Kinetics of the reactions of tert-butanol with C2-C5 alcohols on sulfo cation exchangers

Article abstract of DOI:10.1134/S0023158413020067

The kinetics of etherification of tert-butanol with aliphatic alcohols on gel KU-2×8 and macroporous KU-23 sulfo cation exchangers was studied. The first order of reaction with respect to tert-butanol and the -SO₃H groups of a catalyst was established. The activation energy of the process observed on KU-2×8 was 60-95 kJ/mol. It was shown that the etherification of tert-butanol on KU-2×8 occurred in a surface layer. The reactivity of primary alcohols introduced into the reaction with tert-butanol increased with their molecular weights (C₂-C₅). The rate of reaction with secondary alcohols was lower than that with primary alcohols.

Full text of DOI:10.1134/S0023158413020067

ISSN 0023ꢀ1584, Kinetics and Catalysis, 2013, Vol. 54, No. 2, pp. 179–183. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © A.A. Golovanov, V.S. Pisareva, M.V. Levshenkov, 2013, published in Kinetika i Kataliz, 2013, Vol. 54, No. 2, pp. 188–192.
Kinetics of the Reactions of tertꢀButanol with C –C Alcohols
2
5
on Sulfo Cation Exchangers
A. A. Golovanov, V. S. Pisareva, and M. V. Levshenkov
Togliatti State University, Togliatti, 445667 Russia
eꢀmail: aleksangolovanov@yandex.ru
Received January 26, 2012
Abstract—The kinetics of etherification of tertꢀbutanol with aliphatic alcohols on gel KUꢀ2×8 and
macroporous KUꢀ23 sulfo cation exchangers was studied. The first order of reaction with respect to tertꢀ
butanol and the –SO H groups of a catalyst was established. The activation energy of the process observed on
3
KUꢀ2
face layer. The reactivity of primary alcohols introduced into the reaction with tertꢀbutanol increased with
their molecular weights (C –C ). The rate of reaction with secondary alcohols was lower than that with priꢀ
×8 was 60–95 kJ/mol. It was shown that the etherification of tertꢀbutanol on KUꢀ2×8 occurred in a surꢀ
2
5
mary alcohols.
DOI: 10.1134/S0023158413020067
INTRODUCTION
The etherification of tꢀBuOH is accompanied by
the side reaction of intramolecular dehydration
+
Alkyl tertꢀalkyl ethers such as methyl tertꢀbutyl
ether (MTBE), ethyl tertꢀbutyl ether, and methyl tert
H
ꢀ
(
CH3
)
COH ←⎯⎯→
(
CH3
C=СН + H O. (II)
2 2
2
)
3
amyl ether are used as motor gasoline components for
increasing the octane number of gasoline. In recent
years, interest in the homologs of MTBE has quickꢀ
ened because of their higher performance characterisꢀ
tics, namely, a higher octane number and a smaller
solubility in water (which decreases the danger of their
release into ground water). The liquidꢀphase reactions
of the addition of methanol and ethanol to isobutylene
and isoamylenes, which are contained in technical
fractions, are used for the industrial synthesis of alkyl
Earlier, Golovanov et al. [12] found that the selecꢀ
tivity of the synthesis is determined by the
ratio between the products alkyl tertꢀalkyl ethers and
i
ꢀC H8. The occurrence of other side reactions (the diꢀ
4
and trimerization of
dration of ROH, and the isomerization of alkyl tert
alkyl ethers) with the use of the sulfo cation exchanger
catalysts KUꢀ , KUꢀ23, KUꢀ2FPP, and Amberlyst
5 can be ignored. The selectivity of the formation of
alkyl tertꢀalkyl ethers increases with the initial ROH :
ꢀBuOH ratio, the duration of the synthesis, and the
iꢀC H8, the intermolecular dehyꢀ
4
ꢀ
2 8
×
1
tertꢀalkyl ethers [1]. Macroporous sulfo cation
+
t
exchangers in the
H
form are most frequently used as
amount of a catalyst. The highest selectivity for the
formation of alkyl tertꢀalkyl ethers (85–92%) was
reached in a temperature range of 340–370 K.
catalysts. The kinetics and mechanism of these reacꢀ
tions [2–5] and also their thermodynamics [6–8] have
been studied in detail. Highꢀoctane ether additives are
synthesized at many petrochemical plants in Russia
and abroad.
An alternative method for the synthesis of alkyl
tertꢀalkyl ethers is the reaction of the intermolecular
dehydration (etherification) of alcohols:
The hydration of the –SO H groups of sulfo cation
3
exchangers in the course of reaction leads to a decrease
in its catalytic activity [13–15] and selectivity for the
formation of alkyl tertꢀalkyl ethers; moreover, these
effects are expressed more sharply in macroporous
cation exchangers than in gel cation exchangers [16].
+
H
(
CH3 3
)
COH + ROH←⎯⎯→
(
CH3
)
COR + H O. (I) A consequence of this is the significant complication
2
3
of the kinetics of the process [13].
Alcoholꢀcontaining industrial wastes and byꢀprodꢀ
ucts, for example, 2ꢀmethylꢀ2ꢀpropanol (2 ( ꢀBuOH)
t
,
To overcome the effect of catalyst deactivation, the
which is formed upon the oxidation of isobutane and process can be carried out by a reaction–rectification
the epoxidation of propylene with tertꢀbutyl hydroperꢀ method [17] in a hydrocarbon solvent, which makes it
oxide [9, 10] and also the alcohol fractions of the oxiꢀ possible to remove the released water as an azeotropic
dation of cyclohexane [11] and the products of oxo mixture [18]. Under conditions of a 25ꢀ to 30ꢀfold
synthesis, can be raw materials for the synthesis of molar excess of alcohol ROH with respect to tꢀBuOH,
ethers. The use of these alcohols in the synthesis of terꢀ the water concentration per unit weight of sulfo cation
tiary ethers makes it possible to convert industrial exchangers decreases considerably, and the hydration
wastes into valuable products.
of sulfo groups is thus almost prevented. Under these
179

180
GOLOVANOV et al.
Table 1. Characteristics of sulfo cation exchangers
temperature of 95–100 С. The static exchange capacꢀ
°
ity (SEC) was determined with the use of a 0.1 N soluꢀ
tion of NaOH in accordance with GOST 20255.1ꢀ89.
The specific surface area (Ssp) was measured by the
BET method based on the thermal desorption of
nitrogen. Table 1 summarizes the characteristics of the
prepared sulfo cation exchangers.
Sulfo cation
exchanger
Fraction, SEC, mequiv
2
Ssp, m /g
+
mm
[H ]/g
KUꢀ2×8
0.200–0.315
<0.200
4.3–5.0
4.5–5.2
0.1
4.0
KUꢀ23
Ethanol, 1ꢀpropanol, 2ꢀpropanol, 1ꢀbutanol,
ꢀmethylꢀ1ꢀpropanol, 1ꢀpentanol and 3ꢀmethylꢀ1ꢀ
2
conditions, the reaction has first order with respect to
butanol, which contained no less than 99.5% base
materials, were dried before use in accordance with
t
ꢀBuOH and the –SO H groups of the catalyst and
3
pseudoꢀzero order with respect to ROH (R = Pr, Bu,
published procedures [20, 21].
tꢀBuOH (mp 23.0–
and
Because the available kinetic data predominantly
concern only reaction (I) of ꢀBuOH with methanol
iꢀBu) [18].
2
3.5 ; 99.8% purity; water content, <0.08%) was
°С
used without additional purification.
The kinetics of reactions was studied in a liquid
phase. The reactions were carried out at a temperature
t
and ethanol and, at the same time, the homologs of
MTBE are of great interest, a study of the etherificaꢀ
ꢀBuOH with С –С alkanols is undoubtedly of of 332–352 K in a 100ꢀcm3 threeꢀnecked flask
tion of t
2 5
equipped with a stirrer, a thermometer, and a reflux
condenser with a calcium chloride tube. A weighed
portion of a sulfo cation exchangers (0.5 g) was preꢀ
liminarily immersed in alcohol ROH (0.3–0.5 mol)
for 10 h or more (until swelling); thereafter, the flask
considerable current importance. This work was perꢀ
formed for the purpose of obtaining information on
the reactivity of С –С alcohols toward tꢀBuOH.
2
5
EXPERIMENTAL
and macroporous KUꢀ23 sulfo cation
exchangers, which meet the requirements of GOST
State Standard] 20298ꢀ74, were used as catalysts. The
was thermostatically controlled and
tꢀBuOH (0.78 g,
0
.01 mol) was introduced. The composition of samꢀ
Gel KUꢀ
2 8
×
ples taken from the reactor was determined by gas–
liquid chromatography in accordance with a published
procedure [18]. The kinetic curves were constructed
based on 7–13 points, at each of them the degree of
[
+
sulfo cation exchangers were converted into the
form using a standard procedure [19], washed with
distilled water and ethyl alcohol, dried at 105–110
H
tꢀBuOH conversion was brought to 70–80%.
°
С
to constant weight and then for additional 3–4 h in a
flow of dry argon at a pressure of 20–30 Torr and a
RESULTS AND DISCUSSION
Bobylev et al. [15] found that the rate of a reaction
of tꢀBuOH with methanol does not depend on the
lnC0/C
grain size of macroporous KUꢀ23 ion exchanger; on
this basis, they concluded that the reaction occurs in
the kinetic region. We found that, as the grain size of a
1
2.0
1.5
1.0
0.5
KUꢀ
the initial rate of
decreased (by a factor of about 1.5 in the reaction with
2×8
catalyst was increased from 0.16 to 0.40 mm,
3
tꢀBuOH etherification somewhat
2
1
ꢀpropanol at 347 K).
The kinetic curves that describe the dependence of
ꢀBuOH conversion on the reaction time on both KUꢀ
t
2×8
and KUꢀ23 in the semilogarithmic coordinates
become linear (Fig. 1, the coefficients of linear correꢀ
lation are more than 0.99); this fact suggests the first
order of reaction.
For determining the order of reaction with respect
to the catalyst, we studied the dependence of the initial
rate of reaction (w0) and the rate constant (k) on the
concentration of –SO H groups in sulfo cation
exchangers. This concentration was varied in the range
3
0
50
100
t
150
200
, min
of [–SO H] from 0.05 to 0.5 mol/L by changing the
3
weighed portion of the catalyst, which possesses a conꢀ
stant SEC. In the range of [–SO H] from 0.05 to
3
Fig. 1. Kinetic anamorphoses for the reactions of
with ( ) 1ꢀbutanol, ( ) 1ꢀpropanol, and ( ) 2ꢀpropanol in
the coordinates of a firstꢀorder equation. Temperature,
52 K; catalyst, KUꢀ2 8.
tꢀBuOH
0
.2 mol/L, the dependences were linear (Fig. 2a). In
the logarithmic coordinates (Fig. 2b), they took the
form of a straight line with a slope close to unity (0.895
1
2
3
3
×
KINETICS AND CATALYSIS Vol. 54
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2013

KINETICS OF THE REACTIONS OF tertꢀBUTANOL
–logr0 [mol L–1 s–1]
5.0
181
4
–1
k
×
10 , s
16
4
3
2
(
а)
(б)
1
4.5
4.0
3.5
3.0
1
2
8
4
0
2
1
4
3
2.5
0.25
0.2
0.4
–SO H], mol/L
0.6
0.75
1.25
–log[–SO H] [mol/L]
1.75
[
3
3
Fig. 2. Dependence of (a) the rate constant and (b) the initial rate of reaction on the concentration of –SO H groups in the KUꢀ
3
2×
8 sulfo cation exchanger: (
1) 2ꢀpropanol, (2) 1ꢀpropanol, (3) isobutanol, and (4) 1ꢀbutanol. Temperature, 352 K; [tꢀBuOH] =
0.21 mol/L.
at R = Pr, 0.902 at R = Bu, 0.907 at R =
at R = ꢀPr). Analogous dependences were observed on the KUꢀ
when the reaction was performed under the conditions processes.
i
ꢀBu, and >0.9 to consider that the rate of etherification of
tꢀBuOH
s
2×8
catalyst is not determined by diffusion
of a stoichiometric molar ratio between the reactants
ROH : ꢀBuOH = 1 : 1). Thus, the reaction is of first
order with respect to the –SO H groups of the catalyst.
Thus, under the used experimental conditions
pseudoꢀzero order of reaction with respect to ROH),
the reaction is described by the general secondꢀorder
(
t
(
3
At [–SO H] > 0.3 mol/L, the dependences ceased to equation
3
be linear (Fig. 2a). This effect can be supposedly
explained as follows: With increasing the concentraꢀ
dCtꢀBuOH
w =
= kCtꢀBuOHC−SO3H
.
(2)
dt
tion of –SO H groups, the amount of
t
ꢀBuOH bound
to them into a reaction complex gradually increases.
At a –SO H concentration of 0.3–0.5 mol/L, ꢀBuOH
3
At constant catalyst amount and activity, the conꢀ
centration of –SO H groups can be put in the rate
3
t
3
constant:
in the reaction mixture is entirely bound to the cation
exchanger and a further increase in the concentration
dCtꢀBuOH
w =
= k'CtꢀBuOH
.
(3)
of the –SO H groups is no longer accompanied by an
3
dt
The applicability of formalꢀrate equation (3) to the
and also the high values of
constants showed that the reaction is satisfactorily activation energies suggest the occurrence of the reacꢀ
increase in the reaction rate.
The study of the temperature dependence of rate test process on KUꢀ2 8
×
described by the Arrhenius equation
tion in the kinetic region [22, 23]. In this case, it is
most likely that the decrease in the initial rate of reacꢀ
(1) tion with grain size can be explained by the predomiꢀ
nant occurrence of the process in a thin layer on the
–1
Ea
ln k = ln A −
,
RT
–1
where
А
is the preexponential factor (L mol s ), surface of KUꢀ
2 8 [24]. The reaction in a surface layer
×
Ea is the apparent activation energy (kJ/mol),
R
=
is a rateꢀlimiting step of the reaction on this catalyst.
–1
–1
8.314 J mol
K is the gas constant, and Т is temperꢀ
The use of macroporous KUꢀ23, which possesses a
ature (K).
dense network of pores with a total volume of about
3
The apparent activation energies of reaction (I) 4 cm /g, results in the more rapid occurrence of the
(
Table 2) are very close to each other and fall in a range process (Tables 2 and 3). However, as follows from
of 80–86 kJ/mol (reactions with the participation of published data [16], the inhibiting action of the
2
ꢀpropanol and 1ꢀpentanol are the exception), which released water is stronger in this case. Water blocks the
is substantially higher than the activation threshold of –SO groups of the cation exchange to decrease the
diffusion (42 kJ/mol [22]). Consequently, it is possible rate and selectivity of reaction (I) [16]. At the same
H
3
KINETICS AND CATALYSIS Vol. 54
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2013

182
GOLOVANOV et al.
Table 2. Rate constants and activation parameters of the reactions of
t
ꢀBuOH with alcohols ROH on KUꢀ2×8 (SEC =
+
4
.50 mequiv [H ]/g) in a temperature range of 332–352 K
Rate constant
342 K
k
'
×
10 , L mol s–1
3
–1
Correlation
coefficient
of Eq. (3)
–
10
A
×
10
,
R
Ea, kJ/mol
–1
–1
L mol
s
332 K
347 K
352 K
Et
0.12 ± 0.05
0.43 ± 0.02
0.23 ± 0.01
0.69 ± 0.02
0.92 ± 0.05
1.56 ± 0.05
0.29 ± 0.08
0.82 ± 0.01
0.75 ± 0.05
1.91 ± 0.05
1.95 ± 0.04
2.08 ± 0.09
1.48 ± 0.04
0.46 ± 0.04
2.35 ± 0.10
1.10 ± 0.12
2.93 ± 0.03
4.12 ± 0.05
4.80 ± 0.18
2.08 ± 0.07
–
84
14.5
3.69
–
0.999
0.920
0.988
0.996
0.991
0.962
0.984
Pr
3.25 ± 0.11
1.67 ± 0.03
3.94 ± 0.07
5.71 ± 0.37
4.80 ± 0.18
3.11 ± 0.03
82
s
ꢀPr
96
Bu
86
2.91
2.19
–
i
ꢀBu
85
Pent
61*
81*
i
ꢀPent 0.58 ± 0.03
3.34
*
Approximate value.
time, water is more easily removed from the surface of than 1ꢀpentanol. As applied to С5 alcohols, this reguꢀ
KUꢀ
2
×
8
SO H
and it is likely that the reaction equilibrium
larity can be explained by increasing steric hindrances
upon the formation of a reaction complex with
–
⋅
H O + ROH SO H ⋅ ROH + H O,
3
3
2
2
3ꢀmethylꢀ1ꢀbutanol.
is shifted to the rightꢀhand side to a greater extent.
When the etherification of ꢀBuOH was performed
in an excess of methanol at 337 K, the reaction rate
was found low so that it could not be measured experꢀ
imentally. Obviously, this was a consequence of cataꢀ
lyst deactivation by methanol, which acts similarly to
water in its considerable excess in the reaction mixture
The rate constants of all reactions of ROH with
t
t
ꢀBuOH on macroporous KUꢀ23 are higher than
those on gel KUꢀ (Table 3). The ratio
k' k'
between rate constants (at the equivaꢀ
2×8
КУ−23П
КУ−2×8
lent concentrations of the catalytically active –SO H
3
groups in both catalysts) varies from 1.30 to 1.74 for
primary alcohols, and it increases on going from ethaꢀ
nol to butanol. For branched and secondary alcohols,
this ratio varies from 2.55 to 2.81.
[
13]. Tables 2 and 3 summarize the rate constants
the reactions of ꢀBuOH with С –С alcohols on KUꢀ
and KUꢀ23, respectively. As can be seen, the reacꢀ
tivity of ROH increases with their molecular weights.
In this case, the dependence of log on the Taft inducꢀ with С –С5 aliphatic alcohols at low degrees of conꢀ
tion constants for linear primary alcohols (ethanol, version, when the amount of released water is small,
ꢀpropanol, ꢀbutanol, and pentanol) on KUꢀ is the KUꢀ23 catalyst is more active than KUꢀ
nearly linear (Fig. 3; correlation coefficient, 0.994). However, in the course of the process, KUꢀ23 more
The values of log for 2ꢀpropanol and 2ꢀmethylꢀ1ꢀ rapidly loses its activity and selectivity because it is
propanol (R = ꢀPr and ꢀBu, respectively) do not lie more sensitive to the action of water [16]. KUꢀ
, on
in a common straight line of log ' = *). In this which the reaction occurs in a surface layer, also
case, the rate constant of a reaction of ꢀBuOH with retains its activity and selectivity at higher degrees of
k' of
t
2
5
2 8
×
Thus, in the etherification reactions of tꢀBuOH
k'
2
σ
*
n
n
2
×
8
2 8.
×
k'
s
i
2 8
×
k
f
t
(
σ
secondary propanol is approximately a half of that of a conversion. This can be explained by the fact that the
reaction with a primary alcohol. In terms of reactivity, released water is more easily removed from the surface
1
3
ꢀmethylpropanol is superior to 1ꢀbutanol, and of KUꢀ
ꢀmethylꢀ1ꢀbutanol (R = ꢀPent) reacts more slowly
2
×
8
than from the pore volume of KUꢀ23.
i
CONCLUSIONS
Table 3. Rate constants of reaction (I) on macroporous
KUꢀ23 sulfo cation exchanger at 347 K
Thus, based on the results of this study, we can
make the following conclusions:
k
' × 10 , L mol s–1
3
–1
R
k'
k'
(1) The temperature dependence of the rate conꢀ
stants of etherification of 2ꢀmethylꢀ2ꢀpropanol with
KUꢀ23P
KUꢀ2×8
Et
Pr
0.60 ± 0.14
3.19 ± 0.17
2.81± 0.11
5.11 ± 0.25
9.99 ± 1.07
5.84 ± 0.51
1.30
С –С5 alcohols on the KUꢀ
2 8 sulfo cation
×
2
1.36
2.55
1.74
2.43
2.81
exchanger obeys the Arrhenius equation (apparent
Ea = 61–96 kJ/mol).
sꢀP
r
(
8
2) The etherification of tertꢀbutanol on the KUꢀ
catalyst does not meet steric hindrances; in this
case, the reaction predominantly occurs on the exterꢀ
nal surface of the ion exchanger.
Bu
2
×
i
ꢀBu
i
ꢀPent
KINETICS AND CATALYSIS Vol. 54
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2013

KINETICS OF THE REACTIONS OF tertꢀBUTANOL
183
' [L mol–1 s–1]
logk
7. Rozhnov, A.M., Safronov, V.V., Alenin, V.I., and
Sharonov, K.G., Zh. Fiz. Khim., 1988, vol. 57, no. 11,
p. 2902.
8. Sharonov, K.G., Rozhnov, A.M., Churkina, A.Yu., and
Karaseva, S.Ya., Zh. Prikl. Khim., 1996, vol. 69, no. 8,
p. 1382.
–
Et
3
3
3
3
3
2
2
2
.9
s
ꢀPr
.7
.5
.3
.1
.9
.7
9
. Bobylev, B.N., Farberov, M.I., Tepenitsina, E.P., Epshꢀ
tein, D.I., and Dormidontova, N.V., Neftekhimiya
1976, vol. 16, no. 2, p. 255.
Pr
,
iꢀBu
Bu
1
0. Farberov, M.I., Bobylev, B.N., and Epshtein, D.I.,
Dokl. Akad. Nauk SSSR, 1976, vol. 266, no. 6, p. 1384.
11. Golovanov, A.A., Pisareva, V.S., Dorokhov, V.S., and
Ukolov, A.I., Izv. Vyssh. Uchebn. Zaved., Khim. Khim.
Tekhnol., 2009, vol. 52, no. 7, p. 6.
Pent
1
1
1
2. Golovanov, A.A., Pisareva, V.S., Khimanych, E.S.,
Pleshchev, M.I., Gracheva, I.A., and Potemkina, E.I.,
Bashkir. Khim. Zh., 2010, vol. 17, no. 3, p. 43.
3. Rozhkov, S.V., Bobylev, B.N., Farberov, M.I., and
Rabotnova, M.I., Kinet. Katal., 1977, vol. 18, no. 6,
p. 1429.
.5
0
.09
0.14
–σ*
0.19
Fig. 3. Correlation between the rate constants of reaction
I) and the Taft induction constants on KUꢀ2×8 at 342 K.
(
4. Rozhkov, S.V., Bobylev, B.N., and Farberov, M.I.,
Kinet. Katal., 1979, vol. 20, no. 3, p. 640.
(
3) Alcohols ROH are arranged in the following 15. Bobylev, B.N., Rozhkov, S.V., Farberov, M.I., and
order according to their reactivity in the etherification
of tertꢀbutanol in the presence of the KUꢀ sulfo
cation exchanger: ethanol < 2ꢀpropanol < 1ꢀpropanol < 16. Golovanov, A.A., Gracheva, I.A., Pisareva, V.S., and
ꢀbutanol < 2ꢀmethylꢀ1ꢀpropanol < 1ꢀpentanol. A
similar order is also observed on KUꢀ23: ethanol <
ꢀpropanol < 1ꢀpropanol < 1ꢀbutanol < 2ꢀmethylꢀ1ꢀ 17. Aiouache, F. and Goto, S., Chem. Eng. Sci., 2003,
propanol. The logarithms of the reaction rate conꢀ
stants of primary alcohols on KUꢀ
related to the Taft induction constants.
Rabotnova, M.I., Osn. Org. Sint. Neftekhim., 1979,
no. 11, p. 24.
2×8
1
Pleshchev, M.I., Izv. Vyssh. Uchebn. Zaved., Khim.
Khim. Tekhnol., 2010, vol. 53, no. 11, p. 16.
2
vol. 58, no. 10, p. 2065.
2
×
8
are linearly 18. Golovanov, A.A., Pisareva, V.S., and Pleshchev, M.I.,
Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol.,
010, vol. 53, no. 3, p. 44.
2
1
9. Polyanskii, N.G., Gorbunov, G.V., and Polyanskaya, N.L.,
Metody issledovaniya ionitov (Ion Exchangers: Methods
of Study), Moscow: Khimiya, 1976, p. 82.
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