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Applied Catalysis A: General 205 (2001) 6169

One-step synthesis of methyl isobutyl ketone from acetone and


hydrogen over Pd/(Nb2 O5/SiO2 ) catalysts
Y.Z. Chen a, , B.J. Liaw b , H.R. Tan a , K.L. Shen a
a

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.

librium does not favor aldol formation, and the yields


of the other two steps are relatively low. A corrosive
problem also occurs due to liquid base and acid catalysts. Increasing attention has been paid to one-step
synthesis of MIBK from acetone and hydrogen using
a catalyst with condensation, dehydration and hydrogenation functions. This multiple-functional catalyst
can act by shifting the equilibrium in the condensation step in favor of MO by simultaneously and
irreversibly hydrogenating it to MIKB.
Several catalytic systems have been reported for
the one-step synthesis of MIBK in a liquid phase at
moderate to high pressure (10100 atm), in which
high selectivity to MIBK (>90%) was achieved. These
have included palladium supported on KOHAl2 O3 or
MgOSiO2 [1], CaOMgOSrOAl2 O3 [2], Nb2 O5
[3,4], zirconium phosphate [5], ZrO(OH)2 -carbon
[6], Ce, Hf and/or Ta oxides-carbon [7] and cation

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

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Y.Z. Chen et al. / Applied Catalysis A: General 205 (2001) 6169

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.

exchange resins [1]. Recently, some catalytic systems


for the one-step synthesis in the gas phase at atmospheric pressure have encompassed palladium supported on SAPO-34 [8], SAPO-11 [9], KH-ZSM-5
[10] or calcined Mg/Al hydrotalcite [11], nickel on
MgO [12] or ALPON [13], platinum on H-ZSM-5
[14] and HMFI [15], and copper supported on MgO
[16]. The one-step process in the gas phase is simpler
and more economical, but the selectivity of MIBK
(6080%) is much lower than that in the liquid phase
and the deactivation of catalysts remains a major limitation. Thus, finding a new or improved catalyst to
operate in the gas phase or liquid phase is a priority
concern.
Niobia in its hydrated form is known as an active
catalyst for esterification, hydration, dehydration and
aldol condensation [17]. The palladium catalyst supported on niobia has a high activity and selectivity
of MIBK in the liquid phase for the one-step process
[18]. Although the bulk oxide of niobia does not have
a large surface area nor good thermal stability, niobia
can be spread and deposited on SiO2 to form stable
surface-phase oxides [19,20]. Although one oxide
deposited onto another to form a surface-phase oxide
might lose its original bulk properties, Nb2 O5 grafted
onto SiO2 still possesses acidic sites for dehydration
[21,22]. Therefore, the catalytic properties of niobia
deposited on SiO2 for condensation and one-step
synthesis of MIBK are well worth exploring.
In this work we prepared and characterized the
surface-phase oxides of Nb2 O5 /SiO2 and the catalysts

The surface-oxides of Nb2 O5 /SiO2 were prepared


by incipiently impregnating silica with a hexane
solution of niobium(V) ethoxide. The impregnated
samples were placed in a vacuum oven overnight to
remove the solvent. Then the samples were decomposed in a stream of nitrogen at 400 C for 2 h and calcined in air at 500 C for 2 h. The amount of niobium
ethoxide required for the first monolayer of Nb2 O5 on
SiO2 was obtained from a stoichiometric calculation
based on the surface area of SiO2 and 16 2 occupied by each NbO2.5 unit [19]. The procedure was
repeated to deposit a second and a third monolayer
of Nb2 O5 . The resultant surface-phase niobia oxides
were designated as NS(1), NS(2) and NS(3) for one,
two and three layers of niobia on silica and were used
as supports. The Pd/NS(x) catalysts were prepared by
incipient impregnation of acidified aqueous solution
of PdCl2 (aqueous solution of Ni(NO3 )2 6H2 O), dried
at 100 C for 24 h and calcined in air at 400 C for 4 h.
2.2. Characterization
The BET surface areas and pore size distributions
of NS(x) were obtained from an ASAP 2010 apparatus
from nitrogen adsorption at 196 C. X-ray diffraction
(XRD) patterns were collected in a Siemens-500 X-ray
photometer operating at 40 kV and 30 mA and using
Cu K radiation (=0.1542 nm).
The acid sites of catalysts were determined via a
TPD-method that adsorbed n-butylamine. The catalysts were first pre-treated at 400 C for 1 h under a
carrier gas of helium, then cooled to room temperature for adsorption of n-butylamine for 0.5 h and then

Y.Z. Chen et al. / Applied Catalysis A: General 205 (2001) 6169

63

flushed at 120 C for 1 h. The adsorbed n-butylamine


was desorbed from 120 to 400 C.
2.3. Reaction
The one-step synthesis of MIBK was conducted in
a semi-batch reactor in which a fixed amount of acetone was loaded and hydrogen was continuously supplied to compensate for the consumed hydrogen to
maintain the total pressure at 20 atm and the temperature at 160 C. The life time test for catalysts was performed in a continuous fixed bed reactor equipped
with a back pressure regulator keeping the system at
a total pressure of 20 atm. The reaction mixture was
analyzed by a gas chromatograph with a 1/8 in.6 ft
Carbowax 20 M column attached to a flame ionization
detector.

3. Results and discussion


3.1. Characterization of supports and catalysts
The surface-phase oxides of Nb2 O5 /SiO2 with various niobia loads were prepared and used as supports.
Table 1 lists the BET surface areas, pore volumes and
average pore sizes of these supports. The pore volume
per gram of SiO2 and average pore diameter slightly
declined below the niobia loading of 27%. Although
the surface areas per gram of sample decreased with
the loading of niobia, the surface areas on a gram
of SiO2 basis increased up to the loading of 40%.
This increase demonstrated that the surface niobia was
homogeneously distributed on the substrate of SiO2
and that the pores of SiO2 were not obviously blocked.

Fig. 1. Pore size distribution of NS(1) and SiO2 .

The pore size distribution of NS(1) nearly coincided


with that of SiO2 substrate as presented in Fig. 1.
The distribution of the surface niobia on NS(1)
was also examined by the energy dispersive analysis (Fig. 2). The elemental mapping is displayed in
Fig. 2(b and c), while the sample region is represented
in Fig. 2(a). The good correlation between the elemental maps of Si and Nb also indicated an uniform
distribution of niobia on the substrate SiO2 .
Fig. 3 demonstrates the X-ray diffraction results of
the surface-phase niobia of NS(x) after calcination at
600, 700 or 800 C for 6 h. No Nb2 O5 crystalline was
found at 600 C (Fig. 3(a)), as the diffraction peaks corresponding to Nb2 O5 crystalline evolved for NS(3) at
700 C (Fig. 3(b)), and for NS(2) and NS(3) at 800 C
(Fig. 3(c)). NS(1) exhibited better thermal stability

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)

Nb2 O5 loading (wt.%)

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

Pore volume (cm3 /gSiO2 )

Average pore diameter (nm)

1.58
1.51
1.38
1.26
1.04

17.5
17.2
16.8
14.5
13.1

SiO2

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Y.Z. Chen et al. / Applied Catalysis A: General 205 (2001) 6169

Fig. 2. X-ray energy dispersive analysis of NS(1). SEM micrograph of (a) the image region, (b) Si map and (c) Nb map.

than NS(2) and NS(3), because of the wetting of the


first monolayer of surface niobia on silica through the
bonding of NbOSi [19,20].
The amounts of acid sites for NS(x) supports were
determined by the adsorption of n-butylamine and are

listed in Table 2. The amount of acid sites per square


meter increased with the loading of niobia (or the number of layers deposited on SiO2 ). According to these
results, the surface niobia above the first monolayer
was not homogeneously distributed layer by layer in
atomic scale. Shirai et al. discovered that Nb2 O5 deposited on SiO2 possesses both Lewis and Brnsted
acid sites [23] and their distributions depend on the
loading and structure of the surface niobia.
3.2. Catalytic test
3.2.1. Effects of mass transfer
The revolution rate of stirring for a gassolidliquid
reaction system is a critical factor for mass transfer.
Table 3 summarizes the results of the one-step synthesis of MIBK over 0.3% Pd/NS(1) conducted at the revolution rate between 200 and 800 rpm. Two acetones
Table 2
Amount of acid sites on 0.1% Pd/NS(x) catalysts
Catalyst

Fig. 3. XRD patterns of NS(1), NS(2) and NS(3). Pre-treated at


(a) 600 C, (b) 700 C and (c) 800 C.

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

Y.Z. Chen et al. / Applied Catalysis A: General 205 (2001) 6169

65

Table 3
Effect of revolution rate on MIBK synthesis for 0.1% Pd/NS(1)
catalysta
Conversion and
selectivity

Revolution rate (rpm)


200

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

a Reaction conditions: T=160 C, P=20 atm, acetone/0.1% Pd/


NS(1)=50 g/0.4 g, reaction time=2 h and C9+ =DIBK+TMB+
PHO+ISOP+unknown.

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

Fig. 4. Effect of 0.1% Pd/NS(1) catalyst loading on the conversion


of acetone for one-step synthesis of MIBK. T=160 C, P=20 atm,
acetone=50 g and reaction time=2 h.

the transfer rate of acetone between the liquid and


solid phases. Moreover, the catalyst loading of 0.4 g
and the revolution rate of 700 rpm were used for the
following catalytic tests in order to discriminate the
effect of mass transfer in this gassolidliquid system.
3.2.2. Compare NS(1) with other supports
SiO2 , CHT (calcined Mg/Al hydrotalcite), Al2 O3 ,
CaO-modified Al2 O3 , SiO2 Al2 O3 and NS(1) were all
used as supports for palladium catalysts with 0.3 wt.%
loading for one-step MIBK synthesis. Table 4 summarizes the catalytic results for 2 h over these catalysts at
160 C and 20 atm. Pd/NS(1) with Lewis and Brnsted
acid sites displayed the highest activity and the best
selectivity for the formation of MIBK of the catalysts
tested. However, Pd/SiO2 Al2 O3 with Brnsted acid
sites possessed a low activity. Pd/Al2 O3 with Lewis
acid sites and some base sites, and Pd/CaOAl2 O3
and Pd/CHT with base sites, had considerable activities and selectivities, but were less active than 0.3%
Pd/NS(1).
Only the supports were used for the condensation of
acetone (Table 5) and the dehydration of diacetone alcohol (Table 6) under the same reaction conditions as
the one-step synthesis of MIBK to understand the effects of supports. The SiO2 Al2 O3 support displayed

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Y.Z. Chen et al. / Applied Catalysis A: General 205 (2001) 6169

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

Acetone conversion (%)

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

a Reaction conditions: T=160 C, P=20 atm, acetone/support=


50 g/0.4 g, reaction time=2 h and C9+ =DIBK+TMB+PHO+ISOP
+unknown.

a Reaction conditions: T=160 C, P=20 atm, DAA/0.3% Pd/


support=50 g/0.4 g, reaction time=2 h and C9+ =DIBK+TMB+
PHO+ISOP+unknown.

the lowest reactivity for condensation; this result is


coincident with the low activity for the formation
of MIBK. Clearly, the Brnsted acid sites were not
the only sites needed for acetone condensation. The
steps in Scheme 2 were proposed [24] for the condensation reaction on acid catalysts. Lewis acid sites
are needed for the formation of enol from the rearrangement of one molecule of acetone. Moreover, the
intermediate of enol successively reacts with another
acetone chemisorbed on Brnsted acid sites to form
DAA or MO.

DAA was used to replace acetone as the reactant


for dehydration tests. Most diacetone alcohol was
reversed to form acetone and some diacetone alcohol was dehydrated into mesityl oxide, as listed in
Table 6. Although most DAA was reversed to acetone,
NS(1) showed the highest reactivity for dehydrating
DAA to MO. As compared with Al2 O3 , CaOAl2 O3
and CHT, this high activity for dehydration might
account for why NS(1) assumes a good reactivity for
the formation of MIBK (Table 1).

Scheme 2. Condensation reaction of acetone on acid catalysts.

Y.Z. Chen et al. / Applied Catalysis A: General 205 (2001) 6169

Fig. 5. Conversions and selectivities during the time courses for


one-step synthesis of MIBK. T=160 C, P=20 atm and acetone/
0.1% Pd/NS(1)=50 g/0.4 g.

3.2.3. Deactivation of Pd/NS(1) catalysts in


liquid-phase process
Fig. 5 presents the conversions and selectivities for
the synthesis of MIBK during the time courses in a
semi-batch system. The conversions did not increase
linearly as the reaction time continued beyond 4 h. Although deactivated during the courses of reaction, the
catalyst of Pd/NS(1) could be regenerated by flushing
in a stream of hydrogen at the reaction temperature of
160 C. We speculated that the deactivation of the catalyst was attributed to the accumulated water from the
dehydration of DAA. Various amounts of water introduced into the reaction system to confirm the effect of
water verified that the conversion of acetone declined
sharply with the amount of water added (Fig. 6).
3.2.4. Effects of palladium and niobia loading
Only a suitable number of metal sites on Pd/NS(1)
was needed, since the hydrogenation of mesityl oxide
was not the controlling step in the one-step process.
The loading of Pd on Pd/NS(1) was reduced from 0.3
to 0.03%; the results are summarized in Table 7. The
conversion of acetone and the selectivity of MIBK
were slightly affected down to the loading of 0.05%.
At 0.03% loading the conversion of acetone and the
formation of MIBK decreased markedly, a considerable amount of mesityl oxide was observed, and the

67

Fig. 6. Effect of water content on the conversion of acetone


for one-step synthesis of MIBK. T=160 C, P=20 atm and acetone/0.1% Pd/NS(1)=50 g/0.4 g.

products of C9+ increased and IPA decreased. The


density of metal sites for the loading of 0.03% was
too low to reduce MO to MIBK and facilitate the
formation of C9+ from secondary condensation reactions on acid sites. The optimal loading of palladium
for Pd/NS(1) catalyst ranged between 0.05 and 0.1%.
Table 8 summarizes the effects of niobia loading
for 0.1% Pd/NS(x) catalysts, the reactivities based on
Table 7
Effect of Pd loading on MIBK synthesis for x% Pd/NS(1) catalystsa
Conversion and
selectivity

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

a Reaction conditions: T=160 C, P=20 atm, acetone/x% Pd/


NS(1)=50 g/0.4 g, reaction time=2 h and C9+ =DIBK+TMB+
PHO+ISOP+unknown.

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Y.Z. Chen et al. / Applied Catalysis A: General 205 (2001) 6169

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

a Reaction conditions: T=160 C, P=20 atm, acetone/0.1%


Pd/NS(x)=50 g/0.4 g, reaction time=2 h and C9+ =DIBK+TMB+
PHO+ISOP+unknown.

a square meter of catalyst increased with the niobia


loading and the formation of MIBK decreased and
C9+ increased slightly. These results were coincident
with the number of acid sites on NS(x) supports.
The increase of acid sites facilitates the condensation of acetone, which is the controlling step of this
one-step process, and also facilitates the secondary
condensation.
3.2.5. Effects of pre-reduction temperature of
catalyst, and temperature and pressure for reaction
As the Group VIII metals supported on Nb2 O5 , the
SMSI effect on the Pd/NS(1) catalyst reduced at a
higher temperature for the depression of hydrogen adsorption was found in our previous studies [25]. According to our results [25], MIBK increased from 45 to
75% and IPA decreased from 44 to 5% as the reduction
temperature of Pd/NS(1) rose from 300 to 400 C for
the synthesis of MIBK in the gas-phase at atmosphere
pressure. However, this effect was not found in this
work for the one-step synthesis in the liquid-phase, as
illustrated in Table 9.
As the reaction temperature rose from 150 to 180 C,
the conversion obviously increased from 13 to 26%
and the selectivity of MIBK reduced slightly from
92 to 89%. This one-step synthesis process in the
liquid-phase was not affected by the total pressure, as
it was high enough (>20 atm) to maintain the reaction
system in the liquid phase.
To expel the deactivated effect of accumulated water as described above, a fixed bed continuous flow

a Reaction conditions: T=160 C, P=20 atm, acetone/0.1%


Pd/NS(1)=50 g/0.4 g, reaction time=2 h and C9+ =DIBK+TMB+
PHO+ISOP+unknown.

reaction system was used for the life time testing


for 0.1% Pd/NS(1) catalyst at 150 C, 20 atm, 5 h1
WHSV and H2 /acetone=0.2 (Fig. 7). The conversion
only declined from 28 to 25% and the selectivity was
maintained around 90% for 177 h of time on stream.
The 0.1% Pd/NS(1) catalyst was effective and stable
for the one-step synthesis of MIBK in the liquid phase.
We believe that Pd/NS(x) catalysts are promising

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.

Y.Z. Chen et al. / Applied Catalysis A: General 205 (2001) 6169

69

alternatives to Pd/Nb2 O5 in the one-step synthesis


process.

the Republic of China for financially supporting this


research under Contract No. NSC88-CPC-E008-010.

4. Conclusions

References

The niobia can be spread homogeneously on silica


to form the surface-phase oxide of Nb2 O5 /SiO2 . Although the first deposited layer wetting on the SiO2
substrate exhibited good thermal stability, the surface
niobia sintered into crystallites at high temperature
above the first layer. The surface niobia possessed a
considerable amount of acid sites, which were effective for condensation and dehydration. The amount
of acid sites on NS(x) increased with the loading of
niobia on silica.
The surface-phase niobia could be used to replace bulk niobia as supports for palladium catalysts
Pd/NS(x), which were effective for the one-step synthesis of MIBK in the liquid phase. The reactivities of
Pd/NS(x) catalysts based on unit surface area were increased with the loading of niobia. The condensation
of acetone was the controlling step in this one-step
synthesis process; therefore, the mass transfer of hydrogen between gas and liquid phase was not a critical
limitation for this gasliquidsolid reaction system.
The 0.050.1% loading was enough for the Pd/NS(x)
catalysts for hydrogenation of MO to MIBK. Water
produced from the dehydration of DAA accumulated
in a batch reaction system and evidently deactivated
the Pd/NS(x) catalysts. Nevertheless the accumulated
water could be expelled in a fixed bed continuous
flow reaction system.

Acknowledgements
The authors would like to thank the Chinese
Petroleum Corp. and the National Science Council of

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