Supported Aqueous Phase Catalysis in the Pores of Silica Support

9636

Ind. Eng. Chem. Res. 2005, 44, 9636-9641

Supported Aqueous Phase Catalysis in the Pores of Silica Support: Kinetics of the Hydroformylation of 1-Octene Ulises J. Ja´ uregui-Haza,† Osmell Dı´az-Abı´n,† Anne M. Wilhelm,*,‡ and Henri Delmas‡ Centro de Quı´mica Farmace´ utica, Apdo. 16042, C. Habana, Cuba, and Ecole Nationale Supe´ rieure d’Inge´ nieurs en Arts Chimiques et Technologiques, 118 route de Narbonne, 31077 Toulouse, France

The kinetics of the hydroformylation of 1-octene by supported aqueous-phase catalysis, with water-soluble complex [Rh2(µ-StBu)2(CO)2(TPPTS)2], when the reaction occurs inside the pores of the silica support with particle size 60-200 µm at mild conditions (0.5-1 MPa, 353-373 K) has been studied. The rate was found to be first order with respect to catalyst concentration and partial order with respect to partial pressure of hydrogen. The reaction was inhibited by high values of initial concentration of 1-octene and of partial pressure of carbon monoxide. During the reaction, no hydrogenation, no isomerization, nor oxidation products were observed. The selectivity in lineal aldehyde did not vary, neither during the course of reaction nor when varying the studied parameters in the tested range. Two different empirical kinetic models were tested. The best kinetic model showed a good agreement with the experimental data, with the average relative error of estimation less than 6.5%. The values of the activation energy (71 kJ/mol) as well as the values of the partial orders in CO, H2, and octene were found to be similar to the values obtained previously for the hydroformylation of 1-octene at the external surface of the DS50 silica. Introduction Multiphase catalytic reactions involving hydrogenation, oxidation, carbonylation, hydroformylation, oxidation, and amination have been expanding into diverse areas of applications. To enhance the catalytic activity, selectivity, and stability of the catalysts and improve environmental compatibility of these processes, many new concepts have been developed.1 Among these new processes, we can find the supported aqueous-phase catalysis (SAPC), where the reaction proceeds at the interface between the organic phase and the immobilized aqueous phase in the pores of hydrophilic support2 or at the external surface of porous3 or nonporous support.4 One of the reactions widely studied by SAPC is the hydroformylation of higher olefins5-11 because of the higher conversion if compared to biphasic catalysis. At the same time, it is well known that kinetic measurements and modeling are of outstanding importance in reactor modeling and design. In biphasic and SAPC hydroformylation of olefins, the rate of reaction will be governed by several phenomena such as transfer of CO, H2, and olefins in both organic and aqueous phases, solubility of these components in both liquid phases, and the intrinsic kinetics of the reaction. However, limited information is available on the kinetics of hydroformylation of olefins by SAPC.6,8,12-14 The aim of this article is to present the study of the kinetics of hydroformylation of 1-octene by SAPC with the water soluble complex [Rh2(µ-StBu)2(CO)2(TPPTS)2] (Figure 1) when the reaction occurs inside the pores of * To whom correspondence should be addressed. E-mail: [email protected]. Fax: +33562885600. † Centro de Quı ´mica Farmace´utica, Apdo. 16042, C. Habana, Cuba. ‡ Ecole Nationale Supe ´ rieure d’Inge´nieurs en Arts Chimiques et Technologiques, 118 route de Narbonne, 31077 Toulouse, France.

Figure 1. Schematic representation of the rhodium complex [Rh2(µ-StBu)2(CO)2(TPPTS)2].

the silica with particle size 60-200 µm (S60) under mild conditions (0.5-1 MPa, 353-373 K). Two kinetic models were evaluated, and the best model was selected based on the minimum average error. The kinetic parameters have been evaluated in the studied temperature range. Experimental Setup and Procedures To study the kinetics of the hydroformylation of 1-octene by SAPC on S60 using the water soluble complex [Rh2(µ-StBu)2(CO)2(TPPTS)2], several experiments were carried out in the range of conditions shown in Table 1. The average experimental error, determined from parallel experiments, was 6.8%. Tris(m-sodiumsulfonatophenyl)phosphine (TPPTS) was used as a water-soluble ligand. The complex [Rh2(µ-StBu) (CO) (TPPTS) ] was prepared as described by 2 2 2 Kalck et al.15 Reagents and solvents were used without further purification. Distilled, deionized water was used in all operations requiring water. All solvents were degassed by three freeze-pump-thaw cycles. The S60 silica was used as support to prepare the supported aqueous-phase catalyst (SAPc). The detailed physical characterization of the silica S60 (Brunauer-EmmettTeller (BET) surface area ) 439 m2/g) has been reported before.16

10.1021/ie0502887 CCC: $30.25 © 2005 American Chemical Society Published on Web 07/16/2005

Ind. Eng. Chem. Res., Vol. 44, No. 25, 2005 9637 Table 1. Experimental Design for Kinetic Study of the Hydroformylation of 1-Octene by SAPC on S60 Using the Water Soluble Complex [Rh2(µ-StBu)2(CO)2(TPPTS)2] runa

N

Ccat × 104, kmol/m3

COct, kmol/m3

PCO, MPa

PH2, MPa

1, 14, 27 2, 15, 28 3, 16, 29 4, 17, 30 5, 18, 31 6, 19, 32 7, 20, 33 8, 21, 34 9, 22, 35 10, 23, 36 11, 24, 37 12, 25, 38 13, 26, 39

1 3 1 1 1 3 1 1 3 1 1 1 3

1.85 3.71 7.41 3.71 3.71 3.71 3.71 3.71 3.71 3.71 3.71 3.71 3.71

0.389 0.389 0.389 0.195 1.062 2.124 4.248 0.389 0.389 0.389 0.389 0.389 0.389

0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.15 0.25 0.35 0.55 0.35 0.35

0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.35 0.35 0.35 0.35 0.15 0.55

a The runs 1-13 were carried out at 353.15 K, 14-26 at 363.15 K, and 27-39 at 373.15 K.

Figure 2. Typical concentration-time profile for the hydroformylation of 1-octene by SAPC when the reaction occurs inside the pores of the silica S60 (T ) 373 K; P ) 1 MPa; H2/CO ) 1; Ccat ) 3.71 × 10-4 kmol/m3; Coct,0 ) 0.389 kmol/m3).

All hydroformylation experiments were carried out in a high-pressure stirred stainless steel reactor of 500 mL capacity, supplied by Autoclave Engineers. The experimental setup was described elsewhere.17 In a typical run, the required amounts of TPPTS, [Rh2(µ-StBu)2(CO)2(TPPTS)2], and 13.8 g of S60 support were placed in the autoclave. The molar ratio of rhodium to TPPTS used was 1:6 to ensure the optimal conditions for the stability of the catalytic complex.3 The solids were covered with toluene and 1-octene (385 mL of organic phase) and 6.9 mL of water, the amount necessary to reach a support hydration ratio of 39.7%. Previously, it was shown that, at this hydration percentage, the reaction takes place inside the pores of the S60 silica with the best results in conversion.17 Then, the autoclave was closed, and the content was flushed twice with syngas consisting of CO and H2 in different ratios. After the stabilization of the temperature at a desired value, the autoclave was pressurized at constant working pressure, and then the reaction started by switching the stirrer on. Samples of 2 mL of liquid phase were withdrawn every 15 min as shown in Figure 2 (the overall sample volume is 22 mL, which represents only 6% of the reactor liquid volume). Initial rates of reaction were then calculated. The organic phase was analyzed by gas-phase chromatography on a HP 5890 chromatograph equipped with a flame ionization detector and a capillary column HP-FFAP (25 m × 0.2 mm × 0.33 µm), Tdet ) 200 °C.

Figure 3. Effect of PCO on initial rate of hydroformylation (PH2 ) 0.35 MPa; Ccat ) 3.71 × 10-4 kmol/m3; P/Rh ) 6; Coct,0 ) 0.39 kmol/ m3). The points correspond to experimental data and the line to estimated values.

Results and Discussion Effect of Different Parameters on Reaction Rate. The effect of agitation speed on the rate of hydroformylation was studied at 353.15 and 373.15 K to verify the importance of mass transfer. It was found that, beyond a stirring speed of 1850 rpm, the reaction rate was independent of agitation, indicating kinetic regime. Hence, all the experiments of the present kinetic study were conducted at an agitation speed of 2000 rpm. When the hydroformylation of 1-octene takes place at the external surface of the saturated in water silica Degussa 50 (DS50, BET surface area ) 488 m2/g), the kinetic regime was reached for a similar speed: 1750 rpm.14 Figure 2 shows typical concentration-time profiles of 1-octene and products (n-nonanal and 2-methyloctanal) as functions of time. There was roughly a 10min induction period before the formation of the reaction’s products was observed. This phenomenon could be explained by the stabilization of the active form of the SAPc. In all experiments, the consumption of 1-octene and syngas was found to be stoichiometrically consistent (>95% material balance) with the formed aldehydes. No hydrogenation, isomerization, and oxidation products were observed. The selectivity in lineal aldehyde (77.5-84%) did not vary, neither during the course of reaction nor when varying the studied parameters in the tested range. The effect of the partial pressure of CO on the rate of hydroformylation of 1-octene is shown in Figure 3. The rate first increased with increasing PCO, passed through a maximum, due to inhibition of kinetics at higher partial pressure of carbon monoxide. The increase in CO after the maximum will cause the formation of inactive Rh species,18 and hence lower rates of reaction will be observed. A similar behavior of CO concentration on the rate of hydroformylation has been previously reported for homogeneous19-21 and biphasic systems18,22-24 and SAPC,6,14,25 when different Rh complexes have been used. Figure 4 shows the influence of partial pressure of hydrogen (PH2) on the rate of reaction. The initial rate is accelerated and is positively dependent on the partial pressure of hydrogen with a partial order. A similar result was observed when the hydroformylation of 1-octene was studied in the biphasic system in the presence of cosolvent22-24 and by SAPC at the external surface of the silica DS50.14 Presumably, in the case of SAPC, as was also reported earlier in biphasic cataly-

9638

Ind. Eng. Chem. Res., Vol. 44, No. 25, 2005

Figure 4. Effect of PH2 on initial rate of hydroformylation (PCO ) 0.35 MPa; Ccat ) 3.71 × 10-4 kmol/m3; P/Rh ) 6; Coct,0 ) 0.39 kmol/ m3). The points correspond to experimental data and the line to estimated values.

Figure 5. Effect of initial concentration of 1-octene on initial rate of hydrofrmylation (P ) 1 MPa; H2/CO ) 1; Ccat ) 3.71 × 10-4 kmol/m3; P/Rh ) 6). The points correspond to experimental data and the line to estimated values.

sis,26 there are other possible interactions with solvent, which may lead to a partial order dependence of hydrogen. The influence of initial 1-octene concentration on reaction rate was studied at a PCO and PH2 of 0.5 MPa and a catalyst concentration of 3.71 × 10-4 kmol/m3. The results are shown in Figure 5 as a plot of reaction rate vs initial concentration of olefin. The rate was found to increase with an increase in concentration up to a certain limit, beyond which it decreased with increasing 1-octene concentration. This substrate-inhibited kinetics has been observed before in the hydroformylation of 1-octene using a water-soluble Rh complex,14 and it is consistent at all studied temperatures. A similar behavior was reported when the hydroformylation of 1-hexene in homogeneous system was investigated.21 In regard to the role of the concentration of the catalytic complex [Rh2(µ-StBu)2(CO)2(TPPTS)2], a linear dependence was observed between the reaction rate and the catalyst concentration, in the range under investigation (Figure 6). The increase in the catalyst concentration will enhance the concentration of the active catalytic species and hence the rate. Finally, the influence of the temperature was studied. As it is shown in Figures 2-5 and in Figure 7, where the dimensionless initial rate (R0,dimensionless ) R0/ K R353.15 ) is plotted as a function of the temperature, 0 the rate was found to increase exponentially with an increase in temperature.

Figure 6. Effect of catalyst concentration on initial rate of 1-octene hydroformylation (P ) 1 MPa; P/Rh ) 6; Coct,0 ) 0.39 kmol/m3). The points correspond to experimental data and the line to estimated values.

Figure 7. Effect of dimensionless temperature on initial rate of hydroformylation of 1-octene by SAPC in the pores of S60 silica. The area inside draft lines corresponds to the 10% of the average dimensionless initial rate.

In general, higher reaction rates were observed when reaction takes place inside the pores, if compared with those obtained during the hydroformylation of 1-octene by SAPC at the external surface of the silica DS50.14 This can be explained by a higher available total interface area when reaction takes place in the pores of the silica S60. Kinetic Model. Since a phenomenological rate model based on the mechanism of hydroformylation of 1-octene using the complex [Rh2(µ-StBu)2(CO)2(TPPTS)2] by SAPC has not been developed before, two different semiempirical kinetic models were evaluated, taking into account the general trends observed in the experiments:

R0 )

R0 )

kCH2CCOCcatCoct (1 + KBCCO)m(1 + KDCoct)n kCH2CCOCcatCoct

(1 + KACH2)l(1 + KBCCO)m(1 + KDCoct)n

(1)

(2)

Model 1 was used for the kinetics of homogeneous hydroformylation of 1-hexene considering the substrate inhibition when the concentration of olefin and carbon monoxide increased.21 However, the rate of reaction was found to be first order with respect to catalyst concentration and partial pressure of hydrogen. The second model was proposed by Ja´uregui-Haza et al.14 To use the rate models it was assumed that:

Ind. Eng. Chem. Res., Vol. 44, No. 25, 2005 9639 Table 2. Comparison of Studied Rate Models for the Hydroformylation of 1-Octene by SAPC When the Reaction Occurs Inside the Pores of the Silica (In Model 1: m ) 2.5, n ) 2.1; In Model 2: l ) 1, m ) 3, n ) 3.63) model 1 2

T (K)

k (m9 kmol-3 s-1)

353 363 373 353 363 373

62.34 102.08 241.06 80.83 149.32 295.70

KA (m3 kmol-1)

KB (m3 kmol-1)

KD (m3 kmol-1)

SS × 1010 (kmol2 m-6 s-2)

Fcal

SEE (%)

49.66 41.25 31.53

44.45 36.58 42.08 36.09 32.90 36.65

0.22 0.24 0.23 0.21 0.24 0.23

0.54 1.17 4.02 0.48 0.87 2.61

4.63 7.11 7.22 4.69 8.71 10.13

10.0 8.78 9.75 6.46 4.57 5.79

(1) The reaction takes place on the organic-aqueous interface located inside and outside of the support as it was suggested by Horva´th in SAPC.5 In this case, it can be considered that the water-soluble complex remains mainly in the aqueous phase thanks to the sulfonated groups, but the rhodium can emerge with carbonyl groups to the organic part of the organic-aqueous interface.5 (2) Mass transfer is not limiting in the range of studied conditions. Then, the concentrations of hydrogen, carbon monoxide, and 1-octene are the same on the organic side of the aqueous-organic interface and in bulk organic phase. Thus, the concentration of reactants in the organic layer of aqueous-organic interface are varied in the following ranges: hydrogen concentration: 5.69 × 10-3-2.21 × 10-2 kmol/m3 carbon monoxide concentration: 1.27 × 10-2-4.65 × 10-2 kmol/m3 catalyst concentration: 6.23 × 10-3-2.50 × 10-2 kmol/m3 The catalyst concentration was recalculated, considering that the catalytic rhodium is only located inside the pores of the support. The higher developed interface in SAPC explains why the hydroformylation of heavy alkenes (C g 4) takes place with high conversions if compared with biphasic catalysis. Then, the proposed model considers that the role of the inert support is to increase the interfacial area and then the contact between catalyst and reagents. For the evaluation of the rate parameters, an optimization sequential routine was used by calculating first the solubility of gases and then the kinetic parameters. The solubility values of CO and H2 in water, toluene, 1-octene, and nonanal in the range of 298-373 K27-32 were used for calculating the solubility of these gases in organic phase by the method proposed by Hildebrand and Scott.33 The values of the constants m and n in the denominator of model 1 were 2.5 and 2.1, respectively, and the values of the constants l, m, and n in model 2 were 1, 3, and 3.63 as found previously by optimization with another support.14 Regressions of the experimental data to the rate models were performed using a corrected Newton algorithm. The procedure calculates the values of the model parameters, which minimize the average standard error of estimation (SEE) n

∑ i)1

SEE ) 100‚

pred exp |R0,i - R0,i | exp R0,i

adequate model was performed using Fisher’s test (Fcal) n

(n - l) Fcal )

2 exp (R0,i - Rexp ∑ 0 ) i)1

(4)

n

(n - 1)

(R0,i ∑ i)1

exp

- R0,i

pred 2

)

where Rexp is the mean value of the vector of observed 0 initial rates and l is the number of adjusted parameters of the model. Table 2 summarizes the results of the nonlinear regression analysis. Both evaluated models described adequately the kinetics of hydroformylation of 1-octene when the reaction takes place inside the pores of the silica, the predicted values of the reaction rate being in good agreement with the experimental data. Regarding the values of the sum of squares (SS), the standard error of estimation and the calculated Fisher parameter, it can be concluded that the best fit was obtained for the second model with a SEE less than 6.5% at all studied temperatures, which is within the range of the experimental error. In Figures 2-5, the lines represent the estimated values of the reaction rate using eq 2. Figure 8 presents the correlation between experimental and estimated initial rates of reaction. The outliers to the 5% error curve correspond to the maximum experimental values in Figures 2 and 4. Then, it can be concluded that the proposed model underestimates the maximum values of reaction rates, obtained when CO concentration and initial 1-octene concentration increase following a substrate inhibition behavior. The activation energy calculated from the temperature dependence of the rate constants for the empirical model, using the Arrhenius equation, was found to be 71 kJ/mol, similar to the value obtained when reaction takes place at the external surface of the support.14

(3)

exp where R0,i are the elements of the vector containing pred are the correthe given experimental initial rate, R0,i sponding values calculated by the model, and n is the number of data points. The selection of the most

Figure 8. Correlation between experimental and calculated by model 2 values of the initial reaction rate. The area inside draft lines corresponds to the errors of estimation lower than 5%.

9640

Ind. Eng. Chem. Res., Vol. 44, No. 25, 2005

Conclusions The effects of different parameters such as concentrations of 1-octene and catalyst and partial pressures of carbon monoxide and hydrogen on the rate of the hydroformylation of 1-octene in the presence of watersoluble complex [Rh2(µ-StBu)2(CO)2(TPPTS)2] by SAPC when the reaction occurs inside the pores of S60 support was studied in a temperature range 353.15-373.15 K. The initial rate was found to be first order with respect to catalyst concentration and partial order with respect to partial pressure of hydrogen. But it was inhibited by high values of initial concentrations of 1-octene and of partial pressure of carbon monoxide. Two different empirical kinetic models were tested. The best kinetic model showed a good agreement with the experimental data, where the average relative error of estimation was less than 6.5%. The activation energy was found to be 71 kJ/mol, similar to the value reported for the hydroformylation of 1-octene at the external surface of the DS50 silica. Acknowledgment U.J.J.H. expresses his gratitude to the INP-Toulouse for covering his stay at ENSIACET as invited professsor. This work was financially supported by the CNRS (France), the ENSIACET-INP-Toulouse (France), and the Ministry of Public Health (Cuba). Nomenclature Ccat ) catalyst concentration, kmol/m3 CCO ) carbon monoxide concentration, kmol/m3 CH2 ) hydrogen concentration, kmol/m3 Coct ) initial 1-octene concentration, kmol/m3 Fcal ) calculated Fisher parameter k ) rate constant, m9 kmol-3 s-1 KA, KB, KD ) model parameters, m3 kmol-1 N ) Number of parallel experiments PCO ) partial pressure of carbon monoxide, MPa PH2 ) partial pressure of hydrogen, MPa R0,dimensionless ) dimensionless initial reaction rate exp ) experimental initial rate of reaction, kmol/(m3 s) R0,i pred R0,i ) predicted initial rate of reaction, kmol/(m3 s) SEE ) standard error of estimation, % SS ) sum of squares, kmol2 m-6 s-2 T ) temperature, K

Literature Cited (1) Chaudhari, R. V.; Mills, P. L. Multiphase Catalysis and Reaction Engineering for Emerging Pharmaceutical Processes. Chem. Eng. Sci. 2004, 59, 5337-5344. (2) Arhancet, J. P.; Davis, M. E.; Merola, S. S.; Hanson, B. E. Hydroformylation by Supported Aqueous-Phase Catalysis: A New Class of Heterogeneous Catalysts. Nature 1989, 399, 454-455. (3) Ja´uregui-Haza, U. J.; Dessoudeix, M.; Kalck, Ph.; Wilhelm, A. M.; Delmas, H. Multifactorial Analysis in the Study of Hydroformylation of Oct-1-ene Using Supported Aqueous Phase Catalysis. Catal. Today 2001, 66, 297-302. (4) Li, Z.; Peng, Q.; Yuan, Y. Aqueous Phosphine-Rh Complexes Supported on Non-Porous Fumed-Silica Nanoparticles for Higher Olefin Hydroformylation. Appl. Catal., A 2003, 239, 79-86. (5) Horva´th, I. T. Hydroformylation of Olefins with the Water Soluble HRh(CO)[P(m-C6H4SO3Na)3]3 in Supported AqueousPhase. Is it Really Aqueous? Catal. Lett. 1990, 6, 43-48. (6) Arhancet, J. P.; Davis, M. E.; Hanson, B. E. Supported Aqueous-Phase, Rhodium Hydroformylation Catalysts. I. New Methods of Preparation. J. Catal. 1991, 129, 94-99. (7) Arhancet, J. P.; Davis, M. E.; Merola, S. S.; Hanson, B. E. Supported Aqueous-Phase, Rhodium Hydroformylation Catalysts.

II. Hydroformylation of Linear, Terminal and Internal Olefins. J. Catal. 1991, 129, 100-105. (8) Fremy, G.; Monflier, E.; Carpentier, J. F.; Castanet, Y.; Mortreux, A. Enhancement of Catalytic Activity for Hydroformylation of Methyl Acrylate by Using Biphasic and Supported Aqueous Phase Systems. Angew. Chem., Int. Ed. Engl. 1995, 34 (12-13), 1474-1476. (9) Kalck, Ph.; Miquel, M.; Dessoudeix, M. Various Approaches to Transfers Improvement During Biphasic Catalytic Hydroformylation of Heavy Alkenes. Catal. Today 1998, 42, 431-440. (10) Davis, M. E. Transitions to Heterogeneous Techniques (SAPC and Variation). In Aqueous-phase organometallic catalysis; Cornils, B., Herrmann, W. A., Eds.; Wiley-VCH Verlag GmbH: Weinheim, Germany, 1998; pp 241-251. (11) Anson, M. S.; Leese, M. P.; Tonks, L.; Willians, J. M. J. Transition Metal Catalyzed Reactions Using Glass Bead Technology. J. Chem. Soc., Dalton Trans. 1998, 21, 3529-3538. (12) Dos Santos, S.; Tong, Y.; Quignard, F.; Choplin, A.; Sinou, D.; Dutasta, J. P. Supported Aqueous-Phase Catalysts for the Reaction of Allylic Substitution: Toward an Understanding of the Catalytic System. Organometallics 1998, 17 (1), 78-89. (13) Riisager, A.; Eriksen, K. M.; Hjortkjær, J.; Fehrmann, R. Propene Hydroformylation by Supported Aqueous-Phase RhNORBOS Catalysts. J. Mol. Catal., A 2003, 193, 259-272. (14) Ja´uregui-Haza, U. J.; Pardillo-Fontdevila, E.; Kalck, Ph.; Wilhelm, A. M.; Delmas, H. Supported Aqueous Phase Catalysis: A New Kinetic Model of Hydroformylation of Octene in a GasLiquid-Liquid-Solid System. Catal. Today 2003, 79-80, 409-417. (15) Kalck, Ph.; Escaffre, P.; Serein-Spirau, F.; Thorez, A.; Besson, B.; Coleuille, Y.; Perron, R. Water-Soluble Dinuclear Rhodium Complexes as Catalytic Precursors for the Hydroformylation of Alkenes in a Two Phases System. New J. Chem. 1988, 12, 687-690. (16) Ja´uregui-Haza, U. J.; Wilhelm, A. M.; Delmas, H.; Canselier, J. P. Adsorption of Benzenesulfonic Acid, 3,3′,3′′-Phosphinidynetris-, Trisodium Salt and Di (µ-Tertiobutylthiolato) Dicarbonyl, Bis (Benzenesulfonic Acid, 3,3′,3′′-Phosphinidyne-Tris-, Trisodium Salt) Dirhodium from Aqueous Solutions on Silica. J. Chem. Eng. Data 2001, 26(2), 281-285. (17) Ja´uregui-Haza, U. J. Hidroformilacio´n del octeno por cata´lisis en fase acuosa soportada. Cine´tica, para´metros de ingenierı´a y propiedades fı´sico-quı´micas del sistema. Tesis de Doctorado, ENSIACET-CQF, Toulouse-Havana, 2002. (18) Monteil, F.; Que´au, R.; Kalck, P. Behaviour of WaterSoluble Dinuclear Rhodium Complexes in the Hydroformylation Reaction of Oct-1-ene. J. Organomet. Chem. 1994, 480, 177-184. (19) Evans, D.; Osborne, J. A.; Wilkinson, G. Hydroformylation of Alkenes by Use Of Rhodium Complex Catalyst. J. Chem. Soc. 1968, 3133. (20) Brown, C. K.; Wilkinson, G. Hydroformylation of Alkene with Hydrido Carbonyl Tris Triphenyl Phosphine Rhodium I Catalyst. J. Chem. Soc., A 1970, 2753-2759. (21) Deshpande, R. M.; Chaudhari, R. V. Kinetics of Hydroformylation of 1-Hexene Using Homogeneous HRh(CO)(PPh3)3 Complex Catalyst. Ind. Eng. Chem. Res. 1988, 27, 1996-2002. (22) Purwanto. Reaction gaz-liquide-liquide: hydroformylation de l’octene-1 par un complexe hydrosoluble du rhodium. The`se de Doctorat, INPT, Toulouse, 1994. (23) Deshpande, R. M.; Purwanto; Delmas, H.; Chaudhari, R. V. Kinetics of Hydroformylation of 1-Octene Using [Rh(COD)Cl]2TPPTS Complex Catalyst In a Two-Phase System in The Presence of a Cosolvent. Ind. Eng. Chem. Res. 1996, 35, 3927-3933. (24) Lekhal, A. Etude du transfert de matie`re gaz-liquide dans les syste`mes gaz-liquide-liquide: application a l’hydroformylation de l’octe`ne-1 par catalyse biphasique. The`se de Doctorat, INPT, Toulouse, 1998. (25) Arhancet, J. P.; Davis, M. E.; Merola, S. S.; Hanson, B. E. Supported Aqueous-Phase Catalysts. J. Catal. 1990, 121, 327339. (26) Herrmann, W. A.; Kohlpaintner, C. W. Water-Soluble Ligands, Metal Complexes, and Catalysts: Synergism of Homogeneous and Heterogeneous Catalysis. Angew. Chem., Int. Ed. Engl. 1993, 32, 1524-1544. (27) Purwanto; Deshpande, R. M.; Chaudhari, R. V.; Delmas, H. Solubility of Hydrogen, Carbon Monoxide, and 1-Octene in Various Solvents and Solvent Mixture. J. Chem. Eng. Data 1996, 41, 1414-1417.

Ind. Eng. Chem. Res., Vol. 44, No. 25, 2005 9641 (28) Pray, H. A.; Schweickert, C. E.; Minnich, B. H. Solubility of hydrogen, nitrogen and helium in water at elevated temperatures. Ind. Eng. Chem. 1952, 44, 1146. (29) Crozier, T. E.; Yamamoto, S. Solubility of Hydrogen in Water, Seawater and NaCl Solutions. J. Chem. Eng. Data 1974, 19, 242-244. (30) Brunner, E. Solubility of Hydrogen in 10 Organic Solvents At 298.15 And 373.15 K. J. Chem. Eng. Data 1985, 30, 269-273. (31) Nair, V. S.; Mathew, S. P.; Chaudhari, R. V. Kinetics of Hydroformylation of Styrene Using Homogeneous Rhodium Complex Catalyst. J. Mol. Catal. 1999, 143, 99-110. (32) Ja´uregui-Haza, U. J.; Pardillo-Fontdevila, E.; Wilhelm, A. M.; Delmas, H. Solubility of Hydrogen and Carbon Monoxide in

Water and Some Organic Solvents. Lat. Am. Appl. Res. 2004, 34(2), 71-74. (33) Hildebrand, J. H.; Scott, R. L. Solubility of electrolytes and nonelectrolytes; American Chemical Society: Washington, DC, 1948; p 424.

Received for review March 1, 2005 Revised manuscript received June 6, 2005 Accepted June 13, 2005 IE0502887