YAN Et Al, 2022
YAN Et Al, 2022
YAN Et Al, 2022
A R T I C L E I N F O A B S T R A C T
Keywords: Glycidyl esters, as a class of terminal epoxides, are important raw materials for the synthesis and modification of
Dehydrohalogenation epoxy resins. Their synthetic routes via the dehydrochlorination of β-chlorohydrin esters are typically conducted
Microreactor under heterogeneous condition. Under the control of multiphase mass transfer, the inherently fast reaction can
Mass transfer
exhibit a very low observed reaction rate. Here we developed a continuous microflow system to determine the
Glycidyl ester
kinetic parameters of dehydrochlorination in the presence of aqueous NaOH solution. The same device was
applied for the continuous production of glycidyl esters, and the conditions including flow velocity, alkali
concentration, phase ratio and temperature were fully optimized. Comparing the obtained reaction performances
in the microreactor with the conventional batch reactors, the required reaction time was shortened by 1/20 and
the space–time yield was increased by 15 times, which is attributed to the mass transfer enhancement and the
continuous operating mode. Finally, a mathematical model was established to calculate the volumetric mass
transfer coefficients, whose value were in the range of 0.005–0.03 s− 1. The established microflow system and
research methods could have high merit for guiding the kinetic studies and process intensification of other
dehydrohalogenation reactions.
widely used one is still the aqueous solution of alkali metal hydroxide
1. Introduction [16] and calcium hydroxide [17]. Many efforts have been made to study
the reaction kinetics of dehydrochlorination process in the presence of
Terminal epoxides are a class of important materials in chemical alkali solution. Ma et al. [18] established a stirred reactor assembled
industry and are crucial building blocks in organic synthesis [1–3]. The with a conductivity measurement device to determine the variation of
small molecule terminal epoxides such as ethylene epoxide, propylene OH– concentration in situ. In this way, the dehydrochlorination kinetics
epoxide and epichlorohydrin, act as monomers in the ring-opening of dichloropropanol was determined in the timescale of 0–10 s, and the
polymerization to prepare polyether rubber [4]. In addition, the termi intrinsic kinetics was demonstrated to be extremely fast under homo
nal epoxides with long aliphatic or aromatic chains can play versatile geneous condition. Zhang et al. [19] used a microreactor to investigate
roles in pharmaceutical community [5], coating industry [6] and envi the kinetic parameters of dehydrochlorination of 2,3-dichloro-1-propa
ronmental engineering [7]. Glycidyl products are a large class of this nol, and presented the dehydrochlorination mechanism. Then, consid
kind of terminal epoxides, mainly including glycidyl esters (glycidyl ering the effect of water concentration on the reaction rate, Filho et al.
methacrylate [8], glycidyl neodecanoate [9]) and glycidyl ethers [20] further obtained the intrinsic dehydrochlorination kinetics in a
(diglycidyl ethers of bisphenol-A [10]), they are vital synthetic blocks to continuous milliscale tubular reactor. The studies on the dehydrochlo
produce and modify epoxy resins and waterborne coatings. rination kinetics of dichloropropanol are relatively sufficient, but for
Dehydrochlorination of β-chlorohydrin is the final reaction step in β-chlorohydrins with long aliphatic and aromatic carbon chains, the
the chlorohydrin method to prepare terminal epoxides. There are many related research is lacking. It is relatively difficult to obtain the homo
types of alkaline that can be used in the dehydrochlorination processes, geneous dehydrochlorination kinetics because the reaction is very fast
including basic ion-exchange resin [11], metal oxide [12,13], solid and the side reactions including hydrolysis and ring-opening could occur
caustic soda [14] and halohydrin dehalogenase [15], whereas the most at high temperature [21]. Thus, it is meaningful to establish an effective
Abbreviations: CHPDA, 3-chloro-2-hydroxypropyl neodecanoate; ECH, epichlorohydrin; EPDA, 2, 3-epoxypropyl neodecanoate; GC, gas chromatography; MIBK,
methyl isobutyl ketone; NDA, neodecanoic acid.
* Corresponding author.
E-mail address: gsluo@tsinghua.edu.cn (G. Luo).
https://doi.org/10.1016/j.cej.2022.136498
Received 28 December 2021; Received in revised form 11 April 2022; Accepted 16 April 2022
Available online 21 April 2022
1385-8947/© 2022 Elsevier B.V. All rights reserved.
Z. Yan et al. Chemical Engineering Journal 444 (2022) 136498
Fig. 1. Typical reaction conditions of dehydrochlorination of β-chlorohydrins to produce glycidyl esters, including (a) glycidyl methacrylate [25], (b) 3-Chloro-2-
hydroxypropyl 4-(chloromethyl)benzoate [24] and (c) glycidyl neodecanoate [21,23].
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greatly shortening the reaction time and improving the space–time yield analyzed after extraction. The set-up shown in Fig. 2(b) was also used to
in EPDA production. produce EPDA via the heterogeneous dehydrochlorination process. At
this time, CHPDA was no longer dissolved in ethanol but delivered as a
2. Materials and methods neat reagent. Unlike the operating procedures in kinetic determination,
the quench agent (phosphate buffer solution) was pre-added to the
2.1. Chemicals sample vessel. After collecting samples within 1–5 s, the vessel was
shaken to terminate the reaction.
The β-chlorohydrin, 3-chloro-2-hydroxypropyl neodecanoate
(CHPDA), was prepared via the acidolysis ring-opening reaction of
2.3. Sample analysis
neodecanoic acid (NDA) and epichlorohydrin (ECH) according to the
related patents [23] and our previous works [33]. Vacuum distillation
Gas chromatography (GC) can be applied to analyze the concentra
(75 ◦ C, vacuum degree > 0.095 MPa, 2 h) was applied to remove the
tion of CHPDA, EDPA and NDA, however, the samples containing a large
trace amount of water and ECH in the product. After purification, the
amount of brine cannot be directly analyzed by GC. Thus, octane was
prepared product contained CHPDA (92 wt%), 2,3-epoxypropyl neo
used as the extractant to extract the dissolved and dispersed organic
decanoate (EPDA, 4 wt%), diester (3 wt%), 1,3-dichloro-2-propanol (0.5
substances into the oil phase. The distribution coefficients of CHPDA,
wt%) and NDA (0.5 wt%). NDA was purchased from Shanghai Ethyl
EPDA and NDA in octane/water system were determined in shaker tests,
Chemical Co., LTD, with the purity of 99 wt% tested by titration. EPDA
and the values were all larger than 50 at room temperature and 7.0 pH.
was purchased from Guangdong Weng Jiang Reagent, and its epoxy
This means more than 98% of organic substances could be extracted into
group content was 4195 mmol/kg (corresponding to 95.8 wt% purity).
oil phase by using 1:1 volumetric ratio of octane to water. After
All other reagents were purchased from Aladdin Chemistry Co., LTD and
extraction and 30 min for phase separation in static state, the oil phase
classified as analytical grade. The purities of these reagents could meet
was analyzed by GC. The testing conditions are listed in Table 1. The
the experimental requirements, so the purification steps were not
relative correction factor of CHPDA, EPDA and NDA in the internal
required.
standard method were 1.264, 1.127, and 1.020 respectively, and the
correlation coefficients of the standard curves were all larger than 0.999.
2.2. Experimental procedures The hydrolysis of the terminal epoxy group of EPDA could lead to the
formation of glycerin neodecanoate, but no such hydrolysis product was
The target reaction of this work, dehydrochlorination of 3-chloro-2- detected by GC. In addition, the hydrolysis of the ester group in CHPDA
hydroxypropyl neodecanoate (CHPDA), is displayed in Fig. 2(a), and the and EPDA generated sodium neodecanoate, which further converted to
set-up is shown in Fig. 2(b). In the experiments to determine reaction NDA and transported to oil phase during the extraction process. In this
kinetics, CHPDA was dissolved in ethanol and NaOH was dissolved in way, the degree of hydrolysis can be obtained via GC analysis. The re
water, both with the concentration of 0.05–0.2 mol/L. The two reactants sults showed that the hydrolysis rates were lower than 1% in all of our
were delivered by constant-flux pumps (also called HPLC pumps, Beijing experiments. Thus, the side reactions caused by hydrolysis were
Satellite Co. Ltd.) and preheated to the reaction temperature in stainless neglected.
steel capillaries with inner diameter of 0.5 mm and external diameter of Conversion of CHPDA (X) is the key parameter to analyze the reac
1.6 mm. Later, the two streams mixed in a T-micromixer (aperture of the tion kinetics and performances, it is calculated by Eq. (1), where ωC (%)
mixed position is 0.25 mm) and constituted a homogeneous system, then is the mass fraction of CHPDA in the organic phase after extraction,
flowed into a stainless-steel capillary coil with inner diameter of 2 mm
Mo (g) is the mass of organic phase after extraction, FC0 (g/s) is the initial
and external diameter of 3 mm to proceed the reaction. The reaction coil
mass flow rate of CHPDA, ts (s) is the sampling time, which is calculated
with different lengths (1, 2, 3, 5 and 7 m) were used to adjust the re
by dividing the mass of the sample Ms (g) by the total mass flow rate
action time. The preheating coil, the mixer and the reaction coil were
Ft (g/s).
immersed into an oil bath to control temperature. When leaving the oil-
bath zone, an excessive amount of phosphate buffer solution (NaH2PO4 ωC Mo ωC Mo
X = 1− = 1− (1)
and Na2HPO4 dissolved in water, pH = 7.0) was pumped into the FC0 ts FC0 MFts
reacting system to quench the dehydrochlorination by consuming the
remaining hydroxide ions. The samples were collected at the outlet and Space-time yield (η, g⋅cm− 3⋅h− 1) is another important parameter to
evaluate the reactor performances. It is calculated by Eq (2), where
FC0 (g/s) is the initial mass flow rate of CHPDA, X is the conversion of
CHPDA, VR(cm3) is the reactor volume, MEPDA and MCHPDA are molec
ular weights of EPDA and CHPDA, whose values are 228.3 and 264.8 g/
mol respectively.
MEPDA F 0C X
η = 3600 × (2)
MCHPDA VR
Table 1
GC testing conditions.
Device: Agilent GC-7890A Detector: FID
Injection temperature: 300 οC
Detection temperature: 300
ο
C
Column: HP-5 / 30 m × 0.32 mm × 0.25 μm Sample: 1 μL
Carrier gas: N2, 1 ml/min; Split ratio: 30:1 Quantitative method: internal
standard
Column temperature: start at 50 οC, maintain for 2 Internal standard substance:
min; 10 οC/min to 160 οC; 5 οC/min to 200 οC; 10 methyl benzoate
ο
C/min to 300 οC, maintain for 3 min
Fig. 2. Experimental procedures and set-up.
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Fig. 3. Kinetic results to obtain the reaction order of CHPDA. (a) The time profile of CHPDA concentration. (b) The conversion of CHPDA versus residence time.
Reaction conditions: the initial concentration of NaOH and CHPDA after mixing were 0.680 mol/L and 0.0614 mol/L respectively; the total flow rate was 19.5 ml/
min; temperature was 30 ◦ C.
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Fig. 5. (a) Plot of f(X) versus residence time at temperature range of 30–50 ◦ C. (b) Plot of lnk versus 1/RT. Reaction conditions: the initial concentration of NaOH and
CHPDA after mixing were 0.0676 mol/L and 0.0758 mol/L respectively; the total flow rate was 19.8 ml/min.
(3) The slug flow pattern was observed at the outlet of microtube
Table 2
reactor. It was demonstrated that the residence time distribution
Comparison of homogeneous dehydrochlorination kinetics of CHPDA and 1,3-
of slug flow in microtubes is narrow [34], thus the plug flow
dichloro-2-propanol in NaOH solution.
model was applied to calculate the average residence time (Eq
Entry CHPDA 1,3-dichloro-2-propanol (8)), where VR is the volume of reactor, Qw and Qo are volumetric
[20]
flow rate of aqueous and organic phases respectively.
Setup for kinetic research Microreactor Microreactor
Determination method Gas Gas chromatography VR
τ= (8)
chromatography Qw + Qo
Timescale 0–60 s 0–25 s
Kinetic equation r = kCNaOH CCHPDA r = kCNaOH CDCP The time profiles of CHPDA conversion obtained in the heteroge
Activation energy (kJ/mol) 75.9 ± 5.0 82.6 ± 1.2 neous and homogeneous dehydrochlorination are shown in Fig. 7, in
Pre-exponential factor 1.47 × 1012 4.84 × 1014 which the heterogeneous results were measured by experiments and
(L⋅mol− 1⋅s− 1)
homogeneous results was calculated according to reaction kinetics by
k at 50 ◦ C (L⋅mol− 1⋅s− 1) 1.45 21.2
assuming that the two phases were miscible. The results indicate that the
observed reaction rate under heterogeneous condition is significantly
lower than that in homogeneous condition, and the most prominent
reason is that the liquid–liquid heterogeneous mass transfer restricts the
dehydrochlorination reaction.
Fig. 6. The reaction mechanism of dehydrochlorination of β-chlorohydrin with 3.2.1. Effect of flow velocity
hydroxide ions. Fig. 8 shows the observed reaction rates of dehydrochlorination at
different flow velocity in the microtube reactor. There is no significant
of effective collisions between reactant molecules. Considering both difference in the conversion-time curves of these three experiments. This
effects, the dehydrochlorination of CHPDA is slower than 1,3-dichloro- phenomenon indicates that as the velocity reached 2.12 cm/s, simply
2-propanol (e.g., the reaction rate constant of CHPDA dehydrochlori increasing the flow rate cannot further facilitate the mass transfer and
nation at 50 ◦ C is only one fifteenth of 1,3-dichloro-2-propanol), but it is improve the observed reaction rate.
still a fast reaction.
(1) The mutual solubility of the organic and aqueous phases is Fig. 7. CHPDA conversion in the heterogeneous experiment and the results
extremely low because of the high hydrophobicity of CHPDA. calculated according to reaction kinetics using pseudo-homogeneous model.
(2) The change of volumetric flow rate of organic and aqueous phases Reaction conditions in heterogeneous experiment: mass fraction of NaOH was
before and after the dehydrochlorination is measured to be less 20 wt%; flow rate of NaOH/H2O = 6 ml/min; flow rate of CHPDA = 2 ml/min;
than 3%. It is reasonable to ignore this small variation. temperature was 50 ◦ C.
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Fig. 9. The effects of NaOH concentration on the dehydrochlorination of CHPDA. (a) Time profiles of CHPDA conversion at different initial mass fractions of NaOH.
Reaction conditions: flow rate of NaOH/H2O = 6 ml/min; flow rate of CHPDA = 2 ml/min; temperature was 50 ◦ C (b) Interfacial tension between EPDA and NaOH/
H2O solution with concentration range of 0–40 wt%, measured by pendant drop method (DataPhysics Instruments, OCAH220) at 20 ◦ C, 101 kPa.
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Fig. 11. The effect of temperature on the performances of heterogeneous Combining Eqs. (9) and (10), the mass balance equation in differ
dehydrochlorination reaction. Reaction conditions: NaOH concentration = 40 ential form is expressed as given by Eq (11).
wt%, flow rate of NaOH/H2O = 4 ml/min, flow rate of CHPDA = 4 ml/min.
dM
= − ko aCCHPDA (11)
dV
Substituting the expression of M (Eq (12), φ = QOQ+Q
O
W
is the volume
fraction of oil phase) in Eq (11), the relation between CHPDA concen
tration and residence time can be deduced as given by Eq (13).
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Table 3
Reaction conditions and performances of dehydrochlorination of CHPDA in the microreactor and conventional batch reactors.
No. Reactor types NaOH concentration (wt Molar ratio n(NaOH): n Temperature Reaction time Conversion Space-time
%) (CHPDA) (◦ C) (min) (%) yield
(g⋅cm− 3⋅h− 1)
φ 1
ko a = ln( ) (15)
τ 1− X
Fig. 14 shows the calculated values of ko a at different reaction
temperature, which is distributed in the range of 0.005–0.03 s− 1.
Comparing with the obtained intrinsic reaction rate, mass transfer pro
cess still controls the dehydrochlorination of CHPDA although enhanced
by microreactor. The process could be further intensified by increasing
Fig. 12. Mass balance of CHPDA in a differential volume of microtube reactor. the specific surface area, for example, using micropacked bed reactors
[37].
M = QO CCHPDA = φ(QO + QW )CCHPDA (12)
4. Conclusion
dM d[φ(QO + QW )CCHPDA ] dCCHPDA
= =φ = − ko aCCHPDA (13) The dehydrochlorination of CHPDA with aqueous NaOH solution is
dV dV dτ
systematically studied in a microtube reactor. The reaction kinetics was
Through integration, the equation of conversion versus residence
determined under homogeneous condition by using ethanol as solvent.
time is obtained:
The orders of CHPDA and NaOH are both first, the activation energy and
1 pre-exponential factor are 75.9 ± 5.0 kJ⋅mol− 1 and 1.47 × 1012
φln( ) = ko aτ (14)
1− X L⋅mol− 1⋅s− 1 respectively. Furthermore, in the same reaction set-up, the
Fig. 13 shows the excellent linear relation between φln(1−1 X) and τ continuous production of EPDA via the dehydrochlorination of CHPDA
is conducted without any organic solvent, constituting a liquid–liquid
when the molar ratio of NaOH to CHPDA is larger than 10, which proves
heterogeneous reaction system. It was demonstrated that the heteroge
the feasibility of the model. The volumetric mass transfer coefficient
neous reaction is definitely controlled by mass transfer because the
(ko a), which is the slope of the curve, is calculated to be 5.84 ± 0.36 ×
observed reaction rate is much lower than that under homogeneous
10-3 s− 1.
condition. It was demonstrated that increasing the concentration of
Under the obtained optimal dehydrochlorination conditions, in
NaOH solution is the most direct and effective way to enhance mass
which the phase ratio is 1:1 and molar ratio of NaOH to CHPDA is 4:1,
transfer because it can improve the concentration gradient and reduce
the volumetric mass transfer coefficient can be calculated according to
the interfacial tension. In order to keep dehydrochlorination at a high
Eq (15), and the point with CHPDA conversion less than 20% is selected
rate, the NaOH concentration should be maintained higher than 30 wt%.
for calculation because the change of NaOH concentration is so small
Under the optimal dehydrochlorination conditions (CNaOH = 40 wt%,
that the promise of ignoring the mass transfer resistance in the aqueous
phase ratio (water to oil) = 1:1, temperature = 50 ◦ C), 93.8% conversion
phase is still valid.
of CHPDA is obtained within 2.7 min. Compared with the conventional
batch processes to produce EPDA, the space–time yield is enlarged by 15
Fig. 13. The curve of φln(1−1 X) versus residence time in microtube reactor. Fig. 14. Volumetric mass transfer coefficients in the organic phase at different
Reaction conditions: NaOH concentration = 40 wt%, temperature = 50 ◦ C. QO reaction temperatures. Reaction conditions: NaOH concentration = 40 wt%, QO
= 2 ml/min, QW = 6 ml/min, molar ratio of NaOH to CHPDA was 12.4. = 4 ml/min, QW = 4 ml/min, molar ratio of NaOH to CHPDA was 4.0.
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Z. Yan et al. Chemical Engineering Journal 444 (2022) 136498
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