Ind. Eng. Chem. Res.

2005, 44, 9853-9859 9853

Stability and Kinetic Studies of Supported Ionic Liquid Phase

Catalysts for Hydroformylation of Propene
Anders Riisager,† Rasmus Fehrmann,† Marco Haumann,‡ Babu S. K. Gorle,‡ and
Peter Wasserscheid*,‡
Department of Chemistry and Center for Sustainable and Green Chemistry, Technical University of Denmark,
Building 207, DK-2800 Kgs. Lyngby, Denmark, and Lehrstuhl für Chemische Reaktionstechnik,
Universität Erlangen-Nürnberg, Egerlandstrasse 3, D-91058 Erlangen, Germany

Supported ionic liquid phase (SILP) catalysts have been studied with regard to their long-term
stability in the continuous gas-phase hydroformylation of propene. Kinetic data have been
acquired by variation of temperature, pressure, syngas composition, substrate concentration,
and residence time. The activation energy was determined to be 63.3 ( 2.1 kJ mol-1, which is
in good agreement with known results from biphasic hydroformylation. The results from the
kinetic studies confirmed previously published results on the homogeneous nature of the
heterogenised Rh-SILP catalyst. Long-term stability exceeded 200 h time on stream with no
loss in selectivity. A small decrease in activity could be compensated by a vacuum procedure
regaining the initial activity.

Introduction pressure which makes them attractive as alternative

The hydroformylation of alkenes, discovered in 1938
by Otto Roelen at Ruhrchemie, Oberhausen, Germany,1
is one of the largest applications of homogeneous transi-
tion metal catalysis in industry. Worldwide production
capacities exceeded 8 mio t/year in 1995.2 Industrial
hydroformylation catalysts are based on cobalt and
rhodium complexes exclusively, with the rhodium pro-
cesses operating at much milder conditions (typically
80 °C, 15 bar) than the cobalt processes (typically 200
°C, 300 bar). The aldehydes formed by the addition of
hydrogen and carbon monoxide to the olefinic double
bond are important precursors for, e.g., plasticizers and
detergent alcohols. Besides the desired linear n-alde-
hydes, branched iso-aldehydes are obtained in a parallel
reaction as depicted in Scheme 1. The selectivity of the
catalyst can be influenced by the use of sterically
demanding ligands such as sulfoxantphos 1 (see Scheme
1) and is referred to as n:iso ratio or linearity (in
percentage).
In 1984, a biphasic propene hydroformylation process,
introduced by Ruhrchemie/Rhône-Poulenc (RCH/RP),
made use of the immiscibility between an aqueous phase
containing the water-soluble Rh complex and the or-
ganic product phase.3 Simple product separation and
quantitative catalyst recovery were achieved in a de-
cantation unit, thus overcoming the drawbacks of
homogeneous catalysis. Ever since, a variety of im-
mobilization concepts for hydroformylation catalysts
have been studied, ranging from biphasic fluorous
phase4 over microemulsions5 to supported catalysis.6
Among the biphasic catalysis concepts the use of ionic
liquids has gained significant interest over the past
decade both in academia and industry.7 Ionic liquids
consist entirely of ions and have no measurable vapor
* To whom correspondence should be addressed. Phone:
(+49) 9131-8527420. Fax: (+49) 9131-8527421. E-mail:
peter.wasserscheid@crt.cbi.uni-erlangen.de.
† Technical University of Denmark.
‡ Universität Erlangen-Nürnberg.
10.1021/ie050629g CCC: $30.25 © 2005 American Chemical Society
Published on Web 11/11/2005
solvents for homogeneous catalysis. Their polar nature
allows the stabilization of ionic transition metal com-
plexes as well as complexes being susceptible to hy-
drolysis. The use of ionic liquids in catalysis has been
reviewed recently.8
However, besides their advantageous properties as
solvents, ionic liquids are relatively expensive, even
though being commercially available now.9 Further-
more, ionic liquids are normally highly viscous solvents,
thus having low diffusion coefficients for hydrogen and
carbon monoxide.10 In case of fast chemical reactions
this may result in mass transfer limitations, where only
the catalyst in the diffusion layer of the biphasic system
is utilized. In an ideal system, a thin film of catalyst
containing ionic liquid the size of the diffusion layer
would make use of all of the catalyst and ionic liquid
(see Figure 1).
Such a film can be immobilized by physisorption,
tethering or covalent anchoring of ionic liquid fragments
on a highly porous material, thus creating a large
reaction surface. Furthermore, a solid catalyst that can
be applied in conventional fixed-bed reactors is preferred
from an industrial point of view. Such supported ionic
liquid-phase (SILP) catalyst systems have recently been
reported by us and other researchers for hydroformyl-
ations,11 hydrogenations,12 hydroaminations,13 and Heck
reactions.14 The SILP catalytic concept offers a very
efficient ionic liquid utilization and provides relatively
short diffusion distances of reactants compared to
conventional two-phase organic-ionic liquid catalyst
systems. In addition, the negligible vapor pressure, large
liquid range, and thermal stability of ionic liquids
ensure that the solvent is retained on the support in
its fluid state at common reaction conditions, e.g.,
elevated temperatures, which makes SILP catalysts
highly suitable for continuous processing. Moreover, the
ionic liquid solvent properties are tuneable by the choice
of the cation/anion combination, which further leads to
advantages of the SILP concept such as, e.g., compat-
ibility with hydrolytically labile catalyst complexes,
9854 Ind. Eng. Chem. Res., Vol. 44, No. 26, 2005
Scheme 1. Propene Hydroformylation Using Rh-Sulfoxantphos Catalyst Complex
specific solubility properties, and possible catalyst ac-
tivation by liquid-catalyst interaction.
We have recently demonstrated15 the applicability of
selective (n:iso ratios up to 23.7, i.e., 96.0% linearity)
unmodified silica gel SILP rhodium catalysts (Rh-SILP)
containing the bisphosphine sulfoxantphos 1 (Figure 1)
with physisorbed hexafluorophosphate and n-octyl sul-
fate ionic liquids [BMIM][X] (X ) PF6 or n-C8H17O-
SO3) for the gas-phase propene hydroformylation in a
continuous-flow process. The ionic liquid film proved to
be a prerequisite for an active, selective, and stable
catalyst. Experiments without the ionic liquid revealed
a deactivation of the catalyst within 10 h time on
stream, indicated by a loss of both activity and selectiv-
ity. The homogeneous nature of the Rh-SILP catalyst
was verified by in situ FTIR experiments. A proper
thermal pretreatment, reducing the content of surface
silanol groups of the support material, has been identi-
fied to be crucial for long-term stability of the catalyst.
NMR measurements on the Rh-SILP catalyst indicated
that more than 50% of the excess ligand was bound to
the remaining acidic sites of the support, thus making
a higher L:Rh ratio than in biphasic catalysis a prereq-
uisite for obtaining a stable and selective catalyst
system.
In this work we present further evidence for the
homogeneous nature of the Rh-SILP catalyst based on
kinetic results. The results strongly support the previ-
ous spectroscopic results. Furthermore, the catalyst
performance has been studied for more than 200 h time
on stream in order to verify the long-term stability of
the Rh-SILP catalyst.
Experimental Section
Catalyst Preparation. All syntheses were carried
out using standard Schlenk techniques under prepuri-
fied argon. The silica gel 100 (particle size 0.06-0.2 mm,
pore volume 0.966 mL g-1, Merck), was calcinated in
Figure 1. Schematic principle of SILP catalysis.
air at 450 °C for 24 h and stored under argon prior to
use. The ligand sulfoxantphos 1 has been synthesized
by sulfonation of xanthene (Aldrich) according to lit-
erature procedures.16 Rh(CO)2(acac) (0.0512 g, 0.2 mmol)
(Aldrich), was dissolved in 20 mL of dried MeOH and
stirred for 10 min. Ligand 1 (1.57 g, 2 mmol) were
added, and the orange solution was stirred for another
10 min. Afterward, 1 mL (1.06 g) of ionic liquid [BMIM]-
[n-C8H17O-SO3] (pH ) 8.3, H2O < 500 ppm, Cl- < 100
ppm, Solvent-Innovation) was added to the solution.
After being stirred for 30 min, 10 g of calcinated silica
were added and the solution was stirred for 60 min. The
MeOH was removed in vacuo, and a pale red powder
was obtained. The supported ionic liquid-phase catalyst
was stored under argon until further use.
Kinetic Experiments. The long-term stability and
kinetic studies were carried out in a continuous fixed
bed reactor setup depicted in Chart 1. The SILP catalyst
was filled into the reactor (4), and the complete rig was
evacuated at room temperature. The rig was pressurized
with 50 bar helium and left under pressure for 30 min
while monitoring the pressure. If no pressure drop was
observed, the reactor was heated to reaction tempera-
ture under helium pressure. The complete setup was
evacuated and flushed with helium three times before
syngas and propene were fed into the system.
Propene (2.8, Linde) was taken out of a reservoir in
the liquid state and fed into a heated evaporator (2) via
a HPLC pump (1) (Knauer) to control the molar flow of
the substrate. Both carbon monoxide (3.5, Linde) and
hydrogen (5.0, Linde) flows were adjusted by means of
mass-flow controllers (MFC, 5850 S series, Brooks
Instruments). The preheated gases were combined with
the propene in the mixing unit (3), which was filled with
glass beads in order to ensure proper mixing and
isothermal conditions. The gas mixture could then either
enter the reactor (4) or exit the system via a bypass.
The reactor (4) consisted of a stainless steel tube (10
mm diameter, 220 mm length) equipped with a bronze
sinter plate for catalyst placement. After the reactor,
the gas mixture passed a 7-µm filter in order to avoid
Chart 1. Flow Scheme of the Continuous
Hydroformylation Reactor Setup
 Ind. Eng. Chem. Res., Vol. 44, No. 26, 2005 9855

decontamination of the tubing with catalyst or solid Table 1. Rh-SILP Hydroformylation of Propene at
particles. A back-pressure regulator valve (5) (Samson) Various Substrate Concentrationsa
was used to maintain the desired reaction pressure and temperature ppropene conversion TOF n-butanal
outlet gas flow. After the regulator valve, the gas stream entry (°C) (bar) (%) (h-1) (%)
was split and a minor flow was passed through a 134- 1 65 0.9 0.86 4 95.9
µL sampling loop mounted on a gas chromatograph (HP 2 65 1.8 0.91 8 95.9
5890 II plus). Samples were taken at regular intervals 3 65 3.2 0.93 17 95.8
by injecting the volume of the sampling loop via a 6-port 4 82 0.9 2.13 9 95.7
valve into the gas chromatograph. 5 82 1.8 2.09 19 95.6
6 82 3.2 2.54 45 95.4
Gas Chromatography (GC). The conversion of 7 100 0.9 6.54 29 95.2
propene as a function of process conditions was mea- 8 100 1.8 7.48 67 95.2
sured using on-line GC technique. A HP 5890 GC 9 100 3.2 9.82 175 95.1
equipped with a Pona column (50 m, 0.2 mm diameter, 10 120 0.9 20.5 91 94.1
0.25 µm coating) and a flame ionization detector (FID) 11 120 1.8 21.1 188 93.8
12 120 3.2 21.4 381 93.5
precalibrated for propene, n-butanal, and iso-butanal
13 130 0.9 27.6 123 93.4
(allowing the peak areas to be transferred into propene 14 130 1.8 32.8 292 92.9
conversion) was applied: Injector temperature 150 °C, 15 130 3.2 28.1 501 90.1
split ratio 43:1, helium carrier gas flow 2.4 mL min-1, 16 140 0.9 21.0 94 92.5
detector temperature 250 °C. To detect possible high- 17 140 1.8 26.9 240 92.3
boiling byproducts (heavies), the following temperature 18 140 3.2 28.1 500 87.7
program was used: initial temperature 50 °C, initial a Standard conditions: 10 bar syngas pressure, H :CO ) 1:1,
2
time 5 min, heating ramp of 50 °C min-1, final temper- nRhodium ) 8.17 × 10-5 mol, τ ) 0.9 s.
ature 150 °C, final time 3 min, cooling ramp 50 °C
min-1, final temperature 50 °C.
GC mass spectroscopy data have been recorded on a
Varian Saturn 2100T equipped with a CP 8410 au-
tosampler, ion trap detector, and Varian factor four
capillary column (15 m, 0.25 mm diameter, 0.25 µm
coating): Injector temperature 220 °C, split ratio 50:1,
helium carrier gas flow 1 mL min-1. The following
temperature program was used: initial temperature 50
°C, initial time 5 min, heating ramp of 10 °C min-1, final
temperature 220 °C, final time 10 min.
Inductively Coupled Plasma (ICP) Analysis.
During the long-term stability experiments the exit gas
streams from the GC and reactor were combined and
collected in a cold trap filled with liquid nitrogen. The
liquid samples were subsequently analyzed by ICP.
Calculations. The residence time τ was calculated
from the total amount of Rh in the catalyst divided by
the total molar flow Ftotal of substrates
Figure 2. Differential analysis of the hydroformylation at various
nRhodium propene partial pressures and temperatures. 10 bar total pressure,
τ) [s] H2:CO ) 1:1, nrhodium ) 8.17 × 10-5 mol, τ ) 0.9 s.
Ftotal
stream, no change in activity and selectivity was
The turn-over frequency (TOF) was calculated from the observed. On the basis of this preliminary result, the
molar flow of aldehydes divided by the amount of kinetic data were acquired within the first 36 h of a
rhodium freshly installed catalyst sample.
Variation of Propene Pressure. The hydroformyl-
Faldehyde FpropeneX -1 ation has been performed at propene partial pressures
TOF ) ) [h ]
nRhodium nRhodium of 0.9, 1.8, and 3.2 bar partial pressure and in the
temperature range 65-140 °C with a residence time of
The rate of reaction was calculated from the converted 0.9 s. Table 1 compiles the results of these variations.
propene and the residence time At 65 and 82 °C, the reaction rates observed were low
with TOFs in the range of 4-45 h-1 (entries 1 to 6).
∆ppropene ppropene,0X bar The highest TOFs were obtained at high propene partial
r)
τ
)
τ [ ]
s
pressure and high temperature (entries 15 and 18).
However, the activities at 140 °C were not as high as
Results and Discussion could be expected assuming a normal Arrhenius tem-
perature dependence. This might be attributed to the
Stability. In a first set of experiments, the Rh-SILP formation of high-boiling byproducts, namely, 2-ethyl-
catalyst system has been applied for the hydroformyl- hexanal and 2-ethyl-hexanol (“heavies”), which can
ation of propene at 100 °C and 10 bar syngas pressure dissolve in the ionic liquid layer, thus lowering the
(H2:CO 1:1) over a period of 36 h time on stream. TOFs effective catalyst concentration (for more details, see
between 71 and 74 h-1 and selectivities for n-butanal later Deactivation-Reactivation Studies). A differential
of 95% (n:iso ) 19) were obtained in good agreement analysis of all data was made by plotting ln(rate)
with previously published data.15 After 36 h time on against ln(ppropene). The reaction order n of propene was
9856 Ind. Eng. Chem. Res., Vol. 44, No. 26, 2005
Figure 3. Integral analysis of propene hydroformylation at
different residence times and temperatures. 10 bar syngas pres-
sure, H2:CO ) 1:1, nrhodium ) 8.17 × 10-5 mol, ppropene ) 2.1 bar.
Figure 4. Activity of the Rh-SILP catalyst as a function of partial
pressure of CO. 100 °C, nrhodium ) 7.98 × 10-5 mol, τ ) 0.8 s,
phydrogen ) 1.3 bar, ppropene ) 1.8 bar (balanced with He).
calculated from the slope of the curves and the rate
constant k from the intercept. Figure 2 shows the results
of the differential analysis.
The hydroformylation of propene with the Rh-SILP
catalyst under investigation was found to be first order
in propene and the activation energy was calculated
from an Arrhenius plot (see Figure 6) to be 61.9 kJ mol-1
with a collision factor k0 of 3.7 × 107 s-1.
Variation of Residence Time. At a constant pro-
pene partial pressure of 2.1 bar, the residence time
inside the catalyst bed was varied by altering the total
reactant flow. From the results in Table 2, it can be seen
that shorter residence times generally resulted in lower
conversions, whereas at longer residence times the
conversions were higher. Under nondifferential condi-
tions at higher conversions (entries 29-38), the ob-
served TOFs decreased slightly with longer residence
time representing the lower mean level of propene
present in the reactor.
The selectivity for the desired linear aldehyde de-
creased only slightly from 96.2-93.6% by increasing the
residence time and temperature. At temperatures of 120
°C, TOFs between 320 and 470 h-1 could be achieved.
Figure 5. Activity of the Rh-SILP catalyst at different syngas
compositions (H2:CO ratios) and total pressures of 10, 15, 20, and
30 bar. 100 °C, nrhodium ) 7.98 × 10-5 mol, τ ) 0.8 s.
Figure 6. Arrhenius plots based on propene pressure and
residence time variations.
By assumption of a first-order reaction with respect to
propene, integration of the rate expression
dppropene
r)- ) kpn
dτ
resulted in
ln(ppropene) - ln(ppropene,0) ) -kτ
Plotting ln(ppropene) - ln(ppropene,0) against the residence
time τ resulted in a linear dependence as shown in
Figure 3.
The rate constants were determined from the slopes
of the graphs, and the activation energy was found to
be 64.8 kJ mol-1 in good agreement with the one
obtained from variation of substrate partial pressure
(see Figure 6). The collision factor k0 of 7.1 × 107 s-1
was higher than the one determined by substrate
pressure variation.
Variation of Total Pressure and Syngas Com-
position. At 100 °C, the partial pressure of CO was
varied between 0.7 and 5.2 bar, while the hydrogen and
propene partial pressures were kept constant at 1.3 and
1.8 bar, respectively. Helium was used as inert gas to
 Ind. Eng. Chem. Res., Vol. 44, No. 26, 2005 9857

Table 2. Rh-SILP Hydroformylation of Propene at rhodium-catalyzed hydroformylations using sulfonated

Various Residence Timesa ligands in aqueous media and supported aqueous media.
temperature residence conversion TOF n-butanal The activation energy of propene using Rh-SILP
entry (°C) time (s) (%) (h-1) (%) catalysts is slightly lower than the one determined by
19 65 2.0 0.72 7 95.3 Mao et al. for HRh(CO)(TPPTS)3 in water.20 Compared
20 65 1.5 0.96 12 95.0 with HRh(CO)(TPPTS)3 in supported aqueous phase
21 65 1.2 1.02 16 95.4 (SAP) catalysis of higher alkenes,22,23 the activation
22 65 1.0 0.82 16 96.2
energy for propene hydroformylation is in good agree-
23 65 0.8 0.68 17 96.2
24 84 2.0 4.66 44 95.4 ment. This comparison provides additional evidence that
25 84 1.5 3.67 46 95.5 the Rh-SILP catalyst truly acts as a homogeneous
26 84 1.2 3.11 49 95.4 catalyst in the ionic film immobilized on the silica.
27 84 1.0 2.13 48 95.4 Deactivation-Reactivation Studies. The stability
28 84 0.8 1.75 44 95.7
29 100 2.0 10.3 97 95.2
of the Rh-SILP catalyst was initially studied at 100
30 100 1.5 8.57 108 95.2 °C and 10 bar syngas pressure (H2:CO ) 1:1) over a
31 100 1.2 7.31 115 95.1 period of 36 h with no loss in activity or selectivity. This
32 100 1.0 5.46 103 95.1 time on stream was extended to 180 h to test the long-
33 100 0.8 5.57 140 95.1 term stability of the system. Figure 7 shows the results.
34 120 2.0 34.3 324 94.5
35 120 1.5 29.1 367 94.4 The selectivity toward n-butanal remained constant
36 120 1.2 25.5 401 93.9 around 95% (n:iso ) 19) during the reaction whereas,
37 120 1.0 23.1 437 93.8 the TOFs slightly decreased from 74 to 61 h-1, corre-
38 120 0.8 18.7 471 93.6 sponding to a total loss in activity of 17% or 0.1% per
a Standard conditions: 10 bar syngas pressure, H :CO ) 1:1,
2
hour. Since the selectivity remained unchanged, it was
nRhodium ) 8.17 × 10-5 mol, ppropene ) 2.1 bar. assumed that the catalyst did not decompose, as ob-
served in previous studies when using low L:Rh ra-
maintain constant volume flow and total pressure of 10 tios.11,15 All ICP analyses of the exit gas streams
bar. The activity decreased with increasing pCO as condensed in liquid nitrogen showed rhodium contents
depicted in Figure 4, while the selectivity for n-butanal below the detection limit of 3 ppm. Instead, the forma-
remained unchanged at 95%. tion of high boiling side products dissolving in the ionic
The total syngas pressure was increased to 15, 20, liquid layer is expected to be the cause of the slow
and 30 bar with pCO varied in the range between 1.0 deactivation. The effective rhodium concentration would
and 7.8 bar (ptotal ) 15 bar, pH2 ) 2.0 bar, ppropene ) 1.3 be lowered by the dissolved byproducts. Furthermore,
bar), 1.3 and 10.4 bar (ptotal ) 20 bar, pH2 ) 2.6 bar, the film thickness might be increased and smaller pores
ppropene ) 1.8 bar), and 2.0 to 15.6 bar (ptotal ) 30 bar, can be flooded, which will lead to a lower reaction
pH2 ) 3.9 bar, ppropene ) 2.7 bar), in all cases balanced surface. To confirm this hypothesis, the gas flow was
with Helium gas. As can be seen from Figure 4, the stopped after 180 h time on stream and the setup was
activity increased with increasing total pressure. From evacuated for 10 min at 100 °C using a vacuum pump.
the slopes of the linear fitting a negative order with When the experiment was continued after this proce-
respect to pCO of -0.4 can be calculated according to dure, the activity had indeed increased by 80% from 60
to 108 h-1. Within the next 20 h, the TOFs decreased
r ) kpCOx (r expressed as TOF) again from 108 to 76 h-1 and the selectivity reestab-
lished at 95% n-butanal. A second vacuum period of 10
In Figure 5, the activity, expressed as ln(TOF), has been min resulted in improved TOFs of 116 h-1, as depicted
plotted against ln(ptotal). The slope of the linear fitting in Figure 8. In both cases, the observed “overshooting”
should give the order m with regard to total syngas of the activity by evacuation might be caused by
pressure according to simultaneous removal of CO ligand of the Rh complex
leading to higher activity. A lower selectivity is expected
r ) kptotalm (r expressed as TOF) and is indeed observed for a short while after evacua-
tion. Thereafter, the catalyst solution is again saturated
For pH2:pCO ratios of 0.25, 0.33, 0.67, and 2 an order m with CO gas, and both the activity and the selectivity
) 0.4 has been calculated from the fitted graphs in are approaching the initial levels.
Figure 5. Both the negative order in CO17 and the first These findings confirm the interpretation that the
order in substrate concentration18 are known from observed slight deactivation over time is not due to
literature and can be derived from Wilkinson’s mecha- catalyst decomposition. Our previously published results
nism for modified rhodium-catalyzed hydroformyla- clearly indicated that catalyst deactivation due to ligand
tion.19 degradation is accompanied with loss of selectivity,15
In Figure 6, the ln(k) was plotted against T-1 in an which is not observed in this case. In this context, we
Arrhenius-type diagram based on substrate and resi- expected the formation of 2-ethyl-hexanal and 2-ethyl-
dence time variation. hexanol to be of relevance. At higher temperatures,
The activation energies calculated from the indepen- traces of these high-boiling side products were observed
dent experiments are similar and can be accounted to in the GC chromatograms of the gas outlet streams.
be 63.3 ( 2.1 kJ mol, clearly indicating that the Rh- To further support this interpretation of our results,
SILP catalyst is operating under kinetically controlled the deactivated catalyst was removed from the reactor
reaction conditions. The collision factors k0 determined and the pale-yellow catalyst particles were placed in two
from the Arrhenius plots range between 2.7 × 107 s-1 round-bottom flasks containing (i) cyclohexane and (ii)
(based on residence time) and 9.8 × 107 s-1 (based on ethanol. Immediately, the ethanol solution became
propene pressure). In Table 3, the results from this orange in color, whereas the cyclohexane solution
study are compiled and compared with results for remained colorless. As expected the ethanol wash leads
9858 Ind. Eng. Chem. Res., Vol. 44, No. 26, 2005
Table 3. Comparison of Results for Rh-SILP Hydroformylation with Literature Results
substrate catalyst
Propene HRh(CO)2(1)
Propene HRh(CO)(TPPTS)3
1-octene HRh(CO)(TPPTS)3
1-octene HRh(CO)(TPPTS)3
Linaloolb HRh(CO)(TPPTS)3
1-dodecene HRh(CO)(TPPTS)3
a IL ) [BMIM][ n-C H O-SO ]. b Linalool ) 3,7-dimethyl-1,6-octadien-3-ol.
8 17 3
d Cetyltrimethylammoniumbromide surfactant used.
Figure 7. Long-term hydroformylation stability experiment. 100
°C, 10 bar syngas pressure (H2:CO ) 1:1), nrhodium ) 3.53 × 10-5
mol, ppropene ) 1.8 bar, τ ) 0.38 s.
Figure 8. Reactivation of Rh-SILP catalyst by consecutive
application of vacuum. 100 °C, 10 bar syngas pressure (H2:CO )
1:1), nrhodium ) 3.53 × 10-5 mol, ppropene ) 1.8 bar, τ ) 0.38 s.
to the complete removal of the ionic catalyst phase from
the support, while the cyclohexane wash does not. The
ethanol solution was distilled in order to separate
nonvolatile ionic liquid fragments and the distillate was
analyzed by means of GC-MS. The cyclohexane solution
was directly analyzed by GC-MS. In both cases, small
amounts of byproducts 1-butanol, 2-ethyl-hexanal and
2-ethyl-hexanol were detected (the GC signals were
further confirmed by injection of the respective pure
compounds as references). These results indicate that
relatively unpolar heavies were washed or extracted
from the Rh-SILP catalyst by both ethanol and cyclo-
hexane.
Additionally, infrared analysis of both used and
unused Rh-SILP catalysts was carried out. The used
catalyst showed an absorbance band at 1730 cm-1
EA
(kJ mol-1) solvent support ref
63.2 ILa SiO2 this work
77.0 water 20
65.9 water 21
71.0 water SiO2 22
60.7 water SiO2 23
72.8/70.9c waterd 24
c Two different algorithms were used for data analysis.
(corresponding to the CdO stretching frequency), clearly
indicating the presence of aldehydes in the catalyst.
Conclusion
In this work, we have demonstrated the long-term
stability of a homogeneous rhodium hydroformylation
catalyst, which has been immobilized by the use of the
new SILP technique. No loss in selectivity for linear
butanal was observed during the experiments. The
activity decreased by 17% within 180 h time on stream
due to formation of high boiling side-products. These
heavies could easily be removed from the catalyst by a
vacuum procedure, after which the initial activity could
be regained.
The activation energy of 63.3 ( 2.1 kJ mol-1 added
evidence that the catalyst is indeed a homogeneous
complex dissolved in an ionic liquid film on a support.
Furthermore, the Rh-SILP catalyst performed very
similar to a homogeneous catalyst with regard to
variation in syngas composition. This work further
confirms the high technical potential of the SILP
catalysis concept as it allows combining molecular
defined homogeneous catalysis with heterogeneous,
fixed-bed technology.
In perspective, we believe that the knowledge gained
in this and previously published work will accelerate
significantly the successful development of new SILP
catalysts and future SILP catalysis applications (e.g.,
other C-C couplings, hydrogenations, etc.). The SILP
concept is most advantageous for continuous gas-phase
reactions, where the combination of well-defined cata-
lyst complexes, nonvolatile ionic liquids, and solid,
porous supports can enhance the process economics with
respect to product separation and catalyst recovery. If
mechanical and chemical removal of the ionic liquid film
can be prevented, the SILP technology can also be
applied in multiphase slurry reactions. The higher
utilization of the catalyst species and the ease of catalyst
recycling by filtration will offer advantages compared
to classical biphasic systems. We therefore anticipate
that the SILP catalysis concept will help bridging the
gap between homogeneous and heterogeneous catalysis
and will lead to improved catalytic processes in the
future.
Acknowledgment
This work was supported by the framework “Smart
ligands - smart solvents” of ConNeCat financed by the
German Federal Ministry for Education and Research
(BMBF). Financial support (M. Haumann) by the Deut-
sche Forschungsgemeinschaft and by the Danish Re-
search Council for Technology and Production is grate-
fully acknowledged. The authors thank Dipl.-Ing. Helmut
Gerhard for support regarding the GC analysis, Ber-

thold Melcher for doing the syngas variation experi-
ments, and Dr. Christine Ernst for support with the
catalyst synthesis. Dipl. Chem. Guido Henze (Univer-
sität Dortmund, Lehrstuhl für Technische Chemie A)
is acknowledged for the ICP analyses.
Nomenclature
acac ) Acetylacetonate
BMIM ) n-Butyl-methyl-imidazole cation
CO ) carbon monoxide
EA ) Arrhenius activation energy (kJ mol-1)
F ) Molar flow (mol s-1)
GC ) gas chromatography
GC MS ) gas chromatography coupled with mass spec-
troscopy
H2 ) hydrogen
ICP ) Inductively Coupled Plasma
IR ) infrared spectroscopy
k ) rate constant (for nth order reaction) ((mol L-1)1-n s-1)
k0 ) collision factor (for nth order reaction) ((mol L-1)1-n
s-1)
m ) reaction order with respect to total syngas pressure
MFC ) mass-flow controller
MeOH ) methanol
n ) reaction order with respect to propene
n-butanal ) linear butanal
n:iso ) linear-to-branched ratio of products
NMR ) nuclear magnetic resonance spectroscopy
nrhodium ) molar amount of rhodium in reactor (mol)
p ) pressure (bar)
PF6 ) hexafluorophosphate anion
r ) reaction rate (mol L-1 s-1)
RCH/RP ) Ruhrchemie/Rhône-Poulenc (now part of Eu-
ropean Oxo and Oxeno)
Rh-SILP ) Rhodium sulfoxantphos immobilized by SILP
SILP ) supported ionic liquid phase
τ ) residence time (s)
T ) temperature (°C)
TOF ) turn-over frequency (h-1)
x ) reaction order with respect to partial pressure of CO
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Received for review May 30, 2005
Revised manuscript received August 19, 2005
Accepted September 27, 2005
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