Vapor-phase catalytic dehydration of 2,3-butanediol into 3-buten-2-ol over Sc2O3

Article abstract of DOI:10.1246/cl.140662

Vapor-phase catalytic dehydration of 2,3-butanediol (2,3-BDO) was investigated over rare earth oxide (REO) catalysts as well as In₂O₃. In the dehydration of 2,3-BDO, 3-buten-2-ol (3B2OL) was produced together with 3-hydroxy-2-butanone (3H2BO), butanone (MEK), 2-methylpropanal (IBA), 2-methyl-1-propanol (IBO), etc. Sc₂O₃ and In₂O₃ showed hi gher 3B2OL select ivities than other REOs. In particular, Sc₂O₃ converted 2,3-BDO into 3B2OL with an excellent selectivity of 85.0% at 99.9% conversion.

Full text of DOI:10.1246/cl.140662

Received: July 11, 2014 | Accepted: July 29, 2014 | Web Released: August 5, 2014
CL-140662
Vapor-phase Catalytic Dehydration of 2,3-Butanediol into 3-Buten-2-ol over Sc2O3
Hailing Duan, Yasuhiro Yamada, and Satoshi Sato*
Graduate School of Engineering, Chiba University, Yayoi, Inage-ku, Chiba 263-8522
(E-mail: satoshi@faculty.chiba-u.jp)
Vapor-phase catalytic dehydration of 2,3-butanediol (2,3-
BDO) was investigated over rare earth oxide (REO) catalysts as
well as In2O3. In the dehydration of 2,3-BDO, 3-buten-2-ol
(3B2OL) was produced together with 3-hydroxy-2-butanone
(3H2BO), butanone (MEK), 2-methylpropanal (IBA), 2-methyl-
1-propanol (IBO), etc. Sc2O3 and In2O3 showed higher 3B2OL
selectivities than other REOs. In particular, Sc2O3 converted
2,3-BDO into 3B2OL with an excellent selectivity of 85.0% at
99.9% conversion.
with the smallest cation radius always shows great selective
catalytic activity in the dehydration of terminal diols with
long carbon chain such as 1,6-hexanediol, 1,7-heptanediol,
1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-
dodecanediol to the corresponding unsaturated alcohols.15,16
In this paper, we investigated the dehydration of 2,3-BDO over
the REOs and bixbyite In2O3, which has catalytic activity in
the dehydration of 1,4-butanediol to produce 3-buten-1-ol.17,18
The catalytic reaction was performed in a fixed-bed down-
flow glass reactor at an atmospheric pressure. Prior to feeding
the reactant, the catalyst bed has been preheated in an H2 flow at
325 °C for 1 h. The reactant was fed into the reactor at a rate
of 1.06 g h¹1. The liquid products recovered every hour at 0 °C
were analyzed on a gas chromatograph (FID-GC, Shimadzu
GC-8A, Japan) with a 60-m capillary column (DB-WAX). The
products were identified by gas chromatography with a mass
spectrometer (GCMS-QP5050A, Shimadzu) and a 30-m capil-
lary column (DB-WAX). Gaseous products such as 1,3-
butadiene were analyzed by online gas chromatography (GC-
8A) with a 6-m packed column (VZ-7).
Table 1 shows that all the REOs showed their catalytic
activities to convert 2,3-BDO into 3B2OL with great differences
in the yield. The main by-products were 3H2BO and MEK,
but BD was a rare product. It also suggests that at such a low
reaction temperature of 325 °C, the REO catalysts such as
Y2O3, Pr6O11, Nd2O3, La2O3, Sm2O3, and Tb4O7 showed high
dehydrogenation abilities to 3-hydroxy-2-butanone (3H2BO)
rather than the dehydration abilities to 3B2OL. On the other
hand, the selectivity to 3B2OL over Yb2O3 and Dy2O3 exceeds
20%. In contrast, Sc2O3, In2O3, and ZrO2 effectively catalyzed
the dehydration of 2,3-BDO to produce 3B2OL. Especially,
Sc2O3 gave not only the highest 3B2OL selectivity of
85.0 mol % but also a conversion of 99.9% in an average of
the initial 5 h. Next to Sc2O3, In2O3 as well as ZrO2 showed
high catalytic activity to produce 3B2OL with a 65.8%
selectivity at a 59.4% conversion. We have discussed the
properties and the activities of ZrO2 in our previous work.12
In the present work, we will focus on the catalytic activities of
Sc2O3 and In2O3.
With the development of biotechnology, 2,3-butanediol
(2,3-BDO) can be produced from biomass via fermentation, and
it is expected to be a chemical resource.1-4 The dehydration
of 2,3-BDO to 1,3-butadiene (BD), butanone (MEK), and 3-
buten-2-ol (3B2OL) (Scheme 1) has been investigated since the
1940s.5-9 It seems that the dehydration of 2,3-BDO generally
results in good yields of MEK over acidic catalysts.6-9 In the
pioneering work of Winfield, it was reported that ThO2
catalyzed the dehydration of 2,3-BDO into 3B2OL with a yield
of 70.3% at 350 °C, and a BD yield of 62.1% was obtained with
a 3B2OL yield of 8.4% at 500 °C.5 It is also known that 3B2OL
is used as an important intermediate in the synthesis of monomer
esters and medicines.10,11 3B2OL production from bio-2,3-BDO
is highly anticipated. Unfortunately, ThO2 cannot be applied as
an industrial catalyst due to its radioactivity.
In order to find safe catalysts for the formation of 3B2OL
from 2,3-BDO, we have investigated several possible metal
oxide catalysts and found that highly crystallized monoclinic
ZrO2 exhibits high catalytic activity in the dehydration of 2,3-
BDO to 3B2OL (Scheme 1).12 However, the catalytic activities
of rare earth oxides (REOs), which have always performed well
as catalysts for dehydration, have not been confirmed, except
La2O3 and Yb2O3.
In our previous work, we have also reported several
examples of the syntheses of unsaturated alcohols in the
vapor-phase catalytic dehydration of alkanediols over REOs.13
Catalytic activity of REOs depends on the position of OH
groups of reactant diols: 1,3-diols are effectively dehydrated
into 3B2OL and 2-buten-1-ol by CeO2; 1,4-butanediol can be
dehydrated to 3-buten-1-ol by Er2O3, Yb2O3, and Lu2O3;13 1,5-
pentanediol to 4-penten-1-ol by Sc0.5Yb1.5O3.14 Lattice parame-
ters of the cubic REOs seem to affect the adsorption and
activation of alkanediols.14 Among all the REO catalysts, Sc2O3
Figure 1 shows the relationship between the formation rate
of 3B2OL from 2,3-BDO and the average ionic radius of the
rare earth metal cations, In3+, and Zr4+. In our previous work,
we found that REO with small ionic diameter of rare earth metal
cation is effective in the formation of unsaturated alcohols from
diols.13 In the present work, the highest formation rate of 3B2OL
was obtained at the smallest ionic radius of Sc3+, although the
rate for Sc2O3 at 325 °C was underestimated due to the high
conversion. This indicates that an active site may generate on
surface adsorption sites of a compact size over Sc2O3 catalyst. It
is reasonable that In2O3 and ZrO2 also displayed high formation
rate of 3B2OL since their ionic radii are just next to Sc2O3.
A similar tendency was also observed in the dehydration of
HO
O
O
REO
+
OH
+
OH
OH
2,3-BDO
3B2OL
3H2BO
MEK
Scheme 1. Conversion of 2,3-BDO into 3B2OL over REOs.
Chem. Lett. 2014, 43, 1773–1775 | doi:10.1246/cl.140662
© 2014 The Chemical Society of Japan | 1773

Table 1. Synthesis of 3B2OL from 2,3-BDO over REOs calcined at
800 °C for 3 h
Table 2. Dehydration of 2,3-BDO over Sc2O3 calcined at different
temperatures
Selectivity/mol %a
3B2OL MEK 3H2BO Othersb
Selectivity/mol %a
3B2OL MEK 3H2BO Othersb
Catalyst
(1.0 g)
Conversion
/mol %a
Calcination
temp./°C
SA
/m2 g
Conv.
/mol %a
¹1
Sc2O3
In2O3
ZrO2
Sc1.5Yb0.5O3
ScYbO3
Sc0.5Yb1.5O3
Lu2O3
Yb2O3
Tm2O3
Er2O3
Y2O3
Ho2O3
Dy2O3
Tb4O7
Gd2O3
Eu2O3
Sm2O3
CeO2
99.9
59.4
62.5
35.1
28.4
22.6
16.5
17.5
1.9
14.3
11.5
7.3
11.3
9.9
85.0
65.8
48.6
53.4
47.8
33.6
19.8
28.1
0.0
14.5
7.6
3.9
20.3
3.9
12.9
4.3
2.8
4.0
16.0
3.1
3.9
3.8
7.6
1.8
6.7
2.4
2.7
17.1
3.9
3.2
4.8
4.3
2.8
36.5
5.4
6.2
7.3
0.2
16.5
14.9
16.7
23.7
34.3
42.4
39.5
40.2
45.9
49.7
39.8
40.9
53.6
45.4
43.8
52.2
21.5
49.4
51.8
47.8
12.0e
13.7e
20.5e
26.8
24.6
28.3
30.2
30.6
53.1
37.2
40.0
39.2
34.9
39.3
36.9
47.6
39.4
40.7
40.4
40.7
39.9
As-obtained
600
98.4
72.1
66.2
51.5
51.5
45.4
31.9
69.8
99.0
97.1
99.9
96.6
95.8
94.7
19.7
91.0
10.5
96.5
52.3
79.8
83.1
85.0
72.1
84.1
84.8
71.8
88.3
50.6
88.2
9.2
4.9
4.0
2.8
7.5
4.3
4.9
4.5
2.0
12.4
1.4
11.4
0.3
0.9
4.9
1.0
1.1
1.2
12.9
1.3
21.2
3.5
27.1
15.0
12.0
7.3
19.4
10.5
9.1
10.8
8.4
15.8
6.9
c
700
800
800c
900
1000
d
d
d
c
As-obtainedd 33.0
800d
As-obtainede
800e
28.0
®
10.7
aReaction temperature, 325 °C; carrier gas, H2, 45 cm3 min
catalyst weight, 1.0 g; average conversion and selectivity in the
initial 5 h. The specific surface areas of the Sc2O3 catalyst supplied
by Kanto Chemical Co., Inc. were cited from ref 20. bOthers
;
¹1
10.0
10.9
8.9
39.1
7.4
include IBA, IBO, BD, propylene, ethylene, 1- and 2-butanol, etc.
5.6
1.3
4.8
1.3
cCarrier gas, N2, 45 cm3 min
.
dSupplied by Mitsuwa Chemical
¹1
Co., Ltd., carrier gas H2, 80 cm3 min
.
eSupplied by Sigma-
¹1
Nd2O3
Pr6O11
La2O3
Aldrich Co., Ltd., carrier gas H2, 45 cm3 min
.
¹1
8.2
7.0
c
5.0
terminal diols such as 1,6-hexanediol and 1,10-decanediol: the
highest formation rate of the corresponding unsaturated alcohols
is obtained over Sc2O3.16
aReaction temperature, 325 °C; carrier gas, H2, 45 cm3 min¹1; all
the REO catalysts were purchased from Kanto Chemical Co., Inc.
Average conversion and selectivity in the initial 5 h. bOthers
include IBO, IBA, BD, propylene, ethylene, 1- and 2-butanol, etc.
cData cited from ref 12. dSamples were prepared in ref 14. eDetail
product distribution is summarized in Supporting Information.
Table 2 summarizes the catalytic dehydration of 2,3-BDO
over Sc2O3 calcined at different temperatures. High calcination
temperature enhanced the catalytic activities of Sc2O3 for the
selective formation of 3B2OL. The calcination led to large
Sc2O3 catalyst particles with a well-crystallized structure,19
which might have offered small but active surface for the
dehydration of 2,3-BDO to 3B2OL. In order to confirm the roles
of calcination, Sc2O3 samples supplied by other suppliers such
as Mitsuwa Co., Ltd. and Sigma-Aldrich, Co., Ltd. were also
investigated as comparison. After being calcined at 800 °C,
they showed not only high conversions but also high 3B2OL
selectivities. These results are in good accordance with that of
Sc2O3 purchased from Kanto Chemical Co., Inc.
The catalytic activities of In2O3 calcined at different tem-
peratures were also investigated (Table 3). In2O3 with the same
bixbiyte structure17 as Sc2O3 also showed a high conversion of
2,3-BDO, whereas the highest selectivity was obtained when it
was calcined at a low temperature of 400 °C but not at 800 °C.
Figure 2 shows the effect of reaction temperature on the
catalytic activity of Sc2O3 and In2O3. The conversion of 2,3-
BDO increases with increasing reaction temperature over Sc2O3
and In2O3. Both of them showed the highest yield to 3B2OL at
325 °C. The selectivity to 3B2OL decreased while BD increased
slightly with increasing reaction temperature.
Cubic bixbyite
Cubic flourite
Monoclinic
Monoclinic+Cubic
Hexagonal
Sc
0.2
0.1
0
In
Zr
a, Sc0.75Yb0.25
b, Sc0.5Yb0.5
c, Sc0.25Yb0.75
Sc
(300°C)
Sc
Lu Er
Gd
Y
(275°C)
Yb
Ce
Dy
b
a
Eu
Ho
Nd
c
Tm
Tb
Sm Pr
La
0.07
0.08
0.09
0.1
0.11
Figure 3 shows the change in the catalytic activity with time
on stream over Sc2O3 catalyst calcined at 800 °C. It was
confirmed that the catalytic activity of Sc2O3 was stable at
325 °C: 100% conversion of 2,3-BDO was maintained in the
initial 5 h of the reaction, and the selectivity to 3B2OL slightly
increased with time on stream. At low temperatures, the
conversions are stable in the initial periods. On the other hand,
In2O3 calcined at 400 °C showed slight decline in the 2,3-BDO
conversion at 325 °C (Figure not shown).
Ionic radius /nm
Figure 1. Formation rate of 3B2OL in the 2,3-BDO dehydration at
325 °C with average ionic radius of rare earth cations. Rate data were
calculated from the conversion data in Table 1 and Figure 3. The ionic
radius of trivalent rare earth cations with coordination number 6 (Ce4+
with coordination number 8) was cited from the work of Shannon,19
and the specific surface area of the REO catalysts used for calculating
the formation rate and crystal phase were cited from our previous
work.12,14,20
1774 | Chem. Lett. 2014, 43, 1773–1775 | doi:10.1246/cl.140662
© 2014 The Chemical Society of Japan

Table 3. Dehydration of 2,3-BDO over In2O3 calcined at different
temperatures
100
80
60
40
20
325°C
300°C
Selectivity/mol %a
3B2OL MEK 3H2BO Othersb
Calcination Conversion
temp./°C
/mol %a
As-obtained
400
66.5
51.9
98.0
55.7
72.9
73.6
79.6
75.2
75.2
68.5
1.7
1.5
4.9
1.9
1.8
7.8
11.6
7.8
14.3
9.2
16.9
7.3
12.1
8.6
Conv.
400c
3B2OL Selec.
600
800
20.5
¹1
aReaction temperature, 305 °C; carrier gas, H2, 45 cm3 min
;
catalyst weight, 1.0 g; average conversion and selectivity in the
initial 5 h. bOthers mainly include IBA, IBO, BD, propylene,
275°C
c
¹1
ethylene, 1- and 2-butanol. Carrier gas, N2, 45 cm3 min
.
0
1
2
3
4
5
100
Time on stream / h
a
(A) Sc2O3
Figure 3. Stabilities of Sc2O3 calcined at 800 °C in the dehydration
80
of 2,3-BDO at different temperatures; the flow rate of H2,
¹1
45 cm3 min¹1; catalyst weight, 1.0 g; feed rate of 2,3-BDO, 1.06 g h
.
b
60
stable conversion of 99.9% at 325 °C. In2O3 calcined at 400 °C
also showed a good selectivity of 79.6% to 3B2OL at 2,3-BDO
conversion of 51.9%. Calcination at proper temperatures could
produce the well-crystallized structure of Sc2O3 (800 °C) and
In2O3 (400 °C) for the formation of 3B2OL with a high
selectivity.
40
20
c
d
e
Supporting Information is available electronically on J-STAGE.
0
260
280
300
320
340
360
Reaction temperature /°C
Reference
100
1
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d
c
360
260
280
300
320
340
Reaction temperature /°C
Figure 2. Influence of reaction temperature on the dehydration of
2,3-BDO over (A) Sc2O3 calcined at 800 °C and (B) In2O3 calcined
at 400 °C. (a) Conversion of 2,3-BDO, (b) selectivity to 3B2OL,
(c) selectivity to BD, (d) selectivity to MEK, and (e) selectivity to
3H2BO; the flow rate of H2, 45 cm3 min¹1; catalyst weight, 1.0 g; feed
¹1
rate of 2,3-BDO, 1.06 g h
.
It is concluded that 3B2OL can be obtained over Sc2O3 and
In2O3 in the vapor-phase 2,3-BDO conversion. In particular,
Sc2O3 calcined at 800 °C effectively catalyzed the dehydration
of 2,3-BDO with an excellent 3B2OL selectivity of 85.0% and a
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Chem. Lett. 2014, 43, 1773–1775 | doi:10.1246/cl.140662
© 2014 The Chemical Society of Japan | 1775