isobutene 28-46 10-25 45-55
cooling water temp (°C) 40 40 40 1-butene 30-45 8-15 0
isobutene conversion (%) 2-butenes 5-15 15-35 0
overall 88 79 79 C4 paraffins 4-8 30-60 45-55
to MTBE 21 37 60
product composition (% by weight)
C8 79.2 88.3 92.6 weight) and a C4 feedstock from steam cracking after
C12 19.7 10.9 7.1 butadiene extraction (Raffinate-1) were used.
C16 1.1 0.8 0.3
a Catalyst ) Amberlyst 15; LHSV ) 5.5 h-1. Chemistry
The composition of the mixture of C8 hydrocarbons
Every batch of resin has been washed with distilled produced by isobutene dimerization in the presence of
water, dried in air, and heated up in vacuum to constant methanol is strictly related to the composition of the
weight before use. C4 cut.
Since the particle distribution of these resins is quite For instance, when feedstocks from isobutane dehy-
narrow, no further sieving has been performed. drogenation units are used, the only possible reaction
Chemicals. In the bench-scale experiments, reagent- for isobutene besides the etherification to MTBE is the
grade methanol (purity > 99.9% by weight, water < addition to a tert-butyl ion to form a higher molecular
0.1% by weight) (Carlo Erba, Milan, Italy), isobutene, weight carbocation; this ion may add another molecule
n-butenes, and isobutane with purity > 99.5% (SIAD, of isobutene (oligomerization) or eliminate a proton to
Milan, Italy) have been used. form two C8 isomers (DIB), namely, 2,4,4-trimethyl-1-
In the pilot-plant runs, methanol (water < 0.1% by pentene and 2,4,4-trimethyl-2-pentene (Figure 2).
 Ind. Eng. Chem. Res., Vol. 36, No. 11, 1997 4455

Figure 3. Etherification reactions.

Figure 4. Isobutene conversion (overall and to MTBE) vs catalyst type: Amberlyst 35 (squares); Amberlyst 15 (triangles).

Table 5. Effect of Feedstock Type on Selectivity and Table 6. Composition of a C8 Olefinic Fraction from a
Product Compositiona Steam-Cracking Feed
FCC SC dehydrogenation species ID % by weight
isobutene (% by weight) 22 38 45 2,4,4-trimethyl-1-pentene DIB 61.98
reaction temp (max) 70 75 75 2,4,4-trimethyl-2-pentene DIB 17.40
cooling water temp (°C) 50 45 40 2,2-dimethylhexenes DMHE 7.55
isobutene conversion (%) 2,3-dimethylhexenes DMHE 6.62
overall 90 89 91 2,3,3-trimethylpentenes TMP 0.72
to MTBE 41 42 45 2,3,4-trimethylpentenes TMP 1.63
product composition (% by weight) 3,4,4-trimethylpentenes TMP 3.80
C8 90.3 90.2 88.2 other dimethylhexenes and DMHE 0.30
C12 9.4 9.8 11.4 methylheptenes
C16 0.3 0.01 0.4
C8 composition (% by weight)
DIB 69.8 79.4 98.6
DMHE 8.5 14.5 0
TMP 21.7 6.1 1.4
a Catalyst ) Amberlyst 35; R ) 0.4; LHSV ) 4.4 h-1.
When linear butenes are present, e.g., for feedstocks
from FCC units or steam crackers, the mechanism is
more complex: in this case, linear butenes may react
with isobutene to form codimers. The first step is still
the formation of a tert-butyl ion, but reactions with
isobutene, 2-butenes, and 1-butene are now possible
(Figure 2). The addition of a linear olefin gives a
primary carbocation which eventually rearranges, form-
ing other trimethylpentenes (TMP) (from 2-butenes) and
dimethylhexenes (DMHE) (from 1-butene). In every Figure 5. Etherification/dimerization of isobutene. Typical prod-
case, codimerization reactions are slower than isobutene uct composition.
dimerization.
At high temperature, when linear butenes are present bond isomerization to 2-butenes and etherification to
in high concentration with respect to isobutene, 1-butene 2-methoxybutane (MSBE) may be observed. The pro-
4456 Ind. Eng. Chem. Res., Vol. 36, No. 11, 1997
Figure 6. Temperature and products profiles. R: [, 0.3; 0, 1. Tin (reactor inlet temperature) ) 58 °C, LHSV ) 7 h-1, isobutene ) 45%
by weight.
duced diisobutenes may eventually react at very small
extents with methanol, forming the corresponding ethers
(Figure 3).
Results and Discussion
Experiments of isobutene dimerization have been
carried out first in the absence of methanol using
Amberlyst 15 as the catalyst and a 53% by weight
isobutene feed (as from isobutane dehydrogenation). A
great difficulty in limiting the temperature of the water-
cooled bench-scale reactor below 120 °C was met since
isobutene oligomerizes very quickly even at low tem-
peratures. However, results in good agreement with
previously reported data have been obtained, despite
some differences in experimental setup and operating
conditions (Table 2).
An extensive formation of heavy species which fall in
the upper end (C12) or even outside (C16) the gasoline
boiling range (35-180 °C) was observed.
An impressive increase in selectivity to dimers to-
gether with a strong decrease in the formation of C16
was obtained by introducing methanol into the reacting
system (methanol/isobutene ) 0.2-0.6 mol/mol) (Table
3). As a matter of fact, methanol influences the
isobutene dimerization process in a number of ways.
First, because of its high polarity, methanol is prefer-
entially adsorbed on the active sites of the catalyst
according to the following reaction:
SO3-H+ + MeOH a MeOH2+ + SO3-
Since MeOH2+ is a species less acid than SO3-H+ (Gates

Figure 7. Adiabatic runs. Temperature and products profiles. R ) 0.4, LHSV ) 7 h-1, isobutene ) 28% by weight.
and Rodriguez, 1973), the rate of oligomerization reac-
tions is much reduced; this positively affects the selec-
tivity to dimers. Further, since isobutene is more
rapidly converted to MTBE than to dimers, the concen-
tration of free isobutene is also reduced, resulting in a
lower tendency to oligomerization.
In order to select the most efficient catalyst for the
synthesis, the performances of Amberlyst 15 (4.8 mequiv
of H+/g) and Amberlyst 35 (5.3 mequiv of H+/g) were
compared in runs carried out at different methanol/
isobutene molar ratios. As for the MTBE production
(Miracca et al., 1996), Amberlyst 35 resulted in a more
active catalyst than Amberlyst 15; in fact, the catalytic
activity of these ion-exchange resins is strongly depend-
ent on their acid capacity (Parra et al., 1997). For
instance, using Amberlyst 35, isobutene conversions
5-10% higher than those with Amberlyst 15 were
obtained under similar space velocity, temperature, and
reactants concentration conditions (Figure 4). It is
worth noting that this improvement is mainly related
to the increased formation of dimers since MTBE has
always been found close to its equilibrium concentration.
Since the selectivity to dimers was almost unaffected
by the catalyst type, further experimentation was
carried out using Amberlyst 35 only.
Feedstock composition, i.e., the relative content of
linear olefins and paraffins, is one of the most important
factors influencing the selectivity of the process. It is
known that, depending on its source, a C4 cut may
contain linear butenes besides isobutenes (Table 4).
Through experiments carried out on the bench-scale
reactor, it has been verified that linear butenes posi-
tively affect the selectivity. Since linear butenes are
preferentially adsorbed on the catalytic sites with
respect to the formed dimers, oligomerization reactions
are hindered even when isobutene has been almost
completely converted. On the contrary, paraffins cannot
Ind. Eng. Chem. Res., Vol. 36, No. 11, 1997 4457
be adsorbed on the catalyst; for such a reason, when
feedstocks from isobutane dehydrogenation are used,
the methanol/isobutene molar ratio (R) should be slightly
increased in order to minimize the formation of heavy
species (Table 5).
A detailed composition of a dimeric fraction from a
steam-cracking feed is reported in Table 6.
The influence of R on product composition has been
studied by processing a feed from steam cracking on the
pilot plant. The reactor was first operated at R ) 1 (i.e.,
MTBE synthesis condition); afterward, the methanol
feed was progressively reduced to R ) 0.2. A reduction
in the selectivity to dimers was observed; however, at
R ) 0.3 they still accounted for about 90% of the whole
hydrocarbon fraction (Figure 5).
In Figure 6 profiles obtained during pilot-plant runs
under typical MTBE (R ) 1) and dimerization conditions
(R ) 0.3) are compared. In the latter case the temper-
ature profile is much sharper and, in the first part of
the reactor, more isobutene is converted both to MTBE
and to dimers. Although much less methanol is used
with respect to the MTBE synthesis, isobutene is still
quite selectively converted to MTBE in the first part of
the reactor. Only when methanol is almost completely
converted, i.e., when MTBE equilibrium is reached, does
dimerization become the main reaction. It is worth
noting that under dimerization conditions an increase
in the isobutene conversion is always observed along
the whole catalytic bed, while in the MTBE synthesis a
steady level corresponding to the thermodynamic equi-
librium is approached. This means that, per single pass,
more isobutene can be converted to dimers than to
MTBE since, at least under the conditions in the present
study, the equilibrium for the isobutene dimerization
is completely shifted toward the formation of dimers.
Finally, to assess the influence on the synthesis of
different reactor configurations, runs under adiabatic
4458 Ind. Eng. Chem. Res., Vol. 36, No. 11, 1997
conditions have also been performed on the pilot reactor.
To operate as close as possible to the adiabatic regime,
the reactor jacket, used to provide heat transfer through
water circulation, was thorougly drained and dried by
flowing nitrogen. The reactor adiabaticity was assessed
by checking the energy balance (i.e., comparing the
observed reactor outlet temperature with values calcu-
lated through the knowledge of the effluent composition
and reaction enthalpies). The pilot reactor turned out
to be satisfactorily adiabatic; in fact, the observed
temperature increases were only 5-10% lower than the
calculated ones. In Figure 7 typical temperature and
composition profiles for adiabatic runs are reported. A
steady temperature between 100 and 110 °C was
approached. This behavior was rather unexpected.
Actually, reactor runaway was considered likely to occur
since oligomerization reactions are not equilibrium
limited. Instead, through the presence of methanol, an
otherwise impossible smooth control of the adiabatic
dimerization process was achieved, although most of the
reactor worked close to its threshold for the catalyst
stability.
The existence of a steady temperature proves that the
heat released by the isobutene dimerization (∆Hr ) -9.5
to -10.5 kcal/mol of isobutene) (Rehfinger and Hoff-
mann, 1990) is completely taken up by the endothermic
MTBE decomposition reaction (∆Hr ) +9.5 kcal/mol);
in fact, for temperatures higher than 100 °C these two
reactions proceeds at a similar rate, as can be seen by
reported products profiles (Figure 7). It should be noted
that more dimers can be produced in an adiabatic
reactor because the higher the temperature, the lower
the MTBE equilibrium concentration. However, meth-
oxybutanes (MSBE) have been more extensively formed
in the adiabatic runs with respect to runs in which the
reactor was operated with water cooling (5% by weight
vs 0.1-0.3% by weight). When feedstocks containing
linear butenes are used, adiabatic operation gives lower
selectivity to MTBE. It is worth noting that methoxy-
butanes have poor properties for gasoline blending
(RON, MON < 80). When a feedstock from an isobutane
dehydrogenation unit is processed, methoxybutanes
cannot be formed but the reaction is still preferentially
carried out by providing heat transfer since a too fast
catalyst aging may occur due to the higher temperatures
of the adiabatic operation.
Conclusions
The reaction described in this study may be exploited
to produce a mixture of high octane branched C8
saturated hydrocarbons and MTBE in a wide range of
proportions by varying the amount of methanol fed to
the system.
Several factors influence the synthesis, e.g., feedstock
type, methanol/isobutene molar ratio, etc.; knowledge
about these factors is important in order to safely run
the reactors and to obtain products having suitable
properties for gasoline blending.
Also a proper reactor design is important in order to
carry out the synthesis in the most favorable conditions.
A water-cooled tubular reactor is an optimal choice; as
the reaction heat is removed as long it is released along
the catalyst bed, a thorough temperature control can
be achieved, resulting in higher selectivities to desired
products and in a lower catalyst aging compared to other
kinds of reactors.
Finally, this reaction can be attractive for industrial
applications; in fact, it brings flexibility both to already
existing and future MTBE plants that could be run in
the most effective way in order to fulfill the market
needs for oxygenates and alkylate.
Acknowledgment
ECOFUEL SpA support is gratefully acknowledged.
Authors thank all the people working on this project.
Literature Cited
Gates, B. C.; Rodriguez, W. General and Specific Acid Catalysis
in Sulfonic Resin. J. Catal. 1973, 31, 27-31.
Haag, W. O. Oligomerization of isobutylene on cation exchange
resins. Chem. Eng. Prog. Symp. Ser. 1967, 63, 140-147.
Izquierdo, J. F.; Vila, M.; Tejero, J.; Cunill, F.; Iborra, M. Kinetic
study of isobutene dimerizations catalyzed by a macroporous
sulphonic acid resin. Appl. Catal. A 1993, 106, 155-165.
Miracca, I.; Tagliabue, L.; Trotta, R. Water Cooled Multitubular
Reactors for Etherifications. Chem. Eng. Sci. 1996, 51 (10),
2349-2358.
Parra, D.; Izquierdo, J. F.; Cunill, F.; Tejero, J.; Iborra, M.; Fitè,
C. Catalytic Activity of Acidic Ion Exchange Resins in Methyl
tert-Butyl Ether Liquid Phase Synthesis. Proceedings of The
First European Congress on Chemical Engineering, Florence,
Italy, 1997; Vol. IV, pp 3001-3004.
Rao, P.; Vatcha, S. R. Solid-acid alkylation process development
is at crucial stage. Oil Gas J. 1996, Sept 9, 56-61.
Rehfinger, A.; Hoffmann, U. Formation of Di-isobutene, Main By-
Product of Methyl Tertiary Butyl Ether Synthesis Catalyzed
by Ion Exchange Resin. Chem. Eng. Technol. 1990, 13, 150-
156.
Scharfe, G. Convert butenes to high octane oligomers. Hydrocarbon
Process. 1973, 53 (4), 171-173.
Unzelman, G. H. Global TrendssImpact of Fuel Reformulation.
NPRA Annual Meeting, San Antonio, TX, 1997; Paper AM-97-
26.
Vila, M.; Cunill, F.; Izquierdo, J. F.; Gonzales, J.; Hernandez, A.
The role of by-products formation in methyl tert-butyl ether
synthesis catalyzed by a macroporous acid resin. Appl. Catal.
A 1994, 117, L99-L108.
Received for review January 31, 1997
Revised manuscript received June 3, 1997
Accepted June 17, 1997X
IE9700932
X Abstract published in Advance ACS Abstracts, September
15, 1997.