Applied Catalysis A: General 358 (2009) 211–214

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Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

Catalytic activity of the RhH(CO)(TPPTS)3 precursor in the biphasic

hydroformylation reaction of C5–C7 alkenes from a real naphtha cut
Marı́a Modroño Alonso a, Victor Guanipa a, Luis G. Melean a, Merlin Rosales b,
Angel Gonzalez b, Pablo J. Baricelli a,*
a
Centro de Investigaciones Quı´micas, Facultad de Ingenierı´a, Universidad de Carabobo, Valencia, Venezuela
b
La Universidad del Zulia (L.U.Z.), Facultad Experimental de Ciencias, Departamento de Quı́mica, Laboratorio de Quı´mica Inorgánica, Apdo. 526, Maracaibo, Venezuela

A R T I C L E I N F O A B S T R A C T

Article history: The complex RhH(CO)(TPPTS)3 [TPPTS = P(m-C6H4SO3Na)3 = tris(sodium-m-trisulphonated-triphenyl-

Received 28 January 2009 phosphine] was used as catalyst precursor for the hydroformylation of several C6–C7 alkenes from a real
Received in revised form 9 February 2009 Venezuelan naphtha cut without dilution, under mild reaction conditions: 800 psi of syngas 1:1 (H2/CO),
Accepted 12 February 2009
substrate/catalyst molar ratio 400:1, 80 8C and 760 rpm. The olefin contents in the organic phase were
Available online 21 February 2009
about 42%. The catalytic precursor is active in the hydroformylation reaction of the naphtha cut
obtaining conversion of 86% of the olefins in aldehydes during 200 h of reaction. The oxigenated products
Keywords:
were nearly completely identified and agrupated according to the carbon atom number in order to
Aqueous biphasic catalysis
facilitate our discussion.
Hydroformylation
Rhodium complexes ß 2009 Elsevier B.V. All rights reserved.

1. Introduction refinery naphtha (the basis of gasoline) contains up to 50 vol.% of

C5–C7 alkenes of different structures, while specifications for the
Hydroformylation process continues to be one of the more final product allow no more than 12%. Actually, when the
important classes of homogeneously catalyzed reactions by environmental controls are very strict, researchers are looking
transition metal complexes [1–7]. One of the main problems for new method or techniques in order to decrease the
associated with homogeneous catalysis is related to the difficulty contaminant emissions to the environment and also improve
in separating the products from the catalyst and of course in the the quality of the gasoline. The elevated amount of olefins from
recycling of expensive noble metals. The aqueous biphasic the refinery catalytic cracking process is higher than the required
catalysis is an interesting technology in which the catalysts for gasoline formulation and might produce a very viscous polymer
remain in the aqueous phase and products and substrates in the or solids capable of blocking the carburetors and injectors of the
organic phase. The possibility of recovering and recycling the vehicle. Currently, the excess of olefins in naphtha is lowered by
catalytic precursor from the reaction mixture brings the oppor- hydrogenation over solids catalyst, which is costly and results in a
tunity of the continuous use of the biphasic catalysis in industrial marked decrease in the octane rating of the fuel, which must be
processes [8,9]. corrected by the addition of the highly polluting water soluble
This technique has been applied in the Ruhrchemie/Rhone– methylterbutylether (MTBE). For this reason, biphasic liquid–
Poulenc process for the hydroformylation of propylene to liquid hydroformylation could be a green method for lowering the
butyraldehyde in a two phase medium. The rhodium catalyst, olefin content of naphtha through the in situ conversion of some of
is a water soluble complex coordinated to a triarylphosphine the alkenes present into valuable C6–C8 oxygenates (aldehydes or
ligands modified by introducing highly polar sulfonate groups in alcohols) capable of improving the combustion properties of the
the phenyl rings attached to phosphorus, specially the sodium salt fuel. We have recently reported the use of Ru(II) catalyst
of tris(m-trisulphonated-triphenylphosphine, P(m-C6H4SO3Na)3, containing TPPMS in the aqueous biphasic hydroformylation of
popularly known as triphenylphosphine trisulfonate (TPPTS) alkenes mixtures as models of naphtha components and a
[5–7]. A very interesting new application of the hydroformylation comparative study of the rhodium-catalyzed hydroformylation
reaction involves the treatment of mixtures of valuable medium- of C6 alkenes and alkene mixtures in homogeneous and aqueous
chain alkenes mainly in the C4–C7 range present in refinery cuts biphasic media using PPh3, TPPTS and TPPMS ligands as a further
[6,7,14]. In this order of ideas, we are interested in the fact that demonstration of the considerable potential of these green
technology for applications related to fuel upgrading issues
[15,16]. In this order of ideas, we describe the catalytic activity
* Corresponding author. Tel.: +58 412 3413286; fax: +58 241 8671655. of the RhH(CO)(TPPTS)3 complex in the biphasic hydroformylation
E-mail address: pbaricel@uc.edu.ve (P.J. Baricelli). reaction of olefins present in a real light naphtha cut.

0926-860X/$ – see front matter ß 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2009.02.017
212 M.M. Alonso et al. / Applied Catalysis A: General 358 (2009) 211–214

Fig. 1. Light naphtha characterization.

2. Experimental precolumn HP5 of 5 m and a NIST 98 library. The quantification of

components was achieved by direct integration; internal standards
2.1. General procedure were not used due to the extense variety of components and the
lack of information of naphtha characterizations. The results of the
All manipulations were carried out under nitrogen atmosphere characterization are shown in Fig. 1.
using standard Schlenck techniques [10]. All the organic solvents The chromatographic analysis showed that the light naphtha
were dried and purified by distillation and were stored under inert cut used in our experiments, was constituted by olefins (42%),
atmosphere. The olefins and their respective saturated products parafins (31%), naphthens (19%) and aromatics (7%). Also the
were reagent grade (Aldrich). Water was deionized and treated with olefins present in the naphtha cut was classified according to the
nitrogen prior to use. TPPTS was prepared according to the modified chain length in C5 (5%), C6 (56%) and C7 (39%) and finally, according
reported procedures [11,12]. Rhodium trichloride (Aldrich) was to steric hindrance the olefin content was classified as presented in
used without further purification. Gases were purchased from Table 1.
VENEZUELA-AGA-Gases. The complex RhH(CO)(TPPTS)3 was pre- This olefin distribution is favorable for the hydroformylation
pared according to a previous report [13]. The infrared spectra were process since nearly 55% of them are mono- and di-substituted
recorded in a Perkin Elmer Spectrum 1000 FTIR using samples as KBr which in our experience react rapidly under our best operational
disks. 1H and 31P{1H} NMR spectra were recorded on Bruker conditions [16]. However, the presence of so many sterically
500 MHz spectrometers, using deuterated solvents. All chemical hindered olefins (45%) forces the reaction times to be long in order
shifts are reported in parts per million (d) relative to tetramethylsi- to achieve high conversion into aldehydes.
lane (1H) or 85% H3PO4 (31P). GC analyses were performed on a
Hewlett Packard 5890 Series II chromatograph with a flame 3.2. Aqueous biphasic hydroformylation of C5–C7 olefins from a real
ionization detector coupled to a HP integrator 3392-A and HP-1 naphtha cut using RhH(CO)(TPPTS)3
methyl silicone, 30 m  0.53 mm column. Quantification was
achieved by using the internal standard (naphthalene) method Under reaction conditions analogous to the ones selected for
and the peaks were identified by comparison with pure samples the hydroformylation of C6 alkenes and alkenes mixtures reported
analyzed by a GC/MS 5890/5971 coupled system using Quadrex by our group [16] P = 800 psi, T = 80 8C, S/C ratio 400:1 and stirring
PONA 5% phenyl methyl silicone atomic absorption analyses rate of 760 rpm, the complex RhH(CO)(TPPTS)3 was an efficient
were performed with a Perkin Elmer 5000 instrument. Also GC catalyst precursor for the two phase hydroformylation of C5–C7
analyses were performed on a Agilent 6890 chromatograph with alkenes from a real naphtha cut. A reaction profile under optimized
a flame ionization detector coupled to a mass impact electrons conditions is shown in Fig. 2. The hydroformylation reaction is fast
detector 100 m HP1 with pre column 5 m HP5 and NIST 98 in the first 24 h, achieving a total olefin conversion of nearly 50%
library. which corresponds to the mono an di-substituted olefins present in
the naphtha cut. However, due to the complexity of the olefin
2.2. Biphasic reactions mixture contained in the naphtha cut, a long reaction time (200 h)
was required for a high conversion to be achieved since sterically
In a typical experiment, an aqueous solution of catalyst hindered olefins react slowly.
precursor (110 mg, 0.06 mmol) in water (40 ml) and light naphtha In Figs. 3, 4 and 5 a product distribution of the aldehydes formed
(6 ml, 24 mmol of olefin approximately according to our char- from the corresponding C5, C6 and C7 olefins are presented. From
acterization) were introduced into a glass-lined stainless steel
autoclave (Parr, 50 ml) fitted with internal mechanical stirring, Table 1
Olefin distribution according to steric hindrance.
temperature control unit and sampling valve. The solution was
purged three times with CO/H2 (1:1, 5 atm), then it was charged to Olefin hindrance Double bond Olefin content in naphtha cut (P + 0.02)%
800 psi (54.42 atm), heated to 80 8C, stirring at 760 rpm, which location
Total olefin C5 C6 C7
defined the zero time of the reactions. Samples of the reaction content
mixture were periodically extracted and the total pressure was
Mono-substituted Lineal 2.02 0 0 2.02
adjusted via high pressure reservoir. The samples were cooled, the Branched 6.25 0 0.44 5.81
phases separated and the organic phase analyzed by GC/MS.
Di-substituted Internal 28.88 0,89 21.66 6.33
Terminal with 7.76 1.64 5.53 0.59
3. Results and discussion gen substitution
Cyclic 4.38 0.77 1.02 2.59
3.1. Naphtha characterization
Tri-substituted Internal 24.32 1.13 13.39 9.80
Cyclic 3.55 0 0 3.55
The light naphtha was obtained from ‘‘El Palito’’ refinery in the
Tetra-substituted – 7.76 0 7.76 0
North-Central region of Venezuela. Naphtha characterization was Di-olefins – 4.83 0 0 4.83
performed using a GC–MS Agilent 6890 Plus HP1 of 100 m using a
 M.M. Alonso et al. / Applied Catalysis A: General 358 (2009) 211–214 213

Fig. 2. Biphasic hydroformylation of olefins in naphtha cut.

the C5 olefins, the mayor aldehydes obtained are 2-methyl-

pentaldehyde and cyclopentylcarboxaldehyde (derived from 2-
pentene and cyclopentene respectively) among others. As it is
shown in Fig. 4, the C6 olefins react to give mainly heptaldehyde, 2-
methyl hexaldehyde and 2-ethyl pentaldehyde from 1-hexene and
its isomers. In Fig. 5 it can be seen that 1-heptene and its isomers
react to give octaldehyde, 2-methyl heptaldehyde and 2-ethyl
hexaldehyde as major products.
It is interesting to notice that the content of aromatics, parfins
and naphthens remain constant during the reaction time as it can Fig. 4. Product distribution of the hydroformylation of C6 olefins.
be observed in Fig. 6. Thus the only targets of our catalyst are the
olefins present in the light naphtha cut while the rest of the currently underway to determine the toxicological, environmental
components needed in the final gasoline mixture remain and possible engine fouling of the aldehydes produced in the
unaffected. hydroformylation of naphtha and the results will be presented
As it is known, the chemical potential of the olefins present in elsewhere. Should the studies provide unsatisfactory results, those
naphtha is wasted in hydrogenation reactions, which lower the aldehydes can be reduced to alcohols, well-known additives in
olefin content but also lower the octane number of the gasoline gasoline currently used all over the world. Alternatively, the
produced, requiring the use of oxygenated additives such as MTBE
or TAME to compensate its loss. With our methodology, those
olefins can be transformed into aldehydes in situ, increasing the
oxygen content of the mixture and its anti-knock properties,
eliminating the need of contaminating additives. Studies are

Fig. 3. Product distribution of the hydroformylation of C5 olefins. Fig. 5. Product distribution of the hydroformylation of C7 olefins.
214 M.M. Alonso et al. / Applied Catalysis A: General 358 (2009) 211–214

Fig. 6. Distribution of aromatics, naphthens and parafins in the light naphtha cut during the hydroformylation reaction.

reaction can be run for only 24 h, at which time all the reactive the naphtha cut were unaffected by the reaction, acting merely as
mono- and di-substituted olefins have been transformed to solvents for the biphasic reaction.
aldehydes, leaving the unreactive olefins intact. The produced
aldehydes can be separated from the hydroformylated naphtha cut
and sold independently as products of high added value in the fine Acknowledgements
chemicals and pharmaceutical industries. Thus the chemical
potential of the short olefins present in naphtha is harvested. We thank FONACIT (Caracas) for financial support through the
In general the activity of the title compound has been reported Project F-97003766, CONIPET Project 97-003777 and CODECIH-UC
by our group in several occations [16,17], and it showed to be very Project 94017. We are thankful to Red Iberoamericana de Ciencia y
active in the hydrogenation and hydroformylation of olefins and Tecnologı́a Para el Desarrollo, CYTED, Project V.9 and the
olefin mixtures simulating real naphtha. Recycling studies with 1- Universidad de Carabobo for permiting the publication of this
hexene show that the activity and selectivity of our system work.
remains constant after five reuses, evidence of the stability of the
complex. That same stability allows the complex to remain active References
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