Experimental investigation of ethylene hydroformylation to propanol on Rh

and Co based catalysts

N. Navidi, 1J. W. Thybaut, G. B. Marin

Laboratory for Chemical Technology, Ghent University, Krijgslaan 281 – S5, 9000 Ghent
Belgium; tel. +3292645572, e-mail: [email protected]; 1tel. +3292644519, e-mail:
[email protected]; tel. +3292645517, e-mail: [email protected].

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.

Keywords: Heterogeneous catalysts; Ethylene hydroformylation; Fischer-Tropsch; High-throughput

experiments; Rhodum/Cobalt catalysts

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.

H2C CH2 + CO + H2 C2H5CHO

Figure 1- Ethylene hydroformylation to prapanal

In principle, all the transition metals capable of forming carbonyls, such as Rh, Co, Ir, Ru,..
are potential hydroformylation catalysts. The order of activity from the most to the least active
metal, is as follows: Rh > Co > Ir, Ru > Os > Pt > Pd > Fe > Ni [5].
Commercially, homogeneous Co or Rh complexes are typically applied at temperatures
ranging from as low as 360 K up to 573 K [6,7]. The homogeneous character of industrial
process configurations leads to inherent operational problems such as difficulties in catalyst
separation from products, expensive metal losses and corrosivity of catalytic solutions. The
successful implementation of an active and stable heterogeneous hydroformylation catalyst
would allow avoiding these drawbacks. Although the research into heterogeneously catalysed
hydroformylation is in an early stage, a wide range of research activities has been performed
on experimental heterogeneous hydroformylation with various reactants, catalysts and
operation conditions [8-17].
The present work concentrates on heterogeneous ethylene hydroformylation on a series of Rh
and Co based catalysts. Gas phase experimentation was performed in a high-throughput
kinetics setup to compare the Rh and Co catalysts and to investigate the effect of the operation
conditions on the main and by product formation rates on these catalysts. The results of this
study provide key insight into the corresponding reaction mechanism that may be exploited in
further catalyst design.
 2. Procedures
Gas phase hydroformylation measurements have been performed in a high-throughput kinetic
test set up. The setup consisted of eight reactors in parallel and each individual reactor had
three feed lines for gases and one feed line for a liquid with corresponding mass flow
controllers. The reactor temperature and pressure were controlled per reactor pair. A reactor
tube was made of AISI 316 cold worked steel with 890mm height and 11mm internal
diameter.
The reactors are capable of operating up to 600˚C and 15 MPa, i.e., far beyond the operating
range as required for hydroformylation. A three-zone reactor temperature control was
established, the catalyst being situated at the bottom of the second zone and the top of third
zone.
Between 1 and 10 g of 5%Rh/Al2O3, 1%Co/Al2O3 and 0.5%Rh-0.5%Co/Al2O3 was pelletized.
The fraction with a diameter between 0.3 and 0.5mm was retained and mixed with an
identical mass of dilution material prior to loading into the reactor tubes of the high-
throughput set up. Considering the investigated operating conditions in the literature and some
preliminary experiments that were conducted in the lab, the following operating conditions
were selected. 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 that varied
from 5.4 kgcat.s/molC2H4,in to 149 kgcat.s/molC2H4,in.
Online effluent analysis was performed with a four channel Agilent 3000 micro gas
chromatograph equipped with thermal conductivity detectors (TCDs). Argon as an internal
standard has been added to the reactants stream in order to verify the mass balances. The
conversions and product molar flow rates were calculated using calibration factors as reported
by Diets [18]. In order to compare the performance of the mentioned catalysts under identical
experimental conditions the conversions were reported versus the site time. At first, for
calculating the site time, space time (kgcat..s./moli) was divided by standard atomic weight of
metal catalyst to be converted to (mol cat. atoms.s./moli) thereafter, this value was multiplied by
the fraction of exposed metal atoms to calculate the numbers of accessible moles. The fraction
exposed was calculated employing the relation between the particle size and dispersion [19].
In order to estimate the particle sizes, Transmission Electron Microscopy (TEM) method was
used.
TEM specimens were prepared by applying simple immersion of a carbon-support
film on a nickel grid into the catalyst powder followed by careful shaking
off the excess powder. A microscope JEOL JEM2200FS-Cs-corrected, operated
at 200 kV and equipped with Schottky-type FEG, EDX JEOL JED-2300D and JEOL
in-column omega filter, was used.
It was verified by using the proper correlations, that at the selected operating conditions so-
called intrinsic kinetics are measured, i.e., the observations are not affected by mass or heat
transfer limitations [20].

3. Results and discussion

3.1 catalyst comparison
The measured particle sizes and corresponding fractions exposed of the mentioned catalysts
are reported in Table 1.

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

Figure 3- CO conversion versus molar site time. Temperature 473K; Pressure

(C2H4:CO:H2:Ar=30:30:30:10), 2 MPa
Figure 4- C2H4 conversion versus molar site time. Temperature 473K; Pressure
(C2H4:CO:H2:Ar=30:30:30:10), 2 MPa

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 (×)

The more pronounced temperature effect on hydrogenation than on hydroformlation can be

explained by investigating the selected heterogeneous ethylene hydroformylation mechanism
that is shown in Figure 6 in some more detail.
The depicted mechanism is constituted by the following elementary steps:
1- Ethylene molecular chemisorption : C2H4 + 2M ↔ MMC2H4
 2- Hydrogen dissociative chemisorption : H2 + 2M ↔ 2 MH
3- Partial ethylene hydrogenation : MM C2H4 + MH ↔ MC2H5 + 2M
4- Reductive elimination towards paraffin: MC2H5 + MH ↔ C2H6+ 2M
5- CO molecular chemisorption : CO + 2M ↔ MMCO
6- CO insertion: MC2H5 + MMCO ↔ MC2H5CO
7- Hydrogen addition to metal bound carbonyl: MC2H5CO + MH ↔ MMC2H5CHO
8- Desorption of aldehyde: MMC2H5CHO ↔ C2H5CHO + 2M

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.

Figure 6: Proposed reaction mechanism for ethylene hydroformylation to propanol [21]

 4. Conclusion
Gas phase hydroformylation measurements have been performed on 5%Rh/Al 2O3,
1%Co/Al2O3 and 0.5%Co-0.5%Rh/Al2O3 catalysts in a high-throughput set up. The main
products observed were ethane, propanal and propanol. The Rh catalyst showed the highest
hydroformylation and hydrogenation rates compared to other catalysts at the investigated
operation conditions. Bimetallic catalyst shows slightly higher activity than pure cobalt
catalyst since the fine Co particles in the Rh-Co catalyst enhances the activity of this catalyst.

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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