High selectivity of TaSiBEA zeolite catalysts in 1,3-butadiene production from ethanol and acetaldehyde mixture

Article abstract of DOI:10.1016/j.catcom.2016.01.023

New tantalum-silica based zeolite catalysts (TaSiBEA) were applied in this work for 1,3-butadiene production from ethanol. Tantalum incorporation into vacant T-atom sites of the SiBEA zeolites framework as mononuclear Ta(V) allowed preparing highly selective catalysts for ethanol/acetaldehyde mixture conversion into 1,3-butadiene, with selectivity to 1,3-butadiene of 80-90% at total conversion of the mixture of 45-30%. Effect of Ta content on activity of TaSiBEA zeolite catalysts and the ethanol/acetaldehyde molar ratio in selective production of 1,3-butadiene were demonstrated.

Full text of DOI:10.1016/j.catcom.2016.01.023

High selectivity of TaSiBEA zeolite catalysts in 1,3-butadiene production
from ethanol and acetaldehyde mixture
Pavlo I. Kyriienko, Olga V. Larina, Sergiy O. Soloviev, Svitlana M. Or-
lyk, Stanislaw Dzwigaj
PII:
DOI:
Reference:
S1566-7367(16)30023-1
doi: 10.1016/j.catcom.2016.01.023
CATCOM 4568
To appear in:
Catalysis Communications
Received date:
Revised date:
Accepted date:
13 August 2015
19 January 2016
22 January 2016
Please cite this article as: Pavlo I. Kyriienko, Olga V. Larina, Sergiy O. Soloviev, Svit-
lana M. Orlyk, Stanislaw Dzwigaj, High selectivity of TaSiBEA zeolite catalysts in 1,3-
butadiene production from ethanol and acetaldehyde mixture, Catalysis Communications
(2016), doi: 10.1016/j.catcom.2016.01.023
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ACCEPTED MANUSCRIPT
High selectivity of TaSiBEA zeolite catalysts in 1,3-butadiene production from
ethanol and acetaldehyde mixture
a,
a
a
Pavlo I. Kyriienko *, Olga V. Larina , Sergiy O. Soloviev ,
a
b,c,
Svitlana M. Orlyk , Stanislaw Dzwigaj *
a
L.V.Pisarzhevsky Institute of Physical Chemistry of the NAS of Ukraine,
3
1 Prosp. Nauky, 03028 Kyiv, Ukraine
b
Sorbonne Universités, UPMC Univ Paris 06, UMR 7197, Laboratoire de Réactivité de Surface,
F-75005, Paris, France
c
CNRS, UMR 7197, Laboratoire de Réactivité de Surface, F-75005, Paris, France
Figures: 4
Scheme: 1
Tables: 2
Keywords: tantalum, BEA, ethanol, 1,3-butadiene, catalysis
*
Corresponding authors:
P.I. Kyriienko, E-mail address: pavlo_kyriienko@ukr.net, fax: +38 (044) 525 65 90.
S. Dzwigaj, E-mail address: stanislaw.dzwigaj@upmc.fr, fax: +33 01 44 27 60 33.
1

ACCEPTED MANUSCRIPT
Abstract
New tantalum-silica based zeolite catalysts (TaSiBEA) were applied in this work for 1,3-
butadiene production from ethanol. Tantalum incorporation into vacant T-atom sites of the
SiBEA zeolites framework as mononuclear Ta(V) allowed preparing highly selective catalysts
for ethanol/acetaldehyde mixture conversion into 1,3-butadiene, with selectivity to 1,3-butadiene
of 80–90% at total conversion of the mixture of 45–30%. Effect of Ta content on activity of
TaSiBEA zeolite catalysts and the ethanol/acetaldehyde molar ratio in selective production of
1
,3-butadiene were demonstrated.
2

ACCEPTED MANUSCRIPT
1
. Introduction
,3-Butadiene (BD) is the most important conjugated diene, being the basis of a variety
1
of synthetic polymers [1–3]. BD can be produced from ethanol (EtOH) in two ways. In one-step
process, using a variety of mixed metal oxide catalysts (ZnO-Al O , (ZnO, CuO)/MgO-SiO ,
2
3
2
etc.) [4–11], and in two-step process, using Ta O -silica [12–14] as well as ZrO -silica [15,16]
2
5
2
catalysts in EtOH and acetaldehyde (AA) mixture conversion.
Scheme 1 shows an overall scheme of EtOH conversion into BD [1–3]. It involves
multiple consecutive steps: (1) dehydrogenation; (2) aldol condensation; (3) crotonic
condensation; (4) Meerwein–Ponndorf–Verley (MPV) reduction; and (5) dehydration. The key
steps of the process are (2) [15] and (4) [4].
Angelici et al. [17] showed that the best MgO-SiO catalyst for the one-step process is
2
material composed of small amount of strong basic sites and higher amount of acidic and weak
basic sites. It is well known that EtOH is preferably converted into 1-butanol on magnesium
oxide with strong basic sites [18]. According to the works [16,19,20], the activity of zirconium-
silica catalysts in EtOH to BD process is related to Lewis acidic sites (LAS). Obviously, the
subtle ratio in acidic-basic sites of the catalysts is required to produce selectively BD from
EtOH.
It was recently reported [19] that material based on ZrBEA zeolite is more active in EtOH
to BD process than Zr-loaded SiO and ordered mesoporous silica, probably because of higher
2
amount of LAS on the catalyst surface. Ta/SBA-15 and Ta/KIT-6 show higher selectivity in
transformation of EtOH and AA mixture into BD than Ta-containing conventional silica based
catalysts and greatly improves efficiency of the process [13]. Thus, these literature results
indicate that investigation of Ta-zeolite materials as catalysts for EtOH (or EtOH/AA mixture)
conversion into BD seems to be very interesting. As shown earlier [21,22], TaSiBEA with
isolated mononuclear Ta(V) possesses Lewis acidic-basic pairs which are required for both
processes.
3

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In this paper we report the remarkable selectivity achieved in production of BD from
EtOH and AA over TaSiBEA zeolite catalysts with isolated mononuclear Ta(V). To the best of
our knowledge, this is the first time that such catalytic properties of Ta-zeolite catalysts in this
process have been reported.
2
. Experimental
TaSiBEA zeolites were prepared by two-step postsynthesis method described earlier
21,22]. The method has allowed obtaining Ta(V)-single site BEA zeolite, as evidenced by XRD,
[
FTIR and DR UV-vis (see Supplementary material (SM), section 2 and Figs. S1-S3). Analysis of
acidic-basic properties of the zeolite catalysts was performed by adsorption of pyridine, pyrrole
and deuterated chloroform (CDCl ) followed by infrared spectroscopy. Catalytic activity tests
3
were carried out in a fixed-bed flow reactor. EtOH or EtOH/AA mixtures with the molar ratios
EtOH/AA of 2.2, 2.7 and 3.2 (17.4 mmol of EtOH or EtOH/AA through 1 g of a catalyst per 1 h)
were fed into the catalytic reactor. Catalytic activity was characterized by total conversion of
reagents (EtOH and AA), selectivity of products and BD yield.
Details of catalysts preparation method, catalyst characterization procedures and catalytic
activity measurements are described elsewhere (see SM, section 1).
3
. Results and discussion
3
.1. FTIR characterization of acidic-basic sites: pyridine, pyrrole and CDCl adsorption
3
FTIR spectra of Ta SiBEA and Ta SiBEA after pyridine adsorption are presented in
1
.0
3.0
-1
Fig. 1. The bands at 1613, 1598, 1492 and 1445-1450 cm correspond to pyridine interacting
with LAS, in line with earlier data [22,23]. Intensity of absorption bands attributed to LAS for
Ta SiBEA is higher than that for Ta SiBEA. The intensity of these bands for SiBEA is much
3
.0
1.0
lower [24]. Thus, it proves that upon incorporation of Ta ions in the vacant T-atom sites of
SiBEA the additional LAS are formed in framework of the zeolite. Absence of the bands at 1638
-1
and 1545 cm in FTIR spectra of SiBEA [24] and TaSiBEA (Fig. 1) suggests that Brønsted
4

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acidic sites are not present in SiBEA and are not created upon incorporation of Ta ions in
framework of SiBEA zeolite.
It is well known that pyrrole being an amphoteric molecule can react with either basic
sites or acidic ones. FTIR spectra of Ta SiBEA after pyrrole adsorption are presented in Fig. 2.
1
.0
-1
The bands at 1534, 1470, 1421 and 1379 cm are attributed to the ring-stretching vibrations of
-1
-1
pyrrole [25,26]. The band at 3480 cm combined with the band at 1490 cm indicated the
presence of the pyrrole species interacting with acidic sites [25,26]. The weak shoulder at ca.
-1
3
390 cm in the spectra of TaSiBEA could suggest the presence of basic sites, in agreement with
earlier work [25].
FTIR spectra of Ta SiBEA after CDCl adsorption are presented in Fig. 3. The bands at
1
.0
3
-1
2
558 and 2224 cm are attributed to weak and medium basic sites [17]. The bands attributed to
strong basic sites are absent for TaSiBEA.
Thus, the FTIR investigations of TaSiBEA have shown that these catalysts possess both
Lewis acidic and basic sites with a predominance of the former ones.
3
.3. Catalytic properties of TaSiBEA
Results of the catalytic activity of TaSiBEA catalysts in conversion of EtOH/AA mixture
into BD are presented in Table 1. Stability of BD selectivity and yield over Ta SiBEA and
1
.0
Ta SiBEA at 598 K and 623 K as a function of time-on-stream are presented in Fig. S4 (see
3
.0
SM). The high BD selectivity is maintained after repeated operation cycles, as well as the
stability of the zeolite structure according to XRD and FTIR data (see SM, section 3).
Incorporation of Ta into the BEA framework has allowed preparing catalysts with
remarkable selectivity in production of BD from EtOH/AA mixture. The highest selectivity to
BD (87.3–90.3%) for the TaSiBEA zeolite catalysts is observed at the EtOH/AA molar ratio of
2
.2 (Table 1). At higher molar ratio of EtOH/AA selectivity to BD is lower, but total conversion
of the mixture, as well as BD yield, increases. If only EtOH is present in the feed high selectivity
5

ACCEPTED MANUSCRIPT
and yield of BD are not observed (Fig. 4). The major products at such conditions are AA,
ethylene and diethyl ether (DEE) (Table 2).
EtOH dehydrogenation to AA and dehydration to ethylene/DEE are suggested occurring
on Ta(V)-containing sites, which posses redox [27] and acidic-basic properties [22,23].
However, in Ta(V)-containing zeolite catalysts the acidic-basic properties predominant over
redox one as reported earlier [22]. Substantial amount of AA obtained in step (1) from EtOH
(Table 2) indicates that bridged oxygen of Ta-O-Si is basic site. Nevertheless, amount of the
dehydration products is higher than AA. Consequently, it suggests that acidic properties of
Ta(V)-containing zeolite catalyst prevail its basic properties, in line with the FTIR data of
adsorbed pyridine, pyrrole and CDCl (Figs. 1-3).
3
Increasing BD selectivity in the presence of AA in the feed (Fig. 4) is result of
acceleration of the key step (2). Aldol condensation (2) competes against EtOH dehydration to
ethylene/DEE for acidic Ta(V)-containing sites. Increasing EtOH content (with simultaneous
decreasing of AA) in the feed contributes accelerating the EtOH dehydration and leads to
decrease in BD selectivity. However, increasing EtOH content in the feed promotes more
complete MPV reduction of crotonaldehyde as evidenced by decrease in amount of
crotonaldehyde in the reaction products (Table 1).
The effect of temperature on the conversion of EtOH or EtOH/AA mixture over
TaSiBEA catalysts is shown in Fig. 4. In both cases, BD yield increases with temperature,
-1
because EtOH-to-BD process is endothermic with an enthalpy of 102-109 kJ·mol [2]. If only
EtOH is present in the feed selectivity to BD increases with temperature, and in the case of
EtOH/AA mixture conversion selectivity to BD decreases. Such changing of BD selectivity is
likely to be explained by kinetic factors, related to the activity of the catalyst, in line with results
of thermodynamic analysis for one- and two-step EtOH-to-BD processes [2].
It is important to mention here that increase of the content of Ta atoms in the zeolite
matrix from 1 to 3 wt % does not provide proportional increase of BD yield in the conversion of
6

ACCEPTED MANUSCRIPT
EtOH or EtOH/AA mixture. This may be due to the different accessibility of Ta(V)-containing
sites being active in the process.
It was recently shown [20] that isolated tetrahedral Zr(IV) species linked with four
(closed site) or three (open site) silicon atoms in framework of ZrBEA zeolite constitute LAS.
The open sites of ZrBEA are more efficient in the process of BD production, which can be
related to the higher acidic strength and better steric accessibility of such sites. The same may be
true for the TaSiBEA catalysts with different contents of tantalum. The number of space-
available LAS in Ta SiBEA is not significantly greater than in Ta SiBEA. Thus, the observed
3
.0
1.0
difference in the activity of Ta BEA and Ta SiBEA may be caused by the fact that the number
1
.0
3.0
of sterically accessible active sites capable of promoting target process in Ta SiBEA is greater
3
.0
than that present in Ta SiBEA due to a larger content of tantalum.
1
.0
Conclusions
TaSiBEA zeolite can be used as efficient catalyst for the conversion of ethanol and
acetaldehyde mixture into 1,3-butadiene.
The two-step postsynthesis method of Ta incorporation into vacant T-atom sites of BEA
zeolite has allowed preparing highly selective (80–90 % at total conversion of 45–30 %)
tantalum-silicate catalysts for the conversion of ethanol and acetaldehyde mixture into 1,3-
butadiene.
7

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a
Table 1. Catalytic performance of TaSiBEA catalysts in EtOH/AA mixture conversion
EtOH/AA
ratio
Temp. (K)
Total conver. (%)
Selectivity (C mol%)
diethyl ether
BD yield
(C mol%)
BD
ethylene
croton
others
aldehyde
Ta SiBEA
1
.0
3
2
2
.2
.7
.2
598
23
598
23
598
23
39.2
45.3
31.2
43.0
26.2
34.9
86.4
78.4
86.9
79.6
87.3
88.6
7.4
14.4
3.4
4.0
0.6
1.4
0.1
0.1
0.1
0
2.7
3.2
2.4
3.5
2.3
4.7
33.9
35.5
27.1
34.2
22.9
30.9
6
9.2
0.9
0.5
10.2
6.1
6
15.0
0.1
6
0.5
Ta SiBEA
3
.0
3
2
2
.2
.7
.2
598
23
598
23
598
23
time-on-stream=4 h.
43.7
58.9
39.1
55.2
30.7
42.9
80.9
73.1
84.6
76.2
90.3
87.5
12.1
20.6
9.7
3.9
2.8
1.8
1.8
0.1
0.1
0
3.1
3.5
3.3
3.9
4.6
4.9
35.4
43.1
33.1
42.1
27.7
37.5
6
0
0.6
0.3
4.7
3.5
6
17.8
0.3
6
4.0
a
1
0

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a
Table 2. Catalytic performance of TaSiBEA catalysts in EtOH conversion
Temp. (K)
Total conver. (%)
Selectivity (C mol%)
ethylene
BD yield (C mol%)
BD
AA
diethyl ether
others
Ta SiBEA
1
.0
5
6
98
23
13.3
31.1
16.4
28.9
33.0
21.1
28.3
33.2
20.8
15.3
1.5
1.5
2.2
9.0
Ta SiBEA
3
.0
5
6
98
23
25.6
49.1
12.3
16.2
23.7
17.7
48.6
52.5
14.6
12.9
0.8
0.7
3.1
7.9
a
time-on-stream=4 h.
1
1

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Scheme 1. Overall scheme of EtOH conversion to BD.
1
2

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Figure captions
Figure 1. FTIR spectra of adsorbed pyridine over TaSiBEA catalysts after desorption at different
temperatures.
Figure 2. FTIR spectra of adsorbed pyrrole over Ta SiBEA catalyst after desorption at 338 K.
1
.0
Figure 3. FTIR spectra of adsorbed CDCl over Ta SiBEA at different temperatures.
3
1.0
Figure 4. Total conversion (TC) of EtOH/AA mixture (or EtOH), BD selectivity and yield over
TaSiBEA catalysts at different EtOH/AA ratios in the feed mixtures at 598 K and 623 K (time-
on-stream=4 h).
1
3

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Fig. 1.
Fig. 2
1
4

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Fig. 3
Fig. 4
1
5

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Graphical abstract
1
6

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Highlights
TaSiBEA catalysts were prepared by Ta incorporation into zeolite framework.
Ta-containing zeolites were firstly studied in ethanol/acetaldehyde to 1,3-butadiene conversion.
1
,3-butadiene selectivity of 80-90 % with yield of up to 43 % was achieved.
1
7