J . Chem. Tech. Biotechnol.

1985,35A,234-240

Kinetics of Acetone Hydrogenation Over Pt/A1203Catalysts

F. Rositani, S. Galvagno, Z . Poltarzewski, P. Staiti and P. L. Antonucci
Istituto CNRITA E, Via S . Lucia sopra Contesse 39, 98013 Pistunia-Messina, Italy
(Manuscript received 6'September 1984 and accepted 2 January 1985)

The hydrogenation of acetone to isopropanol has been studied in the vapour phase
over Pt/A1,O3 catalysts. The rate law obtained at a total pressure of 1 atm and
temperatures between 303 and 363 K is of the form V=kePg2 exp (-44 kJ mol-'
RT-'). The kinetic results are consistent with a Langmuir-Hinshelwood hydrogena-
tion mechanism involving a half hydrogenated species and a non-competitive
chemisorption of acetone and hydrogen on the platinum surface. The specific
activity (calculated per platinum surface atom) has been found to be scarcely
dependent on the platinum particle size. It is suggested that the chemisorption sites
are made of a very small ensemble of platinum atoms.
Keywords: Acetone; hydrogenation; kinetics; Pt/A1,03 catalysts.

1. Introduction
Reversible chemical reactions such as hydrogenation-dehydrogenation, hydration-dehydration,
sorption-desorption etc., may be used to achieve a heat pump effect.'-3 Chemical heat pumps
operate in the same way as the better known sorption refrigerator. They consist of two reversible
reactions (one endothermic and the other exothermic) running in at least two reactors kept at
different temperature with the endothermic step carried out at the lower temperature.
Among the reversible chemical reactions which have been proposed for chemical heat pumps,
the acetone-isopropanol system has the following advantages: ( a ) it is possible to run the
endothermic step (dehydrogenation of isopropanol) at near room temperature by photocatalytic
p r o c e ~ s e s(; b~ ) a theoretical efficiency of 0.93 under mild conditions has been r e p ~ r t e d . ~
The feasibility of a chemical heat pump based on this chemical system depends, however, on
the development of catalysts which are able to perform the single reaction steps at a very fast rate
without side products.
In this context the hydrogenation of acetone in the gas phase was studied with the aim of
obtaining information on the kinetic performance of platinum which has been reported to be the
most active metaL6 Literature data on the hydrogenation of acetone over platinum are rather
scanty.
A detailed work has been carried out by Simonikova ef al.' over a series of metals supported
on Kieselguhr but this paper is restricted to only one platinum sample.
In this communication the kinetic results over a series of Pt/AI2O3 samples having different
particle size is reported in order to obtain information on the influence of the operating
conditions (temperature, partial pressure reactants) and metal dispersion on the rate of acetone
hydrogenation.

2. Experimental
Reagent grade acetone (Rudi Pont), ultra high purity H2 and Ar (Multigas) were used. H2 was
passed through Pt/A1203 at 673 K and Ar through an oxygen absorbent (Alltech Associates);
then both were passed through a molecular sieve trap.
The catalyst used was a commercial 0.5 wt% Pt/A1201. In order to obtain samples of different
metal particle size, the original catalyst was subjected to thermal treatments in the temperature
234
Kinetics of acetone hydrogenation 235

range 673-1073 K under a hydrogen or an oxygen atmosphere. Platinum particle sizes were
determined from the metal surface area measured by H2/02 titration using a pulse technique.
The rate of acetone hydrogenation was studied in a flow system employing a tubular reactor at
atmospheric pressure. The Ar stream was passed through an acetone saturator kept at constant
temperature. The acetone feed rate was controlled by changing the Ar flow rate.
In preliminary runs, performed at different flow rates and catalyst grain sizes, the absence of
diffusional limitation was verified.
The reaction rates were measured at conversions <lo% and generally in the range 0.5-596.
Before catalytic activity measurements, catalysts were pretreated in situ in a stream of H2at 673
K for 2 h. The partial pressures of acetone and H2 ranged between SO and 300 torr. The reaction
temperature was varied between 303 and 363 K. No side products were observed.
Effluent analysis was carried out by gas-chromatography (Carlo Erba Model 4200 with flame
detector). The peak areas were measured by a Spectra Physics Model SP 4000 electronic
integrator. The g.c. column employed was filled with silica gel (SCrlOO mesh) and allowed the
separation of acetone and isopropanol at 353 K.

3. Results and discussion

Catalyst samples having a platinum particle size ranging between 3 and 40 nm were obtained by
thermally treating a commercial 0.5 wt% Pt/A1203in the temperature range 673-1073 K, under
H2 or 0 2 atmospheres. Temperature, gas-atmosphere and time of exposure under sintering
conditions were found to influence the growth of platinum crystallites. Metal surface areas were
measured by H2/02 titration assuming the following stoichiometry:
Pt-0+3/2 H2 + Pt-H+H,O (1)
and a platinum surface density of 1.25~10"atoms m-2.8 The mean particle diameters, reported
in Table 1. were calculated by means of the expression:
d=6VIS (2)
where V is the volume of platinum and S is the platinum surface area.
Preliminary experiments showed that under reducing conditions (H2 atmosphere) the growth
of the platinum particles is very slow. Metal particles having larger diameters could be obtained
easily under oxidising conditions (0, atmosphere). This is in agreement with previous results of
. ~ suggested that the growth of small metal particles supported on A1203is
Furhman et ~ l .which
kinetically limited by surface diffusion under oxidising conditions and by interphase transfer
under reducing conditions. The results in terms of particle growth at 1073 K in O2 for 1-3 h are
similar to those previously reported by Furhman et d9
Under the experimental conditions used, the hydrogenation of acetone produced isopropanol
without any side product. Rates of reaction were calculated from the relation:
V=F XIW (moI s-'g-' of Pt) (3)

Table 1. H$O, titration of Pt/AI,03 samples

Metal
HL surface

Catalyst Thermal treatment [ cc (STP)

]?g
area
(m2g-' Pt)
d
(nm)

A 2 h4W"CIH2 0.292 84 3.3

B 1 h-800"C/02 0.053 1s 18.4
C 2 h-800"C/02 0.037 11 26.4
D 3 h-SOO"Ci0, 0.025 7 39.0
236 F. Rasitnni st al.

-5.5 -

'
m
-6-
-

-6.5 -

-71 I I 1 I I I
2.7 2.8 2.9 3.0 3.1 3.2 3.3
I/T x lo3
Figure 1. Arrhenius plot for acetone hydrogenation on Pt!A1203 samples. PH=0.2 atm, Po=O.l atm. 0 , Catalyst A; 0 .
catalyst B; 0,catalyst C; X I catalyst D.

where F represents the feed rate of acetone in moles per second, W is the weight of Pt and X
represents the fraction of consumed acetone.
The influence of temperature on the reaction rates was investigated in the range 303-363 K.
Figure 1 shows the Arrhenius plot for the platinum supported samples. From the slopes of the
straight lines (Figure 1) the apparent activation energies have been calculated and reported in
Table 2 . The activation energies were in the range 42-46 kJ mol-' regardless of the catalyst
metal particle size. Similar values have been previously reported for the hydrogenation of
acetone either in the gas phase" or in the liquid phase."
The influence of partial pressures of hydrogen and acetone on the rate of reaction was
examined at 343 K (Figures 2 and 3 respectively). The dependence of the rate of acetone
hydrogenation on the partial pressure of the reactants can be expressed in the form of a simple
power rate law:
V=K Pk (4)
where Pa and PH are the partial pressures of acetone and hydrogen, respectively.
Kinetic orders n and rn as calculated from the slopes of Figures 2 and 3 are collected in Table
2. On all the catalysts the orders of reaction were zero with respect to acetone and 0.3-0.4 with
respect to hydrogen. Therefore over Pt/A1203 the rate law for acetone hydrogenation, under
experimental conditions such that side reactions can be neglected, can be expressed in the form:
V=K Pg2 exp (-EalRT). (5)

Table 2. Pressure dependence exponents and activation energy for the

acetone-hydrogenation over Pt/AI20,
Reaction Reaction Activation
order in order in energy
Catalyst Thermal treatment Hz acetone (kJ mol-')
A 2 h in H2 at 400°C 0.26 0.05 43
B 1 h in O2 at 800°C 0.34 0.04 43
C 2 h in O2 at 800°C 0.37 0.06 44
D 3 h in O2 at 800°C 0.40 0.04 46
Kinetics of acetone hydrogenation 237

-5.4

-5.5

Figure 2. Rate of C,H,OH formation vs partial

pressure of HZ over Pt/Al,O,. P.=O.l atm,
T=343 K. 0 , Catalyst A; 0 , catalyst B; 0.
catalyst C; X , catalyst D.
-1.1 -1.0 -0.9 -0.8 -0.7 -0.6 -0.5 -0.4
log PH

The most accepted mechanism for acetone hydrogenation over solid catalysts involves the
following steps:"
A + * + A($)
Hz+2* f. 2H(s)
A(s)+H(s) + AH(s)+*
AH(s)+H(s) + IPA(s)+*
IPA(s) + IPA+*
(IPA represents the isopropanol).
Over Raney nickel it has been suggested that the first step in the surface reaction (step c) is
rate controlling and considering that the adsorption constant of hydrogen is much smaller than
that of acetone the following rate expression has been proposed:"

v=c,CSZ/(k,+k*C,)Z (6)
The experimental observation that the order of reaction with respect to hydrogen is about Yz,
agrees with the suggestion that one atom of hydrogen is involved in the rate determining step.
However some modification of the above assumptions are necessary in order to explain the fact
that the order in acetone was never observed to be other than zero. In this respect it is
reasonable to assume that hydrogen does not compete for the sites on which acetone is adsorbed
but chemisorbs on other sites. Designating the sites where acetone adsorbs by (*), the sites where
hydrogen adsorbs by (*') and assuming step ( d ) to be rate determining, a rate law of the
following form is obtained:
V=dIPA/dt=k, [AH(*)] [H(*')] (7)
238 F. Rositani et d.

-5.4

>
0
-
-5.5

-5.6

-5.7

-5.8
~

-
- 0

n
0

0
0
0

0
-5.9-

X
-6.0- X
X
X
X
-6.1 - X x

-6.2 - Figure 3. Rate of C,H,OH formation vs partial

pressure of acetone over Pt/AI20,. P,,=O.2 atm.
-6.3 - T=343 K. 0 . Catalyst A ; 0,catalyst B; 0,
I I I I I I I I catalyst C; x catalyst D.
-1.1 -1.0 -0.9 -0.8 -0.7 -0.6 -0.5 -0.4

by using the steady state approximation to derive an expresion for AH(*) and considering that
the adsorption isotherms describing the surface concentration of H( *’) and AH( *) have the same
behaviour as the Langmuir isotherm, the rate expression can be written as:
V = d I P A / d f = k p , P ~ z / ( l + k , P ,(l+kHPg*)
) (8)
The experimentally observed rate equation (equation 5 ) can therefore be obtained by assuming a
strong acetone chemisorption on the (*) sites (k,P,*l) and a weak chemisorption of hydrogen
on the (*’) sites ( k H P H @ l ) .
Literature data on the hydrogenation of acetone over Pt catalysts are rather scanty and a direct
comparison with the present results cannot be made due to the. different experimental conditions
and catalyst supports used. The detailed kinetic study carried out by Simonikova et at.’ over
Pt/kieselguhr shows a pattern quite different from that found in the present case. In particular
the initial rate of hydrogenation has been reported to be negatively influenced by the partial
pressure of acetone and the kinetic data have been correlated by the following expression:
V=kk,kHP,PH/(1 + k , p , + k ~ P ~ ) ~ (9)
which does not fit with the results over Pt/AI,O,. It should be emphasised that the reaction
model holds for all the Pt/Al,O, samples regardless of metal particle size and a direct influence of
Al2O3 on the catalytic behaviour of Pt is unlikely, especially for the samples having the larger
particles. It is possible that the different support used influences the kinetic performance of Pt.
The influence of platinum particle size on the rate of reaction is reported in Figure 4. In this
figure the rate of reaction has been expressed in terms of turnover number (molecules of acetone
converted per atom of platinum on the surface). It can be noted that catalysts with larger
crystallites (20-40 nm) show a catalytic activity higher than the sample having smaller particles.
The difference is however confined within a factor of three.
Kinetics of acetone hydrogenation 239

I I I I I
10 20 30 40
d (nm)

Figure 4. Specific activity of Pt/AI20jcatalysts as a function of platinum particle size.

The change in catalytic activity can be attributed to a different surface structure of the metal
particles having different size. In fact, the contribution of closely packed planes has been
reported to increase with increasing particle size.” These modifications in the surface structure
can lead to ii different reactivity especially when the reaction requires several adjacent surface
atoms. Hydrogenolysis of C-C bond and ammonia synthesis have been reported as examples of
structure-sensitive reactions. Within this context the hydrogenation of acetone can be regarded as
a reaction which occurs on active sites, made of a small number of platinum atoms, the surface
density of which does not change drastically with particle diameter.
The observation that the rate of reaction (expressed per platinum atom on the surface)
increases only slightly with metal particle size is of great importance in tailoring the optimal
catalyst for acetone hydrogenation. On the basis of Figure 4 it can be concluded that samples
with smaller particle size will be the best catalysts in terms of activity per g of platinum. In fact,
the decrease in the specific reaction rate (per metal atom on the surface) will be overcome by thc
much larger surface area of samples having smaller crystallites.

4. Conclusions
The results reported in the previous section have shown that hydrogenation of acetone over
Pt/AI,O, catalysts occurs with a kinetic order near to zero with respect to acetone and near to ‘/z
with respect to hydrogen. This has been taken as evidence of a reaction mechanism occurring
through a non-competitive chemisorption of acetone and hydrogen, which could result from: ( a )
a stronger chemisorption of acetone with respect to hydrogen and (b) a steric hindrance of the
large acetone molecules which tend to exclude one another from adjacent sites leaving empty
chemisorption sites for hydrogen.
The specific activity (calculated per platinum surface atom) has been found to be scarcely
dependent on the metal particle size. This suggests that the chemisorption sites are made of one
or a very small ensemble of platinum atoms.
From a practical point of view this would suggest the use of a very dispersed platinum catalyst
in order to maximise the acetone conversion.

Acknowledgements
The authors thank Professor N. Giordano for helpful discussion.
240 F. Rositani et d.

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