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Catalysis Today, 15 (1992) 23-49 23

Elsevier Science Publishers B.V., Amsterdam

Developments in the production of methyl teft-butyl ether

GJ. Hutchings, C.P. Nicolaides2 and M.S. Scurrel12

bverhulme Centre for Innovative Catalysis, Department of Chemistry,


University of Liverpool, P 0 Box 147, Liverpool IA9 3BX, United Kingdom
2Catalysis Programme, Division of Energy Technology, CSIB,
P 0 Box 395, Pretoria 0001, South AIkica

SUMMARY
The catalysis of the etherification of alcohol and iso-olefin mixtures is discussed.
Emphasis is placed on the synthesis of MTBE (methyl teti-butyl ether), but
mention is also made of other ethers such as ETJ3E (ethyl tert-butyl ether), SAME
(see-amyl methyl ether) and MIPE (methyl isopropyl ether) and, to a very limited
extent, of hydrocarbon feedstocks other than iso-olefins. Established sulphonated
resin catalysts are described together with various aspects of their catalytic
characteristics, including kinetics, thermodynamics and the occurrence of
side-reactions. The use of alternative inorganic acids, especially xeolites, is covered
and comparisons drawn between these systems and the ion-exchange resins. Finally,
attention is given to the design of commercial processes for the production of
MT-BE.

1. INTRODUCTION

Of all the oxygenates used or contemplated for use as octane improvers in


gasoline, MTElE (methyl terf-butyl ether) has exhibited the highest growth over the
past decade [l]. World capacity has increased approximately ten-fold in this period
[2,3] and currently stands at about 12 million tons/year, with a projection that this
figure will increase to ca 20 million tons/year by 1994. One responsible factor is
the phasing out of lead in leaded gasoline, mandated, for example, by the EPA in
the United States. The EPA, under the 2 % oxygen in fuel definition [l],
permits up to about 12.7 vol % of MTBE or other oxygenates such as ETBE
(ethyl tert-butyl ether) or TAME (tert-amyl methyl ether). There have also been
calls for a 2.7 % oxygen level, corresponding to 15 % MTF$E in unleaded
gasoline. Oxygenates can also play a role in reducing the levels of pollutants

1992 Ebmier Science Publishers B.V.


24

(especially carbon monoxide) in exhaust emissions, and help to extend the supply
of hydrocarbons from crude oil sources. Japan has recently armounced the
approval of the addition of up to 7 vol % MTBE to gasoline.
Although the commercial production of MTBE via the catalytic combination of
methanol and isobutene (equation (l)), using sulphonated ion-exchange resins, is

CH3 a3
acid
EI3c - & = CXl2 + CH3OH ____c H3C! - :: - C!H3 (I)
catalyst
&II 3

now well established, there are several interesting .aspects now enjoying
considerable attention from catalytic scientists and engineers. Among these can be
mentioned:
- the use of alternative catalysts, such as inorganic acids, or perhaps superacids
for the exemption reaction;
- the production of MTBE from syngas, most directly accomplished (at least on
paper!) from the development of a mixed isobutanol-methanol synthesis
followed by conversion of the isobutanol to isobutene or, even more
attractively, by the direct reaction of isobutanol and methanol;
- the advantageous combination of simultaneous catalytic etherification and
distillation in which the catalyst is included in the packing of the distillation
tower. This approach is exemplified by the recently announced ETHERMAX
process from UOP [4].
Issues closely related to h@IBE production concern isobutene availability,
leading to a search for commercially viable catalytic processes for the skeletal
isomerisation of n-butenes [5], and resulting in the application of Phillips STAR
technology for the production of isobutene form n-butane [6]. Finally, the use of
feti-butyl alcohol (TBA) could be contemplated since its gasoline-related properties
are close to those of the fuel ethers, but first, a commercially attractive method of
producing this alcohol must be developed [7].
This review ~nce~ates on three aspects, namely:
- the catalysis of the etherification reaction using established sulphonated resins,
- the etherification by alternative catalysts; and
- the process design/commercial aspects of current and emerging technologies.
26

2. CATALYSIS OF ETHERIFICATION USING ESTABLISHED SULPHONATED


RESINS

Since 1973 a plant based on the SnamprogetWEcofuel (formerly ANIC) process


and with a production capacity of 100 000 tons of MTBE per year has been
operating at Rave- Italy [8]. The process, shown in Fig. 1, uses isobutene,
which is contained in a C4 fraction obtained from steam cracking or catalytic
cracking. After extraction of the butadiene, the C4 feed stream has an isobutene
content which ranges between 35 and 53 wt %. The reaction is carried out in a

Methanol

T
1
C4 Raffinate

rt
b
Butenes t t
Feedstock

Reaction
f

MTBE
YI
I_
2 Methanol
I
MTBE

Methanol-Water
Loop Fractionation Removal Fractionation

Fig. 1. MTBE Process (Smunprogettel-John Brown) [8,2@1.

fixed-bed tubular reactor and uses ion-exchange resins as catalysts. Linear butenes
are completely inert under the operating conditions used and by-product
production is very limited with formation chiefly of diisobutene. The water present
in the reagents reacts with isobutene, producing tert-butyl alcohol. The effluent
from the reactor consists mainly of MTBE and linear butenes. This mixture is
then sent to the purification column in which the Cds are separated from the
MTBE.
26

In commercial practice, cation-exchange resins (for example Bowex 5Ow,


Amberlyst 15 (AlS), Lewatit SPC 118 or Nacite) which are sulphonated
copolymers of styrene and divinylbenzene (DVB), the cross-linking agent, are used
as fixed-bed catalysts for the etherification reaction. These resins are based on the
bead forms of this copolymer which were developed in the late 1940s and early
1950s [9]. Amberlyst 15, produced by Rohm and Haas, is a strongly acidic
macroreticular resin and contains 28 % divinylbenzene. The resin has a surface
area of 43 k 1 m2/g and a mean pore diameter of 240 8, The ion-exchange
capacity determined by titration is 4.8 mequiv. of HSO3/g of dry resin [lo].
The catalyst life in commercial operation has been found to be in excess of two
years. The addition of methanol to isobutene is both highly exothermic (AH&a =
-37.7 kJ/mol) and reversible and the process is carried out in a multi-tubular
reactor with recirculating water between the tubes in order to remove reaction
heat. Using a slight excess of methanol in the feed, the per pass conversions of
isobutene can be close to 100 % [ll]. The reaction temperatures employed range
between 30 and 100 C and the pressure between 7 and 14 atm [12]. Increased
temperature shifts the equilibrium of the process toward the starting materials,
producing a faster reaction at the expense of net conversion, the life of the
catalyst, and the loss of isobutene due to polymerization [13].
The first research report on the use of an ion-exchange resin, in this case
Amberlyst 15, as catalyst for the addition reaction of tertiary olefins and alcohols
to produce ethers was published in 1977 by researchers at Snamprogetti [14]. In
their experiments, which were conducted at 60 C in an autoclave provided with a
mechanical stirrer, the ion-exchange resin was found to display a higher activity for
MTBE synthesis than the soluble anhydrous p-toluene sulphonic acid. Liquid-phase
mass-transfer resistance was negligible and no induction periods were observed.
From the initial reaction rates, the reactivity of primary alcohols with isobutene
was observed to follow the order n-butanol > n-propanol > ethanol > methanol.
Their results also showed a zero order dependence of rate on methanol
concentration for concentrations greater than 4 mov1, with negative orders at lower
concentrations (see Fig. 2) and a first order dependence on isobutene
concentration. A strong dependence of rate on acid group concentration, about
third order, was also observed.
Studies on the reactivity of three isomeric isoamylenes with methanol showed
that 2-methyl-1-butene and 2-methyl-2-butene can undergo both the etherification
and double-bond-shift isomerization reactions whereas 3-methyl-1-butene does not
react at all. These results suggest that a carbenium ion is the common
intermediate and that olefin protonation is a more important kinetic step than the
21

25-

5- 1 2 3 4 5 6
Methanol,initial amcentration,md/litre
7

Fig. 2. Methyl teti-butyl ether synthesis. Initial rate dependence on initial


methanol concentrations at constant isobutene content (4 mol/l).
Temperature: 60 C; catalyst: Amberlyst 15 [14].

interaction with the nucleophile. The observed high order in the 40$-I groups
can be related to a non-linear dependence of protonating power of the resin on
the concentration of sulphonic groups.
In a subsequent paper from the same group [15], the role of the
isobutene/alcohol ratio, a, on the reaction mechanism was further explored. It was
found that the initial rates of the reaction between methanol or n-butanol and
isobutene show different mechanisms, depending on the ratio of the reactants. At
stoichiometric or lower isobutene/alcohol ratios (a < 1.7, see Fig. 3), the initial
rates show a zero order in the alcohol and a first order in the olefins. In this
case the experimental data agree with an ionic mechanism wherein the protonation
of the olefin by the solvated proton is the rate determining step. Under these
conditions, the alcohol, which is in excess in the pores, breaks up the network of
hydrogen-bonded 4QI-I groups, dissociating and solvating the proton. The higher
reactivity of n-butanol versus methanol is a reflection of the acidity order of the
corresponding proton on the alcohol. That is, due to the lower basic@ of
n-butanol, a more acidic and more active ROH$ catalytic species is produced.
On increasing the olefin/alcohol ratio (a > 1.7) the rate increases as the
methanol decreases, until a maximum in the rate is reached. A further reduction
in methanol leads to zero order in the olefin and first order in the alcohol
(a > 10). It is inferred that at this point a real concerted mechanism has been
Fig, 3. MTBE Synthesis. Q&al areas delimited by ratio of reactants at
several hypothesized mechanisms [15].

reached wherein the isobutene is co-ordinated to the associated -SO#I groups and
the interaction with the alcohols is the rate determining step. In addition, at ratios
bigher than 3.5, the dimerization of isobutene also takes place. This was confirmed
by I-Iech et al. [16]. It was concluded therefore that in the reaction of linear
alcohols with tertiary olefins, catalyxed by ion-exchange resins, a transition in
kinetic orders is observed which has been related to the ratios of the reactants
and explained by mechanistic transitions.
Gicquel and Torck [17] also examined the influence of methanol concentration
on the activity of the Amberlyst 15 resin for the formation of MTBE, together
with the effect of the polarity of the medium on the reaction thermodynamics.
The synthesis and decomposition of MTBE were carried out in the temperature
rage of 50 - 95 C using a stainless steel double-jacketed reactor in batch-wise
operation. The reaction medium was agitated at 575 rpm by a m~etic-Eve
turbine. A ~~~-~helwood model rate expression was selected in order to
interpret the results. Relative rate constants and equilibrium constants are given as
a function of temperature and the activation energy and enthalpy of reaction were
also determined. It was concluded by these authors as well that the resin catalysts
29

are sensitive to the concentration of methanol, with the reaction rates increasing
sharply when the concentration is lowered. Furthermore, at a given temperature,
the variation in the apparent equilibrium constant is mainly due to the variation of
the methanol activity coefficient as a function of its molar fraction.
The effect of temperature on the normalised etherification reaction rate of
100 % isobutene hydrocarbon feed for a methanol/isobutene feed ratio of 2 was
also reported by Gulf Canada [12] and their results at high space velocity are
shown in Table 1. In order to test whether the reaction was mass transfer or

Table 1. Integral reactor data for MTBE synthesisa 1121.

Temperature
Space Velocnyb Reaction ROW
C
31.2 13.5 62 1.38
44.1 13.5 80 1.91
58.9 f3.5 89 2.6Q
76.6 13.5 100 3.60
79.1 13.5 107 3.62

Wydrocarbon feed is 100 % ICz; t&OH/K, = 2.0; Selectivity:97 - 99 %.


bBased on IC;.
cBased on dry catalyst.

diffusion rather than kinetically controlled or limited, a series of experiments were


carried out by varying the Reynolds number of fiow through the reactor, while
rn~t~~ the reciprocal space velocity constant and determining the effect on
conversion. The observation that the conversion remained constant (Fig. 4)
iudicates that mass transfer does not control the reaction. Another indication that
chemical kinetics and not mass transfer is rate limiting, is that identical conversion
and reaction rates were obtained with two different catalyst particle sizes (+ 16,
and + 48 to -35 mesh). The results shown in Fig. 5, i.e. identical conversions and
reaction rates were obtained for two different catalyst particle sines, provide
further support that the reaction is not mass transfer controlled.
Another evaluation of Al5 as a catalyst for MTBE synthesis under
non-isothermal conditions believed to be compatible with those in industry was
reported by Voloch et al. [18]. The study was carried out iu a bench-scale,
plug-flow reactor system. Variables considered included temperature, flow rate and
feed composition. An integrated rate expression was used to estimate kinetic
constants at 26, 51 and 67 C using data obtained from the plug-flow reactor.
30

25-

0 I I I I I I I
0 20 40 60 E
Modified Reynolds number

Fig. 4. Check for mass transfer limitations at 104 C with a reciprocal space
velocity based on isobutene of 0.45 [12].

04 I I I I I I 1
160 160 200 220
Temperature *F

Fig. 5. Effect of temperature and catalyst particle size (0 35-48 Mesh,


0 -I-16 Mesh) on the % conversion to MTBE [l2].

Conditions which maximise selectivity and productivity, together with other catalyst
characteristics, were discussed briefly.
Colombo et al. [19] evaluated the equilibrium constant of the reaction in the
liquid phase by means of predictive methods, using available literature values of
the standard free energy of formation for the species involved and the UNIFAC
estimates of activity coefficients to describe the liquid-phase non-ideality. Some
31

experimental values of the equilibrimn concentrations were obtained in a


micro-pilot plant and the predicted equilibrium constants were found to agree
quite well with the experimental values.
In their 1987 report [20], Ancillotti et al. described the modified Snamprogetti
process for the synthesis of MTBE from butadiene-rich steam cracking C4 cuts, As
the authors point out, some problems associated with the presence of butadiene in
the feed streams are undesirable reactions such as peroxidation and pol~e~tio~
and also the reaction between methanol and butadiene to produce butenyl ethers.
The reaction rates for the addition of methanol to the following three olefinic
substrates in units of l/(acid equiv.)(sec) at 80 C are:
isobutene 1 x 1o-2
butadiene 2x lo6
cis-2-butene 2x10
and show that the butadiene reaction rate is greater than that for the linear
butene but less thau that for isobutene. This order of rates is reSected in the
relative carbocation stability according to the two-step reaction mechanism where
the olefin protonation is regarded as the first and rate cornroIling step:

CH3

CJ&-C/H3 r H-CH-=CH=-CH-CH3 > CH3-CH-CH-CH3


gt G3
l!I
Tire butenyl ethers identified in the reaction product were essentially
3-method-l-butene and l-melon-~butene obtained from l-2 and l-4 methanol
addition respectively. The reactivity difference between isobutene and butadiene is
large enough to allow isobutene to react selectively, but only in a narrow area of
operating conditions [21]. The use of contact times exceeding the minimum value
required to reach the equilibrium in MTBE synthesis led to an increased butenyl
ether formation and to MTBE decomposition due to the competitive reaction of
metbauol with butadiene. The typical composition of processed C4 fractions is
indicated iu Table 2 and a detailed analysis of the product is provided in Table 3.
The h4TBE stream shows the presence of very low amounts of astir, such as
the above-mentioned butenyl ethers, along with minor amounts of ter&butyl
alcohol, methanol, 2-methoxy-butane and dimer.
Rebfinger and Hoffmanu [22] recently reported on the determination of the
micrakinetics for the liquid-phase synthesis of MTBE using Al5 and a specially
prepared resin, CVT, which had a lower degree of cross-linking (7.5 % DVB).
The experiments were conducted in a continuously stirred-tank reactor (106 ml,
32

Table 2. Composttlon of processed C4 stream [20].

Wt%

ess 0.04
n- butane 5.12
1.60
1-butene 14.50
lsobutyiene 22.63
fnvlsl-butene 6.16
cis-2-butene 3.66
1,3-butadlene 46.74
1,2-butadlene 0.22
propane (32 ppm)
vlnylacetylene (360 ppm)
1-butyne (210 ppm)
CRS 0.10

Table 3. Composition of MTBE stream [20].

Wt%

MTBE 99.10
methanol 0.01
ten-butylalcohol 0.20
3-methoxy-1-butene 0.47
1-rn~-2-b~~e 0.18
2-methane 0.01
heavy products 0.02
water
peroxvciationinhibitor

stainless steel) in the temperature range of 50 - 90 C. The temperature was


controlled within 0.2 C by immersing the whole reactor in a thermostated water
bath [LB]. The experimental results were described by a three-parameter model
based on a Langmuir-Hinshelwood rate expression in liquid phase activities from
the UNIQUAC method. The developed microkinetic model was found to be
independent of the degree of cross-linking of the resin in the investigated range of
7.5 - 20 % DVB by weight. The nature of the C4 solvent, n-olefin or n-alkane,
does not infiuence the intrinsic rate of MTBE synthesis. Also, no pressure
dependence could be observed up to 21 atm. In the second part of their
study [24], they examined the influence of the macropore diffusion of methanol on
the activity and selectivity of the resin catalyst. In the limiting case of methanol
macropore diffusion as the rate condos step, the results were in agreement
with a shell-core model, according to which almost none of the
33

me~~ol-~n~ core produces the by-product diisobutene, while only the outer
shell forms the main product MTBE. defend effectiveness factors, q, for the
isothermal catalyst beads were determined to be up to q = 5, while the
corresponding theoretically calculated value of 7 was two-thirds of this value.
In order to gain a better insight into the formation of the dimer, diisobutene,
Rebf?nger and Hoffmann [23] conducted additional experiments, studying this
reaction on its own and not as a side reaction of the MTBE synthesis. The
formation of the dimer was studied in the temperature range of 60 - 90 c using
A15 as catalyst_ The reaction showed no steady-state behaviour and the catalytic
activity declined at a rate dependent on the reaction conditions. Time constants
for the activity loss were determined in the range 3.5 - 3.0 h. It was also observed
that the deactivated Al5 catalyst from the diisobutene formation experiments could
be regenerated through subjection to the WE synthesis experiment. The
deactivation was assumed to be caused by blockage of the microparticle gel phase
by higher isobutene oligomers. The fo~tion of ~obutene, using l-butene as
solvent, was second order with respect to isobutene and showed an apparent
activation energy of about 40 kJ/mol.
The vapour-phase addition of methanol to isobutene over an Amberlyst 15
catalyst was recently studied by Tejero et al. [10,25]. The equilibrium constant for
the reaction was determined experimentally in a continuous-flow reactor at
atmospheric pressure and in the temperature range of 40 - 110 C! [WI. When a
mixture in eq~b~~ was fed into the reactor, the temperature of the catalyst
bed did not change. Given that the hFIBE synthesis reaction is fairly exothermic,
this was considered a rough indication that the composition of the mixture did
correspond to the equilibrium composition at the particular temperature. This
method was found to be suitable and the equilibrium constants obtained were
found to agree satisfactorily with the predicted values calculated from literature
data. In addition, the values of AHo, AS0 and AGo at 298 K, deduced from the
variation of the eq~ib~um constant with temperature in the range 40 - 110 C,
agreed with the values calculated from the literature data, within tbe
limits of experimental error. Rate data were also obtained at 41 - 61.5 C [lo].
The best-fitting Langmuir-Hinshelwood-Watson rate equation was derived from a
mechanism whose rate-determinin g step is the reaction between the methanol
adsorbed molecularly on one centre and the isobutene adsorbed on two centres.
The authors also concluded that the proposed mechanism is ~e~o~~y
consistent.
34

3. THE USE OF ALTERNATIVEINORGANICACIDS

As noted in the previous section, the current industrial process for the
production of MTBE utilises acidic cation-exchange resins as catalysts. The
information available on alternative catalyst systems is somewhat scant and mainly
involves recent research concerning zeolites. Early work identified that MTBE
could be synthesized from methanol and tert-butyl alcohol or isobutene in the
presence of mineral acids, such as sulphuric acid [26,2q; however, such a method
was not particularly selective due to by-product fo~atio~ from dehydration
reactions. More recentIy, Bitar et al. [28] of ARC0 have reviewed the features
that should be considered in the design of an optimized process and hence these
features are relevant to the design of an improved catalyst system
1. Temperature: this is required to be as low as possible to maximize the
equilibrium isobutene conversion and to minimize by-product formation.
2. Me~~o~isobut~e ratio: this should be as near stoicbiometric as possible
to reduce the cost of recovery and recycle of the unreacted methanol.
3. Isobutene conversion: for single stage operation with acidic ion-exchange
resins, 90 - 96 % conversion of isobutene is readily achievable; conversions
above this level require the operation of an additional conversion stage,
Clearly, novel catalysts need to match or better these criteria.
4. Catalyst lifetime: operation at low temperature with current exchange resin
catalysts permits lifetimes up to two years to be achieved and this must
therefore serve as a benchmark for the design of improved catalysts.
With respect to catalyst lifetime for heterogeneous catalysts, it is well-known
that for acid-catalyzed reactions, zeolites, particularly the pentasil zeolite ZSM-5,
can demonstrate long operational life, e.g. as demonstrated by H-ZSM-5 for the
methanol-to-gasoline process [29]. It is therefore not surprising that zeolites have
been studied as catalysts for MTESE production.
Chu and Kuhl [30] of Mobil Research and Development Corporation, studied
zeolites @, ZSM-5, ZSM-11, rare-earth-exchanged zeolite Y and mordenite as
catalysts for methanol and isobutene conversion in the vapour phase and their
results are given in Table 4. This work was carried out in the vapour phase so
that the selectivity of the various zeolites could be easily distinguished. From this
preliminary work, it was concluded that the related medium-pore zeolites ZSM-5
and ZSM-11 gave the highest isobutene conversions and MTBE selectivities.
Small-pore zeolites, e.g. synthetic ferrierite, are inactive for this reaction, since
isobutene cannot enter the zeolitic cage structure. Chu and Kuhl rationalised the
Table 4. Formation of MTBE over zeollte catalysts in the vapour phase [30].

Mtienite Beta REHY REAIY ZSMS ZSM-11


ZeOlW
(26) (a) (63)b (5.1)0 (70) (m)
Reaction conditionsd
molar ratio0 1.07 1.14 1.46 1.53 1.20 1.18 1.06 1.04 1.04 1.05 0.98 0.98
tempemture/"C 82 93 8293 8293 82 93 8293 8293

C~~~on~~~s

to MTBE I% 8.4 7.1 13.9 9.1 11.3 10.6 25.3 23.4 30.5 25.3 25.f 21.0
tOc8ddkI/% 6.0 14.1 23.0 27.3 0.47 1.9 0.3 1.3 0 0.1 0.1 0.2
80ieCt~ t0 58.3 33.5 37.7 25.0 96.0 85.0 98.8 94.9 100 99.6 99.4 99.0
MTBE/%
*Figure in brackets gives SiO&120s ratio.
bREHY prepared by ion-exchange of calclnecl RENaY with (NH&SO,,, RE = rare earth.
cREAY prepared by ion-exchange of calcined RENaY with Ai2(S04)B.
dWHSV = 3.4 h-1,totalw&M of methanol and lsobutene per g catalyst.
*Molar ratio methanoilisobutene.

relative reactivity of the zeolites in terms of the difference in diffusion rate of the
reactants within the zeolitic channels. For the medium-pore zeolites ZSM-5 and
ZSM-11, methanol diffuses more rapidly than isobutene and hence an isobutene
molecule migrating within the zeolitic pore system encounters a high excess of
adsorbed methanol and reacts to form MIBE in high selectivity. The lower
selectivities observed for mordenite and zeolite /I were in line with the lack of
shape selectivity in the diffusion of methanol and isobutene in the large-pore
zeolites. The high selectivity observed for rare-earth-exchanged zeolite Y was
considered to be due to the preferential a~o~~on of methanol by the more
polar zeolite of lower SiO&4&03 ratio. One similarity between the large-pore
zeolites tested @, mordenite, Y) and the commercial Amberlyst 15 resin catalyst
was that the selectivity of MTBE increased with temperature, whereas this was not
observed for ZSM-5 and ZSM-11.
Chu and Kuhl PO] compared ZSM-5 and Z-SM-11 with the commercial A15
catalyst under liquid-phase conditions more similar to those used in the
commercial process (Table 5). ZSM-5 was found to give superior selectivity to
MTBE over the broad range of me~~o~isobutene ratios ~v~tigated when
compared to Amberlyst 15, for which the selectivity approached that of the zeolite
only at high ratios (Fig. 6). Chu and K&l, recognising this study to be an
example of a low temperature application of zeolite catalysts, concluded that
xeolites ZSM-5 and ZSM-11 offered a number of distinct advantages over the A15
catalyst, namely:
36

1. bigb thermal stability and no acid efnuent;


2. high selectivity to MTB&
3. less sensitivity to methanol/isobutene ratio;
4. high MTBE output due to operation at high temperature and high space
vel&y;
5. ease of reactivation by standard calcination procedures.

Table 5. Comparison of ZSM-5,ZSM-11 and Amberlyst 15 In the liquid


phase [30].

Ze0lite zsM-5 ZSM-11 Amberiyst 15


molar ratioa 1.00 1.05 1.10 1.05 1.10 1.00 1.05 1.10
WHsvih-' 1.75 1.71 1.68 1.49 1.41 1.03 1.01 1.01
peak temperature/T 108 108 108 8690 77 70 62

c4H8converslon/% 89.6 89.0 90.1 88.7 90.2 93.1 93.4 94.5


MTBE yiddb/% 59.6 89.8 90.1 86.7 90.2 86.0 89.4 92.7
MTBE selectMty/% loo loo loo loo loo 92.4 95.7 98.1

amethand/Isobutene mdar ratio.


b% of theoretical yield.

0.90 Ix) 1.1


CH,CWi-C,,H, Wr ratlo

Fig. 6. Liquid phase selectivity to MTJSEas a function of methanol/isobutene


ratio [30].
37

Subsequent patents to Mobil Oil Corporation [31,32] disclosed the use of zeolite
catalysts in a combined MTO/etherification process for the conversion of methanol
to MTBE.
In a detailed study, Tau and Davis [33] also carried out a comparative study of
a range of solid acid catalysts for the conversion of ethanol and isobutene to form
ETBE, i.e. the analogous ethanol reaction to mE synthesis. Six catalysts were
selected for study: Amberlyst 15, Amberlyst 35, ZSM-5 (SiO$Al& ratio = 60),
Union Carbide zeolite catalyst S-115 ~Si~~2~ ratio = Sot), a opposed
fluorocarbonsulphuric acid polymer catalyst (FCSA) that had previously been noted
as a very strong acid [34], and phenylphosphoric acid resin (PPA) supported on
active carbon. Tau and Davis tested all six catalysts under a wide range of
conditions and the optimal data are given in Table 6 for vapour-phase studies at

Table 6. Comparison of the formation of ETBE over diffwent catalysts at


atmospheric pressure [33f.

-w@ Alii A35 ZSM-s S-Ill PPA FCSA


temperaturePCB 60 69 120 146 200 60
If&H8 conversion/% 43.5 39.3 9.6 es i s 0.5 21.3
ETBE 8electivity/%b 99.6 98.9 100 loo loo loo
cs Sdwltivity/%b 0.3 1.0 - - - -
ethyl ether selectivity/% CO.1 co.2 0.6 - - -
tert-butyialcohol 8electivity/%b <O.l co.1

*wHsv = 3.4-l, ethanolkobutene molar ratio = 1.0.


bbased on isobutene.
chased on ethanol.

atmospheric pressure. S-115 and PPA were not found to be particttlarly active for
EXBE synthesis. For the other four catalysts, the isobutene conversion was
observed to go through a maximum with increasing temperature (Fig. 7).
Tau and Davis further tested catalysts A15, A35, FCSA and ZSM-5 in a
liquid-phase reactor at total pressure of 200 and 300 psi (Table 7). Increasing the
pressure from 200 psi to 300 psi did not lead to a significant increase in the
isobutene conversion. In this study, Tau and Davis noted that the ~nve~ion for
ZSM-5 is considerably lower than that of the commercial Al5 catalysq this is an
observation in contrast to the study of Chu and Kuhl [30] (compare Tables 5
and 7). However, these studies are not directly comparable, as Tau and Davis
utilised a much higher temperature for the ZSM-5 experiment compared to Chu
and Kuhl, and this will limit the equilibrium isobutene conversion that can be
38

IO- (

J
_)(--)
,_)yX
r
I I t t I 1 I t

40 60 60 100 120 Ia4(3


Temperature OC

Fig. 7. The conversion of isobutene over dii&ent acid catalysts as a


tunction of temperature at atmospheric pressure: 0 Al5, q A35,
oFCSA, x ZSM-5 [33].

Table 7. ETBE formation in the liquid phase for different catalysts [33].

Pressure (psi) 200 300


catal ys? Al5 A35 ZSM-5 FCSA Al5 A35 ZSM-5 FCSA
temperaturePC 60 60 125 80 60 60 135 80
IC4Hsconversio~ 86.1 85.8 56.6 72.5 88.9 88.3 61.6 80.4
ETBE 98.8 98.4 99.9 989.8 98.4 97.6 99.5 99.6
cs sektMty/%
selectivit$% 1.2 1.4 - 0.2 1.6 2.2 0.2 0.4

*WHSV = 3.0 h-1, ethanol/lsobutene molar ratio = 1.0.


bbased on Isobutene.

achieved. The high selectivity to the ether, noted by Chu and Kuhl [30] for the
zeolite catalyst, was confirmed in the study of Tau and Davis.
One important result obtained from the study of Tau and Davis was the
observation that the FCSA catalyst exhibited similar activity to that of the A15
catalyst. However, FCSA exhibits a higher selectivity, particularly for
ethanol/isobutene ratios of less than unity. The selectivity difference was typically
1 - 2 % and, in addition, the FCSA appeared to be much less sensitive to
changes in the ethanol/isobutene ratio. The higher temperature stability of FCSA
compared to Amberlyst 15 was also demonstrated by Tau and Davis, who
successfully operated the FCSA catalyst at temperatures up to 130 C without
detecting acidity in the reactor effluent. On the basis of the studies of Chu and
Kuhl [30] and Tau and Davis, it can be concluded that the pentasil zeolite ZSM-5
and the fluorocarbonsulphuric acid polymer catalyst offer considerable scope for
the design of improved catalysts for h0BE production.
More recently, patents to the Mobil Oil Corporation [35,36] have disclosed the
use of zeolite @ for the synthesis of ethers from the reaction of alcohols and
iso-olefins. This is of interest, since the original study of Chu and Kuhl [30]
(Table 4) indicates that the large pore zeolite /I is not particularly selective for
this reaction. Haag and Bell [35] compared the use of zeolite /I with the
commercial catalyst Al5 for the synthesis of set-amyl methyl ether (SAME) from
methanol and isopentene, and showed that the former was more active (Table 8).
In this experiment zeolite t9 was diluted with silica sand and used in extrudate
form. The enhanced selectivity to this bulky ether may be due to the larger pore
size of zeolite j?. Haag and Bell also demonstrated the use of zeolite /I as a
catalyst for the synthesis of methyl isopropyl ether (MIPE) from the reaction of
propene and methanol at 160 - 163 C and WHSV 0.12 - 3.70 h-1. Again very
high selectivities to the ether were reported. Subsequently, Harandi and Owen [36]
disclosed the use of zeolite #I as an etherification catalyst in a two-stage process
for which the first stage involves the isomer&&on of an olefin-containing
feedstock over a silicotitanate catalyst. Based on these disclosures, it is clear that
zeolite /3 also warrants further attention as a potential future commercial catalyst
for MTBE synthesis.

Table 8. Conversion of methanol and P-pentene to SAME [35].

Catalyst Zeolite B Amberlyat 15


time on stream/h 4 5 5 7
WHSV/h-a 4.03 16.36 3.93 3.93
2-C&H10conversion/% 15.2 5.0 6.3 8.6

Reaction effluent/mass %:
water 0.9 0.8 3.6 0.4
methanol 23.6 31.9 9.7 6.2
dimethyiether 2.0 0.3 8.4 13.9
2 pentene 62.9 71.8 68.7
SAME 3.1 6.0 8.3
1.0 0.6 0.6

aTemperature 150 - 152 c, pressure 950 PSI.

A comparative study has been carried out on the use of three different acid
catalysts, viz. the Al5 resin and zeolites Y and ZSM-5, as well as of the triflic
acid-coated counterparts of these zeolites for the gas-phase synthesis of MTBE
[37]. In the case of ZSM-5, its lower acidity cannot be adjusted by loading with
tritlic acid because of the negative influence of the coating on the diffusion of
reactant and product molecules. Triflic acid-loaded zeolite Y, on the other hand,
appears to be as active as Al5 in the gas phase synthesis of MTBE and also has
a much lower production of by-products (see Table 9). Furthermore, it is more
thermally stable than the commercial resin catalyst and could therefore be a valid
alternative to the conventional catalyst.

Table 9. Maximum MTBE yield obtained with the triflic acid-loaded


zeolites [37].

ZSM-5jTFA Y/lFA
Catalyst Amberly8t 15
(3 wt %I (3wt%)
Temperature c 66 65 65
MTBE yield (C-atom %) 47.5 40.6 46.1
Ce yield 9.7 0.2 0.4

Bylira et al. [40] and Adams et al. 1411 reported that ion-exchanged
montmorillonites can catalyse the production of MTBE from methanol and
isobutene or from methanol and tert-butyl alcohol [42]. Methods have also been
described for the acid-treatment of montmorillonite-based catalysts and the
addition of water to improve their catalytic activity for the reaction [43,44].
In a subsequent investigation by Adams et al. [45], montmorillonite-based
catalysts were compared with the Al5 catalyst for the reaction of methanol and
isobutene or TBA, When 1,4-dioxan was used as solvent, Al3+-exchanged
montmorillonites had about half the efficiency of the resin Amberlyst 15 at 60 C,
they were, however, about twice as efficient at this temperature as
Ti3+-montmorillonite or KlO, a commercially available acid-treated bentonite.
Montmorillonite exchanged with Chlorhydrol solutions to give interlayer
WI~WWD~%~ + ions and pillared clays derived from such materials were
poor catalysts, as was K306, a more drastically acid-treated bentonite-based
commercial catalyst. Freeze-drying of the Als+ -exchanged clay before reaction of
isobutene and methanol in dioxan was 44 kJ/mol for an Al3+-clay catalyst
compared with 25 kJ/mol for reactions catalyzed by Amberlyst 15. With no solvent
(as in industrial processes), the rates of reaction were considerably slower for both
the clay- and resin-catalyzed reactions. As has been found previously for
resin-catalyzed reactions using stoichiometric amounts or an excess of methanol,
the rate was proportional to the isobutene concentration, and the rate determining
step appeared to be the protonation of the akene. The performance of the
41

Al3+-clay catalyst was increased by reducing the water content of the clay, In
most reactions the clay catalysts were equilibrated at 12 % relative humidity.
EJxposure of the clay to a low vacuum (10-l torr) before use increased its catalytic
activity from 50 to 60 % of that of Amberlyst 15.

The overall considerations to be takeu iuto account for the design of the
process are:
- the exo~e~~~ of the forward reaction;
- the sensitivity of the resins to temperature in excess of about 90 - 95 Oc,
- the desire to use pressures required to maintaiu olefin feeds in the liquid state;
- the need to debutauixe, i.e. to remove unreactive Cq components, n-butenes,
isobutaue and n-butane;
- ovation of hKIBE usually accompanied by recycle of unreacted methanol.
4.1. HW/UOP [46]
The process layout is depicted iu Fig. 8. The c4 stream typically cousists of
isobuteue first purified to remove resin contammants before combiuiug witb
methanol. Alternatively, FCC light gasoline may be fed and, in this case, tbe
combined feed is reacted over the acid ion-exchange resin contaiued in two
fixed-bed adiabatic reactors (2,3). If the reactive olefin concentration in the feed is
high, as in the case of steam-cracker Cds or C4 dehy~oge~tion products, the
first reactor (2) is either an isothermal rn~ti-~b~~ or adiabatic reactor. In the
latter case, a small slipstream of the first reactor (2) effluent is cooled and
recycled back to the inlet of that reactor. Improved temperature ,control results,
and this leads to improved yield and resin life. Carbon steel ~~~~on is
consistent with the mild conditions required for the reaction.
MTBE is recovered at a very high purity (99 % + ) as bottoms from the
butene cohmm (4). The overhead contaius excess methanol and unreacted C4
hydrocarbons (rafEuate). The excess methanol is recovered with a simple
water-wash system (5,6) and recycled to the inlet of the first reactor. Spent Ct
hydrocarbons are usually sent to au alkylation unit.

Thisuses a single fixed-bed tubular reactor and h4TBE is separated from C&
residue iu a debutanixer (Fig. 1). The conversion of isobutene ranges from 60 to
80 % for dilute catalytic cracker streams and from 97 to 98 % for steam cracker
C&z. Water-washiug of the C4 reduces residual methanol to below 10 ppm.
42

Spent C4 hydrocarbons
to alkyltitlon
l

Cq Hydrocarbons

1 High grade MTBE product


.
Methanol I
__

Fig. 8. Hiils-UOP Process [461.

4.3. Atlantic Richfi~d [47]

Either a single-stage or two-stage reaction train is used, the former resulting in


isobutene conversions of 95 %. The conversion may be raised above 99 % by
installing a debutanizer between the two reactors. The intermediate debutanizer
shifts the equilibrium toward forming more MIBE.

4.4. CD Tech [48] and Ethermax Process [4]

In the CD Tech Process C4 feed is mixed with fresh and recycle methanol,
preheated and fed (Fig. 9) to a fixed-bed downflow adiabatic reactor (1) in which
the liquid becomes heated to bubble point by the heat of reaction, and with small
vapour generation eliminates the need for external cooling. After reaction, the
mixture flows from the primary reactor to a catalytic distillation reaction column
(2) in which further reaction and distillation proceed simultaneously. A reduction
in total installed cost results, with the MTBE being removed from the reaction
43

C4s rafflnate
.
Methanol Recycle Methanol I
1' I t

-
LA -

---dr
Water

MTBE

Fig. 9. MTBE Synthesis (CD Tech) [48].

zone by distillation as it forms. The reaction is thereby permitted to proceed


beyond the thermodynamic limit and higher conversions (99 % +) are achieved.
This type of approach is also a feature of the Ethermax Process recently
announced by UOP [4]. Useful for MTBE production, it becomes even more
attractive for ETBE and TAME production where equilibrium constraints are
higher. For example, isoamylene conversion can be increased from 70 % to 91 %.

4.5. Phillips Petroleum Company [49]

The unique feature of this process consists of the use of a methanol


fractionator which ensures very high recovery. All unreacted methanol is
fractionated away from the MTBE bottoms, saving substantial steam and the
residual butene stream may be sent directly without further treatment to an
alkylation or polymerization unit.

4.6. BP [!50]

A key feature of BPs technology (Fig. 10) is a novel trifunctional catalyst which
performs three reactions simultaneously: etherification of iso-oletins, selective
hydrogenation of unwanted diolefins and hydroisomerization of oleCns by means of
double-bond-shift.
44

Hydrogen c4 to
I alkylatlon

t
1

C4/%
Feed

Methanol
I 1 2

I Recycle
3

Methanol
Mixed
Ethers
t

b 4

Fig. 10. Etherol Process (BP) [48].

In the C& option, feed and methanol are purified (1) and, after the addition
of a small quantity of hydrogen, pass to two fixed-bed reactors (2) and (3)
containing an acid resin catalyst. The reactors operate liquid-filled and some
recycle of cooled first-reactor effluent occurs in order to fine control temperature
to increase yield and extend catalyst life. Debutanizing is effected in (4) while
methanol is recovered in (5) and recycled to the guard vessel (1).

4.7. Other developments

A series of processing steps involving the close integration of the ether&&on


reaction with those of isomer&&ion, dehydrogenation and methanol synthesis have
been outlined by Davy International and Davy McKee [49]. The isomer&&ion of
n-butane (obtained from an LPG fractionation plant) is effected over, for example,
a platinum catalyst at 150 - 200 C and 15 - 30 bar. After distillation, the
isobutane is dehydrogenated (using, for example, Catofin technology developed by
Air Products and Chemicals and now owned by United Catalysts with licensing
through ABB Lummus Crest) and the C4 stream passed to the etherification stage.
In an integrated complex, a common steam system can be employed with
optimization of the steam levels for high pressure use in turbines, medium
45

pressure use in the conversion process and low pressure use in steam boilers.
~~~ utilizationof off-gas streams for use as fuel or feedstock enhances
energy efficiency and product yield.
Finally, a recent development announced by Mobil [50], involving the Mobil
Olefins to Gasoline (MOG) process, is claimed to help reduce the capital costs of
a new MJIBE plant by some 30 %. The MOG process leads to high octane
gasoline from light olefins (including ethylene) contained in low value refinery
streams. The gasoline is produced in a fluidized-bed reactor containing zeolite
ZSM-5 catalyst. Oligomerization, alkylation and skeletal isomerization occur
simultaneously. Integrating the MOG process with MTBE production is made
possible by the fact that MOG can essentially be operated by feeding methanol
directly, when the well-known methanol to olefins reaction occurs (Fig. 11). There
is then no need for a metbanol recovery unit to be installed as is normally the
case.

C$C3 Feed To Fuel


t
__.__, MOG LPG
MeOH Feed b
unreacted UNIT
c
MOG Product
c, Feed Oleflns
J t1 with
Methanol 1 -

1st stage 2nd Stage


MTBE MTBE *1-rnr
Reac to
.._.._,or

Fig. 11. MOG/MTBE Process (Mobil-Badger) [SO].


4.8. MTBE cracking

As a footnote to this review of MTBE production, it is fitting to remark that


the reverse process of MTBE cracking has also received attention, because it
provides a convenient route to high purity isobutene for use in the manufactnre of
elastomers (butyl rubber and polyisobutene) and other chemicals (tert-butyl
derivatives, diisobutene, polybutenes, etc.). Fattore et al. [Sl] discuss the
advantages of recovering isobutene from MTBE, these lie in the absence of
environmental and corrosion problems associated with the conventionally used
systems (e.g. extraction with sulphuric acid) in the high purity of the olefin
obtained and in the decoupling of isobutene production from that of propylene
oxide synthesis. For the reverse reaction, inorganic solid acids would be used since
the temperatures used (in the range 160 - 220 C) are significantly higher than
those associated with stable operation of the ion-exchange resins. A specially
treated y-ahunina [52] appears to offer excellent performance. Problems which
could be encountered include dehydration of product methanol to dimethylether
and some isobutene loss by reaction with the water so formed (leading to TBA).

5. CONCLUSIONS
Despite their success in providing the basis of commercial processes for the
production of MTBE and related ethers, sulphonated ion-exchange resins are being
challenged by alternative catalyst systems. Zeolites ZSM-5 and ZSM-11 appear to
be capable of superior performance, particularly with regard to lower sensitivity of
synthesis to alcohoVolefin ratios and higher outputs. In addition, supported
fluorocarbonsulphuric acid polymer catalyst (FCSA) also has appealing properties
and appears to exhibit higher thermal stability than, for example, Amberlyst 15.
Because MTBE is a relatively low-value chemical, the economics of production
are of critical importance, vis B vis its application as a fuel component.
Considerable attention has therefore been paid to designing high-efficiency
commercial processes and the integration of product distillation and catalytic
etherification is a good example of this. Closer integration of etherification with
other refinery operations (olefin production, methanol synthesis) has been sought
and it is likely that further development in this direction will continue. In
addition, it seems likely that we will see further efforts aimed at the production of
mixtures of fuel ethers from suitable mixed feeds (hydrocarbons and/or alcohols)
where these are available.
The synthesis of fuel ethers presents the classic challenge to catalytic
technologists: a strongly exothermic reaction proceeding at comparatively low
temperature with catalysts having a limited thermal stability. The challenge is being
taken up and severaI novel lines of ~v~~atio~ some already just ears are
anticipated.

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