pubs.acs.

org/journal/ascecg Research Article

Insight into the Mechanism of Glycerol Dehydration and

Subsequent Pyridine Synthesis
Ding Jiang, Shuang Wang,* Hongping Li,* Lujiang Xu, Xun Hu, Bahram Barati, and Anqing Zheng
Cite This: ACS Sustainable Chem. Eng. 2021, 9, 3095−3103 Read Online

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ABSTRACT: In the present study, glycerol was exploited as the

feedstock to synthesize pyridine with ammonia gas as a carrier and
reactant through thermal conversion. A density functional theory
(DFT) at the M06-2X method was applied to understand the
mechanism of glycerol dehydration, the ammonization of oxy-
genated compounds, and the condensation of imines. The results
confirmed that glycerol could be directly converted into pyridine in
ammonia atmosphere at 550 °C. The overall view of the thermal
conversion mechanism of glycerol was compared with the previous
experimental data and the proposed mechanisms, which indicated
that the neutral glycerol dehydration process should mainly produce
acrolein, acetaldehyde, formaldehyde, and acetol. The produced
oxygenated compounds (acrolein and acetaldehyde) can react with
ammonia to form imine, which would further undergo Michael
addition, a Diels-Alder reaction, deammonization, and dehydrogenation to form pyridine. In a catalytic condition, ZSM-5 not only
plays a shape-selective effect on the conversion of glycerol to pyridine but also changes the path of the reaction. The structure of
ZSM-5 limits the formation of multisubstituted pyridine products, which is beneficial to the formation of pyridine and
monosubstituted pyridine. Protonated vinylamine intermediates may be a critical step limiting pyridine yield and selectivity. The
kinetic analysis that is based on transition state theory was consistent with product contribution in experiments. The present study
confirmed the selectivity and the conversion route of glycerol to pyridine.
KEYWORDS: thermal decomposition, glycerol, pyrolysis, pyridine, pyridine synthesis

■ INTRODUCTION
Pyridine is an aromatic heterocyclic compound with a nitrogen
atom contained in it. It has several main derivatives, such as 2-
methylpyridine, 3-methylpyridine, and 4-methylpyridine.1,2
These pyridine rings, as the important raw material for the
preparation of various intermediates, are widely useful in
diverse applications, such as the market areas of agro-
chemicals,3 pharmaceuticals, vitamins, and other fine chem-
icals.4,5 Traditionally, pyridine bases have been separated from
the coal tar as one of the by-products by solvent extraction.6,7
It is not a renewable method for the synthesis of pyridine. The
present commercial feedstocks for the production of pyridines
are carbonyl-containing compounds and ammonia or ammonia
derivatives as the nitrogen source in the presence of various
catalysts.7−9 These chemicals are also nonrenewable and are
the by-products of fossil raw materials. Among them,
formaldehyde is harmful to human health; acrolein is easy to
polymerize into bigger molecules and become toxic. Thus, it is
necessary to exploit a new feedstock for pyridine production in
consideration of energy efficiency and environmental protec-
tion.
In recent years, glycerol has been studied as an important
compound for the synthesis of pyridine precursors.10−13
Glycerol is mostly produced as a by-product in the industrial
biodiesel production process.14,15 It is reported that 10 kg of
glycerol (purity of around 50−55%) can be produced per 100
kg of biodiesel.16 Thus, exploiting glycerol as feedstock in the
synthesis of valuable compounds is an interesting topic to
study. Glycerol can be converted into various valuable
compounds, such as alcohols, lipids, polys, acrolein, etc., via
reduction, esterification, oxidation, etc.,11,17,18 by a non- or
conventional process.19 Nimlos et al. and Geng et al.
conducted a quantum mechanical calculation on dehydration
of glycerol and proposed three types of dehydration reactions.
The calculation results showed that, in addition to the 1,2
dehydration mechanism of acrolein, the cyclic 1,3-dehydration
Received: October 14, 2020
Revised: January 19, 2021
Published: February 15, 2021

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Figure 1. Basic synthesis mechanism of pyridine with glycerol as the feedstock.
is also thermodynamically beneficial to the formation of
formaldehyde and vinyl alcohol.20,21 Katryniok et al. reviewed
the catalytic dehydration of glycerol to acrolein.22,23 They
suggested that glycerol can be dehydrated more frequently in a
protic environment to produce more acrolein and acetol.
Cecilia et al. estimated a porous silicon-based catalyst effect on
the dehydration of glycerol to acrolein and discussed the
catalytic performance of mesoporous catalysts. 14 They
concluded that the strong Bronsted acid center makes zeolite
highly active in the dehydration of glycerol to acrolein.
Corma’s experiment showed that glycerol reacts with zeolite
catalysts in water solution to produce acrolein as the main
product with olefins, carboxylic acid, ketones, and aromatics
via dehydration, cracking, and World Gold Council (WGC)
reactions.24 Yoda evaluated the catalytic reaction of glycerol
over H-MFI, and observed that the main product as acrolein.
Laino et al. proposed a novel mechanism of glycerol
dehydration by means of metadynamics simulations at 800
K.25 The paper suggested that glycidol formation should be the
rate-determining step of the whole process. Sun et al. also
evaluated the reaction of glycerol to glycidol and supported
that glycidol should be produced at high temperatures.26
Although a former researcher has proposed several dehydration
mechanisms of glycerol, researchers have not reached an
agreement on the real mechanism; thus, a complete under-
standing of glycerol pyrolysis is required to be studied. In the
present study, a global insight of the neutral glycerol pyrolysis
mechanism was investigated to understand the product
formation. In order to understand the effect of ZSM-5 on
the mechanism of glycerol dehydration, the catalytic
mechanism of glycerol dehydration was discussed.
As the previous study showed, using glycerol as feedstock
could form many aldehydes that are also the raw materials for
the production of pyridines, such as acrolein, acetol, form-
aldehyde, and acetaldehyde.2,27−29 Thus, it is possible to
convert glycerol to synthesis pyridine. Cullinane et al. reported
the formation of pyridine rings by reacting ammonia with
glycerol.30 Xu et al. conducted several experiments to confirm
the catalytic activity of HZSM-5, which is a one step process
expanding the yield of pyridines, which exhibits an
extraordinary application potential for using glycerol to
synthesize pyridines.31,32 It was suggested that the dehydration
of glycerol, the amination of oxidation products, and the
polymerization of imine substances occurred during the
pyridine synthesis process. Zhang et al. also characterized the
catalytic performance of HZSM-5 in the conversion of glycerol
with ammonia to pyridine bases.1 Additionally, in another
study of Zhang et al., Cu/HZSM-5 was selected as the catalyst
to catalyze this conversion process, which resulted in a 42.8%
yield increase of pyridine in the optimized conditions.6
Previous experiments have proved that the conversion of
glycerol to pyridine is feasible. The mechanism of its
conversion needs to be clarified in more detail.
In the present study, we proposed a mechanism for
converting glycerol to pyridine in ammonia atmosphere in
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the vapor phase at 550 °C via quantum calculation using DFT
methods (M06-2X) with the basis set of 6-311G+ (d, p). A
global insight on neutral glycerol pyrolysis was discussed in the
first part. Then, the ammonization of produced carbonyl
compounds that generate imines were analyzed. The synthesis
of pyridine from imine was thoroughly explained by Michael
addition, dehydrogenation, dehydration, Diels-Alder reaction,
and ammonia elimination. In the last part of this study, to
understand the influence of HZSM-5 on the whole process, a
catalytic model was proposed and calculated.
■ COMPUTATIONAL DETAILS
Density Functional Theory Calculation Methods. All
reaction schemes were calculated in the gas phase using
Gaussian 16 quantum chemical software packages. The M06-
2X functional was proved to be more accurate than B3LYP
functional in main-group thermochemistry, kinetics, non-
covalent interactions, and electronic spectroscopy.33 Therefore,
the equilibrium geometries (stable configurations) of reactants,
intermediates, transition states, and products were optimized at
the M06-2X/6−311 + G (d, p) computational level. According
to the vibrational frequency analysis of the reactants,
intermediates, transition states, and products, all the reactants,
intermediates, and products had no imaginary frequencies,
while for the transition states, only one imaginary frequency
exists.34,35 Each transition state was analyzed for intrinsic
reaction coordinates (IRC) to verify the correctness and
interconnection of intermediates and transition states.36 The
thermodynamic corrections were obtained at 550 °C. To
provide more accurate energies, single-point energies of the
optimized structure were calculated at the same level. The
reported energies were the gas-phase single-point energies
corrected by Gibbs free-energy corrections at atmospheric
pressure and 550 °C.
To discuss the catalytic performance of HZSM-5 during
pyridine synthesis, the model of HZSM-5 with 28 T clusters
has been applied as it was proposed in the previous study37
(see Figure S1 for the optimized 28 T HZSM-5 structure). The
intermediate and transition state configurations were opti-
mized and calculated at M06-2X/6-31G(d) to obtain
thermodynamic parameters, including Gibbs free energy and
vibrational frequency.
Concepts for Discussion. The transitional, rotational,
vibrational, and entropy contributions for each structure at the
reaction condition were estimated by employing the concept of
Gibbs free energy (G). For each path, the changes in thermal
free energy (ΔG) and activation free energy (Ea) were defined
using the following formulas.38
ΔG = G P − G R (1)
Ea = GTS − G R (2)
Herein, GP and GR are the Gibbs free energy of the final
product and the reactant in a reaction mechanism; GTS is the
Gibbs free energy of the transition state.
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Figure 2. Gibbs free-energy profiles for pyrolysis pathways 1−13 at 823.15 K: (a) pathway 1; (b) pathways 2−5; (c) pathway 6; (d) pathways 7
and 8; (e) pathways 9−11; and (f) pathways 12 and 13.
■ RESULTS AND DISCUSSION
The Mechanism of Pyridine Synthesis from Glycerol.
In the previous experimental work, it was found that glycerol
can be used as feedstock to be converted into pyridine with
ammonia as the carrier gas and reactant.31 The optimal
conditions for this synthesis process were achieved with
HZSM-5 (Si/Al = 25) at 550 °C with a weight hourly space
velocity (WHSV) of glycerol to the catalyst of 1 h−1 and
ammonia to a glycerol ratio of 12:1 M. As shown in Figure 1,
Previous literature suggested that glycerol need to undergo
dehydration and a cracking process to produce various
oxygenated compounds, such as acrolein, acetaldehyde,
acetone, and acetol, which can be further converted into
imines with the ammonia participation.1,6,31,39−41 These imines
could be condensed to form cyclic compounds, including
pyridine via Michael addition, dehydrogenation, deamination
and dehydration reactions, etc. In the optimal condition, the
partial product distribution using glycerol and other oxy-
genated compounds (including acetaldehyde and acrolein) as
feedstocks can be seen in Table S1 (Supporting Information).
In most glycerol dehydration studies, acetone and acetol were
not considered as the main product.22,42−44 Thus, the pyridine
formation should be related to the acrolein and acetaldehyde
productions, which are the main products of glycerol pyrolysis.
In the pyrolysis of acetaldehyde with ammonia, the pyridine
selectivity is much different from that in glycerol pyrolysis.
Meanwhile, the copyrolysis of acrolei and acetaldehyde with
ammonia has a similar pyridine selectivity to that in the
glycerol experiment. Similarly, the same results were observed
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in the experiment using acrolein as the feedstock (Supporting
Information, Table S1). The whole process can be separated
into three parts, including glycerol dehydration, ammonization
of oxygenated compounds, and imine condensation, to
understand the mechanisms more clearly.
Kinetic and Thermodynamic Analyses of Proposed
Paths of Neutral Glycerol. In different environmental
conditions, glycerol could undergo a lot of reactions. In the
pyrolysis process, dehydration, decarbonylation, and bond
cracking of neutral glycerol are easy to occur.20,26,42 The main
product generated from glycerol pyrolysis are acrolein,
acetaldehyde, acetone, 2-propenol, and acetol (Supporting
Information, Table S2), which are concluded in previous
experimental study conducted by Corma et al.24 The
dehydration of glycerol is the most likely reaction to happen
in the initial stage of pyrolysis with the presence of the
hydrogen bond between the hydroxy group and hydrogen
atom. Thus, probable paths of glycerol pyrolysis could differ
owing to diverse positions of the hydroxy group and hydrogen
atom. A full overview of the glycerol decomposition
mechanism can be seen in Figure S2 (Supporting Informa-
tion). For simplicity, carbon atoms on the glycerol molecule
were referred as C1, C2, and C3, and hydroxy groups were
referred as −OaH, −ObH, and −OcH. The reaction paths in
the initial stage of glycerol pyrolysis can be divided into three
main types, including dehydration (1,3-dehydration and 1,2-
dehydration), cyclization, and bond cracking (the form-
aldehyde loss mechanism and methanol loss mechanism).
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Figure 3. Configurations of transition states TS1, TS5, and TS6 in paths 1, 4, and 6 (unit: Å).
The 1,3-dehydration and 1,2-dehydration were also
proposed by Nimlos et al.20 Same as the previous results, the
1,3-dehydration was the most energy-favored path with
formaldehyde and acetaldehyde formation, which exhibited a
low rate-determining step (Ea = 69.4 kcal/mol, at 550 °C), as
shown in Figure 2. The transition state of TS1 can be seen in
Figure 3a. It can be seen that the glycerol should initially form
a near six-membered-ring configuration, in which the hydrogen
atom in Oa was transferred to the hydroxyl group (−OcH) to
leave a water molecule. Also, the 1,2-dehydration could lead to
the elimination of the terminal or central hydroxyl group. As
shown in Figure 2, the central hydroxyl elimination mechanism
can produce an acetol molecule. The highest energy barrier
(TS12) in path 6 was higher than that in 1,3-dehydration and
1,2-dehydration (terminal hydroxyl loss), which is consistent
with the previous experimental results.24 The present study
proposed more paths after the formation of propylene glycol
(IM3). Paths 2, 3, and 5 have never been studied previously.
Also, it can be seen that path 3 has the potential to produce
carbonyl compounds (formaldehyde and acetaldehyde) from
lacticaldehyde (IM4) through a synergetic reaction (Figure
3b), which costs an activation energy of 38.2 kcal/mol. From
the perspective of kinetics, IM4 could be further converted to
acrolein (IM6) via TS8. Due to the high energy barriers of
TS6 (Ea = 78.6 kcal/mol) and TS9 (85.0 kcal/mol), both of
which were carbon monoxide elimination reactions, the yield
of ethylene was very low. A similar result can be obtained in
previous experimental data (Supporting Information, Table
S2).24 Propylene glycol could also be converted through a six-
ring configuration (TS10, Ea = 31.5 kcal/mol), as shown in
Figure 3c. The activation energy of TS11 was more than 80
kcal/mol. Generally, the 1,2-dehydration should favor path 4
to produce acrolein. Due to the high temperature, the free-
energy change of acrolein formation should be negative (−45.6
kcal/mol). Meanwhile, in Nimlos’s paper, the forward reaction
was hard to proceed for the endothermic reaction (9.3 kcal/
mol).20 A higher temperature changed the equilibrium of the
reaction to promote the forward reaction. Also, due to the high
energy barrier of TS9 (Ea = 85.0 kcal/mol), acrolein (IM6)
should be the main final product of the 1,2-dehydration path.
Cyclization of glycerol is a dehydration reaction of vicinal dual
hydroxyl (as shown in Figure S2, Supporting Information,
paths 7 and 8) with molecule epoxide (glycidol, IM9)
formation, which also was proposed by Sun et al. and Laino
et al.25,26 Laino considered glycidol as an intermediate between
glycerol and 3-hydropropanal (IM4).25 However, in the
present results, the first elementary reaction (dehydration of
vicinal dual hydroxyls) exhibited an energy barrier (Ea = 71.5
kcal/mol) higher than 1,2-dehydration and 1,3-dehydration. It
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indicates that the cyclization path has a low possibility to
proceed.
Besides the above mechanism, bond cracking has been taken
into consideration. TS18 and TS22 were both higher than 90
kcal/mol. It can be presumed that at high temperatures,
multihydroxyl compounds should first conduct synergetic
dehydration reactions (1,3-dehydration and 1,2-dehydration),
while bond cracking has a low possibility to occur. Therefore,
in thermal chemistry, various carbonyl compounds could have
more possibility to be formed from carbohydrates through
synergetic dehydration with a low energy barrier.
In summary, in the point of kinetic analysis, the possible
path for glycerol conversion should be paths 4, 1, 6, and 2 in
order. Although the first elementary reaction of 1,2-
dehydration was slightly higher than 1,3-dehydration, the
synergetic dehydration (TS10) comprised a relatively low
energy barrier, which makes path 4 more competitive. Thus,
acrolein should be the main product, with formaldehyde and
acetaldehyde as the by-products. From the configurations of
TS1, TS5, and TS10 (Figure 3), synergetic dehydration should
be a proper routine to proceed.
Ammonization of Acetaldehyde and Acrolein. The
synthesis of pyridine from glycerol involves the process of
introducing a nitrogen source into the reaction system.31 The
nitrogen source in this study is ammonia, which could react
with the oxygenated compounds. In the above-discussed
content, the dehydration of glycerol produces a lot of
unsaturated oxygenated compounds, such as aldehydes and
ketones. Similarly, previous experimental studies supported the
production of acrolein, acetol, formaldehyde, and acetalde-
hyde.45,46 Among them, acrolein and acetaldehyde were the
main products. Through reacting with ammonia, the oxy-
genated compounds could be converted to form imine
compounds, which were intermediates in the pyridine
production process. The produced imine compounds could
be further converted to pyridines via the catalytic condensation
reaction.32 As acrolein and acetaldehyde were the most
abundant compounds in glycerol pyrolysis products, the
synthesis of pyridine derivatives should be related to acrolein
and other minor oxygenated compounds. It is also reported
that formaldehyde and acetaldehyde can be condensed through
a cross-aldol mechanism to form acrolein with releasing a
molecule of water.47 When the ratio of reactants acrolein and
acetaldehyde is (1:1) in control experiments (Supporting
Information, Figure S1), the product selectivity is usually
better than when glycerol is used as the feedstock.1,48,49 Thus,
formaldehyde amination has a minor significance in the
selectivity of pyridine. In addition, acrolein and acetaldehyde
should be considered to unveil the mechanism of pyridine
synthesis from acrolein. The amination of carbonyl com-
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pounds, which has been systematically studied by Sprung et al.,
is a key step for introducing ammonia (NH3) into oxygenated
compounds.50 Likewise, Feldmann et al. calculated the path of
methanimine (CH2NH) from formaldehyde with ammonia.51
It was indicated that most of amines were converted from
aldehyde and ketones. Scheme 1 illustrates the ammonization
of acetaldehyde and acrolein. Through the ammonization
process, imines can be formed from oxygenated compounds.
Scheme 1. Ammonization of Acetaldehyde and Acrolein
According to the DFT calculation, the energy profiles of the
ammonization process of acetaldehyde and acrolein can be
obtained, as shown in Figure 4. As the carbonyl group in
Figure 4. Energy profile of ammonization of (a) acetaldehyde and (b)
acrolein.
aldehyde was reactive, the ammonia molecule was prone to
attack the unsaturated bond. The a-t1 was in the transition
state of the first elementary reaction, which added an ammonia
molecule into acetaldehyde, costing an activation energy of
Figure 5. Energy profiles of (a) pathways 1 and 2, and (b) pathways 3 and 4 for ammonization.
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59.2 kcal/mol. Then, the formed aminoethanol (a-2) can
undergo a dehydration reaction via a-t2 with an activation
energy of 48.4 kcal/mol to generate the ethylamine (a-3). The
whole reaction process should be endothermic. Whereas, the
production of acetaldehyde is an exothermic process,
indicating that the energy coupling can promote the
ammonization reaction of oxygenates. For acrolein, it can
follow the same process. As shown in Figure 4, the highest
energy barrier was the dehydration of aminopropanol (a-5)
with an activation energy of 63.3 kcal/mol. The whole process
is also endothermic. Comparing the ammonization of acrolein
with acetaldehyde, the energy profile supports the higher yield
of ethylamine (a-3). Also, the ammonization of acrolein was an
endothermic reaction, indicating that the backward reaction
could prevent the formation of 2-propen-1-imine (a-6).
Pyridine Formation from Polymerization of Imines.
The pyridine synthesis can be conducted using various
feedstocks. In the Chichibabin synthesis mechanism, pyridine
can be produced from formaldehyde and acetaldehyde in a
ratio of 1:2, with ammonia acting as a nitrogen source.48,49
First, acrolein can be formed through aldol condensation from
acetaldehyde and formaldehyde. Then, the acrolein is
condensed with aminated acetaldehyde through Michael
addition reactions and ring closure to form a dihydropyridine,
which can be subsequently transformed to a pyridine through a
dehydrogenation reaction.52,53 Zhang et al. prepared pyridine
from acrolein and ammonia using HF/MgZSM-5.54 They
pointed out that the pyridine should be formed on a strong
acid site. Xu et al. performed a series of experiments to study
the conversion mechanism of synthesizing glycerol to pyridine
over acidic catalysts.31 It indicated that, in ammonia
atmosphere, aminated acrolein mainly produce pyridine
(61.2 wt %) with 3-methylpyridine (33.2 wt %) as the main
by-product. When acrolein was combined with acetaldehyde,
the pyridine has a high selectivity of 74.3 wt %. Thus, using
acrolein and acetaldehyde as feedstocks demonstrates sig-
nificant potential in pyridine synthesis.
Condensation of 2-Propen-1-imine to Pyridine. Figure
S3 (Supporting Information) illustrates the proposed mecha-
nism of 2-propen-1-imine. It can be seen that the 2-propen-1-
imine has four possible paths to be condensed. In path 1, the
acrolein first combines with another acrolein molecule with a
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Figure 6. Energy profiles of pyridine synthesis from ethanimine and 2-propen-1-imine.
Figure 7. Energy barrier diagram of catalytic conversion of glycerol to pyridines. (The dashed line in the structure represents the electrostatic
effect.).
connecting nitrogen atom and C1′. Whereas, in path 2, the
nitrogen atom could also be attacked by C2 of another acrolein.
Regarding the Diels-Alder mechanism, paths 3, 4, 5, and 6 are
proposed to verify the possibility of this reaction under
pyrolysis condition. According to the energy profiles (Figure
5), the activation energies of c-t1 and d-t1 (34.9 and 34.4 kcal/
mol, respectively) are lower than a-t1 (Ea = 52.9 kcal/mol)
and b-t1 (Ea = 55.9 kcal/mol). Path 1 started with the Michael
addition reaction with a moderate energy barrier. Then, the
intermediate a-i2 is further condensed into cyclic compounds
a-i3 via a-t2 (Ea = 65.4 kcal/mol). The last step was
conducted with the deammonization reaction with a low
energy barrier (Ea = 46.1 kcal/mol). Path 2 differed from path
1 in the first elementary reaction, in which the C2 atom first
combined with the nitrogen atom of 2-propen-1-imine. Due to
the electronegativity of the N atom of 2-propen-1-imine, the α-
C presents electrophilicity. Thus, the a-t1 comprises a lower
activation energy to connect the N atom and C1. Compared
with path 2, 3-methylpyridines exhibited a higher yield than 2-
methylpyridine. Paths 3−6 considered Diels-Alder as the initial
reaction. Meanwhile, methylene imine elimination (c-t2, c-t3,
d-t2, and d-t3) demonstrated a high energy barrier over 74.0
kcal/mol, which indicates that in noncatalytic conditions,
pyridine is not the major product. Previous experimental
results (Supporting Information, Table S1) showed a high
selectivity of pyridine among pyridine compounds, owing to
the catalytic effect of HZSM-5. However, the higher selectivity
of 3-methylpyridine than 2-methylpyridine was consistent with
the present calculated results.
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The Condensation Mechanism of Ethanimine and 2-
Propen-1-imine. As the ethanimine is produced through the
ammonization of acetaldehyde, which has been described in
Section 3.3. In consideration of the structural feature of
enthanimine and the stereo-hindrance effect, the condensation
between β-C of 2-propen-1-imine and α-C or imine carbon in
ethanimine (Michael Reaction: R″CC + R−C−R′ → R−
C(C2H4R″)−R′) should not be a moderate elementary
reaction. Thus, this study focused on another synthesis path
from ethanimine and 2-propen-1-imine. Keto-enol tautomer-
ism is a reaction that converts ethanimne to vinylamine
(CH3CH  NH → CH2  CHNH2), which should be an
important intermediate during pyridine synthesis. The energy
barrier of keto-enol tautomerism, as shown in Figure 6, is 65.4
kcal/mol. After that, vinylamine and 2-propen-1-imine can be
easily condensed through the Diels-Alder mechanism to form
nitrogen-containing cyclic compounds. The detailed mecha-
nism can be seen in Figure S4 (Supporting Information), in
which the initial conversion of vinylamine and 2-propen-1-
imine can be separated into four paths according to the
difference of attack orientation. In the first elementary reaction
of paths 1 and 2, the C1′ and C2′ atoms of vinylamine can link
to N and C3 atoms of 2-propen-1-imine, respectively.
Subsequently, the formed tetrahydropicolin (e-i2) can further
undergo a deammonization reaction to generate 1,4-
dihydropyridine (e-i3) or 3,4-dihydropyridine (e-i4) via e-t2
(Ea = 68.9 kcal/mol) and e-t4 (Ea = 48.9 kcal/mol). The
tertiary hydrogen on the N atom is of nucleophilicity, which is
easily attacked by the vicinal amino group with the release of
an ammonia molecule, reasoning the low energy barrier of e-t4.
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The dehydrogenation of 1,4-dihydropyridine costs an
activation energy of 63.4 kcal/mol. Meanwhile, 3,4-dihydro-
pyridine (e-i4) is a more stable chemical molecule that is
difficult to proceed with dehydrogenation (Eae‑t5 = 91.3 kcal/
mol). Due to the structural features of 3,4-dihydrpyridine, it
could easily be combined with other unsaturated heterocyclic
or aromatic compounds to form polymers. In path 3, the first
elementary reactionary energy barrier (Eaf‑t1 = 59.6 kcal/mol)
is higher than e-t1 (Ea = 48.8 kcal/mol). Thus, in noncatalytic
condition, ethanimine should first follow path 2 to form 3,4-
dihydropyridine with a very low yield of pyridine.
HZSM-5 Performance on Pyridine Synthesis. ZSM-5 is
a widely used zeolite catalyst in the industry.55,56 For pyridine
synthesis, researchers used various catalysts to improve
pyridine yields and selectivity and its derivatives.32,41,57,58
The mechanism of pyridine synthesis inside zeolites is
relatively complex, and a large number of different competing
chemical reactions might occur.
The energy barrier of the catalytic reaction for the synthesis
of pyridine from glycerol on the ZSM-5 catalyst is shown in
Figure 7. It is well known that the Bronsted acid site in ZSM-5
is electrophilic, so the hydroxyl oxygen of the glycerol molecule
easily forms hydrogen bonds with the Bronsted acid site to be
adsorbed to the acid site.59 The adsorption energy of glycerol
molecules on ZSM-5 is 8.5 kcal/mol, which is similar to the
adsorption energy of other alcohols at Bronsted acid sites.60,61
With the help of protons, the adsorbed glycerol molecule
undergoes paths similar to those in a noncatalytic reaction (see
Figure S5 for the mechanism diagram). Interestingly, in paths
D3 and D4, glycerol molecules can be directly converted into
propionol aldehydes (D-IM2) through pinacol rearrangement
(Ea = 43.1 kcal/mol), while the energy barrier of path D1 is
increased in the pericyclic dehydration involving protons.
Therefore, in the catalytic dehydration stage of glycerol, the
1,3-cyclic dehydration of reaction path D1 is not easy to occur
on the ZSM-5 catalyst. In addition, the pinacol rearrangement
of reaction path D4 yielded acetol (Ea = 48.2 kcal/mol).
Comparing the four catalytic dehydration paths of glycerol, the
reaction heat of the final product of reaction path D2 is the
largest (ΔG = 35.1 kcal/mol), and the energy barrier of the
speed-determining step of reaction path D3 is the lowest (Ea =
43.1 kcal/mol). Therefore, paths D2 and D3 are two
competing paths, which is consistent with previous exper-
imental results.62
After the formation of acetaldehyde and acrolein, oxy-
genated compounds are added with ammonia molecules and
dehydrated to obtain an ethanimine intermediate (A-R1) or
vinylamine product. The calculation results show that the
energy of ethyleneimine is more stable than vinylamine (Figure
7). Moreover, the catalytic conversion energy barrier of
ethanimine to vinylamine is relatively high (Ea = 83.0 kcal/
mol), indicating that the stable intermediate of ethanimine
produced by ammonization is not favorable to the subsequent
pyridine synthesis. However, the more likely path is the direct
ammonization and dehydration of vinyl alcohol (D-IM1) to
vinylamine. After the production of 2-propen-1-imine and
vinylamine through amination, these molecules can undergo a
Diels-Alder reaction to form cyclic compounds. Meanwhile, it
is more likely to produce disubstituted tetrahydropyridine
(Supporting Information, Figure S3) through single-compo-
nent polymerization of 2-propen-1-imine.27,54 Since the
pyridine synthesis reaction is carried out in the catalyst, the
mass transfer effect of the reactive intermediate in the pyridine
3101
pubs.acs.org/journal/ascecg Research Article
synthesis process needs to be considered together with the
pore size of the glycerol molecule, which is limited to ∼0.55
nm.63 Therefore, the catalysis of ZSM-5 is not conducive to the
formation or diffusion of multisubstituted pyridine products.
Hence, only the case where the Diels-Alder reaction of 2-
propen-1-imine and vinylamine was investigated. As shown in
Figure 7, the highest catalytic energy barrier (Eacat‑e‑t5 = 25.7
kcal/mol) of reaction path P2 is much lower than the
noncatalytic reaction (Ea e‑t5 = 91.3 kcal/mol). Thus, in terms
of kinetics, the pyridine-catalyzed synthesis reaction via
reaction path P2 is more favorable. Comparing the catalytic
and noncatalytic paths together, it can be seen that the catalyst
changes the reaction path of glycerol and makes the
polymerization reaction of imines have a lower energy barrier
and a faster reaction rate.
■ SUMMARY AND CONCLUSIONS
Using glycerol as the feedstock to synthesize renewable
pyridines was studied with density functional theory in the
present study to understand the conversion mechanism. The
results confirmed that glycerol could be directly converted into
pyridine in ammonia atmosphere at 550 °C. A more complete
insight into neutral glycerol thermal conversion suggests that
the glycerol dehydration process should mainly produce
acrolein, acetaldehye, formaldehyde, and acetol. Also, a
catalytic study on glycerol dehydration proposes that a
Bronsted acid site can provide a proton to promote the
dehydration reaction. The pericyclic reaction of glycerol is
inhibited in the pores of ZSM-5, and the pinacol rearrange-
ment effect reduces the dehydration energy barrier of glycerol
dehydration. Enamine, which is directly converted from vinyl
alcohol, is the key intermediate in the ammonization process as
it can be subsequently combined with 2-propen-1-imine to
form tetrahydropyridine through Diels-Alder addition. ZSM-5
can also decrease the energy barrier of the subsequent
deamination reaction and dehydrogenation reaction before
pyridine formation. Generally, the present study confirmed the
pyridine selectivity and conversion route from glycerol to
pyridine.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acssuschemeng.0c07460.
The optimized structure of the HZSM-5 model (28 T),
the thermocatalytic conversion rate of different oxy-
genated compounds, the products’ distribution of
glycerol pyrolysis, the decomposition mechanism of
neutral glycerol, the mechanism of 2-propen-1-imine
polymerization, the polymerization mechanism of
ethanimine and 2-propen-1-imine, the optimized
structure of all reactants and transition states in the
noncatalytic mechanism, and the optimized structure of
all reactants and transition states in the catalytic
mechanism (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Shuang Wang − School of Energy and Power Engineering,
Jiangsu University, Zhenjiang, Jiangsu 212013, China;
orcid.org/0000-0002-4332-7543; Email: alexjuven@
ujs.edu.cn
https://dx.doi.org/10.1021/acssuschemeng.0c07460
ACS Sustainable Chem. Eng. 2021, 9, 3095−3103
ACS Sustainable Chemistry & Engineering
Hongping Li − Institute for Energy Research, Jiangsu
University, Zhenjiang, Jiangsu 212013, China;
Email: hongpingli@ujs.edu.cn
Authors
Ding Jiang − School of Energy and Power Engineering, Jiangsu
University, Zhenjiang, Jiangsu 212013, China
Lujiang Xu − College of Engineering, Nanjing Agricultural
University, Nanjing, Jiangsu 210031, China
Xun Hu − School of Material Science and Engineering,
University of Jinan, Jinan, Shandong 250024, China
Bahram Barati − School of Energy and Power Engineering,
Jiangsu University, Zhenjiang, Jiangsu 212013, China
Anqing Zheng − Guangzhou Institute of Energy Conversion,
Chinese Academy of Sciences, Guangzhou, Guangdong
510640, China; orcid.org/0000-0002-4943-4382
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.0c07460
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors are grateful to the Jiangsu Province “333” Project
(BRA2019277), CAS Key Laboratory of Renewable Energy
(no. Y907k41001), the Six Talent Peaks Project in Jiangsu
Province (XNY-007, 2018), and the Foundation of State Key
Laboratory of Coal Combustion (FSKLCCA1904).
■
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