Applied CatalysisA: General 114 ( 1994) Ll-L7

Letter

Application of a new hydrogenated

aluminophosphate oxynitride (ALPON) as a
catalytic support for the one-step synthesis of methyl
isobutyl ketone from acetone
Luis M. Gandia”, Robin Maim”,
Roger Marchandb, Roland Conanecb, Yves Laurentb,
Mario Montesa**
‘Grupo
de Ingenieria Quimica. Departamento de Quimica Apt&da, Facultad de Quimica, Universidad de1
Pais Vasco, Apdo. 1072, 20080 San Sebastian, Spain
?!.uboratoire de Chimie des MatJriaux, URA 14% CNRS “Verres et Ciramiques”, Universite de Rennes I,
Campus de Beaulieu, 35042 Rennes Ckdex, France

Received4 Match 1994,revised 15 March 1994, accepted 15 March 1994

Abstract

A new hydrogenated aluminophosphate oxynitride (ALPON) obtained by nitridation of AlPO,

can be used as a support to prepare a polyfunctional catalyst with both basic and metallic sites. Ni/
ALPONcatalyst was effectiveforthe low-pressureone-step methyl isobutyl ketone (MIBK) synthesis
from acetone. The selectivity of the process depended on the temperature and time-on-stream of the
hydrogen reduction treatment suggesting that selective MIBK production is achieved by a fine balance
between basic and metallic sites.

Keywords: ALPON; Aluminophosphate oxynitrides: Basic catalyst; Methyl isobutyl ketone production

1. Introduction

Solid basic catalysts have received an increased attention in recent years since
little was known about them compared with acidic catalysts and since there is a
large number of fine chemical processes that need strong basic sites [ 13. One of
the main problems concerned with the traditional basic catalysts [2,3], such as
alkaline-earth metal oxides and alkali metal ion-doped oxides, is their low surface

*Correspondingauthor. Tel. ( + 34-43) 216600,fax. ( +34-44) 212236.

0926-860X/94/$07.000 1994Elsevier Science B.V. All rights reserved

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L2 L.M. Gandia et al. /Applied Catalysis A: General 114 (1994) LI-L7

area. Recently, effort has been focused on the search for high-surface-area basic
solids. Thus, the use of zeolites [4], alkaline-substituted sepiolites [ 51 and hydro-
talcites [6,7] has been reported and their catalytic activity for base-catalyzed
Michael addition, Claisen and Knoevenagel condensation type-reactions has been
demonstrated.
Phosphates, and in particular, aluminophosphates are known to be good acid
catalysts [8-121. A new family of phosphorus and aluminium oxynitrides
(ALPON) has been prepared [ 131 by nitridation of reactive aluminophosphate
powders. The ALPON solids thus resulting maintain the very high starting specific
surface area, and moreover, the incorporation of nitrogen in the aluminophosphate
anionic network seems to be an effective way to modify the surface acid-base
properties of aluminophosphates. In a recent patent [ 141, the preparation of the so-
called ALPON, hydrogenated aluminophosphate oxynitrides and their applications
in condensation reactions have been reported. The most relevant features of these
new solids are as follows: (i) almost all the exposed surface nitrogen is bonded to
hydrogen atoms to give NH, groups, where x = 1,2, 3 or 4, (ii) CO* temperature-
programmed desorption (TPD) experiments have revealed that ALPON solids
have a very strong basic character, (iii) ALPON solids are active catalysts for
Knoevenagel condensation type-reactions and (iv) ALPON solids are suitable
basic supports for dispersed metals, such as nickel, giving rise to effective poly-
functional catalysts for the low-pressure one-step methyl isobutyl ketone (MIBK)
synthesis from acetone.
In this work, the preliminary results obtained in the gas-phase reaction between
acetone and hydrogen at atmospheric pressure with an ALPON-supported nickel
catalyst are reported. In a previous work [ 151, the interest in this process for the
low-pressure one-step formation of MIBK from acetone was presented and good
selectivities (70-80%) to MIBK were obtained with a low-surface-area nickel-on-
magnesia catalyst. This work aims at revealing that a very high surface area
ALPON-supported nickel is a very promising catalyst to obtain MIBK selectively
from acetone in one step.

2. Experimental

The ALPON used as support in this work was prepared in the following manner
[ 131. The starting aluminophosphate material, AlPO, (SBET= 210 m2 g-r), was
obtained by slowly adding 200 cm3 of propylene oxide to a solution formed by
120.7 g of AlC13 * 6H2O (Johnson Matthey, > 99%) and 500 cm3 of a 1 M H3P04
solution at 0°C. The gel formed at room temperature was 2-propanol washed, dried
at 110°C and calcined in air for 90 min at 800°C. The final aluminophosphate
oxynitride, Al59 ( SsET = 190 m2 g-l), was obtained by nitridation of the alumi-
nophosphate in an ammonia stream for five days at 750°C and finally cooled to
room temperature under flowing dry nitrogen. The Al59 hydrogenated alumino-
 LM. Gandh etal. /Applied Catalysis A: General 114 (1994) LI-L7 L3

phosphate oxynitride is well represented by the A1P02.38N1.08 formula, its nitrogen

content being 13.7 wt.-%. A nickel on ALPON catalyst (A159-Ni), ( 1 wt.% Ni,
Sn, = 190 m2 g - ’ ) was prepared by pore volume impregnation with an aqueous
solution of nickel nitrate (Merck p.a.) . After impregnation the solid was dried at
170°C and approximately 5 mbar for 12 h. Acetone hydrogenation was carried out
in a fixed bed reactor operating at 1 atm and 200°C with a feed stream containing
20 mol-% acetone in hydrogen. Prior to catalytic activity measurements, samples
were hydrogen ( 100 cm3 min - ’ ) reduced under various conditions. Reduction
treatments were carried out at 300,400 and 500°C. After heating to the reduction
temperature at a rate of 8°C min- ‘, the time-on-stream of the isothermal part of
the treatment was varied between 0 and 12 h. The W/F*, ratio was kept constant
for all experiments, and was equal to 0.647 g,,, h mol acetone- ‘. Selectivities were
defined as the molar fraction of the reacted acetone which was converted into a
given product.

3. Results and discussion

Fig. 1 shows the overall acetone conversion for the (A159-Ni) catalysts as a
function of the isothermal reduction treatment time. As can be seen, the treatment
at 300 or 400°C gives low (2-3%) overall acetone conversions irrespective of the
reduction time. On the other hand, when reduction is carried out at 5OO”C,the
overall acetone conversion increases with the reduction time and a conversion as
high as 19% is achieved after a 12 h treatment in hydrogen. Fig. 2 shows the
selectivity of the 300°C reduced (A159-Ni) catalysts. As can be seen, diacetone
alcohol (DAA) and mesityl oxide (MSO) are the only reaction products. The
selectivities to these compounds, 85 and 15% respectively, are not affected by the
reduction time. As shown in Fig. 3, after reduction at 4OO”C,in addition to DAA
and MSO, methyl isobutyl ketone (MIBK) is also obtained. Moreover, whereas

Y
r?
r\
6
,.,1..,1...1.~.1~..1..~

0 2 4 6 8 10 12 14
Reduction time (h)
Fig. I. Overall acetone conversion as a function of the reduction time at three different temperatures, 300 (0),
400(*),and500°C(A).
LA L.M. Gandt’a et al. /Applied Catalysis A: General 114 (1994) Ll-L7

01
0 2 4 6 8 10 12 14
Reduction time (h)

Fig. 2. Selectivities to the different reaction products for the catalyst reduced at 300°C. as a function of reduction
time: DAA (A). MS0 ( *).

100

80

0 2 4 6 8 10 12 14
Reduction time (h)

Fig. 3. Selectivities to the different reaction products for the catalyst reduced at 400°C as a function of reduction
time: DAA (A), MS0 (*), MIEJK(0).

the selectivity to both DAA and MS0 continuously decreases, the selectivity to
MIBK increases as the reduction time increases. A noticeably high selectivity to
MIBK (75%) is achieved after hydrogen reduction for 12 h at 400°C. As can be
seen in Fig. 4, MIBK and 2-propanol are the main reaction products when the
reduction is performed at 500°C. However, if heating to 500°C is carried out and
the catalysts is then cooled to the reaction temperature, DAA is the most abundant
product (70% selectivity) whereas lower selectivities to MIBK ( 17%) and MS0
( 11%) are obtained. On the other hand, after 0.5 or 2 h of reduction at 5OO”C,
neither DAA nor MS0 are produced and a very high selectivity (75-80%) to
MIBK is obtained. However, when the reduction time is increased to 12 h a
remarkably high selectivity to 2-propanol (93%) is obtained, whereas the selectiv-
ity to MIBK decreases to 7%.
The high-temperature reaction between acetone and hydrogen can be represented
by an overall reaction scheme which contains two main parallel processes [ 151, as
shown in Fig. 5. Firstly, we have the acetone aldol self-condensation reaction over
 134. Gandia et al. /Applied Catalysis A: General I I4 (1994) LI-L7 L5

0 2 4 6 8 10 12 14
Reduction time (h)

Fig. 4. Selectivities to the different reactionproductsfor the catalyst reducedat 500°C as a function of reduction
time: DAA (A), MS0 (*), MIBK (0,2-propanol (Cl).

Acetoner

2% P-Propanol
Fig. 5. The overall reactionbetween acetone and hydrogen.

basic sites to give DAA. Dehydration of this alcohol yields MS0 which, in turn,
can be selectively hydrogenated over reduced metal sites to finally give MIBK. In
addition to the aldol condensation route, the acetone carbonyl functional group can
also be directly hydrogenated over reduced metal sites yielding 2-propanol. Other
reaction by-products such as methane, propane, diisopropyl ether and diisobutyl
ketone have been detected in some experiments, but in very low amounts, lower
than 2% of the total reaction products.
In this work, a very interesting evolution of the selectivity as a function of the
hydrogen reduction conditions (temperature and time) of a nickel on ALPON
catalyst has been observed. As shown in Fig. 2, after hydrogen reduction at 300°C
neither MIBK nor 2-propanol are obtained, irrespective of the reduction time. As
these two products are formed after a hydrogenation step, this result shows that
300°C is too low as the reduction temperature for the (A159-Ni) catalyst to obtain
metallic nickel, and only products related with the catalyst basicity, such as DAA
and MS0 are obtained. When reduction is carried out at 4OO”C,the selectivity
depends on the reduction time (see Fig. 3)) and MIBK is formed in addition to
DAA and MS0 thus revealing the presence of reduced metallic sites. The longer
the reduction time is, the higher is the selectivity to MIBK; and the shorter the
reduction time the higher the selectivity to DAA and MSO. These results are in
agreement with an increasing amount of metallic sites when the reduction time at
L6 LM. Gandia et al. /Applied Catalysis A: General 114 (1994) LI-L7

400°C is increased. These metallic sites are able to hydrogenate MSO, improving
the selectivity to MIBK. As can be seen in Fig. 4, a dramatic effect of the time of
reduction at 500°C on the (A159-Ni) catalyst selectivity takes place. If only heating
to 500°C is carried out (the reduction time is equal to zero), DAA is the main
reaction product and only a small amount of MIBK is produced. This result shows
that only a small amount of reduced nickel has been obtained during heating in
hydrogen to 500°C. If the reduction time is increased to 0.5 or 2 h, a noticeable
increase in both overall acetone conversion and MIBK selectivity takes place (see
Figs. 1 and 4)) showing very interesting (A159-Ni) catalyst pretreatment conditions
for MIBK production. In addition neither DAA nor MS0 are obtained, and 2-
propanol appears as a new reaction product. If the time of reduction at 500°C is
increased to 12 h, the overall acetone conversion again increases, but now, a very
high selectivity to 2-propanol is obtained, whereas that to MIBK decreases remark-
ably. All these results are in agreement with a strong increase in the proportion of
metallic sites with increasing reduction time at 500°C.
It is interesting to note that the results obtained in this work for the high-
temperature reaction between acetone and hydrogen show that hydrogenation of
MS0 to MIBK by nickel is easier to carry out than that of acetone to 2-propanol,
since 2-propanol is produced only when a high excess of reduced nickel is present
with respect to the nickel required to hydrogenate all the MS0 formed.
These results suggest that the selective production of MIBK, without by-product
(2-propanol) formation, will be achieved by a fine balance between basic and
metallic sites.

4. Conclusions

A new high-surface-area basic catalyst consisting of nickel supported on ALPON

hydrogenated aluminophosphate oxynitride has been described. This catalyst
showed very high selectivity in the low-pressure one-step methyl isobutyl ketone
synthesis from acetone. Improved selectivities to MIBK with this catalytic system
can be obtained by an appropriate balance between acid-base and reduced metal
sites. Optimization of this balance can be achieved by an adequate preparation of
both, support and final catalyst precursor, as well as activation in hydrogen treatment
conditions. Investigations of these aspects are currently in progress in our labora-
tories.

Acknowledgements

The financial support by CEC (cost D5/06/93) is gratefully appreciated. R.

Malm acknowledges the Comett grant from the UETP Southern Sweden.
 L.M. Gandia etal. /Applied Catalysis A: General 114 (1994) Ll-L7 L7

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