One-Step Production of 1,3-Butadiene from 2,3-Butanediol Dehydration

Article abstract of DOI:10.1002/chem.201602390

We report the direct production of 1,3-butadiene from the dehydration of 2,3-butandiol by using alumina as catalyst. Under optimized kinetic reaction conditions, the production of methyl ethyl ketone and isobutyraldehyde, formed via the pinacol–pinacolone rearrangement, was markedly reduced and almost 80 % selectivity to 1,3-butadiene and 1,3-butadiene could be achieved. The presence of water plays a critical role in the inhibition of oligomerization. The amphoteric nature of γ-Al₂O₃was identified as important and this contributed to the improved catalytic selectivity when compared with other acidic catalysts.

Full text of DOI:10.1002/chem.201602390

DOI: 10.1002/chem.201602390
Communication
&
Catalysis
One-Step Production of 1,3-Butadiene from 2,3-Butanediol
Dehydration
Xi Liu,[a, c] Viktoria Fabos,[a] Stuart Taylor,[a] David W. Knight,[a] Keith Whiston,[b] and
Graham J. Hutchings*[a]
Recent work has revealed the potential of 2,3-butandiol
Abstract: We report the direct production of 1,3-buta-
diene from the dehydration of 2,3-butandiol by using alu-
mina as catalyst. Under optimized kinetic reaction condi-
tions, the production of methyl ethyl ketone and isobutyr-
aldehyde, formed via the pinacol–pinacolone rearrange-
ment, was markedly reduced and almost 80% selectivity
to 1,3-butadiene and 1,3-butadiene could be achieved.
The presence of water plays a critical role in the inhibition
of oligomerization. The amphoteric nature of g-Al2O3 was
identified as important and this contributed to the im-
proved catalytic selectivity when compared with other
acidic catalysts.
(BDO) as a promising C4 platform chemical for use in a variety
of industrial applications.[4,5] BDO had been used as the precur-
sor to produce deacetyl, butenes, or 1,3 butadiene before the
availability of processes based on the ready availability of inex-
pensive fossil hydrocarbons were introduced in the 1950s. At
present, BDO has only limited industrial applications as a food
flavor additive.[6] However, the development of the biomass in-
dustry and the abundance of BDO as a by-product have reig-
nited interest in the catalytic conversion of BDO, in particular
its dehydration to 1,3-butadiene (BDE). At present, attempts to
directly produce BDE with a high yield have failed and the re-
action to methyl ethyl ketone, the thermodynamically pre-
ferred product, always predominates.[7–9] The mechanism is
well understood since the consecutive dehydration of the adja-
cent two hydroxyl groups leads to an enol which readily forms
methyl ethyl ketone (MEK). To achieve high yields of the re-
quired product, a two-step process has been designed to con-
vert the diol into the diene by using an acid as an esterifying
agent, or catalytic reductive deoxygenation in the presence of
H2 has been used.[10–12] Both processes are not environmentally
benign and make industrial production less attractive due to
usage of either a stoichiometric acid or a reductant. In addi-
tion, biomass-derived polyols are formed at low concentrations
in aqueous solution. Refining these crude aqueous solutions,
using distillation or membrane separation, is an endothermic
reaction requiring a high-energy input, which also hinders the
overall potential catalytic conversion process.[13,14]
The use of renewable biomass as a resource for chemical and
fuel production has been gaining increasing attention during
the last two decades. This is in response to the present global
challenge related to the use of fossil fuels and the environmen-
tal problems to which their use may contribute. However, in-
stalled production capacity based on renewable resources has
not reached the levels anticipated for economic reasons and it
has increased at a slower rate than originally forecast.[1] One of
the key problems is the production of vast amounts of lower
value by-products which have limited applications, for in-
stance, glycerol generated from biodiesel production and buta-
nediols generated from biomass fermentation or wood hydrol-
ysis. These by-products potentially make the overall process
less efficient and non-profitable.[2] Therefore, the development
of value-added uses for the crude biomass-derived by-products
or the so-called ‘biomass waste’ will contribute to the viability
of the nascent biomass industry.[3] Besides the reduction of
waste with a reduced impact on the environment, the recovery
of energy and useful feedstocks could make these processes
economically practical and competitive against present indus-
trial processes based on readily available fossil fuels.
Here we report a facile method to produce BDE with almost
100% selectivity via the direct dehydration of aqueous BDO
using a commercial alumina catalyst. High selectivity to buta-
diene is achieved by using high flow rates and a smaller
amount of catalysts. Our work suggests that under these opti-
mized kinetic reaction conditions the consecutive dehydroxyla-
tion via 1,2-elimination to BDE by an E2 mechanism is favored.
The activities for the dehydration of BDO (10 wt%) using
a range of catalysts were investigated (Table 1). In most cases,
by using a relatively large amount of catalyst (0.5 g), the major
product was always MEK, which was produced via partial dehy-
dration followed by the pinacol–pinacolone rearrangement
(Equations 1–5).[15] The major by-product was isobutyraldehyde
(IBA), which also generated via the pinacol–pinacolone rear-
rangement (Equations 1, 2, 6–8). BDE was only observed as
a minor product for almost all catalysts, except g-Al2O3, where
BDE selectivity was 21% at 3508C (Table 1, entry 13). This was
almost double the selectivity observed using bentonite and
[a] Dr. X. Liu, Dr. V. Fabos, S. Taylor, Prof. D. W. Knight, Prof. G. J. Hutchings
Cardiff Catalysis Institute, School of Chemistry
Cardiff University, Cardiff CF10 3AT (UK)
E-mail: hutch@cardiff.ac.uk
[b] Dr. K. Whiston
INVISTA Textiles (UK) Limited, P.O. Box 2002,
Wilton Redcar TS10 4XX (UK)
[c] Dr. X. Liu
Syncat@Beijing, Synfuels China Technology Co.,Ltd,
Beijing 101407 (China)
Chem. Eur. J. 2016, 22, 1 – 6
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Table 1. Catalytic performance of various oxides catalysts.[a]
Catalyst
Temp. Conv.
[8C] [%]
Selec. [%]
Carbon
BDE IBA MEK BTO Enenol balance [%]
1
2
3
4
5
6
7
8
9
SiWO/SiO2 350
SiWO/SiO2 260
100 3.7 5.1 91.1
–
–
–
–
–
7.5
–
–
6
3
–
–
–
–
–
–
–
–
–
7
2
–
–
–
4
–
98
80
100
95
99
102
100
75
75
80
100
100
97
96
100
95
95
94
95
60
94
98
98
86
97
34
99
99
0.1
0
0.5 10 89
13 17 70
6.4 12 81
13 17 70
2.5 14 77
1.1 15 84
SiO2
SiO2
350
260
bentonite 350
bentonite 260
CeO2
SAB-6
MoO3
350
350
350
350
350
260
350
260
7
3.8
2
9
8
84
74
10 WO3
12 80
11 a-Al2O3
12 a-Al2O3
13 g-Al2O3
14 g-Al2O3
15 quatz wool 350
16 SiC
18 12 70
7.9
21
7
83
73
80
–
–
4
–
3
5
45 55
350
350
17 graphite
0
[a] Reaction conditions: 10 wt% BDO, 0.02 mLminÀ1
;
75 mLminÀ1 Ar,
500 mg catalysts, BDE, IBA, MEK, BTO, and enenol represent 1,3-buta-
diene, isobutyraldehyde, methyl ethyl ketone, 3-buten-2-ol and other bu-
tenols (2-buten-1-ol and 3-buten-1-ol), respectively.
SiO2 under the identical conditions (Table 1, entries 3 and 5).
Compared to g-Al2O3, a-Al2O3 showed lower productivity of
BDE and much higher productivity of IBA at 3508C (Table 1,
entry 11). At a lower temperature (2608C), the selectivity to
BDE when using g-Al2O3 decreased markedly to 7% at almost
complete conversion. At 2608C, we investigated the influence
of the BDO concentration on the catalytic performance of g-
Al2O3 and complete conversion of BDO was always observed
(Table 2). However, the use of 100% BDO does not favor the
overall catalytic performance as a low carbon balance was ob-
The use of alumina as a catalyst for the dehydration of BDO
has been reported previously,[16] when 42% selectivity to BDE
with 100% BDO conversion was obtained in the presence of
H2. In our case we do not require the presence of H2 to achieve
higher selectivities. Generally, only very limited work can be
found over the past 80 years concerning the selective produc-
tion of BDE from BDO dehydration, apart from the use of
thoria in 1945, which has never been used commercially due
to the radioactive nature of the catalyst.[7] Therefore, there is
no previous mechanistic work on the production of BDE via
stepwise dehydration of BDO. With other oxides such as MoO3
and WO3, low carbon balances were observed due to the pro-
duction of cracking products, for example, propene and pro-
pane. This suggests a negative role of redox-active catalysts in
the dehydration reaction, which could lead to CÀC bond fis-
sion.
Table 2. Catalytic performance of U-Al2O3 at different BDO concentra-
tions.[a]
Catalyst Conc. Conv
Selec.%
Carbon
[%]
[%]
BDE IBA MEK BTO Enenol balance [%]
g-Al2O3
100
95
50
96
99
100
99
4
5
7
7
4
4
3
5
90
89
89
80
2
2
0
4
–
–
0
4
87
96
100
96
10
[a] Reaction conditions: 10 wt% BDO, 0.02 mLminÀ1
500 mg catalysts.
;
75 mLminÀ1 Ar,
We noted that, even at lower temperature (2608C), almost
100% conversion could be obtained with g-Al2O3 (Table 1,
entry 14). Clearly this indicated that we were using too much
catalyst and the reaction was not being operated under kinetic
reaction conditions. Hence, we decreased the amount of the
catalyst from 500 mg to 3 mg (Table 3, entry 1 to 4). For com-
parison, we also tested other oxides and acid catalysts under
the identical conditions. Obviously, employment of lower
amounts of the catalysts led to lower conversions of BDO.
Simultaneously, selectivity to butadiene increased markedly.
This suggested that the presence of diffusion control or strong
served (Table 2, entry 1), which could be attributed to the pro-
duction of di- and tri-oligomers which remained on the cata-
lyst. Addition of a small amount of water (5 wt%) significantly
improved the carbon balance from 86% to 96% (Table 2,
entry 2). No loss in carbon balance was observed upon further
dilution even with high levels of water (i.e. 10 wt% BDO). This
confirmed that the presence of water was key for the inhibi-
tion of oligomerization.[16]
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Table 3. Catalytic activities of oxides and acid catalyst with different cata-
lyst amount.[a]
Table 5. Catalytic performance of various oxides catalysts as function of
flow rate.[a]
Catalyst Mass Conv
[mg] [%]
Selec.%
Carbon
Catalyst Flow rate Conv.
[mLminÀ1] [%]
Selec. [%]
Carbon
BDE IBA MEK BTO Enenol balance [%]
BDE IBA MEK BTO Enenol Balance [%]
1
2
3
4
5
6
7
8
g-Al2O3 500 99
21
22
36
50
3
73
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
97
1
2
3
4
5
6
7
8
g-Al2O3 15
54
45
43
30
20
18
16
13
11
14
2.2
25
6
10
18
8
81
81
98
99
97
97
98
97
95
97
96
101
99
99
98
40
6
100
35
13 65
23 46
47
100
100
98
98
100
98
99
97
97
98
30
45
60
75
20 20 61
35 20 45
50
55 12 32
60 11 29
60 13 11
3
20
SiO2
500 100
3.7 5.1 91.1
16.7 14 69
17
21
3
47
40
10
3
100
23
6
100
82
150
200
300
75
30 49
6
36 55
30 60
12 69
15
40
9
10
11
SiWO
500 100
89
9
41 19
0
40
3
90
14
6
10 SiWO
11
12 a-Al2O3 75
13 300
10 30 60
29 31 36
26 24 50
32 34 30
10
17
23
26
300
5
12 a-Al2O3 500 97
13
14
100
95
99
5
3
67
25
9
67
4
24 50
[a] Reaction conditions: 10 wt% BDO, 0.02 mLminÀ1
3508C
,
3 mg catalysts,
[a] Reaction conditions: 10 wt% BDO, 0.02 mLminÀ1; 75 mLminÀ1 Ar, cata-
lysts, 3508C.
adsorption/re-adsorption, which could reduce the production
of butadiene was present when using large amounts of the
catalyst. The best selectivity of 50% to BDE was still obtained
by using g-Al2O3. The difference in catalytic performance be-
tween g-Al2O3 and a-Al2O3 was also observed; while the former
favored production of BDE and MEK, the latter produced MEK,
BDE, as well as IBA. This suggests that moderate acidity is the
key factor for the selective dehydration of BDO. Reproducibility
of the catalytic performance of g-Al2O3 was also investigated
which confirms the low variability in the results using three
independent tests (Table 4).
Figure 1. Catalytic activity of g-Al2O3 as a function of flow rate.
Table 4. Catalytic performance of U-Al2O3 at different batch.[a]
BDE increased to 60% and the conversion decreased to 18%.
However, with the highest flow rate, the selectivity to BDE did
not increase, but decreased to 40% with the production of
3-buten-2-ol (BTO). No production of MEK was observed with
the highest flow rate of 300 mLminÀ1. This suggested that the
production of BDE came from further dehydration of BTO, gen-
erated via a b-hydride elimination from the terminal methyl
group. In this case, production of MEK via the pinacol–pinaco-
lone rearrangement decreased with higher flow rate. This sug-
gests strong dependence of BDE and MEK on the flow rate
should be associated with different reaction pathways. More-
over, we found that the higher flow rates also favored the pro-
duction of BDE by using other catalysts, such as a-Al2O3 and
silica tungstic acid. This suggests that this is a general trend,
correlated with the production of BDE via a consecutive two-
step dihydroxylation process (Scheme 1), which can be cata-
lyzed by the acidic active sites in these catalysts. However, the
stronger acidity of silicotungstic acid does not favor the pro-
duction of BDE,[17] which suggests moderate acidity is the key
requirement for BDE formation. It is possible that stronger
acidity leads to the isomerization reactions and the production
of MEK and IBA.
Catalyst Batch Conv.
[%]
Selec. [%]
Mass
BDE IBA MEK BTO Enenol balance [%]
g-Al2O3
blank
SiC[b]
1
2
3
1
2
3
1
2
3
20
19
21
0
0
0
1
2
1.5
50
53
52
0
0
0
1
2
–
47
47
48
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
98
96
100
101
100
100
99
98
98.5[c]
[a] Reaction conditions: 10 wt% BDO, 0.02 mLminÀ1, 3 mg g-Al2O3, 3508C.
[b] The whole reactor was filled with SiC. [b] No production of BDE, IBA
or other products was identified.
To reduce the re-adsorption and diffusion-control, we adjust-
ed the contact times by changing the carrier gas flow rate
from 15 mLminÀ1 to 300 mLminÀ1 under the same reaction
conditions using 3 mg g-Al2O3 (Table 5 entry 1 to 9, and
Figure 1). At the lowest flow rate, about 50% conversion of
BDO was observed but with only 10% selectivity to BDE. As
the flow rate was increased to 150 mLminÀ1, the selectivity to
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stable at reaction temperatures ranging from 300 to 3508C,
while no production of MEK was detected. However, at the
higher temperature, production of MEK was observed and in-
creased as a function of reaction temperature. It is suggested
that production of IBA and MEK via the pinacol–pinacolone
rearrangement may occur under different reaction conditions,
with the latter product favored by higher reaction tempera-
ture. The results also suggested that the carbonium ion (Equa-
tion 2) formed via acid-catalyzed extraction of the OH group,
might be the key intermediate for the generation of IBA, BTO,
BDE, and MEK (Scheme 1). Strong acidity or higher tempera-
tures favor the production of MEK due to either strong adsorp-
tion on the catalyst or instability of the intermediate at the
higher temperature. Weaker adsorption assigned to moderate
acidity and decreased re-adsorption could promote the step-
wise elimination of hydroxyl groups, which improved the pro-
duction of BDE.
Scheme 1. Methyl ethyl ketone, isobutyraldehyde and 1,3-butadiene derived
in the dehydration of 2,3-butanedioldehydration.
The performance of g-Al2O3 was also studied under the opti-
mized reaction conditions (Figure 2 and Table 6). No activity of
Dehydration of 3-buten-2-ol by using g-Al2O3 was tested
under similar reaction conditions (10 wt% BTO in water,
0.02 mLminÀ1, 3 mg catalysts, 300 mLminÀ1 Ar, Table 7) to
Table 7. Catalytic dehydration of 3-buten-2-ol.[a]
Catalyst
Temp. Conv.
Selec.%
Carbon
[8C]
[%]
BDE IBA MEK Enenol Balance [%]
g-Al2O3
350
94
96 100
4
–
–
[a] Reaction conditions: 10 wt% 3-buten-2-ol in water, 0.02 mLminÀ1
3 mg catalysts, 300 mLminÀ1 Ar.
,
those used previously for BDO. Almost complete transforma-
tion of BTO to BDE was observed with only a small amount of
IBA being detected in the products. The production of IBA
could be attributed to the rearrangement of 3-buten-2-ol or
addition of water to BDE.
Figure 2. Catalytic activity of g-Al2O3 as a function of reaction temperature.
Table 6. Catalytic performance of g-Al2O3 catalysts at different tempera-
tures.[a]
In this work, g-Al2O3 has been confirmed as a catalyst for the
direct dehydration of BDO to BDE, a valuable monomer for the
production of synthetic rubber. By using trace amounts of cat-
alyst and a high flow rate in a fixed bed reactor, 10% BDO con-
version could be achieved with >80% selectivity to BDE and
BTO. The presence of water efficiently improved the overall
catalytic performance by reducing oligomerization of BDE.
Catalyst Temp. Conv.
Selec. [%]
Carbon
[8C]
[%]
BDE IBA MEK BTO Enenol Balance [%]
1
2
3
4
5
6
7
8
9
g-Al2O3 150
0
1
2
8
–
–
5
52
59
41
57
60
55
–
–
–
–
–
–
0
–
–
–
–
–
6
-
–
–
–
–
200
250
300
340
350
360
380
400
100
78
21
20
19
26 13
15 21
17 24
100
100
99
101
96
98
99
90[b]
17
21
21
40
4
9
11
12
12
18
Experimental Section
5
3
Catalysts, including a-Al2O3 (99.8% trace metal basis, N2 BET surface
area, 1 m2gÀ1) and g-Al2O3 (99.8% trace metal basis, N2 BET surface
area, 105 m2gÀ1) were purchased from Sigma Aldrich and used as
received, and silica tungstic acid was obtained from Johnson Mat-
they. Catalytic dehydration was conducted by using a laboratory
fixed bed reactor equipped with a vaporizer. 2,3-Butanediol (BDO,
10 wt% aqueous solution) was pumped into the middle of the va-
porizer with a flow rate of 0.02 mLminÀ1 where it was vaporized in
a flow of argon carrier gas and fed to the catalyst. The temperature
of the vaporizer was set to the same as the reaction temperature.
All of the catalysts were pressed and sieved to a uniform particle
size distribution of 600–800 mm before use and were packed into
[a] Reaction conditions: 10 wt% BDO, 0.02 mLminÀ1
300 mLminÀ1 Ar. [a] Mass production of propene.
,
3 mg catalysts,
g-Al2O3 was observed at 1508C. At low temperatures (200–
2508C), IBA is the major product with lower production of BDE
and BTO. Once the reaction temperature was increased to
3008C, the selectivity to IBA decreased from 78% to 21%,
whilst the conversion of BDO simultaneously increased from
2% to 8%. The catalytic performance of g-Al2O3 was quite
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a 0.8 mm i.d. stainless steel reactor between plugs of quartz wool.
Catalyst amounts ranged from 3–500 mg. A glass collection vessel
filled with distilled water was connected to the end of the reactor,
which was cooled with ice-water, and then gaseous products were
collected in a gas bag.
Acknowledgements
The authors wish to acknowledge the support of INVISTA Inter-
mediates.
For the first hour of the reaction the products were expelled
through a vent and the product collection was started only from
the second hour onwards to maximize the mass balance recovery
of the products by giving enough time to achieve a proper bal-
ance of substrate/water vapor in the reactor. Then the reaction
products were collected in cold traps filled with a known amount
of distilled water. Two traps were used to ensure that any carry-
over from the first trap was collected in the subsequent trap (how-
ever, for most of the cases, no products were observed in the
second trap). The gas phase was collected in a gas sampling bag
and analyzed offline by gas chromatography. The contents of the
traps were worked-up and also analyzed by gas chromatography.
Keywords: 1,3-butadiene
catalysis · dehydration
·
2,3-butanediol
·
alumina
·
[1] What happened to biofuels? The Economist, September 7, 2013, 18–12.
[2] P. Gallezot, Chem. Soc. Rev. 2012, 41, 1538–1558.
[3] C. O. Tuck, E. Pꢂrez, I. T. Horvꢃth, R. A. Sheldon, M. Poliakoff, Science
2012, 337, 695–699.
[4] M.-J. Syu, Appl. Microbiol. Biotechnol. 2001, 55, 10–18.
[5] A. Shrivastav, J. W. Lee, H. Y. Kim, Y. R. Kim, J. Microbiol. Biotechnol. 2013,
23, 885–896.
[6] M. Dworkin, S. Falkow, The Prokaryotes: Vol. 1: Symbiotic Associations,
Biotechnology, Applied Microbiology, Springer, Heidelberg, 2006, pp. 723.
[7] M. E. Winfield, J. Council Sci. Ind. Res., 1945, 18, 412–423; M. E. Win-
field, Aust. J. Sci. Res. 1950, 3, 290–305.
The product work-up procedure and analysis were as follows. After
addition of a known amount of propanol, as an internal standard
to the traps, 0.75 mL aqueous solution were added to dichlorome-
thane (1–2 mL), which was then dried over sodium sulfate. After fil-
tration the samples were analyzed by using a Varian 430-GC gas
chromatograph equipped with a capillary column (Restek, Stabil-
wax, id 0.25 mmꢁ15 m). Quantification was achieved through a cal-
ibration against five different concentrations of authentic samples
using propanol as an internal standard, for all products. The injec-
tor and detector ports were maintained at 2508C and the oven
was programmed from 408C to 2008C at a rate of 308CminÀ1 after
3 min waiting at the initial temperature of 408C. The column tem-
perature was kept at 2008C for an additional 2 min. Gas phase
analysis was performed using the same gas chromatograph and
column, applying a constant temperature program (358C) for
8 min. The peak of the BDE can be readily distinguished from pro-
pene. Quantification of BDE was achieved through a calibration
against five different concentrations, made by controlling the flow
rates of inert argon gas and BDE. Possible production of CO and
CO2 was analyzed by using a Varian 450-GC gas chromatograph
equipped with FID & TCD detectors, a methanizer, and a CP-SiL5CB
column (50 m, 0.33 mm diameter, He carrier gas). The qualitative
production of the butadiene was also confirmed by GC-MS.
[8] U. V. Mentzela, M. S. Holm, Appl. Catal. A 2011, 396, 59–67.
[9] Q. Zheng, M. D. Wales, M. G. Heidlage, M. Rezac, H. Wang, S. H. Boss-
mann, K. L. Hohn, J. Catal. 2015, 330, 222–237.
[10] H. Duan, D. Sun, Y. Yamada, S. Sato, Catal. Commun. 2014, 48, 1–4.
[11] H. Duan, Y. Yamada, S. Sato, Appl. Catal. A 2015, 491, 163–169.
[12] W. Kim, W. Shin, K. J. Lee, H. Song, H. S. Kim, D. Seung, I. N. Filimonov,
Appl. Catal. A-Gen.; 2016, 511, 156–167; 2016, 511, 156–167
[13] G. W. Huber, S. Iborra, A. Corma, Chem. Rev. 2006, 106, 4044–4098.
[14] I. M. Atadashi, M. K. Aroua, Renewable Energy 2011, 36, 437–443.
[15] R. R. Emerson, M. C. Flickinger, G. T. Tsao, Ind. Eng. Chem. Prod. Res. Dev.
1982, 21, 473–477.
[16] M. H. Haider, N. F. Dummer, D. W. Knight, R. L. Jenkins, M. Howard, J.
Moulijn, S. H. Taylor, G. J. Hutchings, Nat. Chem. 2015, 7, 1028–1032.
[17] Y. Mizuho, A Study on Catalytic Conversion of Non-Food Biomass into
Chemicals Fusion of Chemical Sciences and Engineering, Springer, Heidel-
berg, 1st ed. 2016, CH 1.2, pp. 21.
Received: May 19, 2016
Published online on && &&, 0000
Chem. Eur. J. 2016, 22, 1 – 6
www.chemeurj.org
5
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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These are not the final page numbers! ÞÞ

Communication
COMMUNICATION
The direct production of 1,3-butadiene
from the dehydration of 2,3-butandiol
by using alumina as catalyst is reported.
Under optimized kinetic reaction condi-
tions, the production of methyl ethyl
ketone and isobutyraldehyde, formed
via the pinacol–pinacolone rearrange-
ment, was markedly reduced and
almost 80% selectivity to 1,3-butadiene
and 1,3-butadiene could be achieved.
The amphoteric nature of g-Al2O3 was
identified as important and this contrib-
uted to the improved catalytic selectivi-
ty when compared with other acidic
catalysts
&
Catalysis
X. Liu, V. Fabos, S. Taylor, D. W. Knight,
K. Whiston, G. J. Hutchings*
&& – &&
One-Step Production of 1,3-Butadiene
from 2,3-Butanediol Dehydration
&
&
Chem. Eur. J. 2016, 22, 1 – 6
www.chemeurj.org
6
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!