catalysts

Article
Kinetic Modeling of the Direct Dimethyl Ether (DME) Synthesis
over Hybrid Multi-Site Catalysts
Antonio D’Ambrosio 1 , Alice Bertino 1 , Serena Todaro 2 , Mariarita Santoro 2 , Catia Cannilla 2 ,
Francesco Frusteri 2 , Giuseppe Bonura 2, * , Leone Mazzeo 1, * and Vincenzo Piemonte 1

1 Unit of Chemical-Physics Fundamentals in Chemical Engineering, Faculty of Science and Technology for
Sustainable Development and One Health, University Campus Bio-Medico of Rome, Via Alvaro del Portillo
21, 00128 Rome, Italy; [email protected] (A.D.); [email protected] (A.B.);
[email protected] (V.P.)
2 CNR-ITAE, Istituto di Tecnologie Avanzate per l’Energia “Nicola Giordano”, Via S. Lucia sopra Contesse 5,
98126 Messina, Italy; [email protected] (S.T.); [email protected] (M.S.); [email protected] (C.C.);
[email protected] (F.F.)
* Correspondence: [email protected] (G.B.); [email protected] (L.M.)

Abstract: This paper deals with the proposition of a kinetic model for the direct synthesis of DME via
CO2 hydrogenation in view of the necessary optimization of the catalytic system, reactor design, and
process strategy. Despite the fact that DME synthesis is typically treated as a mere combination of
two separated catalytic steps (i.e., methanol synthesis and methanol dehydration), the model analysis
is now proposed by taking into account the improvements related to the process running over a
hybrid catalyst in a rational integration of the two catalytic steps, with boundary conditions properly
assumed from the thermodynamics of direct DME synthesis. Specifically, the CO2 activation step
at the metal–oxide interface in the presence of ZrO2 has been described for the first time through
the introduction of an ad hoc mechanism based on solid assumptions from inherent studies in the
literature. The kinetic modeling was investigated in a tubular fixed-bed reactor operating from 200
to 260 ◦ C between 1 and 50 bar as a function of a gas hourly space velocity ranging from 2500 to
Citation: D’Ambrosio, A.; Bertino, A.;
60,000 NL/kgcat /h, in a stoichiometric CO2 /H2 feed mixture of 1:3 v/v. A well-detailed elementary
Todaro, S.; Santoro, M.; Cannilla, C.;
mechanism was used to predict the CO2 conversion rate and identify the key reaction pathways,
Frusteri, F.; Bonura, G.; Mazzeo, L.;
starting with the analysis of the implicated reactions and corresponding kinetic mechanisms and
Piemonte, V. Kinetic Modeling of the
Direct Dimethyl Ether (DME)
expressions, and finally estimating the main parameters based on an appropriate modeling of
Synthesis over Hybrid Multi-Site test conditions.
Catalysts. Catalysts 2024, 14, 61.
https://doi.org/10.3390/ Keywords: dimethyl ether; CO2 valorization; hydrogen conversion; hybrid catalysts; kinetic modeling;
catal14010061 fixed-bed reactor

Academic Editors: Enrico Catizzone

and Ana Palčić

Received: 20 December 2023 1. Introduction

Revised: 4 January 2024 In consideration of the growing concern for climate change, the search for novel
Accepted: 11 January 2024 development models based on renewable energy sources with the potential to gradually
Published: 13 January 2024 replace fossil fuels is in the spotlight. On this road to progressive decarbonization, dimethyl
ether (DME), the simplest of the ether compounds (chemical formula CH3 OCH3 ), has been
recently proposed as a very promising alternative fuel [1–3], being characterized by its
high cetane number, low auto-ignition temperature, and near-zero emissions of particulate
Copyright: © 2024 by the authors.
matter, carbon monoxide, and unburned hydrocarbons [4,5]. It also presents chemical and
Licensee MDPI, Basel, Switzerland.
physical properties similar to LPG, enabling the use of existing storage and distribution
This article is an open access article
distributed under the terms and
infrastructure [6]. Additionally, DME can serve as a feedstock for the production of olefins
conditions of the Creative Commons
via the DTO (DME-to-olefins) reaction pathway, which is characterized by high yields and
Attribution (CC BY) license (https:// conversions [7–9].
creativecommons.org/licenses/by/
4.0/).

Catalysts 2024, 14, 61. https://doi.org/10.3390/catal14010061 https://www.mdpi.com/journal/catalysts

Catalysts 2024, 14, 61 2 of 15

However, the real appeal of this compound lies in its potential synthesis reaction
(Equation (1)), since recent research frontiers aim to employ CO2 and H2 as reactants [10,11]:
 
2CO2 + 6H2 ⇌ CH3 OCH3 + 3H2 O ∆H0 = −122 kJ/mol (1)

Using captured CO2 and green H2 produced via electrolysis, it is, therefore, possible
to configure DME as an e-fuel directly produced in a sustainable CCUS (carbon capture
utilization and storage) technology chain [12,13]. Furthermore, even though this aspect
is still under investigation, DME can be steam-reformed, making it a potential circular
hydrogen carrier [14]. For this to be feasible, however, it is necessary to make the synthesis
process more efficient and cost-effective. Currently, DME is primarily produced from
synthesis gas through an indirect method involving the use of two reactors in a typical
cascade process [15]. In the first reactor, methanol synthesis is performed on a ternary
metal–oxide catalyst (typically CZA, which is CuO-ZnO-Al2 O3 ), while the second reactor
allows the dehydration of the previously formed methanol over an acidic catalytic bed
(usually γ-Al2 O3 or a zeolite sample, such as HZSM-5) [10,16–18]. The real challenge is to
achieve effective process intensification by implementing direct synthesis in a single reactor,
using CO2 as a feedstock, thus allowing the valorization of a thermodynamically “inert”
compound, as well as reducing operating and investment costs [19,20]. Certainly, the
main concern is the development of a multi-functional catalyst wherein a long-range inter-
dispersion among metallic, oxide, and acidic functionalities must be achieved to catalyze
both the methanol synthesis and DME production steps [14,21]. Indeed, by hybridizing
the catalytic system for direct DME synthesis, the thermodynamic limitations behind
the CO2 hydrogenation process stopping the formation of methanol can be overcome,
even if unavoidable water generation is a key contributor to possible catalyst deactivation
mechanisms, such as copper sintering or migration of weak acidic sites [22–24].
Given the potential and critical issues associated with the direct synthesis of dimethyl
ether from hydrogen and carbon dioxide, this work aims at investigating the performance,
on a laboratory scale, of a previously optimized hybrid CuO-ZnO-ZrO2 /HZSM-5 catalytic
system [22] by developing a kinetic model suitable to predict its experimental behavior in a
wide set of operating conditions. Particularly, the exchange of alumina (a key component in
the benchmark catalyst for methanol synthesis) with zirconia to enhance CO2 adsorption,
water tolerance, and heat management [25] has been limitedly studied from a microkinetic
point of view [26,27]. Therefore, this knowledge gap inspired an ad hoc 18-parameter model
based on three cascade steps (i.e., CO2 hydrogenation to methanol, methanol dehydration,
and rWGS) occurring in one pot over a hybrid catalytic system. This model aims at
explaining a dual-site mechanism on two different adsorption sites by claiming that the CO2
activation step at the metal–oxide interface is crucial prior to undergoing hydrogenation to
methanol. Acidic functionality is then necessary for the subsequent dehydration into DME.
As a consequence, the corresponding kinetic expressions were derived and appropriately
integrated with all the reactions involved in the process. This resulted in a comprehensive
model for the direct synthesis of DME, which led to the assessment of new mechanistic
clues about the activity–selectivity pattern of the catalyst under investigation as necessary
for further optimization of its design.

2. Experimental Section
This section is divided into two parts: synthesis of the hybrid catalyst and validation
of its performance through a fixed-bed reactor.

2.1. Catalyst Synthesis

The hybrid catalyst was synthesized through the gel oxalate coprecipitation method,
as elsewhere described [28]. Firstly, the nitrate precursors, namely Cu(NO3 )2 ·2.5H2 O,
Zn(NO3 )2 ·6H2 O, and ZrO(NO3 )2 ·nH2 O (in a relative Cu/Zn/Zr atomic ratio of 60/30/10),
were dissolved in an ethanolic solution and added, at room temperature in a slow and
Catalysts 2024, 14, 61 3 of 15

constant mode, to a vigorously stirred ethanolic solution containing oxalic acid (20 wt.%
in excess with respect to the stoichiometric amount necessary to precipitate the metal
precursors) and the finely dispersed HZSM-5 zeolite (Si/Al = 23 mol/mol) in a weight
ratio of 1:1 with respect to the final oxide composition of the catalyst. The precipitate was
stirred for 3 h, then aged overnight. The catalyst was filtered, dried at 90 ◦ C for 16 h, and
then calcined at 350 ◦ C for 4 h.

2.2. Catalyst Testing

In order to assess the activity of the hybrid catalyst, CO2 hydrogenation to DME was
studied in a full kinetic regime, according to conditions designed to rule out the control of
diffusional phenomena [11,17]. All the catalytic measurements were carried out in a fixed-
bed stainless steel reactor with an internal diameter of 4 mm and a length of 21 mm, loaded
with 250 mg of catalyst, and housed within a stainless-steel rod to minimize temperature
gradients. The 40–70 mesh (210–420 µm) fraction was selected as a suitable compromise
between reactor pressure drop and catalyst particle mechanical resistance. Catalytic tests
were carried out at a total pressure of 1, 10, 30, or 50 bar in a temperature range between 200
and 260 ◦ C and gas hourly space velocity of 2500, 8800, and 60,000 NL/kgcat /h, employing
a feed mixture of CO2 /H2 /N2 in a 3:9:1 v/v ratio. Before each test, the catalyst underwent
an in situ reduction at 300 ◦ C for 1 h using pure hydrogen flow at atmospheric pressure.
The reaction stream was analyzed via a gas chromatograph equipped with a three-column
separation system connected to a flame ionization detector (FID) and a thermal conductivity
detector (TCD). No formation of methane or higher hydrocarbons was detected under
the applied conditions. Quantitative data were expressed in terms of CO2 conversion
(XCO2 ), DME yield (YDME ) and DME and CO selectivity (SDME and SCO ), as defined in
Equations (2)–(5):
in − F out
FCO 2 CO2
XCO2 = in
(2)
FCO 2

out
FDME
YDME = in
(3)
FCO 2

out
FDME
SDME = out out + F out
(4)
FDME + FMeth CO
out
FCO
SCO = out + F out + F out
(5)
FDME Meth CO

In Equations (2)–(5), Fiin and Fiout are the inlet and the outlet molar flow rates of
component i, respectively. Conversion and selectivity data were determined by both
internal standard and mass-balance methods, averaging three independent measurements
with an accuracy of ±3%.

3. Kinetic Modeling
The development of a kinetic model for direct CO2 -to-DME hydrogenation was carried
out in two steps:
1. Analysis of the implicated reactions and corresponding kinetic mechanisms and
expressions.
2. Estimation of missing parameters based on appropriate modeling of test conditions.

3.1. Reaction Kinetics Investigation

In direct DME synthesis from CO2 and H2 , three reactions (Equations (6)–(8)) are
involved [10,29–31]:
Catalysts 2024, 14, 61 4 of 15

1. CO2 hydrogenation to methanol (CHM):

 
CO2 + 3H2 ⇌ CH3 OH + H2 O ∆H0 = −49 kJ/mol (6)

2. Methanol dehydration to DME (MDD):

 
2CH3 OH ⇌ CH3 OCH3 + H2 O ∆H0 = −23 kJ/mol (7)

3. Reverse water–gas shift (rWGS):

 
CO2 + H2 ⇌ CO + H2 O ∆H0 = +41 kJ/mol (8)

CO hydrogenation to DME is not considered since it can be obtained from the linear
combination of Equations (7) and (8), and is also significantly inhibited by the production
of formate, an intermediate that strongly binds copper active sites [32,33]. For each reaction,
the kinetic mechanism was reconstructed, identifying the rate-determining step (r.d.s.) [34].
As for methanol dehydration and rWGS, previously elaborated mechanisms from the
literature were adopted due to the conventional nature of the employed catalyst (HZSM-
5 and Cu-based systems, respectively) [35,36], while an ad hoc kinetic mechanism was
developed for CO2 hydrogenation, based on experimental evidence [37]. Finally, the
kinetic expression of the reaction rate was derived for each mechanism, assuming that all
elementary steps, except the r.d.s., were at thermodynamic equilibrium and adopting the
Langmuir–Hinshelwood–Hougen–Watson (LHHW) model [38]. In light of the moderate
operating conditions in terms of pressure and temperature, the gas phase was assumed
to be ideal, with a unitary fugacity coefficient (see Appendix A). A “dual site” model is
thus proposed, distinguishing two different active
  sites on the hybrid catalyst [37,39]: the
∼
metal–oxide site (σ ) and the zeolitic acid site σ .

3.1.1. CO2 Hydrogenation Mechanism

The introduction of zirconia in the catalyst composition, instead of the alumina present
in the benchmark catalyst, has a limited history in the literature related to kinetic model-
ing [26]. Thus, an ad hoc mechanism was developed to further explore its specific behavior.
More in detail, the CO2 activation step is a highly debated aspect, with two generally
proposed alternatives [40,41]: the formate route, based on the formation of HCOO inter-
mediate, and the rWGS route, which involves the conversion of CO2 into CO. Although
an unambiguous agreement on the exact mechanism does not exist yet, most of the re-
cent experimental findings suggest a leaning towards the formate route, as described by
Equations (9a)–(9j):
(3x) H2 + 2σ ⇌ 2Hσ (9a)
CO2 + σ ⇌ CO2 σ (9b)
CO2 σ + Hσ ⇌ CHO2 σ + σ r.d.s. (9c)
CHO2 σ + Hσ ⇌ CH2 O2 σ + σ (9d)
CH2 O2 σ + Hσ ⇌ CH2 O(OH)σ + σ (9e)
CH2 O(OH)σ + Hσ ⇌ CH2 Oσ + H2 Oσ (9f)
H2 Oσ ⇌ H2 O + σ (9g)
CH2 Oσ + Hσ ⇌ CH3 Oσ + σ (9h)
CH3 Oσ + Hσ ⇌ CH3 OHσ + σ (9i)
CH3 OHσ ⇌ CH3 OH + σ (9j)
Catalysts 2024, 14, 61 5 of 15

According to this route, one molecule of CO2 activated on a partially oxidized Cu(δ+)
site (9b) initially reacts with one atom of hydrogen previously activated on a metallic site
(9a), giving rise to a formate species (9c). The latter then reacts with other activated hydro-
gen atoms in a cascade sequence to produce dioxomethylene species (9d), formaldehyde
(9f), methoxy species (9f), and finally methanol (9i) in the last hydrogenation step.

3.1.2. Methanol Dehydration Mechanism

The methanol dehydration reaction strongly relies on the zeolitic component of the cat-
alyst, considering that density, strength, accessibility, and nature of the acid sites (Brønsted
or Lewis) are all features capable of influencing the DME productivity [22,37,42]. Several
kinetic models have been proposed in the literature, primarily differing from the zeolite
topology [26]. However, in terms of reaction mechanism, most studies have converged on
identifying two main alternative pathways [42,43]:
Associative pathway, which involves the formation of DME from two adsorbed
methanol molecules.
The dpathway is characterized by the adsorption of a methanol molecule followed by
its dissociation into a methoxyl group, which then reacts with another methanol molecule
to produce DME.
Overall, due to the relatively low operating temperatures (far below 400 ◦ C) and
the mesoporous structure of the hybrid catalyst utilized [25], it can be concluded that
the predominant pathway is the associative one [44]. Concerning the mechanism over a
HZSM-5 zeolite, Lu et al. [35] proposed the following sequence of elementary reactions
(Equations (10a)–(10d)):
∼ ∼
(2x) CH3 OH + σ ⇌ CH3 OH σ (10a)
∼ ∼
CH3 OH σ ⇌ CH2 σ + H2 O (10b)
∼ ∼ ∼ ∼
CH2 σ + CH3 OH σ ⇌ CH3 OCH3 σ + σ r.d.s. (10c)
∼ ∼
CH3 OCH3 σ ⇌ CH3 OCH3 + σ (10d)

3.1.3. rWGS Mechanism

The rWGS reaction mechanism can be reconstructed based on its counterpart reaction.
More specifically, WGS predominantly occurs on copper sites (at the interface with other
metal oxides), meaning that the introduction of zirconia can act as a promoter, enhancing
the activity of the existing sites without inducing any further reaction [45,46]. It is therefore
possible to refer to some mechanisms already found in the literature that identify the
carboxyl route as the predominant pathway for the WGS reaction [36,47], as exemplified by
the set of Equations (11a)–(11g):

H2 O + σ ⇌ H2 Oσ (11a)

H2 Oσ + σ ⇌ OHσ + Hσ r.d.s. (11b)

CO + σ ⇌ COσ (11c)
COσ + OHσ ⇌ COOHσ + σ (11d)
COOHσ + σ ⇌ CO2 σ + Hσ (11e)
2Hσ ⇌ H2 + 2σ (11f)
CO2 σ ⇌ CO2 + σ (11g)

3.2. Dual-Site Adsorption on the Hybrid Catalyst

While the final dehydration step of methanol to DME is known to be mediated by the
zeolitic acidic site [15,16,18], an adequate concentration of both metallic and metal–oxide
sites is claimed to be somehow necessary for the primary methanol formation [32,33]. In
Catalysts 2024, 14, 61 6 of 15

particular, it should be noted that the adsorption of CO2 can even occur on bare oxides,
while the dissociation of H2 more efficiently takes place on metallic surfaces; however, a
possible activation over metal–oxide surfaces is not ruled out [40,41]. Therefore, this model
proposes the use of a unique metal–oxide site for both CO2 and H2 adsorption, assumed to
be the active center in CO2 hydrogenation to methanol and in rWGS reaction. Accordingly,
the rate equations proposed for this dual-site LHHW mechanism are summarized in
Equations (12)–(14):
 
1/2 PCH3 OH PH2 O
KcinCHM PCO2 PH2 − 5/2
KeqCHM PH
2
rCHM = p
2 (12)
1 + KCO PCO + KCO2 PCO2 + KCH3 OH PCH3 OH + K H2 O PH2 O + K H2 PH2

PCH3 OCH3 PH2 O

 
2
Kcin MDD PCH −
3 OH Keq MDD
r MDD =
2 (13)
1 + K H2 O PH2 O + KCH3 OH PCH3 OH + KCH3 OCH3 PCH3 OCH3
PCO PH
 
KcinrWGS PH2 O PCO − Keq 2 2
rWGS
rrWGS =− p
2 (14)
1 + KCO PCO + KCO2 PCO2 + KCH3 OH PCH3 OH + K H2 O PH2 O + K H2 PH2
Remarkably, since both the steps of CO2 hydrogenation to methanol and rWGS are
characterized by a competition for the same adsorption site (σ), the denominators of Equa-
tions (12) and (14) include the terms for CO adsorption (KCO PCO ) and CH3 OH adsorption
(KCH3 OH PCH3 OH ), respectively, as inhibition contributions for the corresponding reactions.

3.3. Parameter Estimation Method

In order to validate the kinetic expressions, it is necessary to describe the laboratory
setup via a predictive model, which is crucial for parameter estimation. In this light, the
fixed-bed reactor was assimilated to an isothermal and isobaric PFR (plug flow reactor).
The experimental setup was designed to minimize the impact of internal and external
diffusional resistances, which were consequently neglected. Therefore, one-dimensional
steady-state mass balances (Equations (15) and (16)) were written for each compound along
the axial coordinate:
dGi 1 3
= ∑ νij r j (15)
dz L j =1

Gi (z = 0) = yin in
i GTOT (16)
In Equation (15), L represents the reactor length, r j is the rate of reaction j
(Equations (12)–(14)) and νij is the stoichiometric coefficient of compound i in reaction
j. In Equation (16), yin in
i is the inlet molar fraction of component i and GTOT is the total inlet
gas hourly space velocity. The balances are, indeed, expressed in terms of space velocity
of each compound, noted as Gi , which is here defined as the ratio between the molar flow
rate Fi and the total weight of the catalyst Mc (Equation (17)):

Fi
Gi = (17)
Mc

It is important to note that the kinetic expressions of reaction rates (present in

Equation (15)) incorporate temperature-dependent equilibrium, kinetic, and adsorption
constants. While the former can be derived from the existing literature, being only subject
to the thermodynamics of the reactions involved (see Table 1) [48], the latter two constants
are specific to the developed catalyst and require experimental data regression for determi-
nation. More precisely, the Arrhenius and Van ‘t Hoff equations express their temperature
Catalysts 2024, 14, 61 7 of 15

dependence and were reparametrized (see Equations (18) and (19)) to improve numerical
stability in fitting and decrease numerical correlation between estimated parameters [49,50]:

Tri f
  
Kcin j = k cin j exp − E A j −1 (18)
TR

Tri f
  
Ki = k i exp −∆Hadsi −1 (19)
TR

Table 1. Expressions of equilibrium constants’ dependence on temperature [48].

Parameter Temperature Dependence

3066
KeqCHM 10 T −10.592 [bar −2 ]
+ 3.707 · log( T ) − 2.783 · 10−3 · T +
4019
 
KeqMDD exp T
+3.8 · 10−7 · T 2 − 6.561 · 104 · T −3 − 26.64
2073
KeqrWGS 10− T +2.029

In Equations (18) and (19), Tri f is a reference temperature, assumed to be equal to

the experimental mean value of 503.15 K; TR denotes the reactor temperature; k cin j and k i
are pre-exponential factors; and E A j and ∆Hadsi represent energetic terms. The latter were
made dimensionless, according to Equations (20) and (21) (where R is the universal gas
constant), to decrease differences in magnitude orders and reduce computational costs [51]:

E∗A j
EAj = (20)
Tri f R
∗
∆Hads
∆Hadsi = i
(21)
Tri f R
Both pre-exponential factor and energetic terms were estimated by minimizing the
weighted sum ϕ of square relative errors between experimental molar fractions Yik and
model outputs Ŷik (Equation (22)) [52]:
 !2 
Np
Yik − Ŷik
ϕ= ∑ ∑  wi · Yik
 (22)
k =1 i

In Equation (22), Np represents the number of experimental tests, while wi is the

weight assigned to compound i. Optimization was carried out by applying a Matlab
algorithm based on the fmincon function to find the minimum value, providing a set of
100 experimental data points as input. The starting point was varied in different trials,
looking at achieving a global minimum, while an additional set of 60 data points was used
to validate the outcomes obtained.

4. Results and Discussion

4.1. Experimental Results
A sensitivity analysis was carried out to evaluate the influence of temperature and
pressure on product distribution, as depicted in Figure 1.
Catalysts 2024,
Catalysts 2024, 14,
14, 61
x FOR PEER REVIEW 8 of 15
8 of 15

Figure 1. Influence of temperature and pressure on CO2 conversion (a), DME yield (b), DME
Figure 1. Influence of temperature and pressure on CO2 conversion (a), DME yield (b), DME selec-
selectivity (c), CO
tivity (c), and andselectivity
CO selectivity (d), evaluated
(d), evaluated withwith an inlet
an inlet flow flow rate
rate of of 8800
8800 NL/(kg
NL/(kg cat h). cat
h).

On the whole, the results are consistent with the thermodynamic analysis of the sys-
On the whole, the results are consistent with the thermodynamic analysis of the sys-
tem [10,31,53]. High pressure is preferable during the DME synthesis reaction as it leads
tem [10,31,53]. High pressure is preferable during the DME synthesis reaction as it leads
to a decrease in the number of moles. On the other hand, an increase in temperature
to a decrease in the number of moles. On the other hand, an increase in temperature favors
favors CO2 conversion due to its positive kinetic effect on the reaction rate. However,
CO2 conversion due to its positive kinetic effect on the reaction rate. However, it simulta-
it simultaneously decreases DME selectivity while raising CO selectivity, in agreement
neously decreases DME selectivity while raising CO selectivity, in agreement with the
with the thermal tonality both of DME synthesis (exo-) and rWGS (endo-). Although a
thermal tonality both of DME synthesis (exo-) and rWGS (endo-). Although a plateau in
plateau in DME and CO selectivity was observed above 240 ◦ C for runs performed both
DME and CO selectivity was observed above 240 °C for runs performed both at 30 and 50
at 30 and 50 bar, a further increase in reaction temperature unfortunately triggers severe
bar, a further
catalyst increase Indeed,
deactivation. in reaction temperature
a larger amountunfortunately
of water formed triggers
abovesevere
thosecatalyst de-
conditions
activation. Indeed, a larger amount of water formed above those conditions
dramatically determines morphological changes in the catalyst surface, prompting a drastic dramatically
determines
activity decaymorphological
(ca. 20% withchanges
respect tointhe
theinitial
catalyst surface,
activity) in aprompting
few hours ofa drastic
time onactivity
stream
decay (ca. 20% with respect to the initial activity) in a few hours of time on
(<20 h) [17,22]. Therefore, these findings not only indicate that the process performance stream (<20 h)
[17,22].
is Therefore,
governed these[15],
by kinetics findings not suggest
but also only indicate that the
an optimal process performance
compromise between CO is gov-
2 con-
erned by kinetics [15], but also suggest an optimal compromise between
version and DME selectivity at moderately high pressures (30 or 50 bar) and intermediateCO 2 conversion

and DME selectivity

temperatures at moderately
(<260 ◦ C), so as to limithigh
any pressures (30to
issue related orcatalyst
50 bar)lifetime.
and intermediate tem-
peratures (<260 °C), so as to limit any issue related to catalyst lifetime.
4.2. Reaction Kinetics Investigation Results
Falling within the typical range of values reported for similar computational mod-
4.2. Reaction Kinetics Investigation
els [26], the parameters Results
resulting from the estimation procedure are listed in Table 2, with
FigureFalling within the
2 illustrating thetypical rangebetween
comparison of valuesexperimental
reported for data
similar
andcomputational models
model outputs.
[26], the parameters resulting from the estimation procedure are listed in Table 2, with
Figure 2 illustrating the comparison between experimental data and model outputs.
Catalysts 2024, 14, 61 9 of 15

Table 2. Estimated parameters for the proposed kinetic model and corresponding confidence interval
with a level of significance equal to 0.05.

Pre-Exponential Factor Energetic Term

Parameter Unit
(kcinj or ki ) (EAj or−∆Hadsi )
h i
KcinCHM −1 −1
mol · gcat · s · bar −3/2 (2.56 ± 0.05) · 10−4 44.95 ± 1.75
h i
−1 −1
KcinMDD mol · gcat · s · bar −2 0.26 ± 0.01 99.73 ± 1.21
h i
KcinrWGS −1 −1
mol · gcat · s · bar −2 (6.16 ± 0.12) · 10−3 39.52 ± 1.71
(8.54 ± 0.32) · 10−2
 −1 
KH 2 bar −1  33.57 ± 1.38
KCO2 bar −1  9.56 ± 0.10 14.23 ± 0.93
KCO bar −1  8.97 ± 0.49 10.41 ± 0.40
KH 2 O bar −1  8.02 ± 0.43 22.95 ± 0.86
KCH3 OH bar −1  5.70 ± 0.29 7.07 ± 0.11
KCH3 OCH3 bar 5.20 ± 0.10 60.53 ± 0.66

The model provided satisfactory results in calculating the molar fractions of CO2 and
H2 , with an average relative error of 1.5%, which is comparable to the chromatographic
tolerance. Moreover, despite an average relative error of around 40%, the model suitably
also works in the prediction of the molar fractions of DME and CO, considering a minimal
absolute error in the order of 0.001. Only in the case of the other compounds (i.e., CH3 OH
or H2 O), the large number of estimated parameters (which is equal to 18) cannot determine
a lower discrepancy in the model fitting, so that a relatively small error in absolute terms
has a strong impact in relative terms.
In any case, even the highest deviation recorded for large methanol concentrations
(see Figure 2f) cannot be considered a relevant issue since the simulation model targets
the one-pot synthesis of DME and the methanol selectivity always attains relatively low
values (below 10%) under all the experimental conditions applied. More importantly, these
results evidently confirmed previous mechanistic clues on the catalytic behavior, with
positive effects on the process performance played by an increase in space velocity or
reaction pressure. However, further optimization of the hybrid catalyst design is required
for higher CO2 conversion rates below 220 ◦ C, where CO formation can be minimized.
Finally, not only the catalyst formulation but also the reactor configuration should be
Catalysts 2024, 14, x FOR PEER REVIEW 10 of 15
properly designed in order to tackle the issues related to water formed during the process,
dramatically affecting catalyst lifetime and process performance.

Figure 2. Cont.
Catalysts 2024, 14, 61 10 of 15

Figure
Figure 2. 2. Comparisonofofexperimental
Comparison experimental data
data (along
(alongthe
thex-axis) and
x-axis) andmodel results
model (along
results the y-axis)
(along for
the y-axis)
the mole fractions of CO
for the mole fractions of CO (a), H (b), DME (c), CO (d), H O (e), and methanol (f).
2 2 (a), 2H2 (b), DME (c), CO (d),2 H2O (e), and methanol (f).

5. Conclusions
A comprehensive 18-parameter kinetic model was developed for the direct hydrogena-
tion of CO2 to DME over a hybrid CuO-ZnO-ZrO2 /HZSM-5 catalytic system, previously
optimized in terms of composition, preparation method, and tuning of physico-chemical
properties. The model was validated in a wide set of reaction pressure, temperature, and
space velocity, clearly showing a reliable fitting of the estimated parameters, within an
average absolute error of 10−4 , both for the process reactants (i.e., CO2 , H2 ) and the target
product (i.e., DME), with the correspondent experimental values. The accuracy of the
model confirmed previous findings on the multi-site nature of the studied process, mainly
following the formate route, according to which carbon dioxide is activated at the metal–
oxide interface, then reacting with activated hydrogen migrating via spillover from metallic
copper sites. Afterwards, formate species are hydrogenated to methanol, which, in line with
an associative pathway, quickly turns into DME by condensation with another adsorbed
methanol molecule over the acidic sites of the zeolite. Overall, the adequate accuracy in the
prediction of the compositions related to the most abundant process compounds makes
the model promising for further implementation within a plant simulation, prompting an
Catalysts 2024, 14, 61 11 of 15

estimation of the costs associated with the direct DME synthesis process for an assessment
of its actual convenience on an industrial scale.

Author Contributions: Conceptualization, L.M., V.P. and F.F.; methodology, A.D., A.B. and L.M.;
software, A.D.; validation, A.D., A.B. and L.M.; formal analysis, A.D.; investigation, S.T., M.S. and
C.C.; resources, V.P. and G.B.; data curation, A.D.; writing—original draft preparation, A.D.; writing—
review and editing, A.D., A.B., L.M. and G.B.; supervision, G.B.; project administration, V.P.; funding
acquisition, G.B. All authors have read and agreed to the published version of the manuscript.
Funding: This research was financially supported by the European Union’s Horizon Europe research
and innovation program under grant agreement No. 101058540 (project PLASTICE).
Data Availability Statement: Data is contained within the article.
Acknowledgments: The authors also acknowledge Francesco Arena from the University of Messina,
Dip. Ingegneria, for the fruitful discussion about the boundary conditions of the kinetic model.
Conflicts of Interest: The authors declare no conflicts of interest.

Appendix A Fugacity Coefficient Evaluation

When working with real mixtures, it is crucial to determine the fugacity coefficient νi
of each component to measure its deviation from the ideal state. This can be performed by
taking advantage of the fact that ln νi is the partial molar property of ln νm , where νm is the
fugacity coefficient of the mixture, as described in Equation (A1) [54]:
!
∂lnνm
lnνi = lnνm − ∑ y j (A1)
j ̸ =i
∂y j
P,T,yk̸= j̸=i

In Equation (A1), yi denotes the molar fraction of compound i, while νm was computed
through the two-term virial equation of state (Equations (A2)) [55]:

Bm P
lnνm = (A2)
RT
In Equation (A2), P is the reaction pressure, T is the reaction temperature, and R is
the universal gas constant, whereas Bm denotes the second virial coefficient of the mixture,
which can be evaluated from binary coefficients Bij , as in Equation (A3):

7 7
Bm = ∑ ∑ yi y j Bij (A3)
i =1 j =1

The binary coefficients Bij can be calculated through Tsonopoulos’s correlation

(Equations (A4)–(A7)), which extends the virial equation to polar fluids [56]:

Bij PCij       T
= f (0) TRij + ωij f (1) TRij + f (2) TRij where TRij = (A4)
RTCij TCij
  0.33 0.1385 0.0121 0.000607
f (0) TRij = 0.1445 − − − − (A5)
TRij TR2 TR3 TR8
ij ij ij
  0.331 0.423 0.008
f (1) TRij = 0.0637 + 2 − 3 − 8 (A6)
TR TR TR
ij ij ij

  aij bij
f (2) TRij = 6 − 8 (A7)
TR TR
ij ij

The terms f (0) , f (1) and f (2) represent the impact of intermolecular forces from spher-
ically symmetrical molecules, molecular orientation, and polarity, respectively. All the
Catalysts 2024, 14, 61 12 of 15

critical binary properties figuring in Equation (A4) are evaluated from the critical properties
(i.e., critical volume vC , critical temperature TC , and critical pressure PC ) and acentric factors
ω of pure components, as detailed in Equations (A8)–(A11) [57]:
 1 1
3
3 3
vC + vC
i j
vCij = (A8)
8
q
TCij = TCi TCj (A9)
!
TCij PCi vCi PCj vCj
PCij = + (A10)
2vCij TCi TCj
ωi + ω j
ωij = (A11)
2
The aij and bij parameters in Equation (A7) measure polar interactions and are exclu-
sively non-zero for pairs of polar fluids. In such instances, they are assumed to be equal to the
average of the constants of pure components, as outlined in Equations (A12) and (A13) [55]:

ai + a j
aij = (A12)
2
bi + b j
bij = (A13)
2
In the specific case analyzed, the only polar fluids considered are water, methanol,
and dimethyl ether, whose parameters are listed in Table A1.

Table A1. a and b parameters for Equations (A12) and (A13) [55].

Compound a b
Water 0.0279 0.0229
Methanol 0.0878 0.0560
Dimethyl Ether −0.01513 0

Based on the above, in Table A2 are reported the fugacity coefficients as determined
under the most severe operating conditions (i.e., 200 ◦ C and 50 bar). The analysis indicates
that, in nearly all cases, these coefficients are very close to one, resulting in a negligible
correction to the partial pressure. Moreover, although nitrogen shows a measurable de-
viation from its ideal behavior, its fugacity is not present in the kinetic expressions of the
reaction rates (Equations (12)–(14)). Therefore, it was preferred to maintain the validity of
the ideal gas hypothesis against a relatively modest enhancement in the model accuracy
only achievable behind an increased computational complexity.

Table A2. Fugacity coefficients for different compositions, evaluated at 200 ◦ C and 50 bar.

yCO2 yH2 yDME yCO yMeth yH2 O yN2 ϕCO2 ϕH2 ϕDME ϕCO ϕMeth ϕH2 O ϕN2
0.23 0.69 - - - - 0.08 0.97 1.03 - - - - 0.24
0.21 0.67 - 0.02 - 0.02 0.08 0.97 1.03 - 1.02 - 0.96 0.24
0.21 0.67 0.005 0.007 0.002 0.016 0.09 0.97 1.03 0.98 1.01 0.95 0.96 0.24
0.20 0.63 0.01 0.03 0.01 0.03 0.09 0.97 1.03 0.97 1.01 0.94 0.95 0.24
0.19 0.62 0.02 0.02 0.01 0.06 0.08 0.96 1.04 0.97 1.02 0.93 0.94 0.24
Catalysts 2024, 14, 61 13 of 15

References
1. Fleisch, T.H.; Basu, A.; Gradassi, M.J.; Masin, J.G. Dimethyl Ether: A Fuel for the 21st Century. In Studies in Surface Science and
Catalysis; Elsevier: Amsterdam, The Netherlands, 1997; pp. 117–125.
2. Matzen, M.; Demirel, Y. Methanol and Dimethyl Ether from Renewable Hydrogen and Carbon Dioxide: Alternative Fuels
Production and Life-Cycle Assessment. J. Clean. Prod. 2016, 139, 1068–1077. [CrossRef]
3. Makoś, P.; Słupek, E.; Sobczak, J.; Zabrocki, D.; Hupka, J.; Rogala, A. Dimethyl Ether (DME) as Potential Environmental Friendly
Fuel. E3S Web Conf. 2019, 116, 00048. [CrossRef]
4. Park, S.H.; Lee, C.S. Applicability of Dimethyl Ether (DME) in a Compression Ignition Engine as an Alternative Fuel. Energy
Convers. Manag. 2014, 86, 848–863. [CrossRef]
5. Park, S.H.; Lee, C.S. Combustion Performance and Emission Reduction Characteristics of Automotive DME Engine System. Prog.
Energy Combust. Sci. 2013, 39, 147–168. [CrossRef]
6. Semelsberger, T.A.; Borup, R.L.; Greene, H.L. Dimethyl Ether (DME) as an Alternative Fuel. J. Power Sources 2006, 156, 497–511.
[CrossRef]
7. Khadzhiev, S.N.; Kolesnichenko, N.V.; Ezhova, N.N. Manufacturing of Lower Olefins from Natural Gas through Methanol and Its
Derivatives (Review). Pet. Chem. 2008, 48, 325–334. [CrossRef]
8. Cordero-Lanzac, T.; Martínez, C.; Aguayo, A.T.; Castaño, P.; Bilbao, J.; Corma, A. Activation of N-Pentane While Prolonging
HZSM-5 Catalyst Lifetime during Its Combined Reaction with Methanol or Dimethyl Ether. Catal. Today 2022, 383, 320–329.
[CrossRef]
9. Pérez-Uriarte, P.; Ateka, A.; Aguayo, A.T.; Gayubo, A.G.; Bilbao, J. Kinetic Model for the Reaction of DME to Olefins over a
HZSM-5 Zeolite Catalyst. Chem. Eng. J. 2016, 302, 801–810. [CrossRef]
10. Catizzone, E.; Bonura, G.; Migliori, M.; Frusteri, F.; Giordano, G. CO2 Recycling to Dimethyl Ether: State-of-the-Art and
Perspectives. Molecules 2017, 23, 31–58. [CrossRef]
11. Bonura, G.; Cordaro, M.; Spadaro, L.; Cannilla, C.; Arena, F.; Frusteri, F. Hybrid Cu–ZnO–ZrO2 /H-ZSM5 System for the Direct
Synthesis of DME by CO2 Hydrogenation. Appl. Catal. B 2013, 140–141, 16–24. [CrossRef]
12. Wawrzyńczak, D.; Majchrzak-Kuceba, I.; Pevida, C.; Bonura, G.; Nogueira, R.; De Falco, M. The Carbon Chain in Carbon Dioxide
Industrial Utilization Technologies: A Case Study; Taylor & Francis: Abingdon, UK, 2023.
13. Sankhe, S.; Krishna, S.V.M.; Juturu, R.M.; Subrahmanyam, C. Power-to-X (PtX) Technologies and Their Potential Role in the
Transition towards a Fossil-Free Energy Future: A Review of EFuels Synthesis and Direct Air Capture (DAC) Technology. In
Proceedings of the International Conference on Automotive Materials and Manufacturing AMM 2023, Pune, India, 1–3 June 2023;
SAE Technical Paper 2023-28-1333. pp. 1–5. [CrossRef]
14. Catizzone, E.; Freda, C.; Braccio, G.; Frusteri, F.; Bonura, G. Dimethyl Ether as Circular Hydrogen Carrier: Catalytic Aspects of
Hydrogenation/Dehydrogenation Steps. J. Energy Chem. 2021, 58, 55–77. [CrossRef]
15. Azizi, Z.; Rezaeimanesh, M.; Tohidian, T.; Rahimpour, M.R. Dimethyl Ether: A Review of Technologies and Production Challenges.
Chem. Eng. Process. Process Intensif. 2014, 82, 150–172. [CrossRef]
16. Mondal, U.; Yadav, G.D. Perspective of Dimethyl Ether as Fuel: Part I. Catalysis. J. CO2 Util. 2019, 32, 299–320. [CrossRef]
17. Bonura, G.; Migliori, M.; Frusteri, L.; Cannilla, C.; Catizzone, E.; Giordano, G.; Frusteri, F. Acidity Control of Zeolite Functionality
on Activity and Stability of Hybrid Catalysts during DME Production via CO2 Hydrogenation. J. CO2 Util. 2018, 24, 398–406.
[CrossRef]
18. Tokay, K.C.; Dogu, T.; Dogu, G. Dimethyl Ether Synthesis over Alumina Based Catalysts. Chem. Eng. J. 2012, 184, 278–285.
[CrossRef]
19. Akhoondi, A.; Osman, A.I.; Alizadeh Eslami, A. Direct Catalytic Production of Dimethyl Ether from CO and CO2 : A Review.
Synth. Sinter. 2021, 1, 105–125. [CrossRef]
20. Chen, W.H.; Hsu, C.L.; Wang, X.D. Thermodynamic Approach and Comparison of Two-Step and Single Step DME (Dimethyl
Ether) Syntheses with Carbon Dioxide Utilization. Energy 2016, 109, 326–340. [CrossRef]
21. Banivaheb, S.; Pitter, S.; Delgado, K.H.; Rubin, M.; Sauer, J.; Dittmeyer, R. Recent Progress in Direct DME Synthesis and Potential
of Bifunctional Catalysts. Chem. Ing. Tech. 2022, 94, 240–255. [CrossRef]
22. Bonura, G.; Cannilla, C.; Frusteri, L.; Catizzone, E.; Todaro, S.; Migliori, M.; Giordano, G.; Frusteri, F. Interaction Effects between
CuO-ZnO-ZrO2 Methanol Phase and Zeolite Surface Affecting Stability of Hybrid Systems during One-Step CO2 Hydrogenation
to DME. Catal. Today 2020, 345, 175–182. [CrossRef]
23. Ren, S.; Shoemaker, W.R.; Wang, X.; Shang, Z.; Klinghoffer, N.; Li, S.; Yu, M.; He, X.; White, T.A.; Liang, X. Highly Active and
Selective Cu-ZnO Based Catalyst for Methanol and Dimethyl Ether Synthesis via CO2 Hydrogenation. Fuel 2019, 239, 1125–1133.
[CrossRef]
24. Abu-Dahrieh, J.; Rooney, D.; Goguet, A.; Saih, Y. Activity and Deactivation Studies for Direct Dimethyl Ether Synthesis Using
CuO–ZnO–Al2 O3 with NH4 ZSM-5, HZSM-5 or γ-Al2 O3 . Chem. Eng. J. 2012, 203, 201–211. [CrossRef]
25. Frusteri, L.; Bonura, G.; Cannilla, C.; Todaro, S.; Giordano, G.; Migliori, M.; Frusteri, F. Promoting Direct CO2 Conversion to DME
over Zeolite-Based Hybrid Catalysts. Pet. Chem. 2020, 60, 508–515. [CrossRef]
26. Ateka, A.; Rodriguez-Vega, P.; Ereña, J.; Aguayo, A.T.; Bilbao, J. Kinetic Modeling and Reactor Design of the Direct Synthesis of
Dimethyl Ether for CO2 Valorization. A Review. Fuel 2022, 327, 125148. [CrossRef]
Catalysts 2024, 14, 61 14 of 15

27. Hadipour, A.; Sohrabi, M. Synthesis of some bifunctional catalysts and determination of kinetic parameters for direct conversion
of syngas to dimethyl ether. Chem. Eng. J. 2008, 137, 294–301. [CrossRef]
28. Frusteri, F.; Cordaro, M.; Cannilla, C.; Bonura, G. Multifunctionality of Cu–ZnO–ZrO2 /H-ZSM5 Catalysts for the One-Step
CO2 -to-DME Hydrogenation Reaction. Appl. Catal. B 2015, 162, 57–65. [CrossRef]
29. Delgado Otalvaro, N.; Bilir, P.G.; Herrera Delgado, K.; Pitter, S.; Sauer, J. Kinetics of the Direct DME Synthesis: State of the Art
and Comprehensive Comparison of Semi-Mechanistic, Data-Based and Hybrid Modeling Approaches. Catalysts 2022, 12, 347.
[CrossRef]
30. Naik, S.P.; Ryu, T.; Bui, V.; Miller, J.D.; Drinnan, N.B.; Zmierczak, W. Synthesis of DME from CO2 /H2 Gas Mixture. Chem. Eng. J.
2011, 167, 362–368. [CrossRef]
31. De Falco, M.; Capocelli, M.; Centi, G. Dimethyl Ether Production from CO2 Rich Feedstocks in a One-Step Process: Thermody-
namic Evaluation and Reactor Simulation. Chem. Eng. J. 2016, 294, 400–409. [CrossRef]
32. Studt, F.; Behrens, M.; Kunkes, E.L.; Thomas, N.; Zander, S.; Tarasov, A.; Schumann, J.; Frei, E.; Varley, J.B.; Abild-Pedersen, F.;
et al. The Mechanism of CO and CO2 Hydrogenation to Methanol over Cu-Based Catalysts. ChemCatChem 2015, 7, 1105–1111.
[CrossRef]
33. Cao, A.; Wang, Z.; Li, H.; Elnabawy, A.O.; Nørskov, J.K. New Insights on CO and CO2 Hydrogenation for Methanol Synthesis:
The Key Role of Adsorbate-Adsorbate Interactions on Cu and the Highly Active MgO-Cu Interface. J. Catal. 2021, 400, 325–331.
[CrossRef]
34. Campbell, C.T. Finding the Rate-Determining Step in a Mechanism: Comparing DeDonder Relations with the “Degree of Rate
Control”. J. Catal. 2001, 204, 520–524. [CrossRef]
35. Lu, W.Z.; Teng, L.H.; Xiao, W. De Simulation and Experiment Study of Dimethyl Ether Synthesis from Syngas in a Fluidized-Bed
Reactor. Chem. Eng. Sci. 2004, 59, 5455–5464. [CrossRef]
36. Li, Z.; Li, N.; Wang, N.; Zhou, B.; Yin, P.; Song, B.; Yu, J.; Yang, Y. Mechanism Investigations on Water Gas Shift Reaction over
Cu(111), Cu(100), and Cu(211) Surfaces. ACS Omega 2022, 7, 3514–3521. [CrossRef] [PubMed]
37. Bonura, G.; Todaro, S.; Frusteri, L.; Majchrzak-Kuc˛eba, I.; Wawrzyńczak, D.; Pászti, Z.; Tálas, E.; Tompos, A.; Ferenc, L.; Solt, H.;
et al. Inside the Reaction Mechanism of Direct CO2 Conversion to DME over Zeolite-Based Hybrid Catalysts. Appl. Catal. B 2021,
294, 120255. [CrossRef]
38. Motagamwala, A.H.; Dumesic, J.A. Microkinetic Modeling: A Tool for Rational Catalyst Design. Chem. Rev. 2021, 121, 1049–1076.
[CrossRef]
39. Saravanan, K.; Ham, H.; Tsubaki, N.; Bae, J.W. Recent progress for direct synthesis of dimethyl ether from syngas on the
heterogeneous bifunctional hybrid catalysts. Appl. Catal. B Environ. 2017, 217, 494–522. [CrossRef]
40. Din, I.U.; Shaharun, M.S.; Alotaibi, M.A.; Alharthi, A.I.; Naeem, A. Recent Developments on Heterogeneous Catalytic CO2
Reduction to Methanol. J. CO2 Util. 2019, 34, 20–33. [CrossRef]
41. Guil-López, R.; Mota, N.; Llorente, J.; Millán, E.; Pawelec, B.; Fierro, J.L.G.; Navarro, R.M. Methanol Synthesis from CO2 : A
Review of the Latest Developments in Heterogeneous Catalysis. Materials 2019, 12, 3902. [CrossRef]
42. Blaszkowski, S.R.; van Santen, R.A. The Mechanism of Dimethyl Ether Formation from Methanol Catalyzed by Zeolitic Protons. J.
Am. Chem. Soc. 1996, 118, 5152–5153. [CrossRef]
43. Jones, A.J.; Iglesia, E. Kinetic, Spectroscopic, and Theoretical Assessment of Associative and Dissociative Methanol Dehydration
Routes in Zeolites. Angew. Chem. 2014, 126, 12373–12377. [CrossRef]
44. Ghorbanpour, A.; Rimer, J.D.; Grabow, L.C. Computational Assessment of the Dominant Factors Governing the Mechanism of
Methanol Dehydration over H-ZSM-5 with Heterogeneous Aluminum Distribution. ACS Catal. 2016, 6, 2287–2298. [CrossRef]
45. Tang, Q.-L.; Liu, Z.-P. Identification of the Active Cu Phase in the Water−Gas Shift Reaction over Cu/ZrO2 from First Principles.
J. Phys. Chem. C 2010, 114, 8423–8430. [CrossRef]
46. Madon, R.J.; Braden, D.; Kandoi, S.; Nagel, P.; Mavrikakis, M.; Dumesic, J.A. Microkinetic Analysis and Mechanism of the Water
Gas Shift Reaction over Copper Catalysts. J. Catal. 2011, 281, 1–11. [CrossRef]
47. Lacerda de Oliveira Campos, B.; Herrera Delgado, K.; Wild, S.; Studt, F.; Pitter, S.; Sauer, J. Surface Reaction Kinetics of the
Methanol Synthesis and the Water Gas Shift Reaction on Cu/ZnO/Al2 O3 . React. Chem. Eng. 2021, 6, 868–887. [CrossRef]
48. Behloul, C.R.; Commenge, J.-M.; Castel, C. Simulation of Reactors under Different Thermal Regimes and Study of the Internal
Diffusional Limitation in a Fixed-Bed Reactor for the Direct Synthesis of Dimethyl Ether from a CO2 -Rich Input Mixture and H2 .
Ind. Eng. Chem. Res. 2021, 60, 1602–1623. [CrossRef]
49. Agarwal, A.K.; Brisk, M.L. Sequential Experimental Design for Precise Parameter Estimation. 1. Use of Reparameterization. Ind.
Eng. Chem. Process Des. Dev. 1985, 24, 203–207. [CrossRef]
50. Pritchard, D.J.; Bacon, D.W. Statistical Assessment of Chemical Kinetic Models. Chem. Eng. Sci. 1975, 30, 567–574. [CrossRef]
51. Espie, D.M.; Macchietto, S. Nonlinear Transformations for Parameter Estimation. Ind. Eng. Chem. Res. 1988, 27, 2175–2179.
[CrossRef]
52. Ereña, J.; Sierra, I.; Aguayo, A.T.; Ateka, A.; Olazar, M.; Bilbao, J. Kinetic Modelling of Dimethyl Ether Synthesis from (H2 + CO2 )
by Considering Catalyst Deactivation. Chem. Eng. J. 2011, 174, 660–667. [CrossRef]
53. Ahmad, K.; Upadhyayula, S. Greenhouse Gas CO2 Hydrogenation to Fuels: A Thermodynamic Analysis. Environ. Prog. Sustain.
Energy 2019, 38, 98–111. [CrossRef]
54. Marrelli, L. Termodinamica Degli Equilibri Di Fasi Fluide; Edizioni Efesto: Rome, Italy, 2017.
Catalysts 2024, 14, 61 15 of 15

55. De Santis, R. Introduzione al Calcolo Degli Equilibri Di Fasi Fluide; ESA: Paris, France, 1991.
56. Tsonopoulos, C. An Empirical Correlation of Second Virial Coefficients. AIChE J. 1974, 20, 263–272. [CrossRef]
57. Chueh, P.L.; Prausnitz, J.M. Vapor-Liquid Equilibria at High Pressures. Vapor-Phase Fugacity Coefficients in Nonpolar and
Quantum-Gas Mixtures. Ind. Eng. Chem. Fundam. 1967, 6, 492–498. [CrossRef]

Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual
author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to
people or property resulting from any ideas, methods, instructions or products referred to in the content.