Chemical Engineering Science 186 (2018) 251–264

Contents lists available at ScienceDirect

Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

Continuous microwave-assisted reactive distillation column:

Pilot-scale experiments and model validation
Xin Gao a, Xinshuang Liu a, Xingang Li a, Jinsong Zhang b, Yongjin Yang b, Hong Li a,⇑
a
School of Chemical Engineering and Technology, National Engineering Research Center of Distillation Technology, Collaborative Innovation Center of Chemical Science
and Engineering (Tianjin), Tianjin University, Tianjin 300072, China
b
Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110015, China

h i g h l i g h t s

First systematic study of intensified effect in microwave-assisted reactive distillation process.

A set of specialized devices were developed for the microwave reactive distillation experiment.

Pilot-scale experimental verification of feasibility of stable reactant conversion has been obtained.

New mechanism for microwave effect in microwave reactive distillation has been identified.

The work could provide guidance for design and industrialization for microwave reactive distillation.

a r t i c l e i n f o a b s t r a c t

Article history: A concept of microwave-assisted reactive distillation (MARD) processing using microwave heating has
Received 22 January 2018 been proposed recently. However, there is no report about the continuous experiments to evaluate this
Received in revised form 20 May 2018 process which is more difficult to realize. To carry out this investigation, a DN 100 pilot-scale continuous
Accepted 22 May 2018
MARD column has been developed for synthesis of Di-2-ethylhexyl phthalate (DOP), which consists of a
Available online 24 May 2018
10 kW microwave generator, a cavity and a set of novel equipment used in the microwave field. The
experimental results indicate that the esterification performance could be enhanced based on the effects
Keywords:
of microwave on the relative volatility to remove water rapidly. This article also describes the results of a
Reactive distillation
Microwave
modeling study performed to understand the intensification mechanism in continuous MARD process. It
Process intensification points out the trends of both the reactant conversions and the product purities. It is very important to
Esterification understand the MARD process and design large-scale MARD process for industrial application.
This work has been selected by the Editors as a Featured Cover Article for this issue.
Ó 2018 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction chemical reaction by simultaneous product removal (Krishna and

Integration of different functionalities within a single device
represents an important way towards process intensification in
the current chemical engineering field (Gorak and Stankiewicz,
2011). Reactive distillation (RD), one of the best-known examples
of the process intensification, has been widely applied to etherifi-
cation, esterification, hydrolysis, hydrogenation reactions and so
on (Malone and Doherty, 2000). This integration offers several
advantages, such as reduction of investment and operating costs,
improvement of conversion and selectivity for equilibrium-
limited reactions and avoidance of azeotropes. A reactive distilla-
tion column is a multiphase reactor which aims at improving
⇑ Corresponding author.
E-mail address: lihongtju@tju.edu.cn (H. Li).
Sie, 1994). It has received much attention as a substitute of con-
ventional technologies (Chiu et al., 2006; Ehlers and Fieg, 2014;
Huang et al., 2010; Wang and Wong, 2006). However, the key lim-
itation of reactive distillation technology is that the necessary con-
ditions (such as pressure and temperature) for the reaction must
match those of distillation (Li et al., 2016b; Sundmacher and
Kienle, 2006). Owing to this constraint, the reaction conversion
may be adversely affected by unsuitable temperature in the reac-
tion section of RD column.
In recently, reactive distillation with microwave-assisted can be
an attractive alternative to the use of alternative energy forms in
industrial esterification (Altman et al., 2010; Gao, 2011). Selective
energy absorption, non-pollution, high energy efficiency and high
product quality are several advantages of microwave heating
(Bhattacharya et al., 2013). By means of microwave irradiation into

https://doi.org/10.1016/j.ces.2018.05.036
0009-2509/Ó 2018 The Authors. Published by Elsevier Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
252 X. Gao et al. / Chemical Engineering Science 186 (2018) 251–264

Nomenclature

A acid value, mgKOH/g Miso mass fraction of isooctanol

Bmono mass fraction of monoester in the bottom distillate Mmono molar mass of monoisoctyl phthalate, g/mol
CA molar concentration of isooctanol, mol/dm3 mmono mass fraction of monoester in the feeding
CM molar concentration of monoisoctyl phthalate, mol/dm3 N molar concentration of KOH standard solution, mol/L
Dmono mass fraction of monoester in the top distillate R ideal gas constant, 8.314 Jmol1K1
F weight of the sample, g r reaction rate, mol dm3min1
Gbottom mass flow of the bottom distillate, kg/h T reaction temperature, K
Gfeed feeding, kg/h V volume of KOH standard solution consumed, ml
Gtop top distillate, kg/h Win sample weight before evaporation, g
k reaction rate constant, dm3mol2min1 Wre weight of remaining sample after evaporation, g
MKOH molar mass of KOH, g/mol
Mester mass fraction of monoisoctyl phthalate in the sample,
g/mol

reactive distillation column, not only could the reaction rate for a production. Because the second step is reversible and slow
slow reaction be enhanced and efficiency of distillation separation with small chemical equilibrium constant, water needs to be
be improved, but also the irreversibility associated with the distil- continuously removed from the system to attain an ideal
lation separation operation be reduced by bulk heating of micro- conversion. Thus the reaction rate equation of this second-order
wave irradiation, both of which contribute actually to the reaction can be regarded as irreversible. Property data of pure
improvement of reactive distillation system performance. In the components involved is shown in Table 1. Due to the high relative
former situation, reaction sections and separation stages would volatility of these components, both the temperature and reaction
be reduced by improving reaction rate and separation efficiency rate in the column are low and the required residence time is too
(Altman et al., 2010). In the latter situation, smaller column and long. Therefore, any improvement in the reaction and separation
reflux ratio can achieve a specified separation. The improvement functions could have a significant application and direct impact
in system performance can permit further reduction in capital on the esterification production process. Since the VLE between
investment and therefore leads to a more compact process design, polar and nonpolar reactants could be enhanced by microwave
which is one of the main features of process intensification irradiation and water is a polar component compared with other
(Stankiewicz and Moulijn, 2002). components, microwave contributes to the fast removal of water
The aim of this paper is to propose a new process coupling and then pushes this reaction.
intensification technology – microwave reactive distillation tech-
nology to intensify the esterification synthesis reactions and
exploit more applications for reactive distillation. Firstly, we built ð1Þ
a set of equipment for microwave reactive distillation with a
100 mm inner diameter and over 6 m in height column. Then we
experimentally explored the reaction by microwave reactive distil-
lation technology (MRD) and isooctanol stripping microwave reac-
tive distillation technology (IoSMRD), which differ in the feed
location of reactants. In IoSMRD process, the liquid monoester
and gaseous isooctanol are added at the top and bottom of the
microwave reaction zone respectively. The stripping vapor changes ð2Þ
the partial pressure of each component thereby the temperature
and composition profiles differ. Thus the IoSMRD process obtains
a higher conversion. In the latter case, the simulation and analysis
of DOP esterification microwave reactive distillation process using
steady-state equilibrium stage model were carried out. Based on
The principle of this intensified process is depicted in Fig. 1. The
these, the effects of feed condition and location, feed flow and mass
shaded part is a microwave cavity covering the reaction zone
ratio of reactants, reflux flow, the height of the microwave reaction
which is irradiated by microwave. The radiation could allow for
section and rectifying section, microwave power density and liquid
higher reaction speed, less reaction time and smaller reactor vol-
holdup on conversion were investigated.
ume (Ding et al., 2016; Liu et al., 2012; Werth et al., 2015). The
effects of microwave make the conditions of reaction and distilla-
tion match well with each other. On the other hand, to describe the
2. Process description
ability of a material to absorb microwave energy, the dielectric
constant is used as a parameter. Water has the highest dielectric
The esterification of phthalic anhydride with 2-ethylhexanol
constant among all the components involved, therefore, it stores
is a reversible endothermic reaction with the target product,
the most microwave energy (Robinson et al., 2010). Besides, the
di-2-ethylhexyl phthalate (DOP), and the co-product water. The
complete reaction is described by Eqs. (1) and (2). Two step Table 1
processes are involved in the reaction. The first step is irreversible Physical properties of main reactants.
to obtain monoester from the esterification of phthalic anhydride
Property 2-ethylhexanol DOP Water
and 2-ethylhexanol at 130 °C without catalyst. While in the second
step, the intermediate product monoester continues to react with M (g/mol) 130 390 18
Tb (1.013 bar) (°C) 185 370 100
2-ethylhexanol to form DOP and water. It requires catalyst and
Dielectric constant 7.2 5.1 78
tetrabutyl titanate is chosen which is extensively used in industrial
 X. Gao et al. / Chemical Engineering Science 186 (2018) 251–264
Fig. 1. Envisioned reactive distillation column for the esterification of DOP
irradiated with microwave.
relative volatility of the substance in the reactive system is an
important parameter to evaluate the feasibility of the reactive dis-
tillation process. Microwave radiation helps enhance the relative
volatility of two substances (Gao et al., 2013) from the above.
The evaporation of water is stimulated and the instantaneous
withdrawal of water shifts the equilibrium to the product side thus
improving product formation.
3. Experimental section
3.1. Materials
The suppliers and specifications of the chemicals used in this
research are as follows:
Phthalic anhydride, industrial grade, PetroChina Jinzhou Petro-
chemical Company.
2-ethylhexanol (isooctanol), industrial grade, PetroChina Jilin
Petrochemical Company.
Tetrabutyl titanate, analytical reagent, Sinopharm Chemical
Reagent Corporation.
3.2. Structured packing
The performance of packing has a great impact on the catalytic
reactive distillation process so it should be seriously selected
(Kołodziej et al., 2004; Noeres et al., 2002). Firstly, the packing
for microwave assisted reactive distillation is essentially transpar-
ent to the microwave energy with negligible absorption (Meier
et al., 2009). Then it should guarantee sufficient residence time
for liquid reaction and mass-transfer efficiency between vapor
and liquid in this homogeneous reaction to satisfy both the reac-
tion and distillation requirements. Accordingly a specialized por-
ous packing is proposed in this article for the microwave reactive
distillation, called MRDPAK (Microwave Reactive Distillation Pack-
ing). Fig. 2 shows a schematic representation of MRDPAK.
253
Fig. 2. Schematic representation of MRDPAK.
MRDPAK is one of the corrugated structured packing which is
made of the resinous material that is transparent for microwave.
It is porous with a fine three-dimensional network structure and
characterized by high specific area, low structural resistance and
high efficiency for mass transfer (Gao et al., 2012). Moreover, the
thickness of each corrugated sheet is adjustable to control the rela-
tionship between liquid holdup and separation efficiency accord-
ing to the requirements of different microwave reactive
distillation processes. When the reaction rate is limiting, increasing
the corrugated sheet thickness raises the liquid holdup, thereby
increasing the residence time of reactants in the column. When
the chemical equilibrium is limiting, the separation efficiency
increases by decreasing the corrugated sheet thickness.
3.3. Apparatus
A schematic diagram of the apparatus used in the microwave-
assisted reactive distillation process for production of DOP esterifi-
cation is shown in Fig. 3. The microwave reactive distillation (MRD)
column with an inner diameter of 100 mm consists of six parts. The
inner and out sides of the column are made of Teflon and stainless
steel respectively. The first four parts are rectifying section packed
with the SiC corrugated structured packing and each of them is 1 m
long. The other two parts are reaction zone which are made of
microwave transparent materials and packed with the MRDPAK
packing. The height of the two parts in reaction zone can be
adjusted to 1 m, 1.5 m and 2 m according to the specific require-
ments. Liquid distributors with sampling ports are positioned in
the column at equidistant axial positions, 100 mm from each other.
The reaction section of the RD column is placed in the microwave
cavity, which is 0.5 m long and wide and as tall as the reaction sec-
tion. Associated instrument for microwave irradiation comprises a
microwave generator, a rectangular cavity, a three-port circulator,
a rectangular waveguide, a microwave leakage detector, a micro-
wave reflection modulator and a water dummy. The waveguide
propagates microwaves into the cavity. The microwave generator
consists of a 10 kW continuous variable power microwave source
operating at 2.45 GHz. The three-port circulator is used to control
the conduction direction of the microwaves. The microwave reflec-
tion modulator is a three-stub tuner, which measures and controls
the reflected power to ensure that less power is reflected back to
the microwave source (Gao et al., 2013). The water dummy load is
254 X. Gao et al. / Chemical Engineering Science 186 (2018) 251–264

Fig. 3. Diagram of microwave reactive distillation experimental set-up for DOP esterification. (1) material kettle; (2) microwave reactive distillation; (3) microwave cavity;
(4) rectangular waveguide; (5) microwave generator; (6) condenser; (7) liquid-liquid separator; (8) storage tank of isooctanol and catalyst; (9) reflux metering pump; (10)
heat exchanger; (11) feeding metering pump; (12) isooctanol vapor kettle; (13) isooctanol metering pump; (14) microwave reflection modulator; (15) three-port circulator;
(16) water dummy load; (17) variable attenuator; (18) ampere meter; (19) microwave leak detection instrument.

used to remove any irradiation transmitted through the waveguide
and can be used to reach an energy balance on the system.
Vapor is going up through the column and is condensed in the
condenser. Liquid outlet of the condenser connects a liquid-liquid
separator, which separates the aqueous and organic phases and
therefore allows a recycling of unused reactants to increase the
conversion and thereby decreases the costs of the process
(Niesbach et al., 2013). Thus the organic phase which consists of
isooctanol is collected in a storage tank and transferred from the
storage tank to the liquid distributor at the top of the column by
a liquid metering pump. The liquid and gas inlets are set at the
top and bottom of the microwave reaction zone, respectively.
The tetrabutyl titanate catalyst is pumped in the reflux from the
storage tank at the top and can be recycled. The liquid feed is
pumped from a reactant kettle to a heat exchanger in front of
the inlet. The isooctanol liquid is added into a steam kettle by a
metering pump and then transferred to the gas inlet. Some ther-
mocouples are installed at the column body, inlets and distributors
to measure temperature and connected with a recorder to record
the temperatures online. The column, microwave cavity and all
the pipes are wrapped with insulation layers. Each heater is con-
nected with a transformer to guarantee that the heating voltage
is under control.
3.4. Experimental procedure
After the calibration of metering pumps and thermocouples,
leak checks were performed to verify that the device was sealed.
Prior to performing a series of measurements, the setup was oper-
ated at a high vapor feed and reflux rate for a while to ensure thor-
ough wetting of the packing. A certain proportion of phthalic
anhydride and isooctanol were heated slowly at 140 °C in the reac-
tant kettle until the phthalic anhydride was completely dissolved
and the first step of DOP esterification reaction was completed
with the product, monoisoctyl phthalate. Then liquid phase sam-
ples could be taken for analysis. A certain amount of isooctanol
was added for different molar ratios of monoester to isooctanol
as reactants for the following operations.
Firstly, the reactant kettle was heated to 150 °C. The isooctanol
vapor kettle was heated and circulation of cooling water at the
top of the column began at the same time. The metering pump
and the heating voltage were adjusted to ensure a moderate level
in the kettle and a constant vapor rate for the reaction. Then turn
on the power of heat exchanger in front of the liquid inlet until
the oil bath reached 220 °C. Open the valve and pump and adjust
the heating voltage and flow to ensure the feeding a required tem-
perature. Meanwhile the metering pumps at the top of the column
for isooctanol backflow and catalysts were turned on and adjusted
to a desired flow. When the distillate appeared at the bottom, the
microwave generator was started at a predetermined output power
and the water dummy load was also turned on in case the energy
returned to the microwave generator. A microwave leakage detec-
tor was used to determine the leakage of microwave energy. Then
the generator stabilized at a certain power to make the inner col-
umn maintain at less than 255 °C. The power was controlled by
adjusting the microwave reflection modulator for maximum
absorption (Li et al., 2017). Measure the distillate flow rate at both
the top and bottom of the column every once in a while and observe
their fluctuations. When the flow rate and temperature distribution
in the column reached a steady state, the feed at the bottom was
sampled and analyzed. When the composition of the sample kept
constant for a few hours, the operation was considered stable and
samples were taken from top to bottom for analysis.
After sampling, operating conditions were recorded such as
microwave power, flow rate at the top and bottom, temperature
of each point and operating time. Then the experiments were
repeated at different operating conditions.
3.5. Analysis method
The acid value is a number that expresses in milligrams the
quantity of potassium hydroxide required to neutralize the free
 X. Gao et al. / Chemical Engineering Science 186 (2018) 251–264 255

acids present in 1 g of the substance. It reflects the quality of

plasticizer products such as DOP. In this study, monoisoctyl phtha-
late was titrated according to GB1668-81 method. Dissolve 1.00 g
of the monoester in 50 mL anhydrous ethanol and 2–3 drops of
1% phenolphthalein solution were used as indicator. The sample
was neutralized with 0.1 mol/L potassium hydroxide until the pink
color appeared and persisted for at least 15 s.
The acid value of the sample was calculated by
A ¼ N  V  M KOH =F
The mass fraction of monoisoctyl phthalate Mester in the sample
could be calculated by
M ester ¼ N  V  103  Mmono =F
where A is the acid value of sample (mgKOH/g), N is the molar con-
centration of KOH standard solution (mol/L), V is the volume of KOH
standard solution consumed (ml), F is the weight of sample (g),
Mester is the mass fraction of monoisoctyl phthalate in the sample,
MKOH is the molar mass of KOH (g/mol) and Mmono is the molar mass
of monoisoctyl phthalate (g/mol).
Because the boiling point of isooctanol is significantly lower than
that of monoester and DOP, reduced pressure evaporation was used
to measure the content of isooctanol. About 20 g sample was evap-
orated under 8 kPa and 140 °C in a rotary evaporator until no more
vapor appeared. The remaining sample was weighed and the mass
fraction of isooctanol was calculated as follows:
W in  W re
M iso ¼
W in
where Miso is the mass fraction of isooctanol, Win is the sample
weight before evaporation (g) and Wre is the weight of remaining
sample after evaporation (g).
The conversion rate was calculated by
Bmono  Gbottom þ Dmono  Gtop
X ¼1
mmono  Gfeed
4.1. Thermodynamic and physical properties in microwave field
The selection of thermodynamic model is of vital importance
during the simulation of microwave distillation process, especially
the vapor – liquid equilibrium. In our previous papers (Gao et al.,
2013), the vapor – liquid equilibrium experimental data in the
microwave field is depicted by the UNIQUAC equation and
Hayden-O’Connell (HOC) equation. The effect of microwave field
ð3Þ on VLE is more prominent in the binary system with a larger
dielectric constant difference between the two substances. As for
isooctanol/DOP, there’s no noticeable shifting of VLE because of
their narrow difference in dielectric properties. Thus the UNIQUAQ
parameters were modified by VLE data of isooctanol/DOP under 50
ð4Þ W. The VLE data of isooctanol/DOP was obtained by previous
experiments. The modified binary interaction parameters of
UNIQUAC model are listed in Table 2.
4.2. Reaction kinetics in microwave field
The simulation of DOP esterification needs both phase equilib-
rium data and reaction kinetics equations. Microwave radiation
changes not only the thermodynamic properties but also reaction
kinetics, which makes the process more complicated than conven-
tional reactive distillation. Thus, the reaction kinetics model is also
crucial in the simulation process. Since the first step of this ester-
ification reaction is rapid, the reaction rate equation only expresses
the second step, which is a second-order reaction. The reaction
kinetics of DOP esterification was determined in our self-made
ð5Þ
microwave reactor previously (Gao, 2011). And the reaction rate
constant expression is determined by Arrhenius formula. Equa-
tions of DOP esterification are presented as follow:
r ¼ kC M C A ð7Þ
 
43770
ð6Þ k ¼ 1:04  104 exp  ½L=mol  min ð8Þ
RT

where Gbottom , Gtop and Gfeed are the mass flow of the bottom
distillate, the top distillate and the feeding, respectively (kg/h);
Bmono , Dmono and mmono are the mass fraction of monoester in the
bottom distillate, the top distillate and the feeding, respectively.
The measuring method of them is the same as Mester.
where CM is the molar concentration of monoisoctyl phthalate, mol/
dm3; CA is the molar concentration of isooctanol, mol/dm3; k is the
reaction rate constant, dm3mol2min1; r is the reaction rate, mol
dm3min1; R is the ideal gas constant, 8.314 Jmol1K1; T is the
reaction temperature, K.

4. Modelling and simulation 4.3. Energy consumptions in microwave field

In this part, the simulation and analysis of DOP esterification are
on the basis of considering the impact of the microwave field and the
performance of packing (Gao et al., 2010). Then the steady-state
equilibrium stage model of DOP esterification microwave reactive
distillation process is developed, and the simulation and analysis
of DOP esterification microwave reactive distillation process using
this model are carried out. In the modelling, the effect of microwave
power can be divided into two parts. One is regarded as input energy
and the other influences the reaction rate and vapor – liquid equilib-
The microwave energy is assumed to be completely absorbed
by liquid phase as a result of the low density of vapor phase and
the energy is transferred by the pump-around circuit in RadFrac
module. Besides, the input energy is nonuniform and the highest
energy density is at the input port. So the input energy we set
decreases from the input to the output port gradually.
Table 2
Modified binary interaction parameters of UNIQUAC model.

rium. Thus a heat balance is taken into account in the steady-state UNIQUAC Water(i) + Isooctanol(i) + Water(i) +
equilibrium stage model. Rigorous simulations of the DOP esterifica- parameters Isooctanol(j) DOP(j) DOP(j)
tion are carried out using RadFrac model of Aspen Plus software. ri 0.9200 6.1509 0.9200
There are four hypotheses for the simulation: rj 6.1509 16.1015 16.1015
qi 1.4000 5.2080 1.4000
qj 5.2080 12.8480 12.8480
(1) The whole process is under stable condition;
aij 0 -54.8087 0
(2) Reactions occur only in the liquid phase; aji 0 11.8632 0
(3) The liquid and vapor phases are well mixed on each theoret- bij 301.9678 431.148 173.2911
ical stage; bji 177.7914 2112.29 570.2339
cij 0 7.6528 0
(4) The vapor and liquid phases left from each stage are
cji 0 3.6227 0
assumed to be in phase equilibrium.
256 X. Gao et al. / Chemical Engineering Science 186 (2018) 251–264

5. Results and discussion The comparison of concentration profile in column between

The aim of our work is to show the feasibility of di-2-ethylhexyl
phthalate synthesis using microwave reactive distillation process.
These experiments also provide consistent, reliable process data
that can be used for subsequent extensive model validation. The
following parameters are adjusted for analysis: feed condition
and location, feed flow and mass ratio of reactants, reflux flow,
the height of the microwave reaction section and rectifying section,
microwave power density and liquid holdup. Detailed parameters
for experiments and simulations are listed in Table 3.
5.1. Modeling validation
The experimental and simulation parameter values are shown
in Table 3. The experimental and simulation parameters for model
validation are not identical because of limitations of experimental
conditions. If the simulation parameters are identical to experi-
mental ones, the outputs must be quite different and the model
validation loses it significance. Thus the model is able to reproduce
the experiments qualitatively so far.
experimental data and simulation results is shown in Fig. 4a. There
are some deviations because the isooctanol is fed from the bottom
of the column as vapor phase, which is so hard to control that a
slight fluctuation results in the deviation. Besides, a significant
deviation is found at the 11th theoretical stage where two micro-
wave cavities connect. The most probable explanation for this
behavior is that the temperature there is high and some isooctanol
may vaporize in the process of sampling. Another reason is that the
content of isooctanol in the sample is too small to be steamed out
completely during rotary evaporation.
Fig. 4a also presents the concentration profile of four materials:
(1) The content of water in liquid phase is almost zero because of
its low boiling point; (2) The content of DOP peaks below the
microwave reaction zone. It first increases from the top as the reac-
tion accumulates. Then the content decreases because the low-
temperature isooctanol vapor is fed from the bottom and heat
and mass transfer appears. Finally the content of isooctanol is
higher in the bottom; (3) There’s a maximum of monoester’s con-
tent and the position of the maximum changes as the operating
condition. When the reflux flow of isooctanol is high, the

Table 3
Experimental and simulation parameter values.

Parameter Experimental parameter value Simulation parameter value Fixed/changed parameter Fixed/changed parameter
for model validation for model validation value in experiment value in simulation
Microwave power density (W/kgh) 111 25 122 25
0–133 11–56
Isooctanol vapor feed flow (kg/h) 36 33.2 36 –
28–40
Monoester phase feed flow (L/h) 30 30 30 –
20–50
Mass ratio of isooctanol vapor to – – – 1.07
monoester phase feed 0.50–2.50
Reflux flow (kg/h) 2.8 3.8 2.8 0.17
1.4–8.2 0.03–1.4
Mass ratio of monoester to isooctanol 0.834 0.941 0.834 0.442
in monoester phase feed 0.556–1.091 0.714–1.429
Height of microwave reaction section (m) 2.5 – 2.5 –
2–3
Feed location of monoester phase – 8th – 6th
2nd–6th
Feed location of isooctanol vapor phase – 15th – 15th
2nd–15th

Fig. 4. Comparison of concentration profile (a) and temperature profile (b) in column between experimental data and simulation results (IoSMRD). (Dot: experimental value;
Line: calculated value).
 X. Gao et al. / Chemical Engineering Science 186 (2018) 251–264
maximum exists at the lower part of the center and vice versa.
Because when the reflux increases, the withdrawal on the top of
column decreases and the change of isooctanol’s concentration
profile leads to its high content at rectifying section and a reduc-
tion of monoester’s content; (4) Similar to monoester, there’s a
minimum of isooctanol’s content at the lower part of the column.
The concentration decreases gradually from the top because of
its consumption as a reactant and the stripping of isooctanol
results to its increase near the bottom.
At a known pressure, the higher the temperature is, the more
the heavy component accumulates while the lower the tempera-
ture is, the more the light component appears. Thus the concentra-
tion profile is closely linked to temperature. Temperature profile is
also an important factor to the performance of reaction. The com-
parison of temperature profile between experimental data and
simulation results is shown in Fig. 4b. The temperature changes
sharply at the lower part of the column and there’s a maximum
of temperature at the middle of microwave reaction zone because
of the stripping of isooctanol vapor. The addition of isooctanol
vapor from the bottom increases the partial pressure of isooctanol
in the vapor phase and the content of isooctanol in the liquid
phase, then the temperature decreases. While the feeding temper-
ature is under bubble point, the feed needs heating to reach the
bubble point so the temperature increases. Thus there is a maxi-
mum in the middle of the microwave reaction zone.
Overall, the simulation results are basically consistent with
experimental data, which indicates the reliability of the model
although the model is able to reproduce the experiments qualita-
tively but not quantitatively. Some deviations may be caused by
the nonuniformity of packing surface wetting and the nonideal
flow behaviors of the liquid on packing during experiments, which
lead to differences of packing surface utilization percentage and
liquid residence time on packing. Besides, there are many random
factors that are difficult to carry out in simulating. For example, the
kinetics data measured from batch reaction system can’t apply to
continuous reaction exactly. But they are all within the scope of
acceptable. This model will contribute to the subsequent studies.
5.2. Feed condition and location
Two types of experiments are designed and carried out, which
are microwave reactive distillation (MRD) process and isooctanol
stripping microwave reactive distillation (IoSMRD) process. In the
first set of experiment, both monoester and isooctanol are fed into
the column in liquid form at the top of the microwave reaction sec-
tion, whereas in the second set of experiment the liquid monoester
and gaseous isooctanol are added at the top and bottom of the
microwave reaction zone respectively. The catalyst is transported
by the reflux at the top of the column. The effects of two processes
for producing DOP are as follows.
The comparison in Table 4 indicates that with the same micro-
wave power density, the conversion in IoSMRD is much higher
Table 4
Comparison of two processes technology for producing DOP.
Operation parameters
Monoester liquid feed flow rate (L/h)
Isooctanol vapor feed flow rate (kg/h)
Height of microwave reaction zone (m)
Reflux flow (kg/h)
Microwave power density (W/kgh)
Position of monoester liquid feed
Position of isooctanol vapor feed
Mass ratio of monoester to isooctanol in monoester phase feed
Conversion
257
than that in MRD process since stripping vapor changes the partial
pressure of each component thereby the temperature and compo-
sition profiles differ.
As shown in Fig. 5, in IoSMRD process, the temperature in the
middle part is higher than both ends because the temperature of
stripping isooctanol vapor is lower than that in reaction zone and
it flows counter-currently with the liquid reactants until the liquid
reaches bubble point. Where there are more heavy components,
there is a higher temperature. The positions near inlet and bottom
of the column with a high content of light component, isooctanol,
own a lower temperature than the middle.
With the same microwave power density, the highest tempera-
ture in IoSMRD is higher than MRD because of the isooctanol vapor
which provides energy by phase change. The latent heat improves
the liquid temperature to bubble point and microwave energy
increases temperature and content of monoester in the reaction
zone. Furthermore, the vapor provides another reactant isooctanol
for the system continuously. Thus the IoSMRD process obtains a
higher conversion than MRD process and the subsequent studies
are based on the IoSMRD process.
The influences of the location of monoester and isooctanol feed
and the following conditions on conversion are all studied by sen-
sitivity analysis tools. The simulation is performed by systemati-
cally varying the location of one feed at a time and the changes
on the process outputs are studied. As seen in Fig. 6a, when the
feed location of monoester moves from the 2nd to the 8th stage,
the conversion decreases slowly, while when it moves from the
Fig. 5. Comparison of two microwave reactive distillation processes.
Process technology
MRD IoSMRD
30 30
– 36
2.5 2.5
5.6 2.8
111 111
Top of the microwave reaction zone Top of the microwave reaction zone
– Bottom of the microwave reaction zone
0.748 0.834
0.7248 0.9738
258 X. Gao et al. / Chemical Engineering Science 186 (2018) 251–264

Fig. 6. The influence of the location of monoester phase feed (a) and isooctanol vapor feed (b) on conversion by simulations.

8th to the 14th stage, the conversion decreases drastically. It is
because the zone between the 2nd and the 8th stage is rectifying
section while the zone between the 8th and the 14th stage is
microwave reaction section. When the location moves down in
the microwave reaction section, the residence time of reaction
shortens and leads to a low conversion. Moreover, Fig. 6a shows
that when the location of monoester phase feed is higher than
the 6th stage, the monoester concentration in column top increases
to over 0.01 mol/L, which doesn’t meet the industrial requirement.
A high monoester concentration in column top not only wastes
monoester but also increases the capital expenditure and energy
consuming. Based on the above analyses, we can see the optimal
location of monoester phase feed is at the upper part of the
column.
When the monoester phase is fed at the 6th theoretical stage
and the other conditions remain unchanged, the influence of the
location of isooctanol vapor feed on conversion is shown in
Fig. 6b. As the location moves from the 5th to the 15th stage, the
conversion increases monotonically and maximizes at the bottom.
It is because the isooctanol vapor not only supplies enough
isooctanol for the reaction but also reduces the partial pressure
of water in the vapor phase, which removes water from the system
constantly. Thus the optimal location of isooctanol vapor feed is at
the bottom of reaction section.
5.3. Microwave power density
The total mass flow of reactants is 45 kg/h and the impact of
using microwave is expressed by microwave power density. The
effects of microwave power density on the reaction conversion
and temperature in reaction zone are investigated by experiments
with a power density of 0 W/kgh, 67 W/kgh, 78 W/kgh, 89 W/
kgh, 100 W/kgh, 111 W/kgh, 122 W/kgh and 133 W/kgh as
shown in Fig. 7a. It can be seen that without microwave radiation
there is almost no reactions because of the low temperature. Then
the conversion and maximum temperature increase with the raise
of power density, which indicates that microwave irradiation
indeed intensifies chemical reactions. As for conversion, there’s a
marked increase from 67 W/kgh to 122 W/kgh and little change
appears close to 133 W/kgh. However, the maximum temperature

Fig. 7. The influence of the microwave power density on conversion. ((a): experimental results; (b): simulation results).
 X. Gao et al. / Chemical Engineering Science 186 (2018) 251–264 259

in reaction zone increases continuously even though the power Table 6

density is close to 133 W/kgh. From the above analysis, we can The temperature profile in column when microwave input from the top of lower part
of cavity.
see that an optimum power density exists in the microwave reac-
tive distillation process (Bhattacharya et al., 2013) and should be Theoretical stage Microwave input density (W/kgh) Temperature (°C)
determined for separation rather than increasing the power den- 1 – 182.3
sity blindly (Li et al., 2017). Otherwise too high power not only 2 – 185.1
increases energy consumption but also changes the relative 3 – 190.9
4 – 199.5
volatility. 5 – 207.1
As for simulations, there are 7 theoretical stages in rectifying 6 – 211.8
section and 8 theoretical stages in reaction section. When the 7 – 213.9
power is input from the bottom of the cavity, the influence of the 8 1.11 214.1
9 1.67 226.1
microwave power density on conversion is shown in Fig. 7b. The
10 2.22 240.3
conversion increases with the microwave power density and when 11 5.33 252.1
it increases to a certain level, the conversion increases really 12 4.44 256.7
slowly. In order to keep the monoester concentration in column 13 4 254.1
top constant and ensure that the temperature cannot be too high, 14 3.56 243.8
15 3.11 224.2
the reflux needs to be increased. The temperature in column
should be less than 255 °C to prevent side reactions and protect Bold numbers represents the highest temperatures.
the column materials. Thus the optimal power density is between
44 W/kgh and 49 W/kgh.
The discrepancy between experiment and simulation is mainly 5.4. Feed flow and mass ratio of reactants
caused by heat loss and the structure of microwave cavity. Micro-
wave can’t be absorbed sufficiently during experiments on account The consumption of isooctanol vapor is important for evaluat-
of various conditions such as leakage and reflection. While during ing the whole energy consumption of the IoSMRD process. The
simulating we could consider microwave energy is utilized com- effect of isooctanol vapor feed flow on reaction conversion is inves-
pletely. Besides, the structure of cavity may be not optimal, which tigated with the isooctanol vapor feed flow of 28 kg/h, 32 kg/h, 36
influences the absorption of microwave energy. Unsuitable struc- kg/h and 40 kg/h as shown in Fig. 8a. The conversion increases
tures of cavity such as those with corners enhance microwave quickly first then slows down with the raise of isooctanol vapor
reflections thus energy is wasted gradually. Thus the discrepancy feed flow. Because the vapor can not only supply adequate reac-
is allowed here. More remarkable, the microwave power is tants but also reduce the partial pressure of water in the gaseous
regarded as input energy during simulation. We think that the phase in order to remove the co-product water from reaction zone.
power directly influences temperature and then the reaction rate However, a higher vapor feed flow brings little change on the con-
is influenced by temperature. In other words, the reaction rate version but more energy consumption. Therefore, when the vapor
parameters and microwave power are not directly related to each feed flow increases, both conversion and energy consumption
other. increase and there should be a trade-off problem between them.
Besides, the microwave cavity is divided in two parts. The 8th Thus the optimum isooctanol vapor feed flow is 36 kg/h.
to 10th theoretical stage is the upper part of cavity and 11th to The effect of monoester phase feed flow on conversion is inves-
15th is the lower part. The microwave is input from the top tigated with a varied feed flow of 20 L/h, 30 L/h, 40 L/h, 45 L/h and
and bottom of the lower part of cavity respectively. The total 50 L/h as shown in Fig. 8b. It demonstrates that the conversion
power density remains constant. As shown in Tables 5 and 6, increases with the growing monoester phase feed flow at first
the power density maximizes at the input stage and gradually and decreases later. To begin with, the partial pressure of isooc-
decreases as the microwave propagates. And the maximum tem- tanol in the gaseous phase and the content of isooctanol in the liq-
perature is 248.1 °C and 256.7 °C in Tables 5 and 6 respectively, uid phase fall as the reaction goes on. Thereby the temperature and
which means the way of microwave input influences the reaction rate increase. However, when the feed flow reaches 50 L/h,
temperature profile and when it is input from the top, the energy the conversion descends to 0.76. Because the distillate from bot-
is used most efficiently. tom increases as the feed flow rises, which makes the concentra-
tion of isooctanol in the reaction zone higher and the
temperature lower.
Table 5 Effect of mass ratio of monoester to isooctanol in monoester
The temperature profile in column when microwave input from the bottom of lower phase feed on conversion is investigated with a ratio of 0.556,
part of cavity.
0.834, 0.941 and 1.091 as shown in Fig. 8c. When the ratio of
Theoretical stage Microwave input density (W/kgh) Temperature(°C) monoester to isooctanol increases from 0.55 to 0.83, the conver-
1 – 181.5 sion increases because less isooctanol vapor increases the temper-
2 – 181.9 ature in reaction zone. While the ratio increases continuously, the
3 – 182.1 conversion descends instead because the content of isooctanol is
4 – 182.4
insufficient for the reaction. Both mass ratio of monoester to isooc-
5 – 183.6
6 – 187.4 tanol in monoester phase feed and flow ratio of two feeds influence
7 – 196.5 conversion by changing mass ratio of reactants. But in two ways
8 1.11 210.3 the feed location and phase of isooctanol differ, which make a dif-
9 1.67 219.3
ference in reactant concentration profile and then the conversion
10 2.22 230.7
11 3.11 240.8
differs.
12 3.56 247.3 As can be seen from the experiments before, the energy con-
13 4 248.1 suming of isooctanol vapor accounts for 50% of the whole energy
14 4.44 241.7 consuming in the IoSMRD process. Thus the mass ratio of isooc-
15 5.33 224.5
tanol vapor to monoester feed deserves optimizing. Fig. 9a shows
Bold numbers represents the highest temperatures. that the conversion increases as the mass ratio increases firstly.
260 X. Gao et al. / Chemical Engineering Science 186 (2018) 251–264

Fig. 8. Effects of feed flow on conversion by experiments. ((a) isooctanol vapor feed flow, (b) monoester phase feed flow, (c) mass ratio of monoester to isooctanol in
monoester phase feed).

Fig. 9. The influence of the mass ratio of isooctanol vapor to monoester phase feed (a) and mass ratio of monoester to isooctanol in monoester phase feed (b) on conversion
and monoester concentration in column top by simulations.
 X. Gao et al. / Chemical Engineering Science 186 (2018) 251–264 261

When the ratio is more than 1.17, the conversion decreases
because the different content of stripping isooctanol vapor changes
its concentration in column. Besides, the monoester concentration
in column top increases monotonically with the increase of the
ratio. When the ratio is 1.17, the monoester concentration in col-
umn top is over 0.01 mol/L. Thus the optimal mass ratio of isooc-
tanol vapor to monoester feed is 1.07–1.17.
Table 7 shows the relationship between the mass ratio of isooc-
tanol vapor to monoester feed and temperature profile in column.
When the ratio is less than 1.17, as it increases, the location of
maximal temperature moves up and the high temperature and
enough reactants are guaranteed. When the ratio is more than
1.17, as it increases, the location of maximal temperature moves
up continuously but its temperature decreases. It is because too
much isooctanol stripping vapor increases the partial pressure of
isooctanol and its content in liquid phase, which leads to a low
reaction temperature and conversion.
The influence of the mass ratio of monoester to isooctanol in
monoester phase feed on conversion and monoester concentration
in column top is shown in Fig. 9b. It shows that the conversion
decreases monotonically with the increase of ratio and it decreases
more quickly when the ratio is high. It is because that with the
reflux unchangeable, the content of isooctanol in column decreases
as the ratio increases. In addition, more monoester in feed means
more monoester is withdrawn in column top. When the ratio is
more than 1.1, the molar concentration of monoester in column
top is over 0.01 mol/L. But a low monoester feed decreases the pro-
cessing capacity of equipment. Thus when the mass ratio of
monoester to isooctanol in monoester phase feed is in the range
of 0.8–0.85, both the equipment capacity and the conversion
requirements are met.
5.5. Reflux flow
Effects of reflux flow on reaction conversion and monoester
concentration in column top by experiments are investigated with
a reflux flow of 1.4 kg/h, 2.2 kg/h, 3.6 kg/h, 5.3 kg/h, 6.3 kg/h and
8.2 kg/h as shown in Fig. 10a. The conversion decreases as the
reflux flow rises because the increase in reflux flow results in the
reduction of isooctanol distillate at the top of column and the
increase of isooctanol at the bottom, which means the temperature
decreases especially in the reaction zone. Besides, the monoester
concentration in column top descends as the raise of reflux flow.
A low reflux flow rate weakens the separation effect thus some
monoester distillates from the top. In order to balance the factors,
both the reflux flow and the microwave power density need to be
increased. However, the energy consumption in the process
increases, which will be discussed in detail in the simulation part.

Table 7
The relationship between the mass ratio of isooctanol vapor to monoester feed and temperature profile in column.

Theoretical stage Mass ratio of isooctanol vapor to monoester feed

0.67 0.87 1.07 1.17 1.27 1.37 1.57 1.67 1.87 2.17
Top 179.5 180.6 181.3 182.9 184.9 186.5 188.8 189.6 190.9 193.3
2 180.4 181.2 181.8 187.0 191.6 194.5 197.8 198.9 201.3 213.4
3 180.5 181.3 181.8 195.9 202.0 205.0 209.3 211.2 215.0 217.2
4 180.6 181.4 181.9 207.9 212.3 214.5 216.9 217.5 217.7 217.3
5 180.6 181.5 182.3 214.6 216.5 217.4 218.1 218.1 217.7 217.1
6 180.9 182.0 184.4 216.2 217.1 217.5 217.8 217.8 217.5 217.0
7 182.6 185.0 192.6 215.7 216.4 216.9 217.3 217.3 217.2 216.8
8 201.6 204.4 209.8 214.5 215.4 216.0 216.7 216.8 216.9 216.6
9 206.1 209.7 218.5 225.4 226.6 227.3 227.8 227.6 226.9 225.4
10 211.2 216.2 229.0 237.0 237.9 238.2 237.4 236.6 234.7 231.6
11 216.6 223.3 238.7 245.7 245.7 245.0 242.6 241.1 238.0 233.7
12 222.6 230.6 245.4 250.2 249.1 247.4 243.5 241.4 237.4 232.3
13 228.4 236.1 247.1 249.3 247.2 244.7 239.8 237.5 233.1 227.9
14 231.4 236.2 241.7 241.6 238.9 236.2 231.1 228.9 224.9 220.3
Bottom 224.6 224.8 225.2 223.9 221.6 219.4 215.7 214.1 211.4 208.4

Bold numbers represents the highest temperatures.

Fig. 10. The influence of the reflux flow on conversion and monoester concentration in column top ((a): experimental results; (b): simulation results).
262 X. Gao et al. / Chemical Engineering Science 186 (2018) 251–264

In simulation process, as can be seen in Fig. 10b, when the reflux
flow varies from 1 to 3.5, the conversion increases significantly.
Because as the reflux flow increases, the separation efficiency in
rectifying section increases and the molar concentration of monoe-
ster in column top reduces to make sure that enough monoester
returns for reaction. When reflux flow varies from 3.5 to 14, the
conversion increases slowly. But the microwave power density still
needs to be increased for mass balance which makes energy waste
(Stefanidis et al., 2014). Thus reflux flow is a significant parameter
which influences the energy consumption and product quality (Li
et al., 2016a). Considering both energy consumption and conver-
sion, the optimal reflux flow is 6–8.
5.6. Height of rectifying and reaction section
The height of microwave reaction zone decides the residence
time as well as the reaction time, and correspondingly, reactions
will proceed more fully (Li et al., 2012). In the DOP esterification
microwave reactive distillation process, increasing the height of
rectifying and reaction section seems to be advantageous to the
reaction. However, excessive increase of the height increases cap-
ital expenditure (Simasatitkul et al., 2016), operating and main-
taining costs, energy consuming and so on. Due to the limitations
of experimental conditions, there are only 3 different heights
adjusted in the reaction section and the results are shown in the
following Table 8.
With the same microwave power density, the conversion
increases from 0.6420 to 0.9701 when the height varies from 2 m
to 2.5 m because the residence time increases. While the height
reaches 3 m, the power density needs to be increased to 156 W/
kgh to meet the demand of reaction zone. But the conversion only
increases by 0.185% compared to the height of 2.5 m, which is
uneconomical. Thus the selection of height needs to balance both
the energy consumption and the conversion and further study will
be simulated as follow.
The influence of the theoretical stage number on conversion
and monoester concentration in column top is studied by simula-
tions. The reflux flow is 4.15 kg/h. The mass ratio of DOP/isooc-
tanol/monoester in monoester phase is 5.98/1.26/1 and the mass
ratio of isooctanol vapor to monoester phase feed is 1. The height
of reaction section is fixed to 8 theoretical stages and the height
of rectifying section is adjusted constantly to investigate its influ-
ence on conversion.
As shown in Fig. 11a, the conversion increases as the height of
rectifying section increases and there is almost no influence on
conversion when the height is more than 8 theoretical stages.
Because there is much monoester back to reaction section after
separation and almost no water, which pushes the reaction to
the positive direction. Moreover, Fig. 11a shows that the
monoester concentration in column top decreases as the height
of rectifying section increases. When there are more than 4 theo-
retical stages in rectifying section, the requirement on monoester

Table 8
Comparison of three different heights of microwave reaction section.

Operating parameters Height of microwave reaction section (m)

2 2.5 3
Monoester feed flow rate (L/h) 30 30 30
Gaseous isooctanol feed flow rate (kg/h) 36 36 36
Reflux flow (kg/h) 2.8 2.9 2.7
Microwave power density (W/kgh) 111 111 156
Position of monoester feed Top of the microwave Top of the microwave Top of the microwave
reaction zone reaction zone reaction zone
Position of gaseous isooctanol feed Bottom of the microwave Bottom of the microwave Bottom of the microwave
reaction zone reaction zone reaction zone
Mass ratio of monoester to isooctanol 0.834 0.834 0.834
in monoester phase feed
Conversion 0.6420 0.9701 0.9719

Fig. 11. The influence of the theoretical stage number of rectifying section (a) and reaction section (b) on conversion by simulations.
 X. Gao et al. / Chemical Engineering Science 186 (2018) 251–264
Fig. 12. The influence of the liquid holdup of reactive packing on conversion by
simulations.
concentration is met. Thus the optimal theoretical stage number in
rectifying section is 7–8.
Then, with other conditions unchanged, the height of rectifying
section is fixed to 7 theoretical stages and the height of reaction
section is adjusted constantly. From Fig. 11b we can see that the
conversion increases with the raise of theoretical stage numbers
in reaction section and the less the theoretical stages are, the more
quickly the conversion increases. Because higher reaction section
provides more residence time for the reactants but after the con-
version reaches a certain level, the residence time has little influ-
ence on conversion. The conversion mainly depends on the
separating effects in rectifying section, which is mainly controlled
by the water content in liquid phase. Thus the conversion increases
slowly afterwards. When there are 12 theoretical stages in reaction
section, the conversion reaches 99%, which is the optimal height.
5.7. Liquid holdup of reactive packing
The liquid holdup of reactive packing is of vital importance in
reactive distillation process (Mahajani and Kolah, 1996). In this
section, the mass ratio of DOP/isooctanol/monoester in monoester
phase is 5.98/1.26/1 and the mass ratio of isooctanol vapor to
monoester phase feed is 1.07. The reflux flow is 4.15 kg/h. There
are 7 theoretical stages in rectifying section and 8 theoretical
stages in reaction section. As shown in Fig. 12, the conversion
increases with the liquid holdup and when the liquid holdup is
lower, the conversion increases more quickly. It is because large
holdup increases residence time for the reactant then it reacts
more thoroughly. However, too much liquid holdup reduces sepa-
ration capacity of the packing. The best matching between reaction
and separation should be guaranteed to make the most of reactive
distillation process. In this article, the specialized MRDPAK packing
is utilized and its holdup is in the range of 12%18%.
6. Conclusions
In this article, a novel process coupling intensification technol-
ogy – microwave-assisted reactive distillation technology is devel-
oped. DOP esterification reaction system is used as the research
object. The process of microwave reactive distillation esterification
263
and its contents are studied systematically. For the experimental
part of microwave reactive distillation process, the packing spe-
cially used in microwave field packing—MRDPAK packing is devel-
oped. Microwave reactive distillation column with MRDPAK is
established, and experiment is carried out by isooctanol stripping
esterification microwave reactive distillation process technology
developed by this paper. Compared with conventional reactive dis-
tillation and ordinary microwave reactive distillation, the results
show that the process technology of isooctanol stripping micro-
wave reactive distillation is better than other process technologies.
The steady-state equilibrium stage model of DOP esterification
microwave reactive distillation process is developed which could
reproduce experiments qualitatively and the simulations and anal-
yses of DOP esterification microwave reactive distillation process
using this model are carried out. The results of simulations agree
well with experimental results of this paper, indicating that the
model is enough to describe the process. The optimized operation
conditions are achieved by systematic simulations. The relevant
results provide the guidance and reference for design and industri-
alization of DOP esterification microwave reactive distillation
process.
Acknowledgements
The authors are grateful for the financial support from the
National Key Research and Development Program of China
(2018YFB0604905), and the National Natural Science Foundation
of China (Nos. 21336007 and 21306128).
References
Altman, E., Stefanidis, G.D., Van Gerven, T., Stankiewicz, A.I., 2010. Process
intensification of reactive distillation for the synthesis of n-propyl propionate:
the effects of microwave radiation on molecular separation and esterification
reaction. Ind. Eng. Chem. Res. 49, 10287–10296.
Bhattacharya, M., Venkata, S.K., Basak, T., 2013. Role of microwave heating
strategies in enhancing the progress of a first-order endothermic reaction.
Aiche J. 59, 656–670.
Chiu, C.W., Dasari, M.A., Suppes, G.J., Sutterlin, W.R., 2006. Dehydration of glycerol
to acetol via catalytic reactive distillation. Aiche J. 52, 3543–3548.
Ding, H., Liu, M., Gao, Y., Qi, J., Zhou, H., Li, J., 2016. Microwave reactive distillation
process for production of ethyl acetate. Ind. Eng. Chem. Res. 55, 1590–1597.
Ehlers, C., Fieg, G., 2014. Experimental validation of a flexible modeling approach for
distillation columns with packings. Aiche J. 60, 3833–3847.
Gao, X., 2011. Study on Catalytic Reactive Distillation Process Intensified by
Microwave Irradiation, PhD Thesis. Tianjin University, Tianjin.
Gao, X., Li, X., Li, H., 2010. Hydrolysis of methyl acetate via catalytic distillation:
simulation and design of new technological process. Chem. Eng. Process.
Process Intensif. 49, 1267–1276.
Gao, X., Li, X., Zhang, J., Sun, J., Li, H., 2013. Influence of a microwave irradiation field
on vapor–liquid equilibrium. Chem. Eng. Sci. 90, 213–220.
Gao, X., Li, X., Zhang, R., Li, H., 2012. Pressure drop models of seepage catalytic
packing internal for catalytic distillation column. Ind. Eng. Chem. Res. 51, 7447–
7452.
Gorak, A., Stankiewicz, A., 2011. Intensified reaction and separation systems. Ann.
Rev. Chem. Biomol. Eng. 2, 431–451.
Huang, K., Lin, Q., Shao, H., Wang, C., Wang, S., 2010. A fundamental principle and
systematic procedures for process intensification in reactive distillation
columns. Chem. Eng. Process. Process Intensif. 49, 294–311.
Kołodziej, A., Jaroszyński, M., Bylica, I., 2004. Mass transfer and hydraulics for
KATAPAK-S. Chem. Eng. Process. Process Intensif. 43, 457–464.
Krishna, R., Sie, S., 1994. Strategies for multiphase reactor selection. Chem. Eng. Sci.
49, 4029–4065.
Li, H., Cui, J., Liu, J., Li, X., Gao, X., 2017. Mechanism of the effects of microwave
irradiation on the relative volatility of binary mixtures. Aiche J. 63, 1328–1337.
Li, H., Huang, W., Li, X., Gao, X., 2016a. Application of the aldolization reaction in
separating the mixture of ethylene glycol and 1, 2-butanediol: thermodynamics
and new separation process. Ind. Eng. Chem. Res. 55, 9994–10003.
Li, H., Wu, Y., Li, X., Gao, X., 2016b. State-of-the-art of advanced distillation
technologies in China. Chem. Eng. Technol. 39, 815–833.
Li, X., Zhang, H., Gao, X., Zhang, R., Li, H., 2012. Hydrodynamic simulations of
seepage catalytic packing internal for catalytic distillation column. Ind. Eng.
Chem. Res. 51, 14236–14246.
264 X. Gao et al. / Chemical Engineering Science 186 (2018) 251–264
Liu, J.Q., Feng, R., Wang, W., 2012. The design of microwave cavity resonator used
for measuring the moisture content in plant leaves. Adv. Mater. Res. Trans. Tech.
Publ., 4967–4970
Mahajani, S.M., Kolah, A.K., 1996. Some design aspects of reactive distillation
columns (RDC). Ind. Eng. Chem. Res. 35, 4587–4596.
Malone, M.F., Doherty, M.F., 2000. Reactive distillation. Ind. Eng. Chem. Res. 39,
3953–3957.
Meier, M., Turner, M., Vallee, S., Conner, W.C., Lee, K.H., Yngvesson, K.S., 2009.
Microwave regeneration of zeolites in a 1 meter column. Aiche J. 55, 1906–
1913.
Niesbach, A., Kuhlmann, H., Keller, T., Lutze, P., Górak, A., 2013. Optimisation of
industrial-scale n-butyl acrylate production using reactive distillation. Chem.
Eng. Sci. 100, 360–372.
Noeres, C., Hoffmann, A., Gorak, A., 2002. Reactive distillation: non-ideal flow
behaviour of the liquid phase in structured catalytic packings. Chem. Eng. Sci.
57, 1545–1549.
Robinson, J., Kingman, S., Irvine, D., Licence, P., Smith, A., Dimitrakis, G., Obermayer,
D., Kappe, C.O., 2010. Understanding microwave heating effects in single
mode type cavities—theory and experiment. Phys. Chem. Chem. Phys. 12,
4750–4758.
Simasatitkul, L., Kaewwisetkul, P., Wiyaratn, W., Assabumrungrat, S.,
Arpornwichanop, A., 2016. Optimal design and performance analyses of the
glycerol ether production process using a reactive distillation column. J. Ind.
Eng. Chem. 43, 93–105.
Stankiewicz, A., Moulijn, J.A., 2002. Process intensification. Ind. Eng. Chem. Res. 41,
1920–1924.
Stefanidis, G.D., Munoz, A.N., Sturm, G.S., Stankiewicz, A., 2014. A helicopter view of
microwave application to chemical processes: reactions, separations, and
equipment concepts. Rev. Chem. Eng. 30, 233–259.
Sundmacher, K., Kienle, A., 2006. Reactive Distillation: Status and Future Directions.
John Wiley & Sons.
Wang, S.-J., Wong, D.S., 2006. Control of reactive distillation production of high-
purity isopropanol. J. Process. Contr. 16, 385–394.
Werth, K., Lutze, P., Kiss, A.A., Stankiewicz, A.I., Stefanidis, G.D., Górak, A., 2015. A
systematic investigation of microwave-assisted reactive distillation: Influence
of microwaves on separation and reaction. Chem. Eng. Process. Process Intensif.
93, 87–97.