Study of liquid–solid catalytic reaction of epichlorohydrin with sodium butyrate in the presence of tetrabutylammonium bromide

Article abstract of DOI:10.1134/S0036024416080240

The liquid–solid catalytic reaction of epichlorohydrin and sodium butyrate with tetrabutylammonium bromide as a phase transfer catalyst was studied in this paper. The shrinking core model was applied. The analysis of the reaction based on the kinetic model showed a reaction-controlled regime at temperatures varying from 90 to 100°C. The exterior diffusivity was removed between 300 and 400 rpm. The internal diffusivity was removed when the particle size was 2 × 10^–4 m. Reaction rate constants were calculated at different temperatures. The correlation was obtained when the proposed kinetic model was applied to all the experimental data for predictive evaluations and the activation energy was 37.01 kJ mol^–1.

Full text of DOI:10.1134/S0036024416080240

ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2016, Vol. 90, No. 8, pp. 1552–1556. © Pleiades Publishing, Ltd., 2016.
CHEMICAL KINETICS
AND CATALYSIS
Study of Liquid–Solid Catalytic Reaction of Epichlorohydrin
with Sodium Butyrate in the Presence
of Tetrabutylammonium Bromide1
Qiang Huanga, Qingyi Mengb,*, Chunlan Bana, Rui Zhanga, and Yingyu Gaoa
aSchool of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou, Henan, 450001, P.R. China
bLuoyang Yonglong Energy and Chemical Co., Ltd. of Henan Energy Chemical (HNEC), Luoyang, Henan, 471100, P.R. China
*e-mail: mengqingyi2009@sina.com
Received April 2, 2015
Abstract—The liquid–solid catalytic reaction of epichlorohydrin and sodium butyrate with tetrabutylammo-
nium bromide as a phase transfer catalyst was studied in this paper. The shrinking core model was applied.
The analysis of the reaction based on the kinetic model showed a reaction-controlled regime at temperatures
varying from 90 to 100°C. The exterior diffusivity was removed between 300 and 400 rpm. The internal diffu-
sivity was removed when the particle size was 2 × 10–4 m. Reaction rate constants were calculated at different
temperatures. The correlation was obtained when the proposed kinetic model was applied to all the experi-
mental data for predictive evaluations and the activation energy was 37.01 kJ mol–1.
Keywords: epichlorohydrin, sodium butyrate, liquid–solid reaction, catalytic.
DOI: 10.1134/S0036024416080240
1. INTRODUCTION
a new solid product, the pellet retains its spherical shape
and its initial size in the course of the reaction; on the
contrary, the pellet decreases continually. Lopez-Fon-
sec [15] applied this model in the alkaline hydrolysis of
PET. Another model for the catalytic fluid–solid reac-
tions was proposed in presence of structural changes in
the solid phase. The model allowed variation with con-
version in the size distribution of the grains constituting
the reactant solid particulates [16].
A simple treatment for obtaining the solution of
single isothermal gas–solid catalytic reactions was
presented by Gomez-Barea [17]. This model was
based on the local volumetric approach and non-lin-
ear chemical kinetics and structure changes. Another
model [18] of non-catalytic gas–solid reactions was
based on the mass and the heat transport in the pellet.
For the non-catalytic gas–solid reactions, the design
of the reactor was based on the modeling of the reac-
tion of the isothermal Shrinking Core Model [19, 20].
For the reversible or irreversible gas–solid reactions, a
numerical model was presented and designed to simu-
late the kinetics and thermal behavior of a porous pel-
let [21]. A kinetic model was developed [22].
Liquid–solid catalytic reactions were very import-
ant in chemical industries. They are extensively
applied in the preparation of phosphate fertilizers and
nuclear energy materials. Glycidyl butyrate [1] was an
important pharmaceutical component, which was
synthesized from epichlorohydrin and sodium butyr-
ate with tetrabutylammonium bromide (TBAB). It
was important to study the liquid–solid catalytic reac-
tion of epichlorohydrin and sodium butyrate with
TBAB as a phase transfer catalyst [2, 3]. Pais [4] had
developed a sharp interface model for non-catalytic
liquid–solid reversible reactions. Catalytic liquid–
solid reactions can be represented as:
(1)
A f + bB s → cF f + sS s .
( ) ( ) ( ) ( )
There were many examples of catalytic fluid–solid
reactions: reduction, roasting and chlorination of ores,
decomposition reactions [5] and the causticizing reac-
tion [6–9]. Many models have been considered so far:
a sharp interface model (SIM) [10], a volume reaction
model [11], a shrinking core model [12, 13] and a finite
reaction model [14]. The shrinking core model was
extensively used in fluid–solid catalytic reactions. The
characteristic of the model was that reaction occurs at
a sharp interface between inter pellet solid and unre-
acted solid surface. The model had two situations: with
2. MATERIALS AND METHODS
2.1. Chemicals and Analytical Instruments
The nominal purity of epichlorohydrin was above
99%. Sodium butyrate was synthesized from butyric
1
The article is published in the original.
1552

STUDY OF LIQUID–SOLID CATALYTIC REACTION OF EPICHLOROHYDRIN
1553
Table 1. The characteristics of sodium butyrate and epi-
acid and sodium hydroxide, the purity was above 99%.
The materials above were all AR reagents. The charac-
teristics of sodium butyrate and epichlorohydrin were
shown in Table 1. The unreacted component and liq-
uid product were detected by gas chromatograph
(GC9800, Shanghai Kechuang chromatograph
instrument Co., Ltd., China) with the thermal con-
ductivity detector (TCD). The SE30 packed column
(∅3 mm × 1.5 m) was used together with the TCD, the
current was 140 mA. Hydrogen was used as a carrier
gas at a rate of 40 mL min–1 and the column inlet pres-
sure of 0.05 MPa. The temperature of the detector and
vaporizer was kept at 503.15 K. Three analyses were
performed for each sample to ensure accuracy.
chlorohydrin
Molecular
formula
Mw
(g/mol)
Density
(g/mL)
Component
Sodium butyrate C4H7O2Na
Epichlorohydrin C3H5OCl
110.0873
92.5243
1.2067
1.1759
Table 2. The mole fraction (%) of glycidyl butyrate and
fractional conversion (%) of sodium butyrate under differ-
ent rotational rate
Component 150 rpm 200 rpm 300 rpm 400 rpm
2.2. Analytical Method and Model
Glycidyl
butyrate (%)
0.2562
0.9403
0.2555
0.9375
0.2652
0.9732
0.2657
0.9749
The model was based on the shrinking core model
[11, 12]. This model contains the exterior diffusivity,
internal diffusivity and surface chemical reaction. The
function of factors above was as follows
Sodium
butyrate (%)
dnA
dt
dnA
dt
dnB
bdt
dnB
bdt
(2)
(3)
−
= −
= −
= 4πRS2kG
c
− cAS ,
(
)
Ag
From the above function (5), the exterior diffusivity
and the internal diffusivity are contained. We can find
that exterior diffusivity contacts the stir rate and the
internal diffusivity contacts the particle size.
dc
⎛
⎜
⎞
A
−
= 4πRC2Deff
,
⎟
⎝ dR ⎠R=R
C
dnA
dt
dnB
bdt
The fractional conversions of sodium butyrate was
calculated from Eq. (6) in which, Sodinital and Sodfinal
were moles of sodium butyrate before and after the
reaction, respectively.
(4)
−
= −
= 4πRC2kcAC
,
3
⎛
RC
⎞
ρB
MB
ρB
MB
3
4
3
and
nB =
VC =
πRC
xB = 1 −
.
(
)
⎜
⎟
Fractional conversion (%)
R
⎝
⎠
S
The function of the shrinking core model from (2)–
(4) was the following function:
Sodinital − Sod
(6)
xB =
final ×100.
Sodinital
⎧ RS
RS2
6Deff
ρB
bMBcAg 3k
t =
xB +
[1 − 3(1 − xB) 2/3
⎨
3. RESULTS AND DISCUSSION
This work was based on the shrinking core model,
as shown in Fig. 1. The reaction was the following:
⎩
C
(5)
R
k
+ 2(1 − xB)] + S [1 − (1 − xB)1/3] .
}
(li)
O
O
(li)
+ CH3CH2CH2COONa (s)
(7)
+ NaCl (s).
Cl
OOCCH2CH2CH3
The product was synthesized with 30 g Sodium butyr- irregular and resembling more to a rectangular but not
ate and 108 mL epichlorohydrin under the certain
temperature with TBAB. In order to describe the
whole kinetics with the insoluble product layer in the
presence of salt, the following assumptions and sim-
plifications were used:
(a) The whole reaction condition was an isother-
mal process.
a sphere. The particle size of the experiment was quite
small (lower than 9 × 10–4 m), which could be reason-
ably assumed that sodium butyrate particles were
spherical in shape.
(c) The sodium butyrate particles kept constant
and negligible swelling during the reaction.
(b) Sodium butyrate particles consisted of isotropic
spherical particles of equal shrinking diameter.
Besides, they were considered as a homogeneous
phase for mathematical treatment. In fact, after mill-
(d) During the reaction, reversible reaction did not
exist.
(e) The reaction rate was proportional to the parti-
ing, the size of the resulting particles may be certainly cle surface area.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 90 No. 8 2016

1554
QIANG HUANG et al.
For the internal diffusivity, under the different parti-
t × 103, s
cle size including 9 × 10–4, 4.5 × 10–4, 2 × 10–4, and
lower than 2 × 10–4 m, the rotational rate was 300 rpm
when the reaction was continued for a certain time.
From Table 3, it could be seen that there was a small
change between 2 × 10–4 and lower 2 × 10–4. It was
considered that the internal diffusivity was eliminated.
16
14
12
10
8
90°C
95°C
100°C
When the exterior diffusivity and the internal diffu-
sivity were eliminated, the function (5) would be
changed to the next function:
6
ρBRS
bMBcAgk
(8)
t =
[1 − (1 − x)1/3] .
4
2
In order to calculate the k of the function (8), Table 4
showed the data of sodium butyrate conversion and
the mole fraction of glycidyl butyrate at different tem-
peratures.
0
0
1
2
3
4
5
6
7
X × 10−3
ρBRS
bMBcAg
Fig. 1. The relationship of time t (s) and X.
When X =
[1 – (1 – xB)1/3, b = 1, while
function (8) would be as follows:
(f) The grains reacted according to the shrinking
core model with the rate of reaction controlled by the
product layer diffusion and the chemical reaction.
X
(9)
t =
.
k
Firstly, the influence of exterior diffusivity and
internal diffusivity could be eliminated at 100°C,
under the different rotational rate of 150, 200, 300, and
400 rpm. When the reaction was continued for certain
time, the particle size was 2 × 10–4 m. The data of the
fractional conversion of sodium butyrate and the mole
of the product are as shown in Table 2. It could be seen
that the fractional conversion of sodium butyrate had
a small change between 300 and 400 rpm. It could be
considered the exterior diffusivity was eliminated.
Figure 2 showed the relationship between time t and X
at the different temperatures. Table 5 showed the data
on reaction rate constants k at different temperatures.
The relationship between the rate constants and the
reaction temperature was studied. With the Arrhenius
function, we could get the plots of the rate constants
and the reaction temperature. The activation energy for
the catalytic reaction from the slope with linear correla-
tion factor (r2) higher than 0.99 was 37.01 kJ mol–1.
In (reaction rate constan)
−14.50
−14.55
−14.60
−14.65
−14.70
−14.75
−14.80
−14.85
2.67 2.68 2.69 2.70 2.71 2.72 2.73 2.74 2.75 2.76
1/T × 103, K
Fig. 2. Arrhenius plot for sodium butyrate.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
Vol. 90
No. 8
2016

STUDY OF LIQUID–SOLID CATALYTIC REACTION OF EPICHLOROHYDRIN
1555
Table 3. The mole fraction of glycidyl butyrate (%) and fractional conversion (%) of sodium butyrate under different particle size
9 × 10–4
m
4.5 × 10–4
m
2 × 10–4
m
<2 × 10–4
m
Component
Glycidyl butyrate (%)
Sodium butyrate (%)
0.2476
0.9580
0.2479
0.9591
0.2530
0.9789
0.2537
0.9816
Table 4. The mole of glycidyl butyrate (mole) and fractional conversion (%) of sodium butyrate under different tempera-
ture
Glycidyl
butyrate of
mole (mol)
Glycidyl
butyrate of
mole (mol)
Glycidyl
butyrate of
mole (mol)
Time (s)
(1000)
Sodiumbutyrate Time (s)
conversion (%) (1000)
Sodiumbutyrate Time (s)
conversion (%) (1000)
Sodiumbutyrate
conversion (%)
90°C
0.0000
0.0135
0.0626
0.0826
0.1188
95°C
0.0000
0.0204
0.0841
0.2496
0.2487
0.2497
0.2473
0.2485
0.2625
0.2590
0.2480
0.2482
0.2493
100°C
0.0000
0.0148
0.0615
0.1080
0.2331
0.2372
0.2374
0.2303
0.2410
0.2483
0.2483
0.2662
0.0
0.6
0.0000
0.0496
0.2296
0.3029
0.4359
0.8018
0.8308
0.8372
0.8661
0.8484
0.8799
0.8860
0.9552
0.0
0.6
0.0000
0.0748
0.3086
0.9161
0.9127
0.9164
0.9076
0.9120
0.9632
0.9504
0.9102
0.9107
0.9149
0.0
0.6
0.0000
0.0545
0.2259
0.3962
0.8553
0.8704
0.8713
0.8452
0.8843
0.9113
0.9114
0.9770
1.2
1.2
1.2
1.8
9.6
1.8
2.4
10.2
10.8
12.0
12.6
13.2
13.8
14.4
15.0
15.6
7.2
9.0
0.2185
0.2264
0.2281
0.2360
0.2312
0.2398
0.2414
0.2603
7.8
10.2
10.8
11.4
12.0
12.6
13.2
15.6
8.4
9.0
9.6
10.2
10.8
11.4
and 400 rpm, when the particle size was 2 × 10–4.
Reaction rate constants were calculated at different
temperatures. The correlation was obtained when the
proposed kinetic model was applied to all the experi-
mental data for predictive evaluations and the activa-
tion energy was 37.01 kJ mol–1.
4. CONCLUSIONS
Liquid–solid catalytic reaction of epichlorohydrin
and sodium butyrate was studied. The shrinking core
model was considered. The analysis of the reaction
based on the kinetic model showed a reaction-con-
trolled regime at temperatures varying from 90 to
100°C. The exterior diffusivity and the internal diffu-
sivity were considered and eliminated between 300
ACKNOWLEDGMENTS
Thanks the Foundation Research of Henan Prov-
ince support under project no. 082300440040.
Table 5. Reaction rate constant k at different temperature
Correlation factor
Nomenclature
T
k (m/s)
(R2)
A
B
fluid reactant
solid reaction
90°C
95°C
3.6 × 10–7
4.3 × 10–7
5.0 × 10–7
0.980
0.965
0.966
b, c, s stoichiometric coefficients
S
F
solid product
fluid product
100°C
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 90 No. 8 2016

1556
QIANG HUANG et al.
5. L. K. Doraiswamy and M. M. Sharma, Heterogeneous
nA
nB
Rc
Rs
t
Deff
MB
K
xB
T
VC
cAg
fluid mole
solid mole
radius of the unreacted solid particles (m)
initial radius of solid particles (m)
time (s)
effective diffusivity of A within pellet (m2/s)
molecular weight B (g/mol)
reaction rate constant (m/s)
fractional conversion of B at a specific reaction time
temperature (°C)
Reactions: Analysis, Examples, and Reactor Design
(Wiley, New York, 1984).
6. P. Angevine, in Cost-Effective Causticizing, Tech. Asso-
ciation of the Pulp and Paper Industry TAPPI Engineer-
ing Conference Proceedings (TAPPI, Dallas, Texas,
USA, 1983), Vol. 1, Ch. 42, p. 253.
7. B. Blackwell, Pulp Paper Canada 88, 87 (1987).
8. G. M. Dorris and L. H. Allen, J. Pulp. Paper Sci. 11,
J89 (1985).
9. G. M. Dorris and L. H. Allen, in Proceedings of the
Tappi Kraft Recovey Operations Seminar, Ed. by
D. W. Reeve (Tech. Association of the Pulp and Paper
Industry, Orlando, Florida, USA, 1986), Ch. 23, p. 7.
10. S. Yagi and D. Kunii, in Proceedings of the 5th Interna-
tional Symposium on Combustion (Reinhold, New York,
1955), p. 231
volume of the unreacted solid particles (m3)
initial concentration of exterior diffusivity A
(mol/L)
concentration of the exterior diffusivity A (mol/L)
concentration of the internal diffusivity A (mol/L)
transmit mass constant (m/s)
cAS
cA
kG
11. M. Ishida and C. Y. Wen, AIChE J. 14, 311 (1968).
12. J. M. Smith, Chemical Engineering Kinetics, 3rd ed.
(McGraw-Hill, New York, 1981), Ch. 14.
Greek letters
ρ
Subscripts
13. O. Levenspiel, Chemical Reaction Engineering, 2nd ed.
density (g/cm3)
(Wiley, New York, 1972), Ch. 12.
14. J. J. Carberry, AIChE J. 6, 460 (1960).
15. R. Lopez-Fonsec, J. R. Gonzalez-Velasco, and
B
reactant B
J. I. Gutierrez-Ortiz, J. Chem. Eng. 146, 287 (2009).
F, S product F, S
16. A. Bhattacharya and P. Purohit, J. Chem. Eng. 102, 141
(2004).
c
s
fluid
solid
17. A. Gomez-Barea and P. Ollero, J. Chem. Eng. Sci. 61,
3725 (2006).
18. G. Uhde and U. Hoffmann, J. Chem. Eng. Sci. 52,
REFERENCES
1045 (1997).
19. M. Baerns, H. Hofmann, and A. Renken, Chemische
1. Qiang Huang, Qingyi Meng, Chunlan Ban, et al.,
Reaktionstechnik (Thieme, Stuttgart, 1987).
J. Chem. Thermodyn. 50, 57 (2012).
20. Verfahrenstechnische Berechnungsmethoden, Ed. by
2. O. Jogunola and T. Salmi, J. Chem. Tech. Biotech. 87,
S. Wei (VCH, Weinheim, 1987), Ch. 5.
286 (2012).
21. F. Patisson, M. G. Francois, and D. Ablitzer, J. Chem.
3. S. Loiha, K. Fottinger, K. Zorn, et al., J. Ind. Eng.
Eng. Sci. 53, 697 (1998).
Chem. 15, 819 (2009).
4. F. I. C. C. Pais and A. T. G. Portugal, Comput. Chem. 22. Yu. E. Romanenko, A. A. Merkin, A. A. Komarov, and
Eng. 459 (1998). O. V. Lefedova, Russ. J. Phys. Chem. A 88, 1323 (2014).
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
Vol. 90
No. 8
2016