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Applied Catalysis A: General: Mehmet R. Altıokka, Elif O Des
Applied Catalysis A: General: Mehmet R. Altıokka, Elif O Des
A R T I C L E I N F O A B S T R A C T
Article history: The kinetics of esterification of acrylic acid with propylene glycol has been studied in the presence of
Received 8 January 2009 Amberlyst-15 as a heterogeneous catalyst. The reaction was realized in a batch reactor at different
Received in revised form 12 March 2009 temperatures and initial reactant mol ratios. The simultaneous dimerization/polymerization of acrylic
Accepted 15 April 2009
acid and products, in addition to the reversible esterification reaction, was proposed as the reaction
Available online 23 April 2009
mechanism. Kinetic equations corresponding to the reaction mechanism have also been developed.
Temperature dependence of the reaction rates and activation energies was determined.
Keywords:
ß 2009 Elsevier B.V. All rights reserved.
Esterification
Hydroxypropyl acrylate
Heterogeneous catalysis
Kinetic modeling
0926-860X/$ – see front matter ß 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2009.04.028
116 M.R. Altıokka, E. Ödeş / Applied Catalysis A: General 362 (2009) 115–120
was added and the reactor contents were mixed well. After a
Nomenclature
steady value of desired temperature was attained, the second
reactant was added and this was taken as zero time for a run. One
C concentration (mol/L) milliliters of the liquid sample was withdrawn from the reactor at
X conversion regular intervals for analysis and immediately transferred to a
t time (min) crucible in an ice bath in order to ensure that no further reaction
r reaction rate (mol/L min) took place.
CsHPA cesium salt of phosphorous tungstic acid
T absolute temperature (K) 2.4. Analysis
k reaction rate constant (L/mol min)
The samples were analyzed with a gas chromatograph (HP 5890
K equilibrium constant
Series II) equipped with a flame ionization detector (FID) and a
E activation energy (kJ/mol)
capillary column (TRB-FFAP). The column oven was held at 313 K
for 3 min, ramped at 10 K/min to 333 K held for 3 min, followed by
Subscripts 10 K/min ramp-up to 433 K, held for 4 min and then ramped at
A, P, T and W acrylic acid, propylene glycol, hydroxypropyl 10 K/min to 453 K, held for 2 min. The concentration of water in
acrylate and water, respectively the reaction mixture was measured by Karl Fischer titration
(Metrohm KF-784). After verifying that the measured water
content corresponds to the calculated values based on stoichio-
treated clay, Engelhard F-24, was an effective catalyst for the metric equation, the amount of water was determined from
transesterification reaction at moderate temperatures, tetrabutyl stoichiometric mass balance equation.
titanates as catalyst increase cyclohexanol selectivity at higher
temperatures. It was also shown that transesterification reaction 3. Results and discussion
follows LHHW mechanism in the presence of Engelhard F-24 [1].
In another study it has been reported that heteropoly acids, The effects of parameters, such as catalyst type and loading,
such as phosphorous tungstic acid, show higher activities than the temperature and reactant mol ratio, on the reaction rate were
conventional acids in the esterification of methacrylic acid with studied.
tripropylene glycol [17]. Swelling effect of the catalyst was neglected since preliminary
The role of Mn and Fe as promoters of sulfated zirconia has been experiment showed that the swelling process reaches the
studied in the reaction of acrylic acid esterification by 1-butene to equilibrium in a few minutes that the reactions were realized in
sec-butyl acrylate at 343 K. It was reported that Mn and Fe did not the presence of the reasonably stable catalyst. Therefore, the
improve the catalytic activity and selectivity to sec-butyl acrylate proposed model in this work comprises the effect of catalyst
compared with Amberlite resins or sulfuric acid but they strongly swelling.
resist deactivation [18].
In the present work, Amberlyst-15 and Amberlyst-36 and 3.1. Catalyst selection
cesium salt of phosphorous tungstic acid were used as the
heterogeneous catalysts for the esterification of acrylic acid with In the experiments, two types of ion exchange resins
propylene glycol. The best catalyst among them was to be (Amberlyst-15 and Amberlyst-36) as well as cesium salt of
determined in point of activity and selectivity towards hydro- phosphorous tungstic acid exhibiting self-inhibiting effect for
xypropyl acrylate. Thereafter, the kinetic study of esterification polymerization [16], have been tested as the heterogeneous
was to be studied at the present of the selected catalysts among the catalysts. Experiments were carried out at 353 K and reactant mol
catalysts tested. ratio of 1/1 with the same amount of catalyst and inhibitor. Results
are given in Table 2. As seen from Table 2 that Amberlyst-36
2. Experimental accelerates the reaction rate most. But its product selectivity is
considerably lower than that of Amberlyst-15 at the same
2.1. Materials conversion level of 0.45. On the other hand, although its selectivity
is very high (100%), the activity of cesium salt of phosphorous
Acrylic acid (>99.5%) and propylene glycol (>99%) were tungstic acid is very low compared to that of the others and it
obtained from Acros. Toluene, as a solvent, was supplied by should also be noticed that its selectivity is given at very low
Sigma–Aldrich. Properties of catalysts used in this study are given conversion of 0.04. It is believed that this high selectivity cannot be
in Table 1. The catalysts were dried at 80 8C for overnight prior to sustained in entire range of conversion. Therefore Amberlyst-15
the experiment. Phenothiazine used as polymerization inhibitor was chosen as a heterogeneous catalyst in this study.
was obtained from Fluka. Effect of inhibitor, phenothizine, loading was also studied in the
presence of 0.1, 0.3 and 0.5 (wt%) in the reaction mixture. The best
2.2. Equipments ratio was found to be 0.3 (wt%). This ratio was also proposed in
literature [12–14].
The reactor consisted of a two-necked spherical Pyrex flask of
250 ml capacity fitted with a spiral coil condenser and a sample 3.2. Effect of catalyst loading
device. The temperature was controlled within 0.1 K by circulat-
ing water from a thermostat into the water jacket of the reactor. The Experiments were carried out in the presence of 3.11, 5.06 and
reaction mixture was magnetically stirred at about 600 rpm. 8.46 wt% of Amberlyst-15 on dry basis keeping the other
parameters constant. At the conversion levels less than 10% the
2.3. Experimental procedure initial reaction rate can be safely calculated by using Eq. (1):
Table 1
Properties of catalysts reported by manufacturer.
Manufacturer Rohm & Haas Co. Rohm & Haas Co. Nippon Organic Colour
& Chemical Company
Matrix Styrene-divinylbenzene Styrene-divinylbenzene –
(macroreticular) (macroreticular)
Standard ionic form H+ H+ –
Surface area (m2/g) 50a 33 116a
% Moisture 48 55 –
Particle size (mm) 0.23–0.6 0.6–0.85 –
Cation exchange capacity (mmol/g) 4.7 5.4 0.15a
Maximum operating temperature (K) 393 423 –
a
Ref. [16].
Table 2
Effect of catalyst type on the reaction rate and product selectivity at 353 K and in the presence of 0.3 (wt%) inhibitor.
C X
Catalyst Catalyst Conversion Initial Conversion r AðavÞ ¼ A0t A Selectivity
loading (wt%) time (min) concentration (M) (mol/L min 103)
CA0 CP0
a
CsHPA 4.73 180 3.3 2.9 0.04 0.736 1.00
Amb–36 5.57 240 2.7 2.2 0.45 5.047 0.494
Amb–15 5.54 420 2.8 2.3 0.45 3.003 0.736
a
Inhibitor is not used since it has self-inhibiting effect [16].
A plot of the reaction rate, calculated from Eq. (1), vs. catalyst 3.3. Effect of initial concentration
loading is given in Fig. 1. As seen in Fig. 1, the reaction rate
increases linearly, as expected, with catalyst loading since the Initial reaction rate was determined by altering the concentra-
active surface area is proportional to the amount of catalyst. tion of the component under investigation while keeping those of
Intersection of the line with ordinate will give the uncatalyzed the others constant. The results are shown in Figs. 2–5. The
reaction rate at given parameters. The mathematical expression ordinate values of these figures were obtained from Eq. (1) by using
relating the initial reaction rate to the catalyst loading can be the experimental data. It is evident from these figures that all
derived from Fig. 1 as follows: reactants and products are adsorbed on the catalyst since the
initial reaction rate is becoming nearly independent of the
r A0 ¼ 0:0002 þ 0:0004ð% wtÞ mol=L:min (2) concentrations as their corresponding values increase [19].
However, the initial reaction rate, as seen in Figs. 2 and 4, is not
where (wt%) is the weight percent of the catalyst on dry basis in the completely independent of the concentrations of acrylic acid and
reaction mixture. It should also be kept in mind that Eq. (2) is valid product. This is attributed to their dimerization/polymerization
only at the given parameters of 0.3 (wt%) inhibitor, 1/1 reactant reaction.
mol ratio and 353 K at which the experiments were performed.
However, it does not alter the conclusion that the general reaction 3.4. Kinetic modeling
rate increases linearly with the catalyst loading.
As seen in Figs. 2–5, reaction rate is highly temperature
sensitive. It is almost doubling in every temperature rising of 10 K.
Therefore, it is reasonable to accept that the overall reaction is
controlled by the surface reaction since internal and external
Fig. 1. Effect of catalyst loading on the reaction rate at 353 K, 0.3 (wt%) inhibitor, and Fig. 2. Effect of acrylic acid concentration on the initial reaction rate (CP0 = 0.83 mol/
1/1 reactant mol ratio. L, 5 (wt%) catalyst on dry basis, and 0.3 (wt%) inhibitor).
118 M.R. Altıokka, E. Ödeş / Applied Catalysis A: General 362 (2009) 115–120
kðC A C P ðC T C W =KÞÞ
r 00A ¼ (4)
ð1 þ K A C A þ K P C P þ K T C T þ K W C W þ K U C U Þ2
k3
2A ) dimer (5b)
k4
2T ) dimer (5c)
ai ¼ g i c i (7)
Table 3
The average values of rate constant with 95% confidence interval at different temperatures (5 (wt%) catalyst on dry basis, and 0.3 (wt%) inhibitor).
T (K) k1 (104 L/mol min) k2 (104 L/mol min) k3 (104 L/mol min) k4 (104 L/mol min)
Fig. 6. Experimental points and calculated curve from Eqs. (6s) and (8s) (T = 333 K, Fig. 8. Experimental points and calculated curve from Eqs. (6s) and (8s) (T = 358 K,
reactant mol ratio; 1/1, 5 (wt%) catalyst on dry basis, and 0.3 (wt%) inhibitor). reactant mol ratio; 1/1, 5 (wt%) catalyst on dry basis, and 0.3 (wt%) inhibitor).
k2 ¼ expð13:83 7797=TÞ L=mol min; DE ¼ 64:82 kJ=mol (8b) given in Eqs. (8a) and (8b) respectively, as follows:
k1
K¼ ¼ expð1870=T þ 8:33Þ (9)
k2
k3 ¼ expð62:63 24; 710=TÞ L=mol min; DE
¼ 205:44 kJ=mol (8c) The heat of reaction, assuming independent of temperature
ranging from 333 to 358 K, calculated to be
4. Conclusions
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