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Department of Chemical Engineering, National Central University, Chung-Li 32045, Taiwan, ROC
b Department of Chemical Engineering, Nanya Junior College, Chung-Li 32049, Taiwan, ROC
Received 11 January 2000; received in revised form 7 March 2000; accepted 8 March 2000
Abstract
The surface-phase oxides of niobia on silica substrate ((Nb2 O5 /SiO2 ), NS(x)) were prepared and characterized. Such oxides
were used as supports for palladium catalysts. The one-step synthesis of methyl isobutyl ketone (MIBK) from acetone and
hydrogen in liquid phase was also investigated over Pd/NS(x) catalysts. Experimental results indicate that these catalysts were
effective for the formation of MIBK; since little of the parallel by-product of isopropanol (IPA) was formed, these catalysts
reached selectivities of 8892% MIBK and 23% IPA at 3035% conversion. The reactivity of Pd/NS(x) declined obviously
with an increase of water content that accumulated in a semi-batch reaction system. The water could be partially expelled
and the deactivation of catalysts could be improved by using a fixed bed continuous flow reaction system. 2001 Elsevier
Science B.V. All rights reserved.
Keywords: Methyl isobutyl ketone; Pd/(Nb2 O5 /SiO2 ) catalyst; Surface-phase oxide
1. Introduction
Methyl isobutyl ketone (MIBK) is an important product derived from acetone as it is a useful
solvent for paints and protective coating systems.
MIBK is commercially produced by a conventional
three-step process (Scheme 1): (a) the equilibrium,
base-catalyzed liquid phase aldol condensation of
acetone to form diacetone alcohol (DAA). Second,
(b) an acid-catalyzed dehydration of DAA to mesityl
oxide (MO), and (c) a selective hydrogenation of
unsaturated ketone to MIBK with nickel or copper
chromite catalyst.
These production processes are complicated and
the operational costs are high. The condensation equi Corresponding author. Tel.: +886-3-4252-296;
fax: +886-3-4252-296.
0926-860X/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 0 ) 0 0 5 4 5 - 7
62
of Pd/(Nb2 O5 /SiO2 ), as well as their catalytic properties for the one-step synthesis of MIBK in the
liquid phase. Experimental results indicate that the
surface-phase oxides of Nb2 O5 /SiO2 is as reactive
as Nb2 O5 bulk oxide for condensation. Moreover,
Pd/(Nb2 O5 /SiO2 ) systems are promising catalysts for
the one-step synthesis of MIBK from acetone and
hydrogen in the liquid phase.
2. Experimental
2.1. Preparation
Scheme 1. Conventional routes to MIBK.
63
Table 1
Surface areas, pore volumes and average pore diameters of NS(x) supports
Support
SiO2
NS(0.5)
NS(1)
NS(2)
NS(3)
0.0
15.8
27.4
40.8
48.6
Surface area
m2 /g
m2 /g
274
250
226
187
142
272
294
311
315
277
1.58
1.51
1.38
1.26
1.04
17.5
17.2
16.8
14.5
13.1
SiO2
64
Fig. 2. X-ray energy dispersive analysis of NS(1). SEM micrograph of (a) the image region, (b) Si map and (c) Nb map.
0.1%
0.1%
0.1%
0.1%
0.1%
Pd/SiO2
Pd/NS(0.5)
Pd/NS(1)
Pd/NS(2)
Pd/NS(3)
Acid amount
mmol/g cat.
mol/m2 cat.
0.89
1.07
1.20
1.25
3.56
4.74
6.44
8.79
65
Table 3
Effect of revolution rate on MIBK synthesis for 0.1% Pd/NS(1)
catalysta
Conversion and
selectivity
300
500
700
800
Conversion (%)
15.3
16.6
15.3
15.8
15.4
Selectivity (%)
MIBK
C5
IPA
DAA
MO
MIBC
DIBK
TMB
PHO
ISOP
Unknown
C9+
93.0
1.71
0.80
0.65
0.07
0.20
2.50
0.92
0.01
0.02
0.13
3.57
93.0
1.81
0.76
0.63
0.14
0.19
2.58
0.90
0.01
0.02
0.13
3.75
92.2
2.00
1.09
0.93
0.16
0.23
2.36
0.87
0.01
0.12
3.37
92.2
1.94
1.14
0.84
0.17
0.24
2.42
0.88
0.01
0.01
0.16
3.48
92.6
1.97
0.80
0.91
0.16
0.21
2.35
0.88
0.01
0.14
3.39
were first condensated to DAA; then DAA was successively dehydrated to MO on the acid sites of NS(x);
and finally MO was selectively hydrogenated to MIBK
on the metal sites of palladium. Acetone might be
directly hydrogenated to isopropyl alcohol (IPA), or
MIBK and acetone might involve the same reaction
series as the formation of MIBK to form diisobutyl
ketone (DIBK). Some compounds had a low molecular weight (<C5 ) from cracking on acid sites, while
others (unknown) had a higher molecular weight from
secondary condensation.
The conversions and selectivities are slightly affected by the revolution rate of stirring, as presented in
Table 3. Apparently, this one-step synthesis of MIBK
was not limited by the mass transfer of hydrogen.
Thus, the hydrogenation of mesityl oxide to MIBK
was not the controlling step of this one-step process.
As compared with the reactivity of dehydration of
DAA on acid sites, the condensation of acetone was
supposed to be the controlling step in this one-step
synthesis process of MIBK in the liquid phase. With a
revolution rate of 300 rpm, the conversions of acetone
increased linearly with the loading of catalyst in the
reaction medium up to 0.4 g, as illustrated in Fig. 4.
As the loading of catalyst increased beyond 0.4 g, the
condensation of acetone was more or less limited by
66
Table 4
Effect of support on MIBK synthesis for 0.3% Pd/support catalystsa
Catalyst
0.3%
0.3%
0.3%
0.3%
0.3%
0.3%
a
Pd/NS(1)
Pd/SiO2
Pd/Al2 O3
Pd/CaOAl2 O3
Pd/SiO2 Al2 O3
Pd/CHT
Selectivity (%)
16.1
0.6
10.9
10.0
4.2
9.4
MIBK
IPA
DAA
MO
DIBK
91.9
4.4
87.4
91.3
88.5
91.9
1.7
8.0
3.2
0.1
0.1
0.9
92.0
5.5
3.9
8.5
5.7
0.1
2.9
0.1
0.2
1.2
1.0
2.2
0.7
0.7
0.1
0.7
Reaction conditions: T=160 C, P=20 atm, acetone/0.3% Pd/support=50 g/0.4 g and reaction time=2 h.
Table 5
Condensation reaction of acetone on supportsa
Table 6
Dehydration reaction of DAA on supportsa
Support
Support
NS(1)
NS(2)
Al2 O3
SiO2 Al2 O3
CHT
Concentration (mol%)
Acetone
DAA
MO
C9+
94.5
94.5
95.8
91.2
95.4
0.2
0.2
0.2
0.2
0.2
4.9
5.0
3.9
1.6
3.7
0.4
0.4
0.1
0.7
NS(1)
NS(2)
Al2 O3
SiO2 Al2 O3
CHT
Concentration (mol%)
Acetone
DAA
MO
C9+
77.4
76.3
93.2
82.1
97.7
2.1
2.3
3.7
6.9
1.4
19.0
20.2
3.0
10.7
0.9
1.5
1.2
0.2
0.3
67
Pd loading (wt.%)
0.03
0.05
0.1
0.2
0.3
Conversion (%)
14.4
16.6
16.3
16.4
16.1
Selectivity (%)
MIBK
C5
IPA
DAA
MO
MIBC
DIBK
Unknown
C9+
74.5
1.80
1.27
15.5
2.12
3.87
6.92
92.2
1.75
0.92
1.23
0.15
2.33
0.59
3.68
92.4
1.93
0.76
0.90
0.45
0.14
2.33
0.16
3.82
92.4
1.86
1.27
0.93
0.15
0.16
2.23
0.13
3.47
91.9
1.95
1.74
0.93
0.13
0.15
2.23
0.12
3.40
68
Table 8
Effect of Nb2 O5 loading on MIBK synthesis for 0.1% Pd/NS(x)
catalystsa
Table 9
Effect of pre-reduction temperature on MIBK synthesis for 0.1%
Pd/NS(1) catalystsa
Conversion and
selectivity
Loading of Nb2 O5
Reduction temperature ( C)
NS(0.5)
NS(1)
NS(2)
NS(3)
Conversion and
selectivity
300
400
500
Conversion (%)
Reactivity (mmol/h m2 cat.)
16.4
70.9
16.9
80.6
17.4
99.9
17.7
133.3
Conversion (%)
17.0
16.9
16.9
Selectivity (%)
MIBK
IPA
DAA
MO
C9+
92.1
0.41
1.31
0.21
3.66
91.9
0.75
0.87
0.08
3.91
91.7
1.03
0.67
0.05
4.35
Selectivity (%)
MIBK
C5
IPA
DAA
MO
MIBC
DIBK
C9+
91.5
2.41
0.54
1.14
0.13
0.21
2.82
4.08
91.8
2.27
0.75
0.87
0.08
0.25
2.84
3.91
90.3
1.99
2.53
0.94
0.06
0.41
2.87
3.79
91.5
0.88
0.52
0.07
4.60
Fig. 7. Life time test for 0.1% Pd/NS(1) catalyst for one-step
synthesis of MIBK. T=150 C, P=20 atm, WHSV=5 h1 and
H2 /acetone=0.2.
69
4. Conclusions
References
Acknowledgements
The authors would like to thank the Chinese
Petroleum Corp. and the National Science Council of