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Article
Kinetic and reactive distillation for acrylic

acid synthesis via transesterification
Cuncun Zuo, Tingting Ge, Chunshan Li, Shasha Cao, and Suojiang Zhang
Ind. Eng. Chem. Res., Just Accepted Manuscript DOI: 10.1021/acs.iecr.6b01128 Publication Date (Web): 15 Jun 2016
Downloaded from http://pubs.acs.org on June 17, 2016
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Industrial & Engineering Chemistry Research
Kinetic and reactive distillation for acrylic acid synthesis via

transesterification
Cuncun Zuoa, Tingting Geb, Chunshan Lia, *, Shasha Caoa, Suojiang Zhanga, *
a
Beijing Key Laboratory of Ionic Liquids Clean Process, Key Laboratory of Green Process and Engineering, State
Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences,
Beijing 100190, PR China
School of Chemical and Environmental Engineering, China University of Mining & Technology-Beijing, Beijing
100083, PR China
Abstract
Reaction distillation was firstly used for the process of acrylic acid synthesis through
transesterification of methyl acrylate with acetic acid using a strongly acidic cationic exchange resin
catalyst (NKC-9). Pseudo-Homogeneous (P-H) and Langmuir-Hinshelwood (L-H) heterogeneous
kinetic models were presented and fitted with the experiment data obtained from batch reaction. The
key factors of heterogeneous kinetic model were the four components adsorption equilibrium
constants on the catalyst surface and they were determined by adsorption experiments. The activity
coefficients were calculated using the NRTL method. The catalyst stability was evaluated in a
fixed-bed reactor. Catalyst activity had no obviously decrease after 1000 hours running. A reactive
distillation column for acrylic acid synthesis was proposed and designed with process simulation.
Keywords: Reaction distillation; Acrylic acid; Methyl acrylate; Transesterification; Kinetic
*Corresponding author: Chunshan Li. TEL/FAX: +86-10-82544800; E-mail: csli@ipe.ac.cn

Suojiang Zhang.TEL/FAX:+86 10-82627080; E-mail: sjzhang@ipe.ac.cn
ACS Paragon Plus Environment
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1. Introduction
Acrylic acid, an important organic raw material and synthetic resin monomer, is widely used in
adhesives, paints, chemical fibers, leathers, textiles and photosensitive resin plates industries. The
global market for acrylic acid has recently showed strong growth with the increasing demand of
superabsorbent polymers, adhesives, and sealants.1,2 Emerging economies demand superabsorbent
polymers, which has become the main driving force of the acrylic industry. In addition, the booming
construction is another main thrust for the rapid growth in acrylic. Obtaining methyl acrylate using
acrylic acid as the reacted material is a promising method.3-5 The primary drawbacks of methyl
acrylate hydrolysis in synthesizing acrylic acid are the high activation energy and long time to reach
equilibrium.6 Using acetic acid instead of water to synthesize acrylic acid can effectively alleviate
the problems in these two areas.
Transesterification, which is an important chemical reaction in industries, includes three
reaction types-alcoholysis, acidolysis, and ester exchange reaction. These reactions can be performed
using base catalysts7,8 such as metal hydroxides, metal alkoxides, alkaline-earth oxides, and
hydrotalcites. Moreover, acid catalysts9-14 such as sulfuric, sulfonic, phosphoric, and hydrochloric
acids can also be used to catalyze the transesterification reaction. Ion-exchange resin has recently
received much attention because of its significant superiorities over the routine method of conducting
the sequential reaction and separation15-17. The adsorption and kinetic parameters for the
transesterification of methyl acetic with hexanol was determined under different experimental
conditions using the ion-exchange resinAmberlyst-131 as the catalyst18. Y. Liu et al.19 investigated
the kinetic of the transesterification of methyl acetic with n-octanol in a batch stirred reactor
catalyzed by the cation exchange resin Amberlyst 15. Van de Steene et al.16 successfully obtained
methyl acetic by the transesterification of ethyl acetic with methanol over the ion-exchange resin
Lewatit K1221. J. He et al.15 established a non-equilibrium stage model to describe the reactive
distillation and used the Newton-Homotopy method to simulate the transesterification of methyl
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acetic with n-butanol. Alonso et al.20 studied the polarity effect of the esters on the transesterification
reaction rate with sulfuric acid (homogeneous) and Dowex DR2030 sulfonic resin (heterogeneous) as
catalysts; the positive effect of the heterogeneous acid catalysis of H-bond in stabilizing the active
intermediate involved in the rate determining step was identified. Sertet al.18 developed a
heterogeneous LangmuirHinshelwoodHougenWatson (LHHW) type reaction rate model for the
hexyl acetic synthesis , and the UNIQUAC model was used to account for the non-ideal
thermodynamic behavior of reactants and products in the transesterification of methyl acetic
with1-hexanol catalyzed by the cation exchange resin Amberlyst-131.
A strongly acidic cation-exchange resin (NKC-9) was developed in this study for catalyzing
transesterification to synthesize acrylic acid when azeotrope does not exist in the system and the
equilibrium time is shorter compared with the hydrolysis reaction of methyl acrylate. The same
experiment was repeated under different reaction conditions to obtain the optimised operating
parameters, adsorption parameters, and kinetic parameters. Given the non-ideality of the liquid phase
from the ideal solution in the reaction system, the NRTL model was selected to correct the molar
fractions and the activity coefficients were calculated using the UNIFAC method; and the adsorption
equilibrium constants for the four components with NKC-9 were determined by performing
adsorption experiments between two non-reacting species. The kinetic data were correlated with the
PH and LH models. Finally, the simulation and calculation of the catalytic transesterification for
acrylic acid synthesis in the reactive distillation column were performed.
2. Experimental
2.1. Materials
2.1.1 Chemicals
Acetic acid, acrylic acid, and methyl acetic, purchased from Sinopharm Chemical Reagent Co.,
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Ltd., are of analytical grade. Hydrochloric acid and sodium chloride were also purchased from the
same chemical reagent factory. Methyl acrylate with a purity of more than 99.57 wt. %, was bought
by Baishun Chemical Reagent (Beijing) Co., Ltd. Distilled water was homemade in our laboratory
and used to wash the apparatus and catalysts.
2.1.2 Catalyst
NKC-9, a highly cross-linked polystyrene-divinylbenzene resin functionalized with sulfonic
groups, was used as the catalyst in our study. The relevant characteristics of the NKC-9 resin are
summarized in Table 1. Before NKC-9 was used for the catalysts for the transesterification reaction,
the purchased resins were soaked in 10 wt. % NaCl solution for more than 20 h. Then, the salt
solution was removed and the resin was washed with clear water and dried at 353.15 K under
vacuum for 14 h.
Table 1. Physicochemical characteristics of the resin (NKC-9).
2.1.3 Analytics
All samples were analyzed using gas chromatography (GC-2010, Shimadzu, Japan) with a BID
detector and a chromatographic capillary column Rtx-Wax (30m0.25mm0.25m). The column
temperature increased to 433.15 K with a programmed temperature method. The vaporizing chamber
and detector temperatures were set to 433.15 and 453.15 K, respectively. High purity helium gas
(>99.9999%) was used as carrier. An external standard method was used to quantitatively analyze all
samples.
2.2. Apparatus and procedure
2.2.1 Kinetic
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The kinetic experiments of the transesterification of methyl acrylate with acetic acid were
performed in a 250 mL three-neck flask equipped with a reflux condensing tube, thermometer, and
sampling device. A mechanical stirrer was used to mix the reactants. The reaction temperature was
controlled to within 0.1 K by Super thermostat water bath. First, methyl acrylate and the catalyst
were heated to the desired reaction temperature in the reactor. Acetic acid was preheated to the
desired reaction temperature and then quickly poured into the reactor. The transesterification reaction
then started. The kinetic of the transesterification reaction was investigated by analyzing the
composition of small samples which were withdrawn from the liquid mixture at regular intervals.
After a steady state was achieved, the product was collected in a sampling flask.
2.2.2 Adsorption experiments
The adsorption equilibrium constant of liquid on the surface of the catalyst was needed for the
adsorption-based kinetic model. Four binary non-reactive mixtures considered the different reactants
in the NKC-9 surface using the Popken et al. assumption26. The binary liquid mixture was
formulated with a total weight of 20 g and a composition of 25 wt. % of the stronger adsorbing
species at the beginning of the adsorption experiments. The liquid mixture and catalyst were heated
at a constant temperature (298.15 K) for 24 h. The liquid samples were prepared and analyzed by GC
after reaching adsorption equilibrium.
2.2.3 Swelling experiments
Swelling experiments were conducted at 298.15 K in a sealed and graduated cylinder with a
volume of 100.1 cm3 to investigate the swelling capacity of resin catalyst on single substrate.
Approximately 5 cm3 of the vacuum-dried catalyst was placed in the cylinder, and then a single
substrate was gradually added until the liquid level was about 1cm3 higher than the catalyst level. A
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sealed and graduated cylinder was placed in an ultrasonic bath, and the catalyst volume was
measured after 24 h. The experiment was repeated at least thrice in order to increase experimental
accuracy of the results.
2.2.4 Fixed-bed Experiments
To obtain the optimised space-time, we investigated the transesterification in a fixed-bed reactor
packed with the pretreated NKC-9 catalyst. The catalyst load (W) was 0.684 g catalyst/mL reactor
volume for the basic case. The experiment was repeated to study the effect of space-time on the
conversion rate of methyl acrylate with different space-time values.
3. Results and discussion

3.1. Calculation of activities and thermodynamic properties
Considering that the reaction system of acrylic acid synthesis greatly deviated from ideal
solution, the NRTL and UNIQUAC models were chosen to correct the non-ideality of the liquid
phase. The multicomponent expressions for the activity coefficient for the NRTL and UNIQUAC
equations are available in Supporting Information. Moreover, the experimental and calculated VLLE
data for the acrylic acid/methyl acetate and acetic acid/methyl acrylate binary systems are also
clearly listed in Supporting Information. The VLLE data for acetic acid/acrylic acid, acetic
acid/methyl acetate, and methyl acrylate /acrylic acid binary systems are stored in the database of
Aspen. With respect to the VLLE data of methyl acetic/methyl acrylate binary system, Tu et al. have
conducted experiments and obtained detailed data.21 Furthermore, we investigated the deviations
between the calculated and experimental values through the NRTL and UNIQUAC models for
acrylic acid / methyl acetate and acetic acid / methyl acrylate, which were clearly shown in Table 2.
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According to the deviation above, the NRTL model demonstrated better results compared with the
UNIQUAC model. Thus, we only calculate the binary interaction parameters of the NRTL model for
acetic acid, methyl acrylate, acrylic acid, and methyl acetate (Table 3).
Table 2. Deviations between the calculated and experimental values on x1, y1, and T through the
NRTL and UNIQUAC models for acrylic acid / methyl acetate and acetic acid / methyl acrylate.
Table 3. Binary interaction parameters of the NRTL model for acetic acid, methyl acrylate, acrylic
acid, and methyl acetate.
3.2. Kinetic experiments and optimization of transestrification conditions

3.2.1. Elimination of Mass Transfer Resistance.
To study the reaction kinetic, the effects of internal and external diffusion on transestrification
must be excluded. To investigate the internal diffusion involved in the reaction system, NKC-9 resin
catalyst was screened into several different particle sizes, including 28, 32, and 35 mesh. The same
experiment was repeated with different particle sizes at the same stirring speed, reaction temperature,
catalyst load, and reactants molar ratio. The conversion rate of methyl acrylate is defined as the ratio
of the amount of methyl acrylate reacted and the initial amount of methyl acrylate. Figure 1 shows
that when the catalyst particle size is 32 mesh, the conversion rate of methyl acrylate was almost
unaffected by the particle size. However, when the catalyst particle size is 28 mesh, the conversion
rate of methyl acrylates lightly decreased. External diffusion effects could be eliminated by
increasing the stirring speed, and the experiment was repeated with the stirring speed range from 300
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to 500 rpm. As can be seen from Figure 2, when the stirring speed was increased to 300 rpm, the
conversion rate of methyl acrylate was almost constant, which indicated the external mass transfer is
not the rate limiting step at that time.22 Sanz et al.23 investigated the external diffusion and found that
it does not usually control the overall reaction rate unless when the stirring speed was low or when
the reactants were viscous. Thus, all further experiments were performed under stirring speed of 300
rpm. The catalyst particle size of 32 mesh and stirring speed 300 rpm were required to ensure the
experimental accuracy.
Figure 1. Effect of the catalyst particle size on the conversion rate of methyl acrylate using NKC-9 as
the catalyst (300 rpm; 80 C; = 1:1; the catalyst load was 0.10 g catalyst / g liquid mixture).
Figure 2. Effect of the stirring speed on the conversion rate of methyl acrylate using NKC-9 as the
catalyst (28 mesh; 80 C; = 1:1; the catalyst load was 0.10 g catalyst / g liquid mixture).
3.2.2 Effect of Catalyst Load.

The same experiment was repeated at 353.15 K with initial molar ratio of acetic acid and methyl
acrylate being 1 ( = 1: 1), catalyst particle size of 28 mesh, and stirring speed of 300 rpm. The
effect of catalyst load on the conversion rate of methyl acrylate can be determined by changing the
amount of catalyst load. To detection the autocatalytic effect of the acetic acid, a blank assay
experiment was performed in the absence of catalyst. Figure 3 indicated without catalyst the
autocatalytic behavior of acetic acid can be negligible because the conversion rate of methyl acrylate
below to 4% after 30 h. In addition, the reaction equilibrium time of transesterification was
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decreased with the increase in catalyst load. As shown in Figure 4, it is obvious that the reaction rate
constant increases linearly with the addition of catalyst load. The reaction rate constant, k0 and the
concentration of catalyst load, Ccat can be expressed as: k+ / k+ (0.08 g catalyst / g liquid
mixture)=114.7Ccat.(g/ g liquid mixture)-8.26. Such behavior is attributed to the increased amount of
acidic sites for reaction with the addition of catalyst load.23
Figure 3. Effect of catalyst load (NKC-9) on the conversion rate of methyl acrylate (353.15 K,
= 1: 1, 28 mesh, and 300 rpm).
Figure 4. Effect of catalyst load on the forward reaction rate constant at 353.15 K with initial molar
ratio of acetic acid and methyl acrylate being 1.
3.2.3. Effect of molar ratio of acetic acid and methyl acrylate.

The experiments were conducted at the initial molar ratio of acetic acid and methyl acrylate
varying from 1:1 to 3:1 at 353.15 K with catalyst load being 0.1 g/g, catalyst particle size of 28 mesh,
and stirring speed of 300 rpm. According to the theories of reversible equilibrium reaction, increased
the amount of one reactant can enhance the equilibrium conversion rate of the other reactants. Figure
5 shows the effect of molar ratio of reactants on the conversion rate of methyl acrylate. It was
obvious that the conversion rate of methyl acrylate was gradually increased with the increase in the
initial molar ratio of reactants. When the initial molar ratio increased from 1:1 to 2:1, the increment
of equilibrium conversion rate of methyl acrylate was about 8%, and the increment was almost the
same when the initial molar ratio increased from 2:1 to 3:1. However, the residual amounts of acetic
acid were about 51%, 71.5%, and 78.4%, respectively. The separation between acetic acid and
acrylic acid liquid mixture was hard, which can be attributed to the H-bonds interactions of acid
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molecules. Hence, in despite of high conversion rate of methyl acrylate, the high molar ratio of
reactants will increase the difficulty in the separation of acrylic acid at the same time. Combining
two considerations, the initial ratio of reactants of 1:1 was the best choice.
Figure 5. Effect of molar ratio of reactants on the conversion rate of methyl acrylate using NKC-9 as
catalyst (353.15 K, 28 mesh, 300 rpm, and the catalyst load was 0.10 g catalyst/g liquid mixture).
3.2.4. Effect of reaction temperature.

The experiments were conducted at the reaction temperature varying from 343.15 to 363.15 K
with catalyst load being 0.1 g/g, initial molar ratio of 1:1, catalyst particle size of 28 mesh, and
stirring speed of 300 rpm. As shown in Figure 6, the conversion rate of methyl acrylate remarkably
increase with the elevated temperature, but the increment of equilibrium conversion rate for methyl
acrylate from 343.15 to 353.15 K was higher compared with the change in the conversion rate of
methyl acrylate when the reaction temperature increase from 353.15 to 363.15K. According to the
Arrhenius law, high temperature make molecules move faster, collide more vigorously, and therefore
greatly increased the likelihood of bond cleavages and rearrangements, but the excessive high
reaction temperature was inadvisable due to the presence of double bond in methyl acrylate and
acrylic acid. Thus, the optimized reaction temperature for the transeatrification was 353.15 K
through synthetically consideration.8, 24
Figure 6. Effect of reaction temperature on the conversion rate of methyl acrylate using NKC-9 as
the catalyst ( = 1: 1, 28 mesh, 300rpm, and the catalyst load was 0.1 g catalyst/g liquid mixture).
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3.3. Kinetic Model and Equilibrium Constant

The rate expression rA is determined by the hypothesis ofthe reaction mechanism. A
pseudo-homegeneous (PH) and an adsorption Langmuir-Hinshelwood (LH)16, 18, 25, 26 models were
adopted to investigate the kinetic of the catalytic transesterification of methyl acrylate with acetic
acid over NKC-9 catalyst. The reaction rate r expression in a constant volume reactor can be listed as
follows:
=
1 1
(1)

where,
is the quality of the catalyst; is the stoichiometric coefficients of substance in
reaction; is the molarity of substance; t is the recation time.
What is the main difference between the PH (ideal) and PH modelsis that the latter one takes
molecular properties into consideration such as the size, inter-atomic forces, spatial structures.
Moreover, the PH model was modified by using the activity instead of concentration. In the PH
(ideal) model, rPH was listed as below:
=

(2)

where , , and were the molar fraction of acetic acid, methyl acrylate, acrylic acid
and methyl acetate, respectively. and were the forward reaction rate constant and the
equilibrium constant.
In order to simplify the reaction kinetic equation, pseudo homogeneous dynamic model was
applied to the catalysis reaction. With the reference to other ester hydrolysis reaction26, the reaction
was assumed to be the second order reaction. The reaction rate r of reversible reaction can be
expressed as follows:
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"
= # (" " " " ) (3)

After organized and integral, equation was shown as follows:

&=
1
2,C.. (/ g(.* ) + 1
+
= # (4)
g (.* 2,C.. (/ + g(.* ) + 1
Where " , " represent the concentration of acrylic acid and methyl acetate. " was selected
as the variable, and other variables were calculated on basis of stoichiometric numbers and the
following several formulas: g = 4 45, = "( "( , = (C( + "( ), = 1
1/ , where CMA0 and CHAc0 represent the initial concentration of methyl acrylate and acetic acid.
"( , "( , and the equilibrium constant Keq as well as the concentration value of every point
in Figure 6 were brought into the Eq 4, and the relationship of Z and t was plotted in Figure 7. The
straight line was obtained from fitting the data using the least squares method, and the slope
represents the forward reaction rate constant, as shown in Table 4. The correlation coefficient R2 are
all above 0.98, indicating a better linear fitting and reliable experimental data.
Figure 7. The curve of Z and t
Table 4. The reaction rate constants at different temperatures

The experimental results demonstrate the temperature had a great effect on the reaction rate, and
the relationship between them can be described using Arrhenius equation (5):
: = ( ;<(= >? ) (5)
The above formula was taken the logarithm, getting the equation (6):
+: = +( = >? (6)
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ln k1 and 1 / T were plotted in one figure, the forward and adverse reaction rate constant were
illustrated in Figure8, respectively. The slope of the straight line fitted was -E / R.
Figure 8.Relationship between the forward reaction or the adverse reaction rate constant and the
temperature.
The linear equation of the forward reaction rate constant and the temperature was described
with Y=7.722-7.175X, E+ and k+.0 were calculated: =# = 59.65C
E+ F: and #.( = 2.26 10I .
Overall, the relationship formula 9 of forward reaction rate constant and temperature in methyl
acrylate hydrolysis reaction was obtained
# = 2.257 10I exp(7174.8?) (7)
The linear equation of the adverse reaction rate constant and the temperature was described with
Y=-11.368-0.362X, E- and k-.0 were calculated: =F = 3.010C
E+ F: and F.( = 1.156 10F* .
Overall, the relationshipformula10 of adverse reaction rate constant and temperature in methyl
acrylate hydrolysis reaction was obtained
F = 1.156 10F* exp(361.8? ) (8)
Experimental conversion curve of methyl acrylate and the dynamics simulation curve were
compared under the condition that temperature of 353.15 K, catalyst load of 0.75 g/g, and B of 1.
0
The results were shown in Figure 9.
Figure 9. Comparison between the experimental data and simulation data.
As shown in Figure 9, the experimental values and dynamics simulation results had a good
inosculation, indicating the validity of the kinetic equation.
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Related parameter identification based on the above model, kinetic equation of

transesterification were shown the general expression, as follows:
r=
(5 5 5 5 / )

(9)
(1 + 5 + 5 + 5 + 5 )P
where 5 refer to the activity of substances, refer to the adsorption equilibrium constant of
substances; when n=2 or 0, equation will be turned into LH model (assuming the reaction on the
catalyst was the rate determining step) and PH model, respectively. Among of the equations , the rate
constant of reaction, k can be calculated by Arrhenius equation, as shown equation (10).
=,
R (10)
= ( exp Q
>?
Where ke0 and EA,e refer to pre-exponential Arrhenius factor and activation energy.
To sum up, the kinetic models for transesterification were obtained, as shown in Table 5.
Table 5. Different kinetic models and their identification parameters.
3.3.1. Determination of reaction equilibrium constant.

By definition,Chemical reaction equilibrium constant Keq can be solving by Eq 11, where , ,
refer to the mole fraction and activity coefficient of component respectively. The chemical
equilibrium constant for the reaction was shown in Table 6,based on the experimental data.
5 5

, ,
= (
) = Q
R Q
R = S T (11)
5 5
, ,
Table 6. Reaction equilibrium constants at different temperatures.
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According to the equation of Vant Hoff, there was a certain relationship between the chemical
equilibrium constant and temperature. From the equation, the enthalpies of reactions in non-ideal and
ideal liquid were about 57.45 and 56.64 kJ/mol, respectively.
To the activity meter: ln = 6.910 10I /? + 19.12 (12)
To the concentration meter: ln = 6.813 10I /? + 19.09 (13)
3.3.2. Determination of adsorption equilibrium constant.
The results of our measurements of the swelling ratio which is the volume of
solvent-equilibrated resin divided by the dry volume of the resin in a sealed graduated cylinder are
reported in Table 7. The values given are mean values of at least three experiments conducted at
298.15 K. Assuming that the resin beds volume changes in the same way as the volumes of the
individual resin microspheres, adsorbed volumes can be calculated from the swelling ratio. Also
assuming ideal mixing, that is, no excess volume, the adsorbed mass and amount per gram of catalyst
can be calculated.
Table 7. Specific volumetric dilatation of NKC-9 resin catalyst for single substrate.
According to Popken et al.,26 the relationship between the liquid and resin polymer can be
described by Eq. 14:
( (W( WX )
Y WZX
ZY WX
=
(14)

where
( refers to the initial total solvent weight (g);
refers to the catalyst mass (g); W(
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refers to the overall weight fraction of component i; WX and WZX refer to the equilibrium
liquid-phase weight fraction of solvent i and j, respectively;

Y and
ZY refer to the adsorbed mass
of solvent i and j.
Assuming Langmuir-type adsorption based on mass, the following relationship for the mass
coverage mis/ms can be obtained, with ms being the total adsorbed mass and j the liquid phase
activities. K refers to the adsorption equilibrium constant for the solvents.
Y
5
=
(15)
Y 1 + Z Z 5Z
Combining Eqs.14 and 15 for the binary case, the following relation is obtained :
( (W:( W:X )
Y : 5: W4X 4 54 W:X
=
(16)
1 + : 5: + 4 54
Four nonreactive binary pairs including acetic acid/acrylic acid (1), methyl acrylate/acrylic acid
(2), acrylic acid/methyl acetate (3), and methyl acrylate/methyl acetate (4) were investigated to
maximize the adsorption strength differences in order to ensure the experimental accuracy. The
results of a fit of all four adsorption equilibrium constants fited to all the data are illustrated in
Figures 10 and 11 and reported in Table 8.
Figure 10. Relative adsorption of acrylic acid from acrylic acid (AA)/acetic acid (HAc) and acrylic
acid (AA)-methyl acrylate (MA) mixtures over NKC-9 catalyst and calculated dependence assuming
constant adsorbed mass.
Figure 11. Relative adsorption of methyl acrylate from a mixture of methyl acrylate (MA)/methyl
acetic (MeAc) and relative adsorption of acetic acid from a mixture of acetic acid (HAc)/methyl
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acetic (MeAc) over NKC-9 catalyst and calculated dependence assuming constant adsorbed mass.
Table 8. Results of the regression for the nonreactive binary adsorption data at 298.15 K.
3.3.3. Determination ofreaction rate constant, activation energy and pre-exponential.

According to the dynamic model, the relevant parameter was identified by using nonlinear least
square method on the basis of the experimental data. Taking SRS in the Eq 17 as the objective
function of recognition, the identification parameters were obtained when the objective function
acquire the minimum.
P
SRS = ^( _ S` )4 (17)

where _ , S` refer to the value of calculated and experimental reaction rate, respectively.
As shown in Figure 12 and Table 9, different model identification have different refers to the
former factor, this is because of a description of the different model in a different way.27-29 However,
the value of activation energy was almost the same, and equal to 99.75 kJ/mol.
Table 9. Identification of activation energy =, and pre-exponential for ( for different models.
Figure 12. ln ~ 1000/? relationship.
3.3.4. Verification the results of different models.

Based on the kinetic modelsobtained from the experiments, the experimental values (the initial
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conditions) involved in reaction process were recalculted to get a series of caluculated values. By
comparing the experimental and calculation values using mean relative deviation (MRD) as the
standard, the accuracy of the LH and PH models turned out to be higher than that of the LH model
(ideal). Taking the non-ideal of liquid mixture into consideration, the reaction process can be better
described, as shown in Table 10.
MRD/% =
Pghijkl
Ye`_
( ^ f

_ S`
f) 100 (18)
S`
Table 10. Comparison between experimental and calculated values using different models.
3.4. Determination of Space-Time of the Fixed-Bed Reactor.

To investigate the effect of space-time () on the conversion rate of methyl acrylate under the
optimised reaction conditions achieved by the batch reactor, a series of experiments were performed
with different space-time in a fixed-bed reactor packed with NKC-9 resin catalyst. The space-time
for the fixed-bed reactor was defined as the function of the effective volume of reactor (m ) and
volumetric flow rates of reactants (F), and the equation was described as = m /n. As shown in
Figure 13, it is obvious that the conversion rate of methyl acrylate gradually increase before the
space-time achieves to 4h, but the conversion rate value keeps almost as a constant after 4 h. These
results demonstrate that 4h was the optimised space-time for the fixed-bed reactor.
Figure 13. Effect of space-time on the conversion rate of methyl acrylate in the fixed-bed reactor
(353.15 K = 1: 1the catalyst load (W) was 0.684 g catalyst/mL reactor volume).
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3.5. Reaction Distillation.

A simulation model of a reactive distillation process is indispensable to design columns and
optimise processes incorporating the reactive distillation technology. The EQEQ approach, the
simplest modeling approach, was used in our study. Assuming phase and chemical equilibrium in
each stage, a reactive distillation column was modeled. The column was axially discretized into
equilibrium stages and the height of each stage was equivalent to the height of a theoretical plate
(HETP) of the used packing. The kinetic model obtained from the stationary solution in a batch
reactor (Section 3.3) was used to describe the chemical equilibrium of the reactive distillation
column. It was assumed that the chemical equilibrium was reached in each stage in the column. The
RADFRAC block of Aspen Plus30-35 and the Newton homotopy arc length differential method with a
good convergence were used to determine the optimised reactive distillation column set-up, and
maximising yield was the optimisation target.
The reactive distillation column is separated into four sections by two feed inlets, and the four
sections are rectifying section, the extractive distillation section, reaction section, and stripping
section (Figure 14). The main function of the rectifying section is to separate the low-boiling product
and acetic acid, and the important function of the extractive distillation section is to separate some
minimum-boiling point azeotrope by acetic acid to ensure the purity of low-boiling product, although
there is no azeotropic phenomenon in this reaction system. The reaction section is the main place
where the transesterification takes place, and the function of the stripping section is to separate the
high-boiling product (acrylic acid) from the reaction mixtures. Acetic acid is fed at the top inlet, and
methyl acrylate is fed at the bottom inlet. In the paper, the kinetic results obtained from the
experiments in a batch reactor were used for the simulation of the reactive distillation (RD) process,
and the amount of catalyst that is immobilised in the reactive section was set to 0.10 g catalyst / g
liquid mixture. Figure 15 shows the temperature/pressure vs. column height in the reactive
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distillation column. The temperature within the reactive distillation column was in the vicinity of
353.15 K used to study the reaction kinetic. And he operating pressure of the column was 0.065 MPa.
The optimisation of theoretical plates number, reflux ratio, HAc feeding position, and MA feeding
position were clearly shown in the Supporting Information, and the optimization results were given
in Table 11. Figure 16 illustrates the vapor-liquid composition distribution in the reactive distillation
column.
Figure 14. Schematic diagram of reactive distillation column.
Table 11. Parameters and results of simulation and optimization.
Figure 15. Distribution of temperature and pressure in reactive distillation column.
Figure 16. VaporLiquid composition distribution in reactive distillation column.
3.6. Long-life evaluation.

The mixture solution of acetic acid and methyl acrylate with a molar ratio of 1:1 is formulated.
The reaction temperature and space-time were set to 353.15K and 4h to investigate the life of the
catalyst- NKC-9.
Figure 17. Lifetime evaluation of NKC-9.
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As can be seen from Figure 17, the conversion rate and selectivity of methyl acrylate did not
change visibly after a long period of running such as 1200 h in a fixed-bed reactor, which
convincingly verified the long life of the catalyst. Compared with the catalyst after a short time
running, there was a slight decrease in the conversion rate of methyl acrylate, which may be
attributed to the adsorption of macromolecular polymerization inhibitor on NKC-9 resin catalyst.
The macromolecular polymerization inhibitor can occupy the acid site of the catalyst and block its
pore structure, resulting in the weakening of the catalytic activity to some extent. Figure 18 shows
the PM photomicrographs of the fresh and used NKC-9 catalyst in the fixed-bed reactor, the changes
in the catalyst morphology are clearly shown. No. 1 is the photomicrograph of fresh catalyst, which
is an inerratic ball with the smooth and uniform surface. No. 2, 3, and 4 present the morphology
structure of the used catalyst, and there are different damages containing pits, cracks, and
fragmentation caused by collision and squeeze in the fix-bed reactor after over 1000 h long time
running. However, the catalyst breakage was found less than 5 wt. % after sieving the catalyst.
Figure 18. PM photomicrographs (of the fresh and used NKC-9catalyst (1. Fresh catalyst; 2, 3, and 4.
Used catalyst; magnification: eyepiece 20objective lens 30).
4. Conclusions
The NKC-9 resin catalyst has shown a good catalytic activity for the transesterification of
methyl acrylate with acrylic acid. By batch reaction experiments, the optimised operating parameters
were obtained including a catalyst load of 0.1 g catalyst/g liquid mixture, reaction temperature of
353.15 K, molar ratio of reactants of 1:1, stirring speed of 300rpm, and catalyst particle size of >32
mesh. According to the swelling and adsorption equilibrium experiments, the adsorption of methyl
acetic and acetic acid was found to stronger than that of acrylic acid and methyl acrylate. Using
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several models to fit the kinetic experimental data, the LH model turned out to be the most suitable
for the transesterification involved, having taken the activity and adsorption equilibrium constants
into consideration. In addition, 4.0 h was the most appropriate space-time in the fixed-bed reactor for
the acrylic acid synthesis. At last, a reaction distillation process was proposed and simulated, and the
methyl acrylate conversion rate of 94.5 % and the acrylic acid concentration of 98.0% in the tower
bottom were achieved under the optimised parameters.
Acknowledgments
The authors gratefully acknowledge the National Program on Key Basic Research Project (No.
2015CB251401), National Science Fund for Excellent Young Scholars (No. 21422607), Key
Program of National Natural Science Foundation of China (NO. 91434203), and Research Supported
by the CAS/SAFEA International Partnership Program for Creative Research Teams.
Nomenclature of the signs, marks, and simplified characters used.

Signs/marks /simplified characters
Physical meaning/meaning
P-H
Pseudo-Homogeneous
L-H
Langmuir-Hinshelwood
LHHW
LangmuirHinshelwoodHougenWatson
p
initial molar ratio of acetic acid to methyl acrylate
reaction rate
ccat
catalyst load (g catalyst / g liquid)

quality of the catalyst

molarity of substance
stoichiometric coefficient
the recation time
molar fraction
reaction rate constant (L mol-1 s-1)
Keq
thermodynamic equilibrium constant
molar concentration
activity
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activity coefficient
EA/E
apparent activation energy (kJ mol1)
ko
pre-exponential Arrhenius factor (mol s1 g1)
weight fraction
MRD
mean relative deviation
eq
equilibrium
i, j
components
cal
calculated value
exp
experimental value
space-time
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(biodiesel) esterification reaction catalyzed by amberlyst 15 resin. Can. J. Chem. Eng. 2016.
(30) Li, C., Zhang, X., Zhang, S., Suzuki, K. Environmentally conscious design of chemical
processes and products: Multi-optimization method. Chem. Eng. Res. Des. 2009, 87, 233-243.
(31) Gangadwala, J., Surendra Mankar, A., Mahajani, S., And, A. K., Stein, E. Esterification of
Acetic Acid with Butanol in the Presence of Ion-Exchange Resins as Catalysts. Ind. Eng. Chem.
Res .2003, 42, 2146-2155.
(32) Ewa BoekWinkler, Jrgen Gmehling. Transesterification of Methyl Acetate and n-Butanol
Catalyzed by Amberlyst 15. Ind. En. Chem. Res. 2006, 45, 6648-6654.
(33) Lee, M. J., Hsientsung Wu, A., Lin, H. Kinetics of Catalytic Esterification of Acetic Acid and
Amyl Alcohol over Dowex. Ind. En. Chem. Res. 2000, 39, 4094-4099.
(34) Li, C., Wozny, G., Suzuki, K. Design and synthesis of separation process based on a hybrid
method. Asia-Pac. J. Chem. Eng. 2009, 4, 905-915.
(35) Li, C., Zhang, X., Zhang, S. Environmental Benign Design of DMC Production Process. Chem.
Eng. Res. Des. 2006, 84, 1-8.
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Figure and Table Captions

Figure 1. Effect of the catalyst particle size on the conversion rate of methyl acrylate using NKC-9 as
the catalyst (300 rpm; 80 C; = 1:1; the catalyst load was 0.10 g catalyst / g liquid mixture).
Figure 2. Effect of the stirring speed on the conversion rate of methyl acrylate using NKC-9 as the
catalyst (28 mesh; 80 C; = 1:1; the catalyst load was 0.10 g catalyst / g liquid mixture).
Figure 3. Effect of catalyst load (NKC-9) on the conversion rate of methyl acrylate (353.15K, =
1: 1, 28 mesh, and 300 rpm).
Figure 4. Effect of catalyst load on the forward reaction rate constant at 353.15 K with initial molar
ratio of acetic acid to methyl acrylate being 1.
Figure 5. Effect of molar ratio of reactants on the conversion rate of methyl acrylate using NKC-9 as
catalyst (353.15K, 28 mesh, 300rpm, and the catalyst load was 0.10 g catalyst/g liquid mixture).
Figure 6. Effect of reaction temperature on the conversion rate of methyl acrylate using NKC-9 as
the catalyst ( = 1: 1, 28 mesh, 300rpm, and the catalyst load was 0.10 g catalyst/g liquid mixture).
Figure 7. The curve of Z and t
Figure 8. Relationship between the forward reaction or the adverse reaction rate constant and the
temperature.
Figure 9. Comparison between the experimental data and simulation data.
Figure 10. Relative adsorption of acrylic acid from acrylic acid (AA)/acetic acid (HAc) and acrylic
acid(AA)-methyl acrylate(MA) mixtures over NKC-9 catalyst and calculated dependence assuming
constant adsorbed mass.
Figure 11. Relative adsorption of methyl acrylate from a mixture of methyl acrylate(MA)/methyl
acetic(MeAc) and relative adsorption of aceticacid from a mixture of acetic acid(HAc)/methyl
Page 28 of 59
Page 29 of 59
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acetic(MeAc)over NKC-9catalyst and calculated dependence assuming constant adsorbed mass.

Figure 12. ln ~ 1000/? relationship.
Figure 13. Effect of space-time on the conversion rate of methyl acrylate in the fixed-bed reactor
(353.15K = 1: 1the catalyst load (W) was 0.684g catalyst/mL reactor volume).
Figure 14. Schematic diagram of reactive distillation column.
Figure 15. Distribution of temperature and pressure in reactive distillation column.
Figure 16. VaporLiquid composition distribution in reactive distillation column.
Figure 17. Lifetime evaluation of NKC-9.
Figure 18. PM photomicrographs of the fresh and used NKC-9catalyst (1. Fresh catalyst; 2.3.4. Used
catalyst; magnification: eyepiece 20objective lens 30).
Table 1. Physicochemical characteristics of the resin (NKC-9).
Table 2. Deviations between the calculated and experimental values on x1, y1, and T through the
NRTL and UNIQUAC models for acrylic acid / methyl acetate and acetic acid / methyl acrylate.
Table 3. Binary interaction parameters of the NRTL model for acetic acid, methyl acrylate, acrylic
acid, and methyl acetate.
Table 4. The reaction rate constants at different temperatures.
Table 5. Different kinetic models and their identification parameters.
Table 6. Reaction equilibrium constants at different temperatures.
Table 7. Specific volumetric dilatation of NKC-9 resin catalyst for single substrate.
Table 8. Results of the regression for the nonreactive binary adsorption data at 298.15 K.
Table 9. Identification of activation energy =, and pre-exponential for ( for different models.
Table 10. Comparison between experimental and calculated values using different models.
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Table 11. Parameters and results of simulation and optimization.
Page 30 of 59
Page 31 of 59
Figure 1.
50
Conversion rate of methyl acrylate / %
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3
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60
40
30
20
35 mesh
32 mesh
28 mesh
10
0
0
12
15
18
Reaction time / h
21
Figure 2.
55
50
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40
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30
25
20
500rpm
400rpm
300rpm
0 rpm
15
10
5
0
0
10
15
20
Reaction time / h
25
Page 32 of 59
Page 33 of 59
Figure 3.
50
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60
40
30
20
0.12g Catalyst/g Liquid mixture

None
10
0
0
10
15
20
25
Reaction time / h
30
Figure 4.
k+/k+(0.08 g catalyst / g liquid mixture)
1
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3
4
5
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7
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59
60
0.08
0.09
0.10
0.11
Catalyst Concentration (g/g)
0.12
Page 34 of 59
Page 35 of 59
Figure 5.
70
Conversion rate of methyl acrylate/%
1
2
3
4
5
6
7
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60
50
40
B0=3:1
B0=2:1
30
B0=1:1
Pred. B0=3:1
20
Pred. B0=2:1
Pred. B0=1:1
10
0
0
10
15
20
25
Reaction time/h
30
Figure 6.
60
Conversion rate of methyl acrylate /%
1
2
3
4
5
6
7
8
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12
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60
50
40
30
363.15K
353.15K
343.15K
Pred.363.15K
Pred.353.15K
Pred.343.15K
20
10
0
0
10
15
20
25
Reaction time / h
30
Page 36 of 59
Page 37 of 59
Figure 7.
343.15K
353.15K
363.15K
0.4
0.3
1
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3
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59
60
0.2
0.1
0.0
0
10
12
14
Reaction time / h
16
Figure 8.
-11.7
The forward reaction

The adverse reaction
Y=7.722-7.175X
Y=-11.368-0.362X
-12.0
-12.3
lnk
1
2
3
4
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60
-12.6
-12.9
-13.2
2.70
2.75
2.80
2.85
-1
1000/T(K )
2.90
Page 38 of 59
Page 39 of 59
Figure 9.
55
50
45
Conversion ratio of MA / %
1
2
3
4
5
6
7
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60
40
35
30
25
20
15
Experimental data
Model simulation data
10
5
0
0
10
15
20
Reaction time / h
25
Figure 10.
0.2
AA+MA
AA+HAc
0.1
0.0
m0 (w10-w1L)/mcat
1
2
3
4
5
6
7
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9
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59
60
-0.1
-0.2
-0.3
-0.4
-0.5
0.0
0.2
0.4
0.6
0.8
wL AA
1.0
Page 40 of 59
Page 41 of 59
Figure 11.
0.4
MeAc+MA
MeAc+HAc
0.3
m0 (w10-w1L)/mcat
1
2
3
4
5
6
7
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59
60
0.2
0.1
0.0
-0.1
-0.2
0.0
0.2
0.4
0.6
0.8
wL MeAc
1.0
Figure 12.
PH(ideal)
PH
LH
-4
lnke
1
2
3
4
5
6
7
8
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10
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56
57
58
59
60
-5
-6
2.76
2.80
2.84
3
-1
2.88
-1
10 T /K
2.92
Page 42 of 59
Page 43 of 59
Figure 13.
60
Conversion rate of methyl acrylate /%
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
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17
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60
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30
20
10
0
0
Space-time / h
10
1
2
3
4
5
6
7
8
9
10
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12
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60
Figure 14.
Page 44 of 59
Page 45 of 59
Figure 15.
Pressure in the column
0.07
0.08
0.09
0.10
50
MA feeding position
40
Number of theoretical plates
1
2
3
4
5
6
7
8
9
10
11
12
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14
15
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49
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51
52
53
54
55
56
57
58
59
60
30
20
HAc feeding position
10
0
420
400
380
360
340
Temperature in vapor phase / K
320
Figure 16.
1.0
0.9
0.8
Liquid phase composition

HAc
MeAc
MA
AA
0.7
Mass Fraction
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
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53
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58
59
60
Page 46 of 59
0.6
0.5
Vapor phase composition

HAc
MeAc
MA
AA
0.4
0.3
0.2
0.1
0.0
0
10
15
20
25
30
35
Stage Number
40
45
50
Page 47 of 59
Figure 17.
100
80
Ratio / %
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
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25
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49
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51
52
53
54
55
56
57
58
59
60
Selectivity
Yield
60
40
20
0
0
100
200
300
400
500
600
700
800
900
Run time / h
1000 1100 1200
1
2
3
4
5
6
7
8
9
10
11
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13
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17
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56
57
58
59
60
Figure 18.
Page 48 of 59
Page 49 of 59
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2
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42
43
44
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46
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48
49
50
51
52
53
54
55
56
57
58
59
60
Table 1.
Properties
Parameters
Skeleton
Styrene-divinybenzene
Type
Strong acid
Structure
Macroreticular
Functional group
Sulfonic(SO3H)
Ionic form
H+
Moisture (by weight)
Less than 10%
Surface area (m2/g)
50
Particle size
28-35(mesh)
Internal porosity(ml pore/ml bead)
0.36
Concentration of acid sites (meq./g dry)
4.7
Bulk density(Kg/m3)
608
Average pore diameter (nm)
48.2
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
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22
23
24
25
26
27
28
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30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Table 2.
Model
AAD(x1)b
AAD(T)b
AAD(y1)b
VLE for Acrylic acid (1)+ Methyl acetic (2)

NRTL
0.0012
UNIQUAC
0.0029
0.0314
0.0003
0.0336
0.0005
VLE for Acetic acid (1)+ MA (2)

NRTL
0.0025
0.045
0.0002
UNIQUAC
0.0028
0.054
0.0002
S`
S`
S`
AAD(y)b=(1/N)s
r_ q;AAD(T)b=(1/N)s
?_ q;AAD(x)b=(1/N)s
t:qr
t:q?
t:q
_ q
Page 50 of 59
Page 51 of 59
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5
6
7
8
9
10
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12
13
14
15
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17
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19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
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49
50
51
52
53
54
55
56
57
58
59
60
Table 3.
(i)/(j)
uZ
uZ
vZ (K)
vZ (K)
Acetic acid(1)/Methyl acrylate (2)
13.4560
-28.4105
-5151.3602
11039.0889
0.3
Acetic acid (1)/Acrylic acid (3)
283.0157
42.5680
0.3
Acetic acid (1) / Methyl acetic (4)
-239.2462
415.2702
0.3
Methyl acrylate (2)/Acrylic acid (3)
620.1444
-295.8599
0.3
Methyl acetic (4)/ Methyl acrylate (2)
0.5018
-0.6913
463.8299
-361.4648
0.3
Acrylic acid (3)/ Methyl acetic (4)
4.9081
23.5597
-2250.4919
-6440.8516
0.3
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
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25
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30
31
32
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40
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42
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44
45
46
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51
52
53
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57
58
59
60
Page 52 of 59
Table 4.
Forward reaction rate
Adverse reaction rate
Reaction temperature
constants
constants
K
k+106(Lmol-1s-1)
k-106(Lmol-1s-1)
343.15
1.8106
4.1953
353.15
3.2869
6.2853
363.15
6.5658
11.061
Page 53 of 59
1
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Table 5.
Model
Chemical Equilibrium
constant
Pre-exponential
factor
Activation energy
PH(ideal)

(
=,
PH
LH

(
(
=,
=,
Adsorption equilibrium constant

-

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Page 54 of 59
Table 6.
Chemical equilibrium constant
Chemical equilibrium constant
(Activity)
(concentration)
343.15
0.3452
0.4321
353.15
0.6906
0.9224
363.15
1.3727
1.6984
Temperature/K
Page 55 of 59
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Table 7.
Substrate
Swelling ratio of volume
Methyl acrylate
1.267
Acetic acid
1.283
Acrylic acid
1.251
Methyl acetic
1.242
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Table 8.
Equilibrium Adsorbed Mass
mS/mcat= 0.95
Adsorption Equilibrium Constants
KHAc=3.15
KMA=3.07
KAA=2.89
KMeAc=4.15
Page 56 of 59
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Table 9.
Model
PH(ideal)
PH
LH
k (x mol g F: s F:
9.42 10::
1.30 10*
2.17 10*
=, (kJ
E+ F: )
107.84
99.75
99.75
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Page 58 of 59
Table 10.
Model
SRS
MRD/%
PH(ideal)
1.96210-8
4.727
PH
0.195110-8
1.717
LH
0.153410-8
1.302
Page 59 of 59
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Table 11.
parameters
results
Operating pressure
0.065MPa
Theoretical plates number
50
HAc feeding position
11
MA feeding position
45
Reflux ratio
2.5:1
Feed
1.0
Methyl acrylate conversion rate
94.5%
Acrylic acid concentrations in the tower bottom
98.0%

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Kinetic and reactive distillation for acrylic

Industrial & Engineering Chemistry Research is published by the American Chemical

Industrial & Engineering Chemistry Research

Kinetic and reactive distillation for acrylic acid synthesis via

*Corresponding author: Chunshan Li. TEL/FAX: +86-10-82544800; E-mail: csli@ipe.ac.cn

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Table 1. Physicochemical characteristics of the resin (NKC-9).

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3. Results and discussion

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3.2. Kinetic experiments and optimization of transestrification conditions

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3.2.2 Effect of Catalyst Load.

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3.2.3. Effect of molar ratio of acetic acid and methyl acrylate.

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3.2.4. Effect of reaction temperature.

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3.3. Kinetic Model and Equilibrium Constant

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After organized and integral, equation was shown as follows:

Figure 7. The curve of Z and t

Table 4. The reaction rate constants at different temperatures

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The results were shown in Figure 9.

Figure 9. Comparison between the experimental data and simulation data.

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Related parameter identification based on the above model, kinetic equation of

 (5 5 5 5 / )

Table 5. Different kinetic models and their identification parameters.

3.3.1. Determination of reaction equilibrium constant.

Table 6. Reaction equilibrium constants at different temperatures.

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liquid-phase weight fraction of solvent i and j, respectively;

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3.3.3. Determination ofreaction rate constant, activation energy and pre-exponential.

SRS = ^( _ S` )4 (17)

3.3.4. Verification the results of different models.

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3.4. Determination of Space-Time of the Fixed-Bed Reactor.

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(5 5 5 5 / )

SRS = ^( _ S` )4 (17)