Al-doped SBA-15 Catalysts for Low-temperature Dehydration of 1,3-Butanediol into Butadiene

Article abstract of DOI:10.1002/cctc.201601202

SBA-15 catalysts doped with variable aluminum amounts were prepared through a facile evaporation-induced self-assembly process. The textural properties and acidity of the catalysts could be tuned simply by varying the aluminum content. The genesis of acid sites with weak and medium strength during reaction was directly correlated to the catalytic activity for the dehydration of 1,3-butanediol into butadiene (BD). The best performance was achieved over an Al-SBA-15 sample with a silica/alumina ratio of 76, exhibiting a stable BD yield of 59 % at temperatures as low as 200 °C.

Full text of DOI:10.1002/cctc.201601202

Accepted Article
Title: Al-doped SBA-15 catalysts for low-temperature dehydration of
1,3-butanediol into butadiene
Authors: Marc Pera-Titus, Fangli Jing, Benjamin Katryniok, Sebastien
Paul, Lin Fang, Armin Liebens, Ming Shen, Bingwen Hu, and
Franck Dumeignil
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To be cited as: ChemCatChem 10.1002/cctc.201601202
Link to VoR: http://dx.doi.org/10.1002/cctc.201601202
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10.1002/cctc.201601202
ChemCatChem
COMMUNICATION
Al-doped SBA-15 catalysts for low-temperature dehydration of
1,3-butanediol into butadiene
Fangli Jing,[a,c] Benjamin Katryniok,[a] Sébastien Paul,[a] Lin Fang,[b] Armin Liebens,[b] Ming Shen,[d]
Bingwen Hu,[d] Franck Dumeignil,[a] and Marc Pera-Titus[b]*
Abstract: SBA-15 doped with variable aluminum amounts were prepared
through a facile evaporation-induced self-assembly process. The textural
properties and the acidity of the catalysts could be simply tuned by the
aluminum content. The genesis of acid sites with weak and medium
strength during reaction was directly correlated to the catalytic activity for
the dehydration of 1,3-butanediol into butadiene. The best performance
was achieved over an Al-SBA-15 sample with a silica/alumina ratio of 76,
exhibiting a stable BD yield of 59% at a temperature as low as 200 oC.
1,4-BDO dehydration over rare-earth and weak acid oxides (e.g.,
ZrO2) at 300-500 C affords unsaturated alcohols.[12] Promising
o
BD selectivities up to 42% and >90% at full 2,3-BDO conversion
were recently reported over Al2O3 and Sc2O3 below 350 oC, res-
pectively.[13] Finally, HZSM-5 zeolites enriched with mild Brns-
ted acid sites yields mainly methyl ethyl ketone (MEK) upon 2,3-
BDO dehydration,[14] while BD could be achieved at 60% yield at
300-350 oC starting from 1,3-BDO.[15] Here, Al-doped SBA-15
samples were prepared as proto-typical acid catalysts using the
evaporation-induced self-assembly (EISA) method and calcined
under air at 550 oC (see SI for experimental details).[16] The cata-
lysts were denoted as SBA@X, where X indicates the bulk SiO2/
Al2O3 ratio measured by X-ray fluorescence (XRF) (Table S1).
Most of the Al species segregated on the silica mesostructure
and accordingly were not integrated into the silica framework as
inferred from the much larger SiO2/Al2O3 surface ratios (XPS)
compared to bulk SiO2/Al2O3 ratios (XRF) (Table S2). The sam-
ples were further used for catalyzing the gas-phase dehydration
of 1,3-BDO towards BD.
Fossil resources including coal, oil and natural gas give
access directly or indirectly to almost all fuels, chemicals and
materials used in our everyday life with an increasing demand
due to the rapid growth of the world population.[1] Obviously, the
utilization of these finite resources cannot be a long-term policy,
and more and more attention has been paid to the development
of sustainable processes relying on biomass conversion into
high-value added products.[2]
As a paradigmatic example of an petroleum-derived interme-
diate, one can mention butadiene (BD), which is used for the
synthetic rubber and resin industries.[3] The current BD produc-
tion processes rely on naphtha cracking and on the catalytic oxi-
dative dehydrogenation of n-butane and n-butene, which are all
non-sustainable feedstocks.[4] Thus, it becomes urgent to design
alternative routes for BD production using renewable materials.
The Lebedev process has attracted much interest for BD pro-
duction, since bioethanol can be used as starting raw material.[5]
This reaction is usually catalyzed over catalysts combining basic
and acid sites, including the classical MgO/SiO2,[3c,6] and ZrO2/
SiO2,[3b,7] ZnO/γ-Al2O3,[8] and ZnO/ZrO2/SiO2.[3b]
The SBA@X catalysts showed regular type IV N2 isotherms
with symmetric H1-type hysteresis loops according to the IUPAC
classification (Figure S1A), indicating the presence of cylindrical
and independent mesopores.[17] The hysteresis loop evolved
from P/P0 = 0.40-0.62 for SBA@250 to P/P0 = 0.40-0.80 for SBA
@27, reflecting broader pore size distributions (BJH) in the ran-
ge 3-6 nm (Figure S1B). Likewise, the BET specific surface area
increased inversely with the Al content from 492 m2/g for SBA@
27 to 688 m2/g for SBA@250 with ca. 20% of the surface micro-
porosity (Table 1, Figure S2). Such a trend was still found on the
catalysts after reaction at 300 oC for 8 h, even if the surface
areas dropped significantly by 45-53% and the contribution of
microposity declined below 10% for samples SBA@190, SBA@
102 and SBA@76. Notwithstanding this fact, the main porous
features of the catalysts were preserved (especially at SiO2/
Al2O3>76) without any qualitative change on the N2 sorption pa-
tterns (Figure S1C-D). The textural changes can be attributed to
coke formation as confirmed by TGA-MS and XPS (Table 1,
Table S2, Figure S3). Lower carbon (86 mgC/g) was generated
over SBA@190, whereas 111-119 mgC/g was obtained over
SBA@102, SBA@ 76 and SBA@27.
As an alternative to the Lebedev process, butanediols
(BDO) are competitive biobased substrates that can be derived
from glucose, sucrose, glycerol and mixtures of glucose and
xylose by fermentation.[9] The dehydration of BDOs can lead to
different chemicals depending on the starting diol and the cata-
lyst used.[10] Indeed, 1,2-BDO dehydration over ZnSO4 in super-
critical water yields n-butyraldehyde,[11] whereas 1,3-BDO and
[a] Dr. F. Jing, Dr. B. Katryniok, Prof. S. Paul, Prof. F. Dumeignil
Univ. Lille, Univ. Artois, CNRS, ENSCL, Centrale Lille, UMR 8181 -
UCCS - Unité de Catalyse et Chimie du Solide
Bd. Paul Langevin, 59000 Lille, France
[b] Dr. A. Liebens, Dr. M. Pera-Titus
E2P2L UMI 3464 CNRS/Solvay
The total amount and distribution of acid sites on the fresh
and spent SBA@X catalysts was measured by NH3-TPD in the
temperature range 100-1000 oC (Table 2, Figure 1 - blue curves,
Figure S2, S4). In this analysis, we assumed that all the hydro-
xyl groups that could be titrated by NH3 corresponded to
bridged Si-OH-Al sites, but not to weakly acid Si-OH groups far
from Al centers. Two distinctive NH3 desorption bands could be
discerned in the fresh SBA@X catalysts: (1) weak acid sites in
the range 100-240 oC (LT), and (2) strong acid sites in the
range 240-1000 oC (HT). Interestingly, qualitatively similar NH3-
TPD patterns were observed on Al-SBA samples prepared
3966 Jin Du Road, 201108 Shanghai, China.
Email: marc.pera-titus-ext@solvay.com
[c] Dr. F. Jing
School of Chemical Engineering
Sichuan University
No. 24, South section 1, Yihuan Road, 610065 Chengdu, China
[d] Mr. M. Shen, Dr. B. Hu
School of Physics and Materials Science & Shanghai Key Laboratory of
Magnetic Resonance
East China Normal University
3663 N. Zhongshan Road, Shanghai 200062, China
Supporting information for this article is given via a link at the end of the
document.
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10.1002/cctc.201601202
ChemCatChem
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either by direct synthesis (SiO2/Al2O3 = 20-100),[18] or by post-
synthesis Al grafting over SBA-15 (SiO2/ Al2O3 = 38-130).[19]
However, while the LT bands on those catalysts matched the
temperature range observed on our SBA@X catalysts, the (de-
convoluted) HT bands appeared at comparatively lower tempe-
ratures (240-600 oC), reflecting in our case the genesis of
stronger acid sites. The density of weaker sites in the SBA@X
catalysts was very sensitive to the SiO2/Al2O3 ratio, varying
monotonously from 15 mol/g for SBA@250 to 186 mol/ g for
SBA@27. In contrast, by comparing the NH3 loadings on strong
acid sites with the total Al loadings, abnormally high NH3 loa-
dings were measured (Table 2). This observation can be ex-
+
plained by the formation of NH4 .nNH3 associations on strong
Brønsted acid sites, with n decreasing with the SiO2/Al2O3 ratio
until 0.8 for SBA@27.[20] Furthermore, partial conversion of
Lewis into Brønsted acid sites during NH3 adsorption and further
TPD tests cannot be ruled out.[21]
Figure 1. Normalized NH3-TPD profiles per weight of catalyst on 4 fresh (blue)
and spent (red) SBA@X catalysts: SBA@190, SBA@102, SBA@76, SBA@27.
The fresh and spent samples were calcined at 550 oC and 500 oC, respectively,
before the NH3-TPD profiles. The grey curves refer to distributions for the
different acid sites in the spent samples measured after deconvolution (see
detailed data in Table 3). The experimental conditions for TPD profiles can be
found in the SI. Reaction conditions as in Table 1.
The NH3-TPD profiles were also measured on the spent SBA
@X catalysts after calcination at 500 oC to remove the deposited
carbon according to the TGA-MS profiles (Figure 1 - red curves,
Figure S3). Two LT and HT bands ascribed to weak and strong
acid sites, respectively, were also observed. Interestingly, whe-
reas the LT bands appeared at almost the same temperature
range as for the fresh samples, the HT bands showed a flatter
configuration and shifted to higher temperatures. This observa-
tion points out a dramatic change of the surface distribution of
strong acid sites on the catalyst surface during the reaction,
attaining a higher degree of heterogeneity. The LT and HT
bands could be deconvoluted into 2 and 3 elementary bands,
respectively. Weak and medium-strength bands (i.e. species I-
III) were predominant for SBA@76 (Table 3).
Table 2. Acidity of SBA@X catalysts measured from NH3-TPD and pyridine
adsorption-IR
Al
(mol/g)
133
175
326
438
666
1233
NH3 uptake (NH3, mol/g)a
HT /
(Al - LT)
8.3 (-)
5.3 (2.9) 0.38
2.2 (1.1) 0.27
2.6 (1.1) 0.31
B/L
(Pyr)
-
Catalyst
100-240 oC 240-1000 oC
SBA@250
SBA@190
SBA@102
SBA@76
SBA@50
SBA@27
15 (-)
977 (-)
18 (10)
23 (12)
76 (77)
92 (-)
842 (485)
665 (339)
929 (400)
824 (-)
1.4 (-)
0.8 (0.3) 0.28
-
186 (190) 854 (300)
a In parentheses, NH3 uptake measured on spent catalysts after calcination at
500 oC. Additional data can be found in Table S3.
The LT bands exhibited lower NH3 loadings (NH3) for the
spent SBA@190 and SBA@102 compared to the parent cata-
lysts, while almost equal loadings were measured for SBA@76
+
and SBA@27 (Table 2). These observations suggest that NH4 .
nNH3 associations could also be formed on weak acid sites for
SBA@190 and SBA@102, providing in turn evidence for their
Brønsted nature. Furthermore, the NH3 loadings measured on
the spent SBA@76, SBA@50 and SBA@27 catalysts could be
safely used for estimating the acidity of weak acid sites. In the
case of HT bands, these exhibited remarkably lower NH3 loa-
dings than for the parent catalysts, suggesting a minor formation
+
degree of NH4 .nNH3 associations (n = 2.9 for SBA@190, n =
1.1 for SBA@102 and SBA@76, n = 0.3 for SBA@27, Table 2).
These results seem to indicate that partial hydrophobization of
the catalysts due to coke formation can impact the distribution of
strong acid sites, even after calcination at 500 oC.
Figure 2. 27Al-NMR MAS spectra on selected fresh SBA@X catalysts after
calcination at 500 oC (a: SBA@27, b: SBA@76, c: SBA@102, d: SBA@190).
Reaction conditions as in Table 1.
Table 1. Textural properties of SBA@X before (BR) and after reaction (AR)a
The nature of the acid sites in the fresh SBA@X catalysts
was first assessed by pyridine adsorption-IR (Figure S5). All the
samples showed two characteristic vibration bands centered at
1545 cm-1 and 1455 cm-1 that can be attributed to Brønsted (B)
and Lewis (L) acid sites, respectively.[22] Although the intensity of
both bands increased with the SiO2/Al2O3 ratio, the B/L ratio kept
almost unchanged in the range 0.27-0.38 (Table 2). This picture
is qualitative consistent with the 27Al-NMR MAS spectra measu-
red on the fresh samples (Figure 2). The spectra consisted of a
main resonance bands centered at 55 ppm with a shoulder by
SBET (m2/g)
Vg (cm3/g)
(mgC/g)d
BR AR BR AR
D (nm) Carbon
Sample
BRb
ARb
ΔSc
SBA@250 688 (139) 363 (43) 47%
SBA@190 630 (123) 337 (27) 46%
SBA@102 611 (121) 339 (28) 46%
0.58 0.38 3.6 3.6
0.61 0.34 3.6 3.3
0.52 0.36 3.6 3.5
0.57 0.36 3.9 4.0
0.58 0.34 4.0 3.7
0.55 0.26 4.1 3.8
-
86
111
112
-
SBA@76
SBA@50
SBA@27
567 (126) 309 (22) 45%
524 (124) 292 (35) 44%
492 (103) 233 (39) 53%
119
Reaction conditions: 300 oC; ambient pressure; time on stream, 8 h; catalyst
loading, 200 mg; 1,3-BDO flowrate, 2.8 mL/h; carrier N2 flowrate, 60 mL(STP)/min
b In parentheses, micropore surface areas
b ΔS = [SBET(BR) – SBET(AR)] / SBET(BR)
c Measured from TGA-MS in the range 300-680 oC
a
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10.1002/cctc.201601202
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COMMUNICATION
30 ppm, which is indicative of fourfold (AlIV, framework) and five-
fold (AlV, ex-framework) coordinated species, respectively.[21,23]
A second band could be visualized at ca. 0 ppm that can be
assigned to sixfold (AlVI, ex-framework) coordinated species in
either alumina-type phases or phases with ex-framework Al
containing water molecules in the coordination sphere.[21,23a]
A similar structural organization can be inferred from the
27Al-NMR MAS spectra measured on the spent catalysts after
calcination. The tetrahedral Al resonance band shifted to ca. 51
ppm with a slightly larger shoulder at 30 ppm (fivefold species).
Unlike the fresh catalysts, this band showed a markedly lower
intensity. This observation can be attributed to coke formation,
altering the electronic atmosphere around the Al species.[24]
Moreover, the band centered at 0 ppm associated to sixfold
coordinated Al species became very weak after reaction, which
can be explained by either a partial removal or a transformation
of Lewis acid sites (preferentially strong) into Brønsted acid sites
with medium and strong strength in the presence of water.[25] By
comparing the 27Al-NMR MAS spectra on the fresh and spent
catalysts with the NH3-TPD profiles (Figure 1), we can attribute
bands I-IV in the deconvoluted profiles to Brønsted acid species,
whereas band V is expected to refer to strong and almost resi-
dual Lewis acid sites.
C-C cleavage of 3B1ol into PE. Heavy products might be further
generated via PE and BD oligomerization, promoting coke for-
mation. Minor byproducts were also detected including MEK,
methyl vinyl ketone (MVK), 3-buten-2-ol (3B2ol), 1-butanol and
2-butanol. No ether formation was detected.[26]
The catalytic stability was studied on stream over SBA@76
o
at 250 C during 102 h (Figure 3). Full 1,3-BDO conversion was
achieved during the initial 32 h followed by a slow deactivation to
82% after 102 h due to carbon deposition. In parallel, the BD
yield declined slightly from 61% to 51% (the BD selectivity kept
almost constant), giving rise to 3B1ol (increase from 0.5% to
11%), whereas the PE yield kept stable at around 20%. Note-
worthy, the BD, PE and 3B1ol yields did not change appreciably
during operation. These results suggest that the reaction mecha-
nism was not altered during the dehydration reaction despite the
loss of 1,3-BDO conversion. Furthermore, catalytic tests perfor-
med for a time on stream below 32 h ensured a proper measure-
ment of the intrinsic catalytic activity.
Figure 4 and Figure S6 plot the main trends obtained for the
1,3-BDO conversion and the BD, PE and 3B1ol yields over the
SBA@X catalysts, whereas Tables S6-S8 list the BD yields, BD/
PE selectivity ratios and sum of selectivities (S). The tempera-
ture favored PE formation instead of BD, suggesting a higher
activation energy for PE generation from either 3B1ol or 3B2ol.
In contrast, 3B1ol was promoted at lower temperatures, espe-
cially at lower SiO2/Al2O3 ratios (X=27-76). Furthermore, oligo-
merization was favored at lower temperatures. Overall, the best
The catalytic performance of the SBA@X catalysts was
assessed in the temperature range 200-300 oC at WHSV = 14 h-1
(Tables S3-S5). In all cases, the main detected products were
BD, propylene (PE) and 3-buten-1-ol (3B1ol), suggesting a reac-
tion mechanism proceeding by a first dehydration step encom-
passing the formation of 3B1ol as main intermediate followed by
two parallel reactions: (1) dehydration of 3B1ol into BD, and (2)
o
catalytic performance was achieved at 200 C, affording BD/PE
selectivity ratios in the range 3.3-4.5 for SBA@X catalysts (X =
27-190) with moderate oligomerization (S = 72%-84%).
Table 3. Deconvolution of LT and HT bands in the NH3-TPD profiles
Band I (LT)
TM (oC)a
NH3 (%)
Band II (LT)
TM (oC)a
NH3 (%)
Band III (HT)
TM (oC)a
NH3 (%)
Band IV (HT)
T (oC)a
NH3 (%)
Band V (HT)
T (oC)a
NH3 (%)
0.13%
Catalyst





SBA@190
SBA@102
SBA@76
SBA@27
144 (27)
157 (31)
159 (32)
156 (32)
3.9%
7.9%
12%
11%
215 (51)
219 (71)
224 (68)
202 (65)
4.5%
18%
20%
15%
386 (75)
374 (89)
371 (76)
352 (100)
13%
18%
16%
4.3%
635 (194)
671 (186)
632 (180)
535 (270)
78%
55%
50%
69%
961 (28)
961 (70)
960 (75)
961 (80)
0.67%
0.70%
0.52%
a TM = mean temperature; in parentheses, standard deviation (also in oC).
Figure 3. Catalytic stability of SBA@76 at 250 oC. Other detected products
(<1% selectivity) include MEK, MVK, 1-butanol, 2-butanol and 3B2ol. Additio-
nal experimental conditions as in Table 1.
Figure 4. Influence of temperature on the catalytic performance of SBA@X
catalysts for 1,3-BDO dehydration towards BD. Other detected products (<1%
selectivity) include MEK, MVK, 1-butanol, 2-butanol and 3B2ol. Other reaction
conditions as in Table 1. The numbers in the graphs indicate the BD/PE selec-
tivity ratios (in blue) and the carbon balances (in parentheses).
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COMMUNICATION
REALCAT platform benefits from a government subvention
administered by the French National Research Agency (ANR)
within the frame of the ‘Future Investments’ program (PIA) with
the contractual reference ANR-11-EQPX-0037. The Hauts-de-
France Region and the FEDER as well as the Central Initiative
Foundation are acknowledged for their financial contribution to
the acquisition of the equipment of the platform. The authors
would like to express their gratitude to V. Ruaux and M. Daturi
for performing the pyridine adsorption-IR measurements.
Keywords
Keywords: Butadiene • 1,3-Butanediol • Dehydration • Acid
catalysis • Al-SBA-15
Figure 5. 1,3-BDO conversion and yield to main products (BD, PE, 3B1ol)
over the SBA@X catalysts at 200 oC: SBA@250, SBA@190, SBA@ 102, SBA
@76, SBA@ 50 and SBA@27. Other detected products (<1% selectivity)
include MEK, MVK, 1-butanol, 2-butanol and 3B2ol. The numbers in paren-
theses on top of the yield bars indicate the carbon balance, whereas the num-
bers in parentheses in the abscissa axis indicate the density of weak acid sites
on the fresh and spent samples expressed in mol/g (Table 2). Additional
reaction conditions as in Table 1.
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The catalytic performance of the SBA@X catalysts at 200 oC
was very sensitive to the SiO2/Al2O3 ratio (Figure 5). The 1,3-
BDO conversion increased from 61% for SBA@250 to pass
through a maximum at 98% for SBA@76, then dropped slightly
to 93% for SBA@27. The maximum BD yield (59%) was achie-
ved over SBA @76, resulting in a BD productivity as high as 4.9
gBD.gcat-1.h-1. Noteworthy, this productivity is about one order of
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catalytic properties over SBA@76 suggests that this catalyst
presented an optimal distribution of acid sites for BD production.
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weak and medium strength, we can argue that these sites are
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In conclusion, an Al-SBA catalyst with an optimal SiO2/Al2O3
ratio of 76 afforded a stable butadiene yield of 59% at a tempe-
rature as low as 200 oC in the gas-phase dehydration of 1,3-
butanediol. The presence of native Brønsted acid sites with
weak and medium strength was indispensable to achieve a high
selectivity to butadiene as inferred from combined NH3-TPD,
pyridine adsorption-IR, and 27Al-NMR MAS. Carbon deposition
over strong Lewis and Brønsted acid sites was unavoidable
under the reaction conditions. As a result, a decrease of the sur-
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Acknowledgements
Solvay is acknowledged for financial support. The REALCAT
platform is also acknowledged for support in the XRF tests. The
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Entry for the Table of Contents (Please choose one layout)
Layout 1:
COMMUNICATION
An Al-SBA-15 catalyst with a silica/
alumina ratio of 76 was very active
and selective for the production of bu-
Fangli Jing, Benjamin Katryniok,
Sébastien Paul, Lin Fang, Armin
Liebens, Ming Shen, Bingwen Hu,
Franck Dumeignil and Marc Pera-Titus
Coke
tadiene by dehydration of 1,3-butane-
diol at 200 oC due to the generation of
a family of Brnsted acid sites of weak
and medium strength during reaction.
Page No. – Page No.
Al-doped SBA-15 catalysts for low-
temperature dehydration of 1,3-
butanediol into butadiene
Weak
acidity
Medium
acidity
Strong
acidity
Strong
acidity
Temperature (oC)
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