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Cite This: ACS Omega 2019, 4, 8274−8281 http://pubs.acs.org/journal/acsodf

Kinetic Study on the Preparation of Fumaric Acid from Maleic Acid

by Batch Noncatalytic Isomerization
Wangmi Chen,† Xiaoting Chen,‡ and Shouzhi Yi*,‡
†
College of Marine and Environmental Sciences and ‡College of Chemical Engineering and Materials Science, Tianjin University of
Science and Technology, Tianjin 300457, China
*
S Supporting Information

ABSTRACT: In recent years, the increase in demand for

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fumaric acid from industry has resulted in an increased need

for a high-selectivity process for the conversion of maleic acid
to fumaric acid. A highly selective conversion of fumaric acid
was achieved without a catalyst by a simple one-step
hydrothermal reaction. In addition, the competitive con-
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version of maleic acid, fumaric acid, and malic acid was first
systematically investigated in detail without using a catalyst.
The products were characterized by X-ray diffraction and
Fourier transform infrared, which demonstrated that the
product was fumaric acid. The highly selective conversion of
fumaric acid was achieved, and the yield of fumaric acid could
reach 92%. Furthermore, a reaction kinetic model was put forward to study the competitive transformation process. The kinetic
model predictions were found to agree well with the experimental data. The kinetic parameters were used to explain the changes
in the content of every substance at different reaction temperatures and reaction times. In addition, the initial maleic acid
concentration in the reaction was also considered as an influencing factor. These results can facilitate the conditional control
and product control of industrial processes for the production of fumaric acid or malic acid using latter without a catalyst.

■ INTRODUCTION
Fumaric acid, a tetra-carbon unsaturated dicarboxylic acid
classified as an organic acid, is widely distributed in nature. In
2004, fumaric acid was listed as the most promising building
block derived from biomass by Werpy and Petersen due to its
excellent performance.1,2 Fumaric acid has traditionally been
used in the production of food acidity regulators,1 feed
preservatives,3−5 and other high-potency chemical products.6−8
Recently, fumaric acid has been applied in metal−organic
frameworks,9,10 polymer composites,11,12 composite anodes of
high-energy lithium batteries,13 co-crystals,14,15 and micro-
environment tablets.16 Thus, the demand for fumaric acid has
dramatically increased with the expansion of the application
scope for fumaric acid, which has made it necessary to study
effective fumaric acid production methods.
Currently, methods for preparing fumaric acid mainly
include chemical isomerization and biosynthesis.17,18 Chemical
synthesis methods for fumaric acid were investigated in the
1940s and laid the foundation for the industrial production of
fumaric acid. 19 With the continuous development of
biotechnology and the rapid growth of fossil (petroleum)
based chemical production costs, investigations on the
preparation of fumaric acid by biosynthetic methods have
become more popular. Rhizopus,20−23 Torulopsis glabrata,24
Filamentous fungal strains,25−27 Saccharomyces cerevisiae,28,29
Escherichia coli,30,31 and other significant microorganisms32
have been applied to produce fumaric acid. In addition, some
new biotechnologies, such as alkali pretreatment,33 microwave
technology,34 immobilization technology,26,35 and biorefinery
technology,36 have been developed to improve the yield of
fumaric acid. Nevertheless, biosynthesis methods have suffered
from the inherent disadvantages of low yield and efficiency and
a long cycle in the process of production. Thus, researchers
have tried to develop isomerization methods to improve the
synthesis efficiency. Several noteworthy catalysts have been
reported to enhance the reaction conditions and increase the
productivity of fumaric acid, including bromate ion,37,38
vanadium pentoxide,39 hydrochloric acid,40 and poly(4-vinyl
pyridine).41 In a further study, researchers have introduced
microwaves to reduce the reaction time of maleic acid and
malic acid for assisted synthesis.42 By using the chemical
isomerization method, the yield of fumaric acid can reach over
80%, which is far higher than that realized by using a
biosynthesis method.
To further study the chemical isomerization method of
fumaric acid synthesis, more researchers have used kinetic
methods to explore the mutual transformation between
fumaric acid and other acids under certain conditions. For
example, Wojcieszak et al.43 and Delhomme et al.44 discussed
the feasibility of and conditions for the mutual conversion of
Received: February 2, 2019
Accepted: April 30, 2019
Published: May 8, 2019

© 2019 American Chemical Society 8274 DOI: 10.1021/acsomega.9b00316

ACS Omega 2019, 4, 8274−8281
ACS Omega
maleic anhydride, maleic acid, fumaric acid, and malic acid.
Wang et al.40 successfully converted maleic acid and fumaric
acid into malic acid in an acidic aqueous solution at 120 °C.
Ortiz et al.42 studied the kinetics of the transformation from
fumaric acid to maleic acid and malic acid at four different
temperatures in a homogeneous nonisothermal batch reactor
by using hydrochloric acid as a catalyst. The reason for and
processes of the reaction could be explained by the reaction
kinetics, so it was very meaningful to introduce kinetic studies
into the related reaction processes. Our previous work has
demonstrated that the isomerization of maleic acid can
produce fumaric acid in the absence of a catalyst. 45
Nevertheless, no detailed kinetic studies have been reported
in the available literature about the mutual conversion of malic
acid, maleic acid, and fumaric acid, especially the isomerization
of maleic acid to fumaric acid, although such a kinetic study is
significant, regardless of the use of a catalyst.
Researchers have proposed many kinetic models that help to
study the conversion process between maleic acid, fumaric
acid, and malic acid. Rozelle et al.46 studied the hydration
kinetic and thermodynamic models of fumaric acid in a
concentrated hydrochloric acid solution at 125−200 °C, but
they only explored the mutual conversion process between
fumaric acid and malic acid under the condition of hydro-
chloric acid catalysis. In addition, Jwo et al.47 investigated the
kinetics of the conversion of maleic acid to fumaric acid under
the action of bromine and strontium ions, while the model
mainly focused on the one-way conversion of maleic acid to
fumaric acid with a catalyst. Furthermore, Ortiz et al.48,49
converted a low concentration of fumaric acid to maleic acid
and malic acid under the action of hydrochloric acid or no
catalysts. This study only carried out the conversion reaction of
fumaric acid rather than that of maleic acid. However, kinetic
studies on the production of fumaric acid and malic acid using
maleic acid, especially in the absence of a catalyst, have not
been conducted. In addition, previous theoretical studies are
not fully applicable to this process.
In this study, the selectivity of fumaric acid in the mutual
conversion of fumaric acid, maleic acid, and malic acid was
enhanced by conditional control in the absence of a catalyst,
and a more comprehensive model of the reaction kinetics was
established to explain the reaction process for the first time. In
previous studies on the mutual conversion of fumaric acid,
maleic acid, and malic acid, the strong selectivity of specific
acids, especially fumaric acid, has not been studied on the basis
of strengthening the investigation of the experimental
influencing factors and determining better reaction conditions.
In addition, the reaction mechanism of the selective
production of fumaric acid and the mechanism of competition
between various substances were also analyzed. It should be
noted that to obtain a higher yield of fumaric acid in a short
time, the mutual conversion between fumaric acid, maleic acid,
and malic acid was fully considered. In addition, the content of
each substance in the reaction was detected by high-
performance liquid chromatography (HPLC), and the relevant
kinetic parameters were calculated. The kinetic parameters
explained the reasons for the change in the selectivity of each
substance in the reaction as a result of various influencing
factors and provided guidance for the subsequent control of
conditions for the production of fumaric acid and malic acid
without a catalyst.
8275
■
Article
EXPERIMENTAL SECTION
Materials. All chemicals were guaranteed reagents and used
without further purification. The raw material (maleic acid)
was an analytical reagent purchased from China Commeo
Chemical Co., Ltd. Distilled water was used in the isomer-
ization and purification stages. For the analysis and testing
phases, fumaric acid (analytical reagent), maleic acid
(analytical reagent), malic acid (biological grade), and
hydrochloric acid (analytical reagent) were purchased from
China Commeo Chemical Co., Ltd.
Preparation of Samples. The experiments were per-
formed in a 50 mL Teflon-lined autoclave. Maleic acid and
distilled water were added to the inner liner and stirred to
achieve a uniform solution. Then, the Teflon-lined autoclave
was sealed and placed in a blast drying oven. Once the
temperature of the mixture reached the preset temperature, the
timing was started. After heating for a preset time, the products
were cooled to room temperature and removed. The
experiments were carried out at 190, 200, 210, and 220 °C
for 0−4 h. The initial reaction concentration of maleic acid
(mass fraction 35−100%) on the selectivity of fumaric acid was
also examined. The reaction experiments were repeated twice.
After adding a certain amount of distilled water, the reaction
mixture was stirred and washed for 1 h. Further, insoluble
matter and the washing solution were separated by suction
filtration, and the filter cake was dried for 2 h by a blast drying
oven at 100 °C to obtain the filtered product. The washing
solution was prepared for HPLC.
Characterization. Fourier transform infrared (FT-IR)
spectra were measured on a TENSOR27 Fourier infrared
spectrometer (Brook Spectrometer, Germany). The dried
samples were characterized by the potassium bromide tableting
method, and the spectra were recorded between 400 and 4000
cm−1.
The X-ray diffraction (XRD) patterns of the samples were
detected by an XRD-6100 (Shimadzu Corporation, Japan),
with graphite monochromated Cu Kα (λ = 1.54178 Å)
radiation operating at 40 kV and 30 mA in the angular range of
2θ = 5−80° at room temperature. The scanning speed and the
scanning step size were 7° min−1 and 0.02°, respectively. The
sample needed to be dried, ground, and placed in a fixed mold
for compaction before testing.
Quantitative Analysis of Samples. All samples were
analyzed by HPLC (Agilent Technologies 1260, Inc.). The
column used was a Kromasil C18 column (5 μm × 250 mm ×
4.6 mm, Japan). The mobile phase was an HCl solution in
ultrapure water (pH 2) at a flow rate of 1 mL min−1 and an
injection volume of 5 μL. The sample detection wavelength
was 210 nm, and the column temperature was 42 ± 0.8 °C.
The water samples were diluted 100 times before testing. The
dilute samples were analyzed by HPLC to determine the
content of each component, providing the necessary
parameters for the kinetic analyses.
The conversion rates of fumaric acid, malic acid, and maleic
acid were calculated by the following equations
CF n
fumaric acid yield(%) = × 100 = F × 100
CMx0 nMx0 (1)
CM n
malic acid yield(%) = × 100 = M × 100
CMx0 nMx0 (2)
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maleicacidconversionrate(%) acid has a higher solubility in water (100 °C, solubility of

392.6/100 g water, 33.84 mol/L) and a higher solubility at
C − CMx
= Mx0 × 100 high temperatures, much higher than the concentration used in
CMx0 the kinetic experiments.50 At the same time, Ortiz et al.48
n − nMx confirmed that the solubility of fumaric acid increased
= Mx0 × 100
nMx0 (3) exponentially with increasing temperature (4.84 mol/L at
189 °C). Therefore, it can be considered that the detected
−1
where CMx0 (mol L ) is the initial concentration of maleic acid reaction is carried out under homogeneous conditions.
and CF, CM, and CMx (mol L−1) are the concentrations of The effect of temperature on the reaction rate constant was
maleic acid and fumaric acid at time t in the respective calculated by the Arrhenius equation, and the activation energy
solutions. nMx0 (mol) is the initial molar mass of maleic acid for the reaction was determined
and nF, nM, and nMx (mol) are the molar masses of maleic acid
and fumaric acid. k = Ae−Ea / RT (8)
Reaction Kinetic Model. The reaction model in Figure 1 −1
where T (K) is the absolute temperature, k (h ) is the
was established to study the kinetics of this series of reaction rate constant at the preset temperature, Ea (kJ mol−1)
is the activation energy, R (8.314 J (mol K)−1) is the general
gas constant, and A (h−1) is a pre-exponential factor. Ea was
estimated based on linear regression analysis of a plot of ln(ki)
and 1/Ti (i = 190, 200, 210, and 220 °C).
The Gibbs free energy of every reaction was calculated by
using the following equation
ki
Kj =
k −i (9)

ΔG = −RT ln(Kj) (10)

−1
Figure 1. Simplified reaction model for the isomerization and where ΔG (J mol ) is the Gibbs free energy at the preset
hydration of maleic acid, fumaric acid, and malic acid. temperature, Kj (j = 1, 2, 3) is the reaction equilibrium
constant, and ki (i = 1, 2, 3) is the reaction rate constant (h−1)
isomerization reactions and hydration reactions, which can for each reaction.
explain the mutual transformation between fumaric acid, malic
acid, and maleic acid. In this context, Mx, F, and M represent
maleic acid, fumaric acid, and malic acid, respectively.
■ RESULTS AND DISCUSSION
Characterization of Products. The products were
According to the model with the assumption of a first-order identified from the measured XRD pattern (Figure 2a). The
reaction, the following set of eqs 4−6 was obtained.
dCMx
rMx = = −(k1 + k 2)CMx + k −1C F
dt (4)

dC F
rF = = k1CMx − (k −1 + k −3)C F + k 3CM
dt (5)

dC M
rM = = k 2CMx + k −3C F − k 3CM
dt (6)
The following two boundary conditions could be determined

l
by the analyses of the experimental process.
o
Figure 2. (a) XRD patterns of the products, standard samples, and

o
o
o
other research products.51 (b) FT-IR spectra of the products,

oCMx = CMx0
o
t=0
o
o
standard samples, and other research products.

m
o
o
o
o
o
o
o
diffraction pattern showed six major diffraction peaks at 2θ =
o
CF = 0

nC M = 0
CMx0 = CMx + C F + CM
(7)
It is worth noting that the reaction involving malic acid was a
pseudo-first-order reaction because water was present in large
amounts during the reaction. Although water was involved in
some reactions, the amount of water in the system was
considered to be constant, and the progress of every reaction
was only related to the concentrations of fumaric acid, maleic
acid, and malic acid.
The kinetic experiments were carried out using a maleic acid
solution having a mass fraction of 60% (12.94 mol/L). Maleic
8276
18.4, 22.8, 28.7, 29.4, 31.2, and 35.8°. Compared with the
peaks in the pattern of fumaric acid standard and fumaric acid
reported in the references,51 the peaks in the XRD pattern of
the products were consistent. This could indicate that the
products had the same crystal structure as fumaric acid and
could be preliminarily identified as fumaric acid. Since there
were no other peaks present in the pattern, the purity of the
products was relatively high.
FT-IR analysis was further carried out to determine the
structure of the product. As shown in Figure 2b, the
characteristic peak at 3081 cm−1 can be assigned to the
stretching vibration of CC−H, while the peaks at 2863 and
1670 cm−1 can be ascribed to the stretching vibrations of
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Table 1. Reaction Rate Constants for Every Reaction Process at Different Temperatures
reaction rate constant (h−1)
T (K) k1 k−1 k2 k3 k−3
463 2.502862914 0.060560596 0.561579371 0.257186356 0.176258077
473 3.550348358 0.099529637 0.983973071 0.338702133 0.199889328
483 5.42534805 0.165669838 1.504939419 0.409023597 0.234727444
493 8.713134203 0.312128031 2.578914071 0.518292295 0.278754867

Table 2. Tuned Model Parameters

rate constant linear equation of ln(ki) and 1/T R2 Eai (kJ mol−1) ΔHj (×107 J kmol−1)
k1 ln(k1) = −9495.4 × (1/T) + 21.386 0.9927 78.94475 −2.39493
k−1 ln(k−1) = −12376 × (1/T) + 23.886 0.9940 102.89406
k2 ln(k2) = −11408 × (1/T) + 24.069 0.9975 94.84611
k3 ln(k3) = −5231.5 × (1/T) + 9.9526 0.9962 43.49469 1.43932
k−3 ln(k−3) = −3500.3 × (1/T) + 5.8087 0.9924 29.10149

saturated C−H and CO, respectively. The peak at 1424 [λ1 , λ 2]

cm−1 was caused by the in-plane bending vibration of the
saturated C−H. The three peaks at approximately 1276 cm−1 − (k ′ + k ″ ) ± (k′ + k″)2 − 4(k′k″ − k −1k‴)
resulted from the stretching vibration of C−O. The peaks at =
2
922 and 643 cm−1 were attributed to the out-of-plane bending (19)
vibration of O−H and the deformation vibration of OC−O,
where ki (i = 1, 2, 3, −1, −3) (h−1) was the reaction rate
respectively. Further, the single peak at 1008 cm−1 was
constant for each reaction stage.
attributed to the trans-substituted characteristic peak. The FT-
The content of each substance was determined by HPLC,
IR analysis further indicated that the product was fumaric acid,
and these concentration equations were used to determine the
which was in accordance with the XRD result.
rate constant under each condition. The Solver function in
Kinetic Study. To determine the rate-limiting step of the
Microsoft Excel was used to find the best values for the
isomerization reaction, the following concentration equations
reaction rate constants. Using the Arrhenius form for the rate
were obtained by analyzing the above differential equation
equations, the activation energy (Ea) and pre-exponential
system (4−6)
factor (A) were calculated for each individual reaction
CMx k 3k −1 temperature using the slope and intercept of ln(ki) (i = 1, 2,
= C1 e λ1t + C2 e λ2t + 3, −1, −3) versus 1/T charts. The specific calculation results
CMx0 k′k″ − k −1k‴ (11)
are shown in Tables 1, 2, and 4.
CF C C As shown in Table 2, R2 was greater than 0.99, which
= 1 (k′ + λ1)e λ1t + 2 (k′ + λ 2)e λ2t suggested that ln(ki) had a good linear relationship with 1/T,
CMx0 k −1 k −1
and the obtained reaction rate constants satisfied the Arrhenius
k 3k′ expression. Compared with the values reported in the
+
k′k″ − k −1k‴ (12) literature, the results from the literature and those currently
adjusted from the experimental kinetic data reported in Tables
CM C C 1, 2, 3, 4, 5, and 6 were almost the same; however, the value of
= − 1 (k′ + k −1 + λ1)e λ1t − 2 (k′ + k −1 + λ 2)
CMx0 k −1 k −1
Table 3. Comparison of the Enthalpy of Reaction (1)
k k + k k ′
e λ 2 t + 2 −1 −3 Calculated in This Study with the Median Value from a
k′k″ − k −1k‴ (13) Previous Study
where data sources ΔH1 (×107 J kmol−1) reference
this research −2.39493

C1 =
λ2 ( k 3k −1
k ′ k ″ − k −1k ‴ )
− 1 − k′ previous study
literature report
−2.83
−2.28
48
52
λ1 − λ 2 (14)

Table 4. Pre-Exponential Factor and Reaction Equilibrium

C2 =
λ1 ( k 3k −1
k ′ k ″ − k −1k ‴ )
− 1 − k′
Constant
λ 2 − λ1 (15)
Kj
k ′ = k1 + k 2 −1
(16) rate constant A (s ) 463 K 473 K 483 K 493 K
k1 5.39 × 105 41.33 35.67 32.75 27.92
k ″ = k −1 + k 3 + k −3 (17) k−1 6.56 × 106
k2 7.88 × 106
k ‴ = k1 − k 3 (18) k3 5.84 1.46 1.69 1.74 1.86
and k−3 9.26 × 10−2

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Table 5. Gibbs Free Energy of Reactions (1) and (3) slightly with temperature, but they did not reach the elevated
level of reaction (1). It was indicated that the high selective
ΔG1 of reaction (1) ΔG3 of reaction (3)
T (K) (×107 J kmol−1) (×107 J kmol−1) conversion of fumaric acid could be well achieved by adjusting
the temperature.
463 −1.432565246 −0.145449544
As indicated in Table 5, with increasing temperature, the
473 −1.40561925 −0.207384381
absolute value of the Gibbs free energy in reaction (1)
483 −1.401000403 −0.223008914
decreased, while that in reaction (3) showed an increasing
493 −1.364562253 −0.254210396
trend. It was suggested that the spontaneous inhibition of the
conversion from maleic acid to fumaric acid was weakened,
Table 6. Selectivities of Fumaric Acid as Defined by eq 20 at
while the spontaneous inhibition of the conversion from malic
Different Reaction Temperatures
acid to fumaric acid increased with increasing temperature.
T (K) tmax (h) S This meant that the conversion from maleic acid to fumaric
463 0.818 6.58 acid and the conversion from fumaric acid to malic acid were
473 0.582 12.57 inhibited by the increase in temperature. This echoed the
483 0.473 14.39 conclusion of Ortiz et al. that a temperature rise reduces the
493 0.314 23.40 selectivity for malic acid.48
Discussion on Product Selectivity. For practical
ΔH1 was better (Table 3) than that reported in other studies.48 purposes, the selectivity of the conversion of maleic acid to
The difference between the reaction rate constants and other fumaric acid and malic acid remains to be studied. The reason
parameters could be explained as being due to the presence of for this is that the rapid conversion of maleic acid to fumaric
a catalyst, different temperatures, and different substrate acid with high selectivity is conducive to the development of a
concentrations. production process for fumaric acid. It is particularly
The calculated data were used to plot the changes in the noteworthy that when the temperature increases from 463 to
three organic acid concentrations over time at each temper- 493 K, the maximum selectivity time for fumaric acid
ature, and the curves were combined with experimental data to decreases. At the same time, the selectivity for malic acid
form Figure 3a−d. It was found that the figures drawn by the decreased first and then increased with reaction time.
Selectivity is determined by using the following equation.
CF
S=
CMx (20)
Analysis of Influencing Factors. Effect of Initial
Reactant Concentration. To evaluate the effect of the initial
concentration of maleic acid on the reaction, the intersub-
stance conversion was investigated. As shown in Figure 4, the

Figure 3. Experimental (symbol) and calculated (solid line) variations

in the concentration of three organic acids with reaction time at
temperatures (a) 190 °C, (b) 200 °C, (c) 210 °C, and (d) 220 °C.
Black for maleic acid; red for fumaric acid; and blue for malic acid.
equations were better matched with the experimental data
points. The trends for the three organic acids were consistent
with that of the graph line, which further proved the accuracy
of the experimental data.
As shown in Table 1, as the temperature increased, the
forward reaction rate constant of reaction (1) (the reaction
rate constant of conversion of maleic acid to fumaric acid)
increased continuously from 2.5 to 8.71 h−1. In addition, at
each temperature, the forward reaction rate constant of
reaction (1) was the largest, and the reverse reaction rate
constant was relatively less than 0.32 h−1. This was because cis-
maleic acid was easily attacked on account of its small steric
effect and was transformed into malic acid and fumaric acid.40
The reaction rate constants of reactions (2) and (3) increased
8278
Figure 4. Concentrations of maleic acid, malic acid, and fumaric acid
vary with the initial maleic acid concentration in the reaction (1 h).
amount of fumaric acid increased with increasing initial maleic
acid concentration. At the same time, the conversion rate of
maleic acid also increased with increasing fumaric acid
concentration. In addition, the yield of malic acid first
increased and then tended to balance out. Because the
reduction in water content was not favorable for the
conversion of maleic acid and fumaric acid to malic acid,
more maleic acid could be converted to fumaric acid, and the
selectivity of fumaric acid was enhanced. Furthermore, once
the temperature was too high, the products were oxidized,
thereby leading to the possibility of coking products being
formed in the reaction vessel.
Effect of Reaction Temperature and Time. The effects of
reaction temperature and reaction time on the mutual
transformation of materials were investigated. A maleic acid
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solution with an initial mass fraction of 60% was selected and
was subject to an experiment from 0 to 4 h at 190, 200, 210,
and 220 °C. As shown in Figure 5a,b, the rate of fumaric acid
Figure 5. Variation in fumaric acid yield with reaction temperature
and reaction time. (a) Fumaric acid yield changes with temperature.
(b) Fumaric acid yield changes with time.
production was faster when the reaction temperature was
increased. This was because the reaction rate constant for the
formation of fumaric acid became larger due to the increase in
temperature. At the same time, the yield of fumaric acid
increased with increasing time in the initial stage, while it
decreased when the reaction time was over 1 h. This was
because the concentration of fumaric acid increased as the
reactions proceeded, thereby promoting the conversion of
fumaric acid to maleic acid and malic acid.
Further analysis of Figure 5a showed that the amount of
fumaric acid increased significantly as the temperature
increased within 0.75 h. However, as the reaction time
continued to increase, the effect of temperature on the reaction
became less pronounced. When the reaction time was over 1 h,
the conversion of fumaric acid decreased with increasing
temperature. This was because the content of fumaric acid
increased with the reaction time, while the content of maleic
acid continued to decrease, which caused the main reactions to
become the reactions of conversion of fumaric acid to maleic
acid and malic acid. As shown in Figure 5b, the maximum yield
of fumaric acid decreased slightly (approximately 1%) and the
time of the maximum conversion rate decreased with
increasing temperature. This could be explained by the fact
that the increase in temperature enhanced the reaction rate
constant for maleic acid, which reduced the reaction time. A
slight decrease was because, although the formation of fumaric
acid was inhibited by the increase in temperature, the
conversion from malic acid to fumaric acid was promoted.
Furthermore, on the falling phase, the higher the temperature,
the faster the fumaric acid decreased. This was because the
reaction rate constants of reactions (3) and (1) increased as
the temperature increased, which caused fumaric acid to be
converted to maleic acid and malic acid more rapidly at a
higher concentration of fumaric acid. The fumaric acid content
at which the final fumaric acid concentration reached an
equilibrium decreased with increasing temperature, which was
illustrated by the change in the Gibbs free energy and the
reaction rate constants with increasing temperature. As the
temperature increased, the absolute value of the Gibbs free
energy of reaction (1) decreased, which indicated that the
selectivity of the reaction to form fumaric acid decreased,
causing more fumaric acid to be converted to maleic acid. At
the same time, since the rate constant of reaction (2) increased
significantly with increasing temperature, more maleic acid was
converted to malic acid. Although the selectivity of reaction
8279
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(3) to produce fumaric acid was enhanced with increasing
temperature, the reaction rate constant for conversion to
obtain fumaric acid was small, and the reaction was not
affected much.
■ CONCLUSIONS
Highly selective conversion from maleic acid to fumaric acid
was achieved by a simple one-step hydrothermal synthesis at
four different temperatures without any catalyst, and the
kinetics of the mutual conversion of maleic acid, fumaric acid,
and malic acid were studied. The highly selective process had
higher stability and fumaric acid yield and could be used to
obtain the desired fumaric acid product without a catalyst.
Through the mutual confirmation of the data spectra and the
kinetic parameters, the mutual transformation of the three
organic acids under hydrothermal conditions was studied
systematically and completely for the first time and reached a
level superior to that obtained in previous reports. Based on
the kinetic data obtained experimentally, 20 reaction rate
constants were determined, and the Ea values of 5 reactions
were calculated. It was found that the time to reach the highest
yield point of fumaric acid could be effectively reduced with
increasing temperature and that a high concentration of
fumaric acid in the conversion process can convert fumaric
acid into malic acid, which provided the guidance on the
development of related production processes. The change in
the Gibbs free energy in each reaction reflected the fact that an
increase in temperature was not favorable for the formation of
fumaric acid from maleic acid, but instead promoted the
formation of fumaric acid from malic acid and reduced the
selectivity of malic acid. This study showed that the highly
selective conversion of fumaric acid can be achieved by a
hydrothermal method and that the conversion of malic acid
can also be achieved by conditional control without a catalyst.
Therefore, the hydrothermal synthesis of fumaric acid and
malic acid without a catalyst has huge commercial potential.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsome-
ga.9b00316.
Typical appearance of the products; SEM image of the
products; 1H-NMR spectrum; analytical method of
solution of the system of ordinary differential equations
given by eqs 4−6 (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: 389085304@qq.com (S.Y.).
ORCID
Wangmi Chen: 0000-0003-4348-4765
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
DOI: 10.1021/acsomega.9b00316
ACS Omega 2019, 4, 8274−8281
ACS Omega
■
ACKNOWLEDGMENTS
The authors wish to acknowledge laboratory teachers and
classmates from the Tianjin University of Science and
Technology for technology support of this study.
■
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8281 DOI: 10.1021/acsomega.9b00316

ACS Omega 2019, 4, 8274−8281