Efficiency of sulfonic cation-exchange resins used in para-tert-butylphenol production: A comparison based on the kinetics of transalkylation in the phenol-tert-butylphenols system

Article abstract of DOI:10.1134/S0023158414060147

The kinetics of transalkylation in the phenol-tert-butylphenols system in the presence of Amberlyst 36 Dry sulfonic cation-exchange resin has been investigated at 353-403 K in the tert-Bu/Ar = 0.10-0.55 mol/mol range. Kinetic characteristics of the o-tert-butylphenol + phenol ai p-tert-butylphenol + phenol (I) and 2,4-di-tert-butylphenol + phenol ai 2p-tert-butylphenol (II) reactions have been determined. The chemical equilibrium in the presence of Amberlyst 36 Dry is reached much sooner than in the presence of KU-23 10/60, a cation-exchange resin used at present. On passing from Amberlyst 36 Dry to KU-23 10/60, the preexponential factor for reaction (I) increases by a factor of 10 and that for reaction (II) increases by a factor of 2000. Thermodynamic characteristics of reaction (I) between 353 and 523 K have been calculated from experimental data and data available from the literature. The thermodynamic characteristics of reaction (II) have been determined experimentally. The enthalpy and entropy of reaction (I) are equal to those of reaction (II). The difference between the equilibrium constants of these reactions is explained. It is recommended that Amberlyst 36 Dry, which proved more efficient than KU-23 10/60, be used in the industrial production of p-tert-butylphenol.

Full text of DOI:10.1134/S0023158414060147

ISSN 0023ꢀ1584, Kinetics and Catalysis, 2014, Vol. 55, No. 6, pp. 705–711. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © I.O. Voronin, T.N. Nesterova, B.S. Strelchik, E.A. Zhuravskii, 2014, published in Kinetika i Kataliz, 2014, Vol. 55, No. 6, pp. 723–729.
Efficiency of Sulfonic CationꢀExchange Resins Used
in paraꢀtertꢀButylphenol Production:
A Comparison Based on the Kinetics of Transalkylation
in the Phenol–tertꢀButylphenols System
,
b
I. O. Voronina , *, T. N. Nesterovaa, B. S. Strelchikb, and E. A. Zhuravskiia
a Samara State Technical University, Samara, 443030 Russia
b SamaraNefteOrgSintez, Novokuibyshevsk, Samara oblast, 446214 Russia
* eꢀmail: radvamnarod@mail.ru
Received January 14, 2014
Abstract—The kinetics of transalkylation in the phenol–tertꢀbutylphenols system in the presence of
Amberlyst 36 Dry sulfonic cationꢀexchange resin has been investigated at 353–403 K in the tertꢀBu/Ar =
0.10–0.55 mol/mol range. Kinetic characteristics of the
oꢀtertꢀbutylphenol + phenol
pꢀtertꢀbutylphenol +
ꢀ
phenol (I) and 2,4ꢀdiꢀtertꢀbutylphenol + phenol pꢀtertꢀbutylphenol (II) reactions have been determined.
2
ꢀ
The chemical equilibrium in the presence of Amberlyst 36 Dry is reached much sooner than in the presence
of KUꢀ23 10/60, a cationꢀexchange resin used at present. On passing from Amberlyst 36 Dry to KUꢀ23
10/60, the preexponential factor for reaction (I) increases by a factor of 10 and that for reaction (II) increases
by a factor of 2000. Thermodynamic characteristics of reaction (I) between 353 and 523 K have been calcuꢀ
lated from experimental data and data available from the literature. The thermodynamic characteristics of
reaction (II) have been determined experimentally. The enthalpy and entropy of reaction (I) are equal to
those of reaction (II). The difference between the equilibrium constants of these reactions is explained. It is
recommended that Amberlyst 36 Dry, which proved more efficient than KUꢀ23 10/60, be used in the indusꢀ
trial production of pꢀtertꢀbutylphenol.
DOI: 10.1134/S0023158414060147
Consumers are imposing increasingly high requireꢀ with this process appeared in 1981–1990. It is in this
ments on products of bulk organic and petrochemical period that the domestic PTBP synthesis technology
syntheses in the context of the presentꢀday severe based on phenol alkylation with isobutylene was develꢀ
competition conditions. Provided that the original oped and commercialized.
technologies have been explored well, there are only a
few ways of improving the quality of the products withꢀ
out reducing the process efficiency. Such technologies
At the contemporary stage of technological develꢀ
opment, a wide variety of nextꢀgeneration sulfonic
cationꢀexchange resin possessing better catalytic and
mechanical properties have appeared on the market
[16, 17]. However, there is no sufficient theoretical
base for passing to other catalytic systems.
The purpose of this work is to find more active and
more selective catalysts through kinetic and thermoꢀ
dynamic experiments.
At present, there is a broad assortment of ionꢀ
exchange resins, and many of them are considered as
catalysts for particular processes. Amberlyst 36 Dry
(Aꢀ36 Dry) is intended for phenol alkylation. Like
KUꢀ23 and KUꢀ2ꢀ8, Aꢀ36 Dry is supplied in active,
hydrogen form. KUꢀ23 and KUꢀ2ꢀ8 have a larger speꢀ
cific pore volume and a wider particle size distribution.
include the synthesis of paraꢀtertꢀbutylphenol (PTBP)
by the catalytic alkylation of phenol with isobutylene
followed by transalkylation of the reaction mixture for
raising the yield of the target product. The industrialꢀ
scale production of PTBP was started in 1978 at
Novokuibyshevsk Petrochemical Plant (now UK
“SamaraNefteOrgSintez” holding). The results of
research in this field [1] had led the company in 1986
to replace the gel catalyst KUꢀ2ꢀ8 with the
macroporous sulfonic cationꢀexchange resin KUꢀ23.
The process is carried out under nearꢀequilibrium
conditions, with liquid isobutylene fed into the
reactor.
At its refinement stage, this technology was Compared to these resins, Aꢀ36 Dry has a higher static
changed to make the process more efficient. This issue exchange capacity (Table 1), which implies a higher
is still significant, and all stages of the process are being sulfo group concentration. The main source of the
studied in detail [1–15]. Most publications dealing high activity of Aꢀ36 Dry in the process considered is
705

706
Table 1. Physicochemical properties of cation cationꢀexchange resin
Property KUꢀ2ꢀ8
VORONIN et al.
KUꢀ23 10/60
Amberlyst 36 Dry
Particle size:
– mesh range, mm
– volume fraction of working fraction, %, no less than
0.4–1.25
96
0.315–1.250
95
0.3–1.18
–
Water content, wt %
48–58
2.7
50–70
3.7
≤
1.65
Specific pore volume in the Hꢀform, cm3/g, no less than
Specific surface area, m2/g
0.2
33
–
5–25
4.5–4.6
93
Total EC, mol/cm3 (mgꢀequiv/cm3), no less than
Osmotic stability, %, no less than
* EC = exchange capacity.
4.5–4.6
96
≥
5.40
–
not associated with the properties of the cationꢀ reaction was dried by vacuum distillation. The residual
exchange resin and has not been divulged by the manꢀ water content of phenol used in the experiments was
ufacturer.
0.08 wt %.
The conversion rate of the reaction components
was measured both in preꢀprepared mixtures introꢀ
duced into the reaction zone and in mixtures prepared
in the reactor. The mixture components were phenol,
EXPERIMENTAL
To determine and compare catalytic activities, we
used the macroporous sulfonic cationꢀexchange resin
Aꢀ36 Dry. Kinetic data on TBP conversion over the
KUꢀ23 and KUꢀ2ꢀ8 cation exchangers were taken
from an earlier work [1].
The kinetic study of the totality of reactions occurꢀ
ring in the phenol–tertꢀbutylphenols system was carꢀ
ried out by the static method in a stirred reactor. Isoꢀ
thermality of the process was ensured by supplying a
temperatureꢀcontrolled heat carrier into the reactor
jacket and by continuous stirring of the reaction mixꢀ
ture.
It was experimentally established that the external
diffusion limitations are eliminated when the rotaꢀ
tional speed of the blade stirrer is 850 rpm or above.
For this reason, in the subsequent experiments the
rotational speed of the stirrer was set to be 850 rpm.
PTBP, orthoꢀtertꢀbutylphenol (OTBP), 2,4ꢀdiꢀtertꢀ
butylphenol (2,4ꢀdiTBP), and, in some experiments,
2,6ꢀdiꢀtertꢀbutylphenol (2,6ꢀdiTBP) and 2,4,6ꢀtriꢀ
tertꢀbutylphenol (2,4,6ꢀtriTBP). At isobutylene : pheꢀ
nol = 0.25 and 353–383 K, 2,6ꢀdiTBP and 2,4,6ꢀtriTBP,
which are sterically hindered compounds, turned
completely into monoꢀTBP and 2,4ꢀdiTBP at a high
rate (which was one order higher than the rate of the
other reactions). The initial point of a kinetic experiꢀ
ment was taken to be the instant the isobutylene supply
was shut off or the introduction of the artificial mixꢀ
ture. Irrespective of the procedure used, the results of
the experiment were absolutely the same. Reaction
mixture samples did not need to be pretreated before
being analyzed.
Kinetic experiments were performed with the same
catalyst batch, which was 8–12% of the weight of the
reaction mixture. The density of the reaction mixture
was determined using the chemical modeling program
HYSYS.Process (version v2.2).
Cationꢀexchange resins (like all ion exchangers)
swell in organic solvents [8]. The catalytic activity of
sulfonic cationꢀexchange resins varies as they swell
and their spatial structure stabilize. The preliminary
swelling of cationꢀexchange resins in phenol at the
measurement temperature for 1 h helped avoid the difꢀ
ficulties associated with the instability of catalyst operꢀ
ation at the early stages of the process.
The reaction mixture was analyzed by GLC on two
chromatographs: Tsvetꢀ800 (Tsvet Co., Russia, 3ꢀmꢀ
long packed column, Chromaton N + 3% OVꢀ17 +
The Aꢀ36 Dry catalyst was prepared by drying the 1% NPGS stationary phase, injection port temperaꢀ
cationꢀexchange resins at 110 to constant weight ture of 623 K, oven temperature of 553 K, helium as
within 0.01% and by washing it with a twice larger volꢀ the carrier gas, inlet pressure of 3 atm) and Kristallꢀ
ume of phenol (whose water content was determined 2000 (Khromatek Co., Russia, 50 m 0.25 mm quartz
°
С
×
by GLC). The residual water content of the catalyst capillary column, grafted SEꢀ50 stationary phase,
was 0.80 0.05 wt %. Phenol to be introduced into the injection port temperature of 543 K, detector temperꢀ
KINETICS AND CATALYSIS Vol. 55
No. 6 2014

EFFICIENCY OF SULFONIC CATIONꢀEXCHANGE RESINS
ln
707
K
1
Mole fraction
4.2
4.0
3.8
3.6
3.4
3.2
3.0
2.8
2.6
2.4
0.8
1
0.7
0.6
0.5
0.4
0.3
0.2
0.1
2
–
–
–
–
Equilibrium [5]
Kinetics our data
(
)
Kinetics [1]
4
3
Approximation
0
5
10
15
20
25
30
35
1.8
2.0
2.2
2.4
2.6
2.8
3.0
, K–1
Time, min
1000/
T
Fig. 1. Results of a typical kinetic experiment: (
) PTBP, ( ) OTBP, and ( ) 2,4ꢀdiTBP.
1) phenol,
Fig. 2. Results of investigation of reaction (I) equilibrium.
(2
3
4
(Table 3), which were used to calculate the enthalpy
and entropy of the reaction.
ature of 473 K, helium as the carrier gas, inlet pressure
of 3 atm, 1 : 15 flow division).
The enthalpy and entropy of the liquidꢀphase reacꢀ
tions (I) and (II) are pairwise equal within the error of
their determination (Table 3). The equilibrium conꢀ
stants of the reactions, which are more sensitive therꢀ
modynamic characteristics, differ significantly
(Table 3, Fig. 3). The data plotted in Fig. 3 suggest that
difference disappears entirely on passing from the liqꢀ
uidꢀphase reactions to the gasꢀphase ones. (The calcuꢀ
lation was carried out under the assumption that
Raoult’s law is valid using vapor pressures from [15,
RESULTS AND DISCUSSION
The kinetic experiments were performed at 353,
373, 383, 393, and 403 K. The molar ratio of tertꢀbutyl
groups to aromatic nuclei was varied in the 0.10–0.55
range, as in the real industrial processes. Figure 1 preꢀ
sents typical experimental data illustrating the time
variation of the concentration of each component and
the entry of the reaction into the thermodynamically
controlled area.
pp. 336–338].) Thus, the fact that the
values are
К2
larger than the values is due to intermolecular, not
К1
Between 373 and 403 K at all reactant ratios, the
system reached the equilibrium and contained only
four components: phenol, OTBP, PTBP, and 2,4ꢀ
diTBP. The rank of the stoichiometric matrix for this
reaction is 2. Therefore, for describing the equilibrium
in this system (as a whole), its is necessary and suffiꢀ
cient to know equilibrium constants for two indepenꢀ
dent reactions. We chose the following ones:
intramolecular factors. This information is significant
for predicting the thermodynamic properties of tert
ꢀ
alkylphenols.
The results of the study of the equilibrium (Table 3)
provided a basis for processing the kinetic data
obtained by us for the following system of reactions:
k1
←⎯⎯⎯
⎯⎯⎯→
OTBP phenol
PTBP + phenol, (1; –1)
+
k−1
OTBP
+
phenol
PTBP + phenol
,
(I)
ꢀ
k2
←⎯⎯⎯
diTBP phenol
PTBP PTBP
.
(II)
2,4ꢀ
+
ꢀ
+
⎯⎯⎯→
2,4ꢀdiTBP
2,4ꢀdiTBP
2,4ꢀdiTBP
+
+
+
phenol
phenol
phenol
PTBP
OTBP
PTBP
+
+
+
PTBP, (2; –2)
OTBP, (3; –3)
OTBP, (4; –4)
k−2
The amounts of experimental data available on
these reactions are different. The liquidꢀphase equilibꢀ
rium in reaction (I) has been comprehensively studied
(Table 2). The information that was provided by the
taskꢀoriented investigation of this equilibrium and was
systematized by Nesterov [5], the data calculated by us
in a similar study, and the results of the kinetic experiꢀ
ment carried out by Rempel [1] are in good agreement
(Fig. 2). The simultaneous processing of all of the data
(Table 2) yielded linear approximation coefficients
k3
⎯⎯⎯→
←⎯⎯⎯
k−3
k4
⎯⎯⎯→
←⎯⎯⎯
k−4
2,4ꢀdiTBP
+
OTBP
PTBP.
(5; –5)
k5
←⎯⎯⎯
⎯⎯⎯→
2,4ꢀdiTBP
+
k−5
KINETICS AND CATALYSIS Vol. 55
No. 6 2014

708
VORONIN et al.
Table 2. Chemical equilibrium data for reactions (I) and (II)
Ki
ortho
Source
Ki
Source
n
*
m
*
n
*
m*
T
, K
T, K
ꢀ
tertꢀButylphenol
para
403
413
417
ꢀtertꢀButylphenol (I)
kinetics
[1] (
12
9
2
71.4 1.1 [5]
69.3 2.9
90
30
3
18
6
34.9
equilibrium
)
(
)
353
373
''
''
1
3
31.9
This work
This work
15
19
3
55.7 3.1
1
30.1 0.5
29.0 0.4 [5] (
28.6 0.5
29.3 1.0
equilibrium
)
3
49.1 0.5 [5]
49.3 1.1
57
35
15
31
40
18
10
46
31
9
8
(equilibrium)
''
''
''
''
''
''
''
''
''
''
''
1
3
423
''
''
16
18
14
25
7
3
51.9 1.5
3
2
50.6 1.9
43
6
24.7 0.7
20.1 0.2
20.2 0.3
20.3 0.9
13.9 0.5
14.1 0.8
15.0 0.6
12.3 0.3
This work
[1]
3
46.8 2.3
42.2
383
393
5
453
483
523
3
kinetics
(
)
This work
[1]
1
44.9 1.1
38.3
2
50
25
44
19
11
19
10
3
7
kinetics
(
)
This work
38.8 0.4
5
6
36.3 0.3 [5]
36.3 0.4
2
equilibrium
(
)
''
403
3
29
5
''
''
2
36.8 0.4
''
16
3
12.1 0.7
2
33.1 0.9
2,4ꢀdiTBP + phenol
PTBP+ PTBP (II)
This work
This work
373
383
393
13
14
8
3
3
1
88.7 5.2
73.3 3.4
62.5 5.2
403
417
27
2
3
59.0 1.1
46.7
''
''
''
''
1
*
n
is the number of successful measurements of the equilibrium constant;
m is the number of significantly different series of determiꢀ
nations of and
K
K .
2
1
Table 3. Thermodynamic characteristics of liquidꢀphase reactions (I) and (II)
Coefficients of the equation lnK = a + 1000b/T
Reacꢀ
tion
Δ
rH0
kJ/mol
(
T
mean),
Δ
rS0
(Tmean),
T
mean, K
J mol–1 K–1
a
b
(I)
–1.3704
–1.3380
1.9865
2.1647
417
394
–16.5 0.8
–18.0 1.0
0
–11.4 1.8
–11.1 2.5
(II)
Tmean is the mean experimental temperature,
0 is the enthalpy of reaction, and
is the entropy of reaction.
S
r
Δ
H
Δ
r
KINETICS AND CATALYSIS Vol. 55
No. 6 2014

EFFICIENCY OF SULFONIC CATIONꢀEXCHANGE RESINS
709
The kinetic model of the process is given by the followꢀ
ing system of differential equations for the key compoꢀ
nents chosen by us—OTBP and 2,4ꢀdiTBP:
ln
K
– K1
4.5
4.0
3.5
3.0
2.5
2.0
– Kp1
d[
OTBP
]/d
τ
= k–1
[
][
]
⎯
k1[ ][ ]
OTBP phenol
phenol
PTBP
– K2
+ 2k3[2,4ꢀ
][
]
diTBP phenol
– Kp2
–
k–
[
] + k4[2,4ꢀ
2
][
]
OTBP
diTBP phenol
3
–
k–4
[
][
] – k5[2,4ꢀ ][
diTBP PTBP
]
OTBP
diTBP OTBP
][ ],
PTBP
5
+
k– [2,4ꢀ
d[2,4ꢀdiTBP]/d
τ
= k
–2[PTBP]2
2
– k2[2,4ꢀ ][
] + k–3
[
]
OTBP
diTBP phenol
–
k3[2,4ꢀ
][ ] + k–4
[
][
PTBP
]
diTBP phenol
– k4[2,4ꢀ
OTBP
][
].
diTBP phenol
The experimental conditions and the data array
used in the calculation of mean rate constants are
listed in Table 4.
The effective rate constants of individual reactions
were calculated by the differential method from the
entire experimental data array and from the equilibꢀ
rium constants of the reactions (Table 3). The optimiꢀ
zation criterion was
1.8
2.0
2.2
2.4
2.6
2.8
3.0
1000/T
, K–1
Fig. 3. Equilibrium constants for reactions (I) and (II) in
the liquid phase (Ki) and in the gas phase ( ).
Kpi
2
dci
dci
⎛⎛
⎞
⎛
⎞
⎞
Σn ꢀꢀꢀꢀꢀ
– ꢀꢀꢀꢀꢀ
= 0,
⎠
⎝⎝
⎠
⎝
⎠
dt
dt
calc
(2) The preexponential factors for the two reactions
are different and decrease in the following order: Aꢀ36
Dry > KUꢀ23 10/60 > KUꢀ2ꢀ8.
The data of this study suggest that the sulfonic catꢀ
ionꢀexchange resin KUꢀ23 10/60 is less active than
Amberlyst 36 Dry. In addition, Aꢀ36 Dry is characterꢀ
ized by a narrower particle size distribution (Table 1),
according to the manufacturer’s data, and is thermally
exp
where n is the number of measurements.
It was established that, in the isobutylene : phenol =
0.10–0.55 mol/mol range, only the rate constants of
reversible reactions (I) and (II) are significant. The k1
and k2 obtained by us for the Aꢀ36 Dry sulfonic cationꢀ
exchange resin are presented in Table 4, where they are
compared with the constants obtained by Rempel [1]
for the same reactions catalyzed by KUꢀ2ꢀ8 and KUꢀ
23 10/60.
With Aꢀ36 Dry, the rate constants of these reactions
are larger even at lower temperatures. Thus, this cataꢀ
lyst makes it possible to reach the equilibrium much
sooner. The calculation of activation parameters for
reactions (I) and (II) (Table 5) confirmed this finding.
more stable (its upper operating limit is 150
°С against
130 for > KUꢀ23 10/60). The deactivation of the
°
С
sulfonic cationꢀexchange resin is mainly due to the
thermally induced washout of sulfo groups from their
surface and also due to mechanical destruction. Based
on the experience in the industrial operation of KUꢀ23
10/60 resin and on the temperature range in which it is
efficient (80–130°С), it can be expected that
Amberlyst 36 Dry will have a longer service life.
Rempel [1] put forward the hypothesis that the
activation energy Ea of each of these reactions is indeꢀ
pendent of the cationꢀexchange resin brand and the
effect of the specific surface area of the catalyst can
Replacing the KUꢀ23 10/60 cation cationꢀ
exchange resin with Amberlyst 36 Dry in the industrial
process will increase the product yield per unit volume
of the reaction zone. In addition, changing to Aꢀ36
Dry will reduce the consumption of washing phenol in
the preꢀoperation treatment of the cation cationꢀ
exchange resin, since the moisture content of asꢀ
received Aꢀ36 Dry does not exceed 1.65 wt %,
while that of KUꢀ23 10/60 is 50–70 wt %.
have an effect only on the preexponential factor ki,
.
0
Here, the mechanism of catalysis should not change
from one catalyst to another and the process should be
controlled by external kinetics. These conditions were
satisfied in our study, enabling us to use this hypothesis
in the processing of experimental data.
The results presented in Table 5 demonstrate the
following:
Thus, based on experimental data and information
available from the literature, we determined thermoꢀ
dynamic characteristics of the independent reactions
describing the equilibrium in the system consisting of
(1) The activation energies of reactions (I) and (II)
occurring over Aꢀ36 Dry are practically equal to the Ea
values calculated by simultaneous processing (within
the above hypothesis) of the entire data array for the
three catalysts (Aꢀ36 Dry, KUꢀ2ꢀ8, and KUꢀ23
10/60).
phenol,
2,4ꢀdiꢀtertꢀbutylphenol.
The kinetics of transalkylation of the tertꢀbutylpheꢀ
nols in the presence of the sulfonic cation exchange
pꢀtertꢀbutylphenol, oꢀtertꢀbutylphenol, and
-
KINETICS AND CATALYSIS Vol. 55
No. 6 2014

710
VORONIN et al.
Table 4. Results of the kinetic study using the mean values of rate constants at different temperatures
k1
×
100**
k2
×
100**
Sulfonic cationꢀexꢀ
change resin
Experimental conditions
*
T
, K
L2 mol–1 kg–1 min–1
tertꢀBu/Ar = 0.25–0.33,
cat = 9–10.5%,
= 47, = 3
353
373
383
393
403
5.358 0.053
15.405 0.151
28.955 0.251
40.604 0.732
69.090 0.053
6.731 0.118
14.658 0.147
30.013 0.176
30.745 0.535
62.156 0.051
n
m
tertꢀBu/Ar = 0.27–0.34,
cat = 9–9.7%,
= 41, = 3
n
m
tertꢀBu/Ar = 0.1–0.55,
cat = 7.7–12.4%,
= 80, = 8
Amberlyst 36 Dry
(this work)
n
m
tertꢀBu/Ar = 0.26–0.32,
cat= 8.2%,
= 10, = 1
n
m
tertꢀBu/Ar = 0.39–0.54,
cat = 8.5–9.1%,
= 49, = 3
n
m
tertꢀBu/Ar = 0.5,
= 75, = 3
393
403
413
1.470 0.018
3.738 0.036
8.700 0.060
0.009 0.000
0.015 0.000
0.029 0.000
n
m
tertꢀBu/Ar = 0.25–0.7,
= 225, = 9
KUꢀ2ꢀ8 [1]
n
m
tertꢀBu/Ar = 0.5,
= 75, = 3
n
m
tertꢀBu/Ar = 0.46–0.51,
= 75, = 3
383
393
403
2.034 0.024
5.424 0.048
13.860 0.120
0.018 0.000
0.032 0.000
0.055 0.000
n
m
tertꢀBu/Ar = 0.5,
= 75, = 3
KUꢀ23 10/60 [1]
n
m
tertꢀBu/Ar = 0.5,
= 75, = 3
n
m
*
tertꢀBu/Ar is the molar ratio of tertꢀbutyl groups to phenol nuclei in the reaction mixture, Cat is the amount of catalyst per unit weight
of the reaction mixture, is the number of measurements, and is the number of experimental series.
n
m
** Mean value of the rate constant at each temperature point examined.
Table 5. Activation parameters of reactions (I) and (II)
Reaction (I)
Catalyst
Reaction (II)
a, kJ/mol
E
a, kJ/mol
lnki,0
E
lnki,0
Amberlyst 36 Dry (separate)
60.9 5.0
64.4
17.8 1.6
53.4 6.2
15.4 1.8
Amberlyst 36 Dry
KUꢀ23 10/60
KUꢀ2ꢀ8
18.9
16.8
15.8
15.5
7.8
51.8
6.6
resin Amberlyst 36 Dry was studied. It was demonꢀ
strated that replacing KUꢀ23 10/60 with Amberlyst 36
Dry, a more efficient catalyst, would increase the tarꢀ
get product yield per unit volume of the reaction zone,
extend the service life of the catalyst, widen the allowꢀ
able process temperature range by lowering the initial
synthesis temperature and raising the final one, and
reduce the consumption of washing phenol at the catꢀ
ionꢀexchange resin pretreatment stage.
It was observed experimentally that the equilibrium
in the system involving Amberlyst 36 Dry is established
much sooner than in the case of KUꢀ23 10/60 or
KUꢀ2ꢀ8. Under the assumption that the activation
energy of the reaction is invariable, it was demonꢀ
strated that, on passing from Amberlyst 36 Dry to
KUꢀ2ꢀ8 and KUꢀ23 10/60, the preexponential factor
of reaction (I) increases by a factor of 20 and 10,
KINETICS AND CATALYSIS Vol. 55
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EFFICIENCY OF SULFONIC CATIONꢀEXCHANGE RESINS
711
9. Nesterova, T.N., Verevkin, S.P., Malova, T.N., and
respectively, and that of reaction (II) increases by a
factor of 7000 and 2000.
Pilshchikov, V.A., Zh. Prikl. Khim., 1985, no. 4, p. 827.
10. Nesterova, T.N., Malova, T.N., Pimerzin, A.A., and
Merdzhanov, V.R., in Termodinamika organicheskikh
soedinenii (Thermodynamics of Organic Compounds),
Gor’kii: Gor’k. Gos. Univ., 1986, p. 38.
11. Verevkin, S.P., Nesterova, T.N., Rempel, R.D., and
Shashkin, N.P., Zh. Prikl. Khim., 1987, no. 2, p. 373.
12. Nazmutdinov, A.G., Nesterova, T.N., and
ACKNOWLEDGMENTS
This study was supported by the Ministry of Educaꢀ
tion and Science of the Russian Federation in the
framework of the base part of the governmental assignꢀ
ment for Samara State Technical University (project
code 1708).
Rempel, R.D., Zh. Prikl. Khim., 1988, no. 8, p. 1937.
13. Verevkin, S.P., Nesterova, T.N., and Rempel, R.D., Zh.
Prikl. Khim., 1990, no. 8, p. 1771.
14. Nazmutdinov, A.G., Tsvetkov, V.S., Rozhnov, A.M.,
and Roshchupkina, I.Yu., J. Chem. Thermodyn., 1990,
vol. 22, p. 365.
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Translated by D. Zvukov
Zh. Prikl. Khim., 1981, no. 11, p. 2592.
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No. 6 2014