0424.NN Chisa Experimental - Investigation
0424.NN Chisa Experimental - Investigation
0424.NN Chisa Experimental - Investigation
Abstract
Hydroformylation, or oxo synthesis, is an important process for the production of aldehydes from
alkenes. Alkene and aldehyde hydrogenation are undesired parallel and consecutive reactions.
Whereas present-day industrial process configurations typically operate in a homogenous mode, the
development of a heterogeneous hydroformylation catalyst is aimed at to avoid the well-known
drawbacks of homogenous catalysis such as catalyst recuperation and corrosiveness. Kinetic
measurements have been performed in a high-throughput kinetic test set up. Temperatures varied from
448 to 498 K, with the total pressure ranging from 1 to 3 MPa. A gaseous feed containing CO, C 2H4
and H2 was used with space times varying from 5.4 kg cat.s/molC2H4,in to 149 kgcat.s/molC2H4,in. Three
catalysts have been investigated, i.e., 5%Rh/Al 2O3, 1%Co/Al2O3 and 0.5%Co-0.5%Rh/Al2O3. The
main products observed were ethane, propanal and propanol. The Rh catalyst showed the highest
hydroformylation and hydrogenation site time conversions in the investigated range of operating
conditions. Moreover it was found that on all investigated catalysts, a temperature increase has a more
pronounced effect on hydrogenation than on hydroformylation.
1. Introduction
The ever increasing crude oil price has led to the exploration of alternative feeds such as
natural gas, and correspondingly new processes for the production of hydrocarbons.
Hydroformylation, or oxo synthesis, that was discovered by the German scientist Otto Roelen
in 1938, is an important process for production of aldehydes from alkenes. Hydroformylation
catalysts are also active in double bound hydrogenation converting the reactant alkene into the
corresponding alkane as well as the product aldehydes into alcohols [1]. Typical
hydroformylation products are in the carbon number range from 3 to 19. The reactant alkene
is selected based on the desired product aldehyde.
Aldehydes are useful intermediates in the production of valuable products such as alcohols,
carboxylic acids, amines, diols, etc. Recently, hydroformylation is also widely applied in fine
chemicals in the production of drugs, vitamins, herbicides and perfumes [2, 3].
The name ‘hydroformylation’ becomes clear when looking at the nature of the products that
are formed. The reaction entails the addition of a formyl group (CHO) and a hydrogen atom to
a carbon – carbon double bond. Depending on the catalyst used, the aldehyde can be further
hydrogenated to the corresponding alcohol. The hydroformylation of ethylene that is shown in
Figure 1, in particular is a spontaneous, exothermic reaction (ΔHº = -129.0 kJ mol -1, ΔGº =
-56.9 kJ mol-1) [4]. Due to high energy barriers, the reaction rate remains low, however.
Table 1- Fraction of exposed metal, accessible metal atoms and site time conversions per catalyst
CO site time C2H4 site time
Particle Fraction of Accessible
conversion conversion
Catalyst size (nm) exposed metal metal atoms
(molCO, converted (molC2H4,converted
TEM (%) (mol/gcat.)
/molcat. atoms /s)* /molcat. atoms /s)*
5%Rh/Al2O3 2 51.11 2.4757×10 -4
0.01356 0.04071
1%Co/Al2O3 11 12.38 0.2098×10-4 0.00359 0.01486
0.5%Rh- 4.3 for Co 28.10 for Co
0.2575×10-4 0.00746 0.02626
0.5%Co/Al2O3 35 for Rh 3.81 for Rh
*
at 473 K, 2.0 MPa and equimolar C2H4/CO/H2 gas phase composition
Based on the TEM results, the 5%Rh catalyst as it is depicted in Figure 2 has well dispersed
particles with a small size (2nm) resulting a high fraction of exposed metal. On the contrary,
in the 1%Rh-Co catalyst rhodium was observed in big particles or clusters (20-50nm).
Figure 2- TEM image of 5%Rh/Al2O3 catalyst
Figures 3 and 4 show the observed CO and C2H4 conversion as a function of the site time at
473 K and 2 MPa. An equimolar feed composition containing CO, C 2H4 and H2 was used with
space times that were varied 5.4 kgcat.s/molC2H4,in to 149 kgcat.s/molC2H4,in
The accessible number of metal atoms and site time conversions are also reported in Table 1.
As it can be seen in these figures and the table, the Rh catalyst shows the highest site time
conversions at the investigated operating conditions.
Based on the site time conversions obtained in monometallic catalysts and the knowledge of
the fractions exposed on the bimetallic catalyst, see Table 1, an expected site time conversion
on this bimetallic catalyst amounting to 0.00429 molCO, converted /molcat. atoms /s was calculated,
which is lower than the experimentally observed site time conversion. Considering the size of
Rh clusters in Rh-Co catalyst, this metal cannot show considerable activity in the
hydroformylation reaction, so the reason that bimetallic catalyst shows slightly higher activity
than pure cobalt catalyst can be explained by the fine Co particles in the Rh-Co catalyst that
enhances the activity of this catalyst. It has been already reported in the literature [8, 14] that
small metal particles exhibit higher hydroformylation activity than large metal clusters.
3.2 Temperature effect
In order to investigate the temperature effect on hydroformylation, a series of experiments
were carried out on two of the mentioned catalysts, i.e., 5%Rh/Al2O3 and 1%Co/Al2O3.
A temperature increase leads to a more pronounced increase of the C 2H4 site time conversion
than of the CO site time conversion on both tested catalysts. As a result, as it is depicted in
Figure 5, the apparent activation energy for ethane formation exceeds that for propanal
formation.
The above observations correspond with an increasing selectivity towards ethane with the
temperature, which is confirmed by the literature [9, 12]. It was observed by Balakos et. al.,
that in heterogeneous ethylene hydroformylation on 4%Rh/SiO 2 with increasing the
temperature from 483 K to 573 K the hydroformylation selectivity, defined as
TOFpropanal/TOFC2H6, decreased from 0.136 to 0.039 [9].
Figure 5- Relation between space-time yield and temperature for hydrogenation site time conversion
on Rh(♦) and Co (▲) and hydroformylation site time conversion on Rh(■) and Co (×)
With increasing temperature, adsorbed C2H4 molecules apparently exhibit a higher affinity
towards reductive elimination into ethane (step 4 in Figure 6) than reacting with adsorbed CO
molecule (step 6) on the catalyst surface. This can be related to the expected evolution in the
hydrogen and CO surface concentrations. Because the chemisorption heat of CO is typically
about the double of that of hydrogen, the CO concentration will decrease much faster with
increasing temperature than the hydrogen concentration. As a result, the relative importance
of hydrogenation in the overall ethylene conversion will increase at the expense of
hydroformylation.
On all investigated catalysts, increasing the temperature has a more pronounced effect on the
hydrogenation rate than on the hydroformylation rate. The overall activation energy for ethane
formation exceeds that for propanal formation which can be related to a higher heat of
chemisorption for CO than for hydrogen. In addition, metal particle size effects also play a
significant role in the selectivity between hydrogenation and hydroformylation. Whereas
small metal particles exhibit high hydroformylation activity, large metal clusters rather favour
hydrogenation reactions.
Acknowledgements
This work was supported by the European research project “TOPCOMBI” (contract NMP2-
CT2005-515792) and Methusalem program.
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