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1 s2.0 S1004954115001743 Main PDF
1 s2.0 S1004954115001743 Main PDF
a r t i c l e i n f o a b s t r a c t
Article history: In this study, the kinetics of isopropyl palmitate synthesis including the reaction mechanism was studied based
Received 17 October 2014 on the two-step noncatalytic method. The liquid-phase diffusion effect on the reaction process was eliminated by
Received in revised form 18 April 2015 adjusting the stirring rate. The results showed that the two-step reaction followed a tetrahedral mechanism and
Accepted 27 April 2015
conformed to second-order reaction kinetics. Nucleophilic attack on the carbonyl carbon afforded an intermedi-
Available online 15 May 2015
ate, containing a tetrahedral carbon center. The intermediate ultimately decomposed by elimination of the leav-
Keywords:
ing group, affording isopropyl palmitate. The experimental data were analyzed at different temperatures by the
Isopropyl palmitate integral method. The kinetic equations of the each step were deduced, and the activation energy and frequency
Reaction kinetics factor were obtained. Experiments were performed to verify the feasibility of kinetic equations, and the result
Chemical reaction showed that the kinetic equations were reliable. This study could be very significant to both industrial application
Preparation and determining the continuous production of isopropyl palmitate.
Chloridization © 2015 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.
Palmitic acid
http://dx.doi.org/10.1016/j.cjche.2015.05.004
1004-9541/© 2015 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.
1336 L. Fu et al. / Chinese Journal of Chemical Engineering 23 (2015) 1335–1339
CH3 ðCH2 Þ14 COOH þ SOCl2 →CH3 ðCH2 Þ14 COCl þ SO2 þ HCl ðaÞ 90
CH3 ðCH2 Þ14 COCl þ ðCH3 Þ2 CHOH→CH3 ðCH2 Þ14 COOCHðCH3 Þ2 þ HCl ðbÞ 88
86
Preliminary experiments showed that the stirring rate had a
certain effect on the conversation rate [14]. To evaluate the 84
liquid-phase diffusion, the two-step reaction was carried out at
different stirring rates of 100, 150, 200, 250 r·min− 1 while keeping 82
other conditions the same: n(thionyl chloride): n(palmitic acid) =
1.4, n(isopropanol):n(palmitoyl chloride) = 1.4, reaction temper- 80
ature 343 K. The results obtained were shown in Figs. 1 and 2, 20 40 60 80 100
when the stirring rate was 200 and 250 r·min − 1 , no significant reaction time/min
differences were found in the conversion of palmitic acid and
palmitoyl chloride. This indicated that the diffusion-controlled Fig. 2. Conversion of palmitoyl chloride vs. time for Reaction (b) at different stirring rates.
process was eliminated by selecting the appropriate stirring rate
to investigate the intrinsic kinetics of the two-step reaction.
Based on this result, the kinetic experiments in this work were all
performed at the stirring rate of 200 r·min− 1. tetrahedral carbon center, the reaction sequence is called tetrahedral
mechanism. The two-step reaction combining palmitic acid acylation
100 [18] and palmitoyl chloride alcoholysis [19,20] follows tetrahedral
100 r·min-1
98 mechanism.
150 r·min-1
200 r·min-1
96
conversion of palmitic acid/%
86 ðcÞ
84
82
80
20 40 60 80 100
reaction time/min
ðdÞ
Fig. 1. Conversion of palmitic acid vs. time for Reaction (a) at different stirring rates.
the tetrahedral intermediate affords IPP. R and R′ stand for –C15H31 Then, the natural logarithm of the Arrhenius equation leads to the
and –CH(CH3)2, respectively, in the following reactions: following Equation, showing a linear relationship between lnk and 1/T:
Ea
ln k ¼ − þ ln A: ð7Þ
RT
ðf Þ
Therefore, based on the slope and ordinate of the line, Ea and A can
be obtained.
dcA
ð−r A Þ ¼ − ¼ kcA cB : ð1Þ
dt
Table 2
If cA0 = cB0, Eq. (1) could be deduced as follows: Effect of temperature on Reaction (b)
dcA
ð−r A Þ ¼ − ¼ kcA cB ¼ kc2A0 ð1−xA Þðβ−xA Þ: ð4Þ
dt
β−xA
ln ¼ cA0 ðβ−1Þkt ðβ ≠ 1Þ ð5Þ
βð1−xA Þ
k ¼ Ae−Ea =RT : ð6Þ Fig. 3. Conversion of palmitic acid vs. time for Reaction (a).
1338 L. Fu et al. / Chinese Journal of Chemical Engineering 23 (2015) 1335–1339
Fig. 4. Conversion of palmitoyl chloride vs. time for Reaction (b). Fig. 5. Line A: lnk vs. 1/T of Reaction (a).
Table 3
Value of k of Reaction (a) at the different temperatures
Table 4
3.4. Determination of reaction kinetics equations
Value of k of Reaction (b) at the different temperatures
According to Eqs. (1) and (6) and the values of Ea and A for each step,
Temperature/K Equation k/L · mol−1·min−1 R2
the kinetics equations of IPP synthesis are as follows:
336 y = 0.034 x 0.03489 0.9978
338 y = 0.038 x 0.03899 0.9975 Step 1:
341 y = 0.0459 x 0.0471 0.9992
343 y = 0.0508 x 0.05213 0.9989 dcPA 46103
345 y = 0.0561 x 0.05756 0.9984 −r PA ¼ − ¼ 4:63 105 e− RT cPA cTC : ð8Þ
dt
Step 2:
dcPC 54:15103
3.3. Determination of Ea and A for the reaction −r PC ¼ − ¼ 9:08 106 e− RT cPC cIPA : ð9Þ
dt
According to the Arrhenius Eq. (7), the plot of lnk vs. 1/T is
shown in Figs. 5 and 6. A line drawn at that abscissa represents 1/
T and ordinate lnk. Based on the slope and ordinate of the lines, In Eqs. (8) and (9), PA is the palmitic acid, TC is the thionyl
activation energy E a and frequency factor A for each step were chloride, PC is the palmitoyl chloride, and IPC is the isopropanol.
obtained. The dynamic model of IPP synthesis was built and expressed in
The slopes of the Lines A and B were − 5532.46 and − 6513.18, Eqs. (8) and (9).
respectively. The ordinate of the Lines A and B were 13.045 and
16.022. The result of the calculation shows that the activation ener- 4. Verified Experiments
gy (Ea1) and frequency factor (A1) for step 1 acylation reaction are
46 kJ·mol− 1 and 4.63 × 105, respectively, and the activation energy To verify the feasibility of kinetic equations, verified experiments
(E a2 ) and frequency factor (A 2 ) were 54.15 kJ·mol − 1 and were performed. Based on the assumption that n(thionyl chloride):
9.08 × 106 for Step 2 alcoholysis reaction. n(palmitic acid) = 1.4, n(isopropanol): n(palmitoyl chloride) = 1.4,
L. Fu et al. / Chinese Journal of Chemical Engineering 23 (2015) 1335–1339 1339
the effect of the reaction time on the conversion for each step was stud- respectively. The frequency factors for the first and second steps
ied at different temperatures. The results from the calculation according were 4.63 × 105 and 9.08 × 106, respectively. The result of the ver-
to Eqs. (8) and (9) agreed well with the experimental values. Figs. 7 and ified experiments showed that the kinetics equations are reliable.
8 show the comparison, indicating that the dynamics equations are This study is very significant for the industrial application and de-
reliable. termining the continuous production process of IPP synthesis.
Nomenclature
A1 frequency factor for Step 1 acylation reaction
A2 frequency factor for Step 2 alcoholysis reaction
Ea1 activation energy for Step 1 acylation reaction, kJ·mol−1
Ea2 activation energy for Step 2 alcoholysis reaction, kJ·mol−1
k rate constant, L·mol−1·min−1
R gas constant, J·mol−1·K−1
rPA reaction rate of palmitic acid, mol·L−1·min−1
rPC reaction rate of palmitoyl chloride, mol·L−1·min−1
T absolute temperature in kelvin, K
xA conversion of palmitic acid or palmitoyl chloride respectively, %
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