Hydroformylation of 1-Dodecene in the Thermomorphic Solvent

Article pubs.acs.org/IECR

Hydroformylation of 1‑Dodecene in the Thermomorphic Solvent System Dimethylformamide/Decane. Phase Behavior−Reaction Performance−Catalyst Recycling Elisabeth Schaf̈ er,† Yvonne Brunsch,‡ Gabriele Sadowski,*,† and Arno Behr*,‡ †

Laboratory of Thermodynamics, TU Dortmund, Emil-Figge-Strasse 70, D-44227 Dortmund, Germany Technical Chemistry A (Chemical Process Development), TU Dortmund, Emil-Figge-Strasse 66, D-44227 Dortmund, Germany

‡

S Supporting Information *

ABSTRACT: An economically meaningful hydroformylation of long-chain olefins requires an efficient combination of both a high-yield reaction step and efficient catalyst recycling. The application of thermomorphic multicomponent solvent (TMS) systems allows for optimal reaction as well as catalyst-recycling conditions. In this work, the TMS concept was applied to the homogeneously rhodium-catalyzed hydroformylation of 1-dodecene in the TMS system dimethylformamide (DMF)/decane using Rh(acac)(CO)2/Biphephos as the catalyst system. Thermodynamic investigations focused on the influence of the olefin (hydroformulation educt) and the aldehyde (hydroformylation product) on the phase behavior of the TMS system. Temperature dependent liquid−liquid equilibrium (LLE) data were measured for the binary systems DMF/decane and DMF/1-dodecene and for the ternary systems DMF/decane/1-dodecene and DMF/decane/dodecanal. Additionally, the corresponding LLE data were modeled applying the Perturbed Chain Polar Statistical Associating Fluid Theory (PCP-SAFT) using a heterosegmented approach for modeling the long-chain aldehyde. On the basis of the LLE data, adequate working points for hydroformylation experiments in the TMS system were selected. In these experiments, aldehyde yields of up to 87% with an n/iso ratio of up to 99:1 were achieved. Moreover, the TMS system was successfully applied to catalyst recycling in eight recycling runs with a catalyst leaching of 7 ppm rhodium at lowest. fluids20−22 have been investigated. Up to date, the main challenge is still to overcome mass transport limitations, which result in poor reaction performances.1 In industry, one approach to hydroformylate higher olefins is to use induced phase separation. The reaction is carried out homogeneously in N-methylpyrrolidone, while catalyst recycling is enabled via water extraction.2 The application of thermomorphic multicomponent solvent (TMS) systems is a promising approach that allows for both optimal reaction and catalyst recycling conditions.3,23−32 The principle of TMS systems is based on the temperature-controlled phase behavior of the reaction medium. TMS systems typically consist of at least one polar and one apolar solvent.3 At high temperatures, the medium is homogeneous, which means that educt and catalyst are in the same phase when the reaction takes place. At low temperatures, preferably at room temperature, two liquid phases exist. The polar phase contains the catalyst while the product is dissolved in the apolar phase. In this way, the catalyst can easily be separated from the product for recycling.3 The TMS system concept has already been applied to different homogeneously catalyzed reactions such as the rhodium-catalyzed cooligomerization of fatty acids with ethylene31 and the hydroaminomethylation of 1-octene with morpholine.30 Besides this, several hydroformylation reactions

1. INTRODUCTION Aldehydes are of great industrial importance, e.g. as intermediates of detergents or as fragrances. They are mainly produced by hydroformylation of olefins via homogeneous organometallic catalysis.1 Major industrial feedstocks include olefins of up to about 20 carbon atoms.2 Linear as well as branched aldehydes can be produced by hydroformylation, although the demand for linear (normal) aldehydes is much bigger.3 Therefore, high normal to iso (n/iso) ratios are required. Rhodium-based catalysts are preferred for hydroformylation catalysis as they are highly active and selective under mild conditions.3 Due to the high cost of rhodium, an efficient recycling of the catalyst is essential for an industrial process. Short-chain olefins like propene are hydroformylated economically in the Ruhrchemie/Rhô ne-Poulenc-Process (RCH-RP).3 In the RCH-RP, an aqueous/organic two-phase system is employed. That is, the reaction medium comprises two liquid phases which allow recycling of the catalyst after the reaction via separation of the organic product phase and the aqueous catalyst phase. However, the water solubility of olefins higher than C4 is marginal. Low water solubility of the olefin results in poor reaction performances as the reaction takes place primarily in the aqueous catalyst-rich phase. Long-chain olefins can therefore not be hydroformylated economically by the classical RCH-RP.1 Numerous attempts have been made to hydroformylate higher olefins employing two-phase systems. Besides aqueous systems,4−14 other strategies like micellar catalysis,14−17 application of ionic liquids,18,19 and supercritical © 2012 American Chemical Society

Received: Revised: Accepted: Published: 10296

February 23, 2012 June 12, 2012 July 3, 2012 July 3, 2012 dx.doi.org/10.1021/ie300484q | Ind. Eng. Chem. Res. 2012, 51, 10296−10306

Industrial & Engineering Chemistry Research

Article

Scheme 1. (a) Hydroformylation of 1-Dodecene Investigated within This Work and (b) Chemical Structure of the Ligand Biphephos

The objectives of this work were twofold. First, the liquid− liquid equilibrium (LLE) of the TMS system DMF/decane as well as the temperature-dependent influence of the hydroformylation educt and product were investigated. LLE data were measured at ambient pressure for the binary system DMF/decane (283.15 to 357.15 K) in order to complement and verify literature data33,34and for the binary system DMF/1dodecene (288.15−333.15 K). In addition, LLE data for the ternary system DMF/decane/1-dodecene at 298.15, 333.15, and 343.15 K and for the ternary system DMF/decane/ dodecanal at 283.15, 288.15, and 293.15 K were determined. The LLE data of the aforementioned systems were also modeled employing the Perturbed Chain Polar Statistical Associating Fluid Theory (PCP-SAFT).35−38 The results obtained by a heterosegmented modeling approach for the long-chain aldehyde were thereby compared to results employing the common homosegmented approach to describe the aldehyde molecule. Second, hydroformylation experiments were conducted focusing on investigating the influence of the solvents and DMF/decane weight ratios on the aldehyde yield and n/iso ratio. The aforementioned LLE data thereby provided the basis for the selection of meaningful working points of the hydroformylation experiments in the TMS system. Furthermore catalyzed recycling was studied for several runs.

have been studied intensively. Hydroformylation of 1-octene using the catalyst system HRh(PPh3)3(CO) and P(OPh)3 was investigated in the TMS system propylene carbonate/ dodecane/1,4-dioxane.29 The conversion of 1-octene and the yield of total aldehydes were 97% and 95%, respectively. Selectivities to the n-aldehyde of up to 89% were achieved and the rhodium leaching to the product phase is stated to be 3%. Catalyst recycling was examined regarding the hydroformylation of 1-octene in the TMS system propylene carbonate/nheptane using the catalyst system HRhCO(PPh3)3/P(OPh)3.29 The experiments revealed a decrease of the n/iso ratio during the recycling runs due to decomposition of the ligand. The isomerizing hydroformylation of the internal olefin 4-octene with Rh(acac)(CO)2/Biphephos as catalyst was studied in the TMS systems propylene carbonate/n-dodecane/N-octyl-2pyrrolidone26 and propylene carbonate/dodecane/p-xylene.27 In both TMS systems, selectivities to the n-aldehyde of more than 80% were reached. Investigation of the catalyst leaching in the TMS system propylene carbonate/dodecane/p-xylene revealed strong rhodium leaching of 47%. Additionally, the influence of the olefin and the produced aldehyde on the liquid−liquid phase behavior of the TMS system was studied for the hydroformylation of 4-octene in the TMS system propylene carbonate/dodecane/p-xylene.27 It was discovered that the aldehyde, in that case nonanal, acts as solubilizer. That is, addition of the aldehyde to the TMS system diminished the miscibility gap of the TMS system. The hydroformylation of 1dodecene has been investigated employing the TMS system polyethylenglycole 400/1,4-dioxane/n-heptane using Rh(acac)(CO)2 with a phosphite ligand as catalyst system.32 Under optimum reaction conditions, the conversion of 1-dodecene was 96% and an aldehyde yield of 94% could be achieved with a moderate n/iso ratio of 1:1. Rhodium leaching into the product phase averaged around 0.65%.32 In the present work, the hydroformylation of 1-dodecene in the TMS system dimethylformamide (DMF)/decane was studied using Rh(acac)(CO)2/Biphephos as the catalyst system (see Scheme 1). Isomeric olefins and dodecane were generated as byproduct from isomerization and hydrogenation of the substrate.

2. EXPERIMENTAL SECTION 2.1. Materials. Table 1 lists the names of all chemicals used for experiments in this work together with information about suppliers and purities. All chemicals were used without further purification. All liquids were stored over molecular sieves for drying purposes. Purity of the chemicals was confirmed by gas chromatography analysis. 2.2. MethodsLLE Measurements. The LLE data were measured using an apparatus which consisted of a doublejacketed, thermostatted glass equilibrium cell additionally placed in a separately thermostatted bath. The heating, respectively, cooling medium was silicon oil (Baysilone KT20). The inner volume of the equilibrium cell was 20 mL. A magnetic stirrer provided extensive mixing in the equilibrium cell. Mixture components were weighed with a precision of 10297

dx.doi.org/10.1021/ie300484q | Ind. Eng. Chem. Res. 2012, 51, 10296−10306


Article

After the reaction time, the autoclave was cooled down to room temperature within a few minutes by cooling in an ice bath. The reactor was depressurized and flushed with argon. Samples were taken from the upper product-containing decane phase for ICP (inductively coupled argon plasma spectrometry) measurements. Before ICP measurements, the samples from the product phase were digested with a Micro μPrep A Microwave (MWS GmbH, Switzerland). Afterward, ICP measurements were carried out on an optical emission spectrometer IRIS Intrepid ICP (Thermo Elemental). In recycling experiments, the DMF-containing catalyst phase was used in the next run adding fresh educt, apolar solvent, and synthesis gas.

Table 1. Chemicals Used for Experiments in This Work

a

substance

supplier

purity [%]

1-dodecene 1-dodecene DMF decane dodecanal Rh(acac)(CO)2 Biphephos CO/H2

VWR Sigma Aldrich Acros Organics Acros Organics Merck Umicore Molisa Messer Industriegase

93−95a 99b 99 99 98 39.9 Rh 97c 99.9999

Used for hydroformylation experiments. measurements. chttp://molisa.biz/.

b

Used for LLE data

3. THEORYPC-SAFT MODEL The PC-SAFT equation of state was derived by Gross and Sadowski35,36 and is based on a thermodynamic perturbation theory which uses a system of freely jointed hard spheres as reference, referred to as hard-chain system. Various types of interactions such as dispersive, associating, and polar interactions can be accounted for as perturbations. According to the perturbation theory, the residual Helmholtz energy ares is calculated by summing the different contributions accounting for the reference system and the different types of perturbations. In eq 1, ahc stands for the contribution of the hard-chain reference system, whereas adisp refers to dispersive, aassoc, to associative, and adipole, to dipolar interactions.

±0.001 g. The composition of samples taken from the equilibrium cell was analyzed via gas chromatography (GC) (Agilent GC 7890, Agilent Technologies Deutschland GmbH, Germany). The gas chromatograph was equipped with a capillary column (HP-5 5% Phenyl Methyl Siloxan) and a flame ionization detector (FID). In this work, the binary LLE data were measured by two different methods: the analytic method and the cloud-point method. The LLE data for the ternary systems were measured by the analytic method. 2.2.1. Analytic Method. The procedure of the analytic method comprised three steps. First, the mixture components were filled into the equilibrium cell and stirred at constant temperature for about an hour. The temperature of the mixture in the equilibrium cell was kept constant within ±0.03 K. Second, stirring was stopped and the heterogeneous system was kept at constant temperature until both of the phases were transparent and a sharp phase boundary appeared. In the third step, samples of the two phases were taken using injection syringes for chemical analysis via GC. 2.2.2. Cloud-Point Method. The procedure of the cloudpoint method comprised two steps. After a mixture of known composition was filled into the equilibrium cell, it was initially heated beyond the cloud point so that the mixture became homogeneous. Then, the mixture was repeatedly cooled and heated in order to detect the cloud-point temperature visually. The samples were stirred continuously throughout the experiment. The cooling, respectively, heating rate was 0.03 K/min. The cloud-point temperature was reproducible within ±0.03 K. 2.3. MethodsHydroformylation Experiments. All hydroformylation experiments were performed in a 300 mL stainless-steel Parr autoclave. Recycling experiments were performed in a 10 mL multiplex autoclave.39 The experimental procedures for the hydroformylation experiments were the same in both autoclaves. In a typical experiment, the educt 1-dodecene (7.56 g, 4.5 × 10−2 mol), the catalyst precursor Rh(acac)(CO)2 (11.6 mg, 4.5 × 10−5 mol), and the ligand Biphephos (177 mg, 22.5 × 10−5 mol) were dissolved in the polar solvent, e.g. DMF (21.8 mL), and the apolar solvent decane (28.2 mL). This reaction solution was filled into the autoclave under inert gas atmosphere. The pressure of the synthesis gas was adjusted at 30 bar CO/H2. The stirrer was adjusted to 800 rpm. All reaction experiments were performed at 373.15 K. Samples for GC analysis were taken during reaction in the 300 mL autoclave with a capillary. These samples were analyzed by GC (Hewlett-Packard). The gas chromatograph was equipped with a capillary column (HP5 5% Phenyl Methyl Siloxan) and an FID.

a res = a hc + adisp + aassoc + adipole

(1)

Accounting for dipolar interactions by the expression proposed by Gross and Vrabec37 leads to the PCP-SAFT equation of state. The PCP-SAFT equation of state is applicable to nonpolar, polar, and associating pure components as well as their mixtures. For more details of the PC-SAFT concept, see refs 35−38 and 40−43. Besides the original, homosegmented PC-SAFT concept, where every component is thought to consist of only one type of spheres, Gross et al. derived the Copolymer PC-SAFT concept based on the idea of introducing heterosegmented components.38 Heterosegmented components may consist of two or more different types of spheres. Generally, employing the PC(P)-SAFT equations of state requires fitting pure-component parameters for each component. The number of pure-component parameters depends on the types of perturbation contributions involved and whether the component is treated as being homo- or heterosegmented. For apolar, homosegmented components, there exist three pure-component parameters, namely the segment number m, the segment diameter σ, and the dispersion-energy parameter ε/k. If the component is treated as being heterosegmented, there exists one segment number accounting for the total number of segments of the molecule. Additionally, one segment diameter and one dispersion-energy parameter for each type of segment as well as the corresponding segment fractions ziα and bonding fractions Biαiβ have to be defined.38 Concerning polar components, the value of the dipole moment μ has to be defined as well. The value of the dipole moment employed for modeling phase equilibria often corresponds to the literature gas phase, respectively, the vacuum dipole moment. However, the gas phase or vacuum value of the dipole moment neglects intermolecular dipole interactions which occur in the liquid state. That is the gas phase or vacuum value of the dipole 10298



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moment does not necessarily represent the dipolar characteristic of the substance in the liquid state correctly. Additionally, the expression for polar interactions proposed by Gross and Vrabec37 does not account for dipole moments perpendicular to the molecular axis which might cause the dipolar contribution to be too low if the literature value of the dipole moment is employed. As a consequence, the dipole moment can also be a fitted parameter,37 which was done also in this work. Modeling mixtures of different components requires one additional binary interaction parameter kij for each binary combination of the components to correct the combining rule for the dispersion-energy. The pure-component parameters are typically fitted to purecomponent liquid-volume and vapor-pressure data. This is also true for the parameter-fitting done in this work. The binary interaction parameters were fitted to LLE data. In this work, the PCP-SAFT equation of state and the heterosegmented PC-SAFT concept were combined to model the long-chain aldehyde. The combination required adapting the dipolar expression by Gross and Vrabec.37 In particular, an additional summation over all segment types has to be accounted for in the perturbation terms. The resulting expression is given in the Appendix.

Figure 1. Liquid−liquid equilibrium of the system DMF/decane. Symbols are experimental data: (●) lit. data;33 (■) lit. data;34 (△) this work cloud-point method; (◮) this work analytic method. The solid line is modeling with PCP-SAFT using the parameters given in Table 2.

4. RESULTS AND DISCUSSION In the following, investigations on the LLE phase behavior of the TMS system DMF/decane, the binary subsystem DMF/1dodecene, as well as the ternary systems DMF/decane/1dodecene and DMF/decane/dodecanal are presented. The gained knowledge is transferred to the hydroformylation experiments which are discussed afterward. 4.1. LLE Measurements. In this section the experimental results of the LLE measurements are given. Modeling results are discussed in the subsequent paragraph. 4.1.1. Binary System DMF/Decane. LLE data for the system DMF/decane were measured by the analytic method and by the cloud-point method. Figure 1 presents the experimental LLE data of this work, determined by the two aforementioned methods, in comparison with literature data33,34 as well as in comparison with modeling results. Concerning the modeling results, see section 4.2 for details. As can be seen from Figure 1, the LLE data measured in this work by the two different methods are consistent. Moreover, the LLE data of this work and literature data33,34 coincide very well in the region of the upper critical solution temperature (UCST) and for the decane-rich part of the miscibility curve. Moderate discrepancies between the LLE data of the different sources occur only at temperatures between 333.15 and 353.15 K at the DMF-rich part of the miscibility curve. The literature data by different authors are obviously not consistent and reveal certain uncertainties in this region. From the thermodynamic point of view, the combination of DMF and decane constitutes an appropriate TMS system due to the strongly temperature-dependent LLE phase behavior of the system. There exists a large miscibility gap at low temperatures (298.15 K and below) required for efficient product, respectively, catalyst separation. At the same time, the UCST (357.76 K33) is far below 373.15 K which is important for optimal reaction conditions. 4.1.2. Binary System DMF/1-Dodecene. LLE data for the system DMF/1-dodecene were measured by the analytic method. Figure 2 shows the experimental data as well as the

corresponding modeling results which are discussed in section 4.2.

Figure 2. Liquid−liquid equilibrium of the system DMF/1-dodecene. Symbols are experimental data. The solid line is modeling with PCPSAFT using the parameters given in Table 2.

Obviously, the miscibility of DMF and 1-dodecene is better than that of DMF and decane since the miscibility gap of the DMF/1-dodecene system is smaller and the UCST lies below 357 K. According to literature data on DMF/hydrocarbon systems,44−48 the miscibility gap of DMF/hydrocarbon mixtures increases with an increasing length of the hydrocarbon chain. As a consequence, the double bond must have a rather strong effect in the system with 1-dodecene. Otherwise the enhanced miscibility of 1-dodecene and DMF compared to that of decane and DMF would not occur. 10299



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4.1.3. Ternary System DMF/Decane/1-Dodecene. The LLE data for the system DMF/decane/1-dodecene were measured by the analytic method at 298.15, 333.15, and 334.15 K. The related miscibility curves are presented in Figure 3 together with modeling results. Concerning the modeling results, see section 4.2 for details.

Figure 3. Liquid−liquid equilibrium of the system DMF/decane/1dodecene. Symbols are experimental data at the following temperatures: 298.15 K (●), 333.15 K (▲), and 343.15 K (■). Lines are modeling with PCP-SAFT at the following temperatures: 298.15 K (solid line), 333.15 K (dashed line), and 343.15 K (dashed-dotted line). Parameters employed for the modeling are given in Table 2.

As can be seen from Figure 3, 1-dodecene acts as moderate solubilizer with respect to the system DMF/decane. That is the miscibility gap between the decane-rich and the DMF-rich phase shrinks, if the weight fraction of 1-dodecene rises. This effect corresponds to the findings described in section 4.1.2 concerning the difference in the degree of miscibility of DMF and decane compared to that of DMF and 1-dodecene. Comparing the miscibility curves for the system DMF/ decane/1-dodecene for different temperatures (298.15, 333.15 and 343.15 K) reveals a relatively strong temperature dependency of the LLE. 1-Dodecene is the educt of the hydroformylation reaction. Due to the solubilizing effect of 1-dodecene, the homogeneous region is enlarged if 1-dodecene is added to the TMS system DMF/decane. As a consequence, the operating window of the reaction is enlarged due to the presence of the educt. 4.1.4. Ternary System DMF/Decane/Dodecanal. The LLE data of this work for the system DMF/decane/dodecanal were measured by the analytic method at 283.15, 288.15, and 298.15 K. In Figure 4a, the experimentally determined miscibility curve at 298.15 K is presented together with modeling results obtained by the homo- as well as the heterosegmented modeling approach for dodecanal at 298.15 K. In Figure 4b, the experimentally determined miscibility curves for all temperatures investigated are shown together with the corresponding modeling results obtained by the heterosegmented approach for dodecanal. In section 4.2, the modeling results are discussed in detail. As can be seen from Figure 4, dodecanal acts as strong solubilizer. The miscibility gap between the decane-rich and the DMF-rich phase shrinks significantly if the weight fraction of dodecanal rises. Compared to the LLE data for DMF/decane/

Figure 4. (a) Liquid−liquid equilibrium of the system DMF/decane/ dodecanal. Symbols are experimental data at 298.15 K (■). Lines are modeling with PCP-SAFT at 298.15 K using the parameters given in Table 2. Comparison between modeling results obtained by the homosegmented approach for dodecanal (dashed-line) and the heterosegmented approach for dodecanal (solid line). (b) Liquid− liquid equilibrium of the system DMF/decane/dodecanal. Symbols are experimental data at the following temperatures: 283.15 K (○), 288.15 K (▲), and 298.15 K (□). Lines are modeling with PCP-SAFT using the heterosegmented approach for dodecanal at the following temperatures: 283.15 K(dashed-dotted line); 288.15 K (dashed line); 298.15 K (solid line). Parameters employed for the modeling are given in Table 2.

1-dodecene at 298.15 K in Figure 3, dodecanal obviously improves the miscibility of DMF and decane much stronger than 1-dodecene does. The reason for this effect is probably due the carbonyl group of the aldehyde which has a distinctive dipolar character. Concerning the temperature dependence of the LLE data for the system DMF/decane/dodecanal, comparison of the data presented in Figure 4 reveals that the miscibility curves do not strongly depend on temperature in the range of 283.15−298.15 K. Regarding the TMS system concept, the solubilizing effect of the product dodecanal is unwanted as the operating area of the separation is reduced. Yet, implementing the TMS system principle of a temperature-controlled phase behavior is still viable from the thermodynamic point of view. 10300



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Table 2. PCP-SAFT Pure-Component Parameters of Substances Employed in This Work As Well As max. RD and ARD Values for Vapor Pressures and Liquid Volumes vapor pressure μib (D)

max. RD (%)f

ARD (%)g

T range (K)

max. RD (%)f

ARD (%)g

19.18 14.59 4.16

7.09 2.29 2.38

243−617 300−630 310−630 390−630

10.82 6.64 2.30

4.39 1.07 1.21

24.01

11.48

390−630

1.97

1.20

substance

refa

decane DMF 1-dodecene dodecanald dodecanale tail head

published36 this work48 this work48 this work48

142.285 73.095 168.32 184.32

4.6627 2.3660 5.0091 6.0915

3.8384 3.6359 3.9413 3.6916

243.87 312.99 254.86 250.64

3.823 0.5249 2.5849

4.12 1.70 2.88

this work48 this work48

184.32

4.6627 1.5599

3.8384 3.0601

243.87 220.56

2.5849

2.88

mi (−)

σi (Å)

εi/k (K)

liquid volume

μic (D)

Mi (g/mol)

a

If parameters were published previously, then references refer to the source of these parameters. Otherwise, the references refer to the source of data employed to fit the parameters. bLiterature value of dipole moment in the gas phase. cFitted value of dipole moment employed to model LLE data in this work. dDodecanal treated as being homosegmented. eDodecanal treated as being heterosegmented. Segment fractions ziα were calculated by miα ziα = ∑α miα Bonding fractions Biαiβ were calculated by Biαiβ =

1 ; ∑α miα − 1

Biαiα =

miα − 1 ∑α miα − 1

with α and β corresponding to the head or the tail of the aldehyde. fThe term “max. RD” is defined as

max. RD = 100 × max

ycalc, i − yexp , i yexp , i

The term “ARD” is defined as

g

ARD = 100 ×

nexp ycalc, i − yexp , i 1 ∑ nexp i = 1 yexp , i

kij = −0.000315T /K + 0.1159

4.2. ModelingLLE Data. 4.2.1. DMF/Decane. Decane is an apolar component whereas DMF is a polar component. That is, dipolar interactions had to be accounted for in case of DMF, but there do not exist associative interactions. Both, decane and DMF were described in this work as being homosegmented which is the usual approach for solvents. The dipole moment of DMF was treated as fitting parameter. Thus, a total of four pure-component parameters was fitted for DMF to vaporpressure and liquid-volume data of DMF. Additionally, experimental LLE data of the system DMF/decane were taken into account in the fitting procedure of the purecomponent parameters of DMF. Table 2 lists the values of the pure-component parameters, the maximum relative deviation (max. RD) as well as the average relative deviation (ARD) between experimental and calculated vapor pressures and liquid volumes for all components employed in this work. Additionally, the literature values of the dipole moments in the gas phase of polar components are given. Comparison of the literature values and the fitted dipole moments shows that the fitted dipole moments are always slightly larger than the gas phase values. This can be explained by the fact that the gas phase values neglect dipolar intermolecular interactions and by the characteristics of the dipolar expression by Gross and Vrabec37 which was mentioned before in section 3. Fitting of the binary interaction parameter, kij for the system DMF/decane resulted in a linear function of temperature:

(2)

As can be seen from Figure 1, modeled and experimentally determined LLE data coincide very well in the temperature range between 283.15 and 333.15 K. Close to the UCST, moderate discrepancies occur primarily with respect to the DMF-rich part of the miscibility curve. 4.2.2. DMF/1-Dodecene. The pure-component parameters for DMF were already discussed in the previous section. 1Dodecene was also treated as polar, homosegmented component. The dipole moment of 1-dodecene was regarded as fitted parameter. The pure-component parameters of 1dodecene can be found in Table 2. Concerning the value of the binary interaction parameter kij, the following linear expression was determined for DMF and 1-dodecene: kij = − 0.000331T /K + 0.1128

(3)

Figure 2 illustrates that experimentally determined and modeled LLE data of the system DMF/1-dodecene exhibit only minor discrepancies. Especially for the 1-dodecene-rich part of the miscibility curve, measured and calculated LLE data match very well. 4.2.3. DMF/Decane/1-Dodecene. The pure-component parameters for decane, DMF, and 1-dodecene were previously introduced. The values of the binary interaction parameters used to model the LLE of the system DMF/decane/1dodecene are listed in Table 3. 10301



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Table 3. Values of the Binary Interaction Parameters kij of the System DMF/Decane/1-Dodecene

a

T (K)

kDMF/decanea

kDMF/1‑dodeceneb

kdecane/1‑dodecene

298.15 333.15 343.15

0.0220 0.0110 0.0078

0.0141 0.0025 −0.0008

0.0000 0.0000 0.0000

component parameters of decane were employed. The values of the parameters for the headgroup were fitted simultaneously to experimental vapor-pressure and liquid-volume data of butanal, octanal, decanal, dodecanal, and tridecanal. That means that one set of head parameters was determined for all the aforementioned aldehydes. As can be seen from Figure 4, conformity of modeled and experimentally determined LLE data is considerably improved in the case of the heterosegmented approach for dodecanal. That is, experimental and modeled LLE data correspond much better for the heterosegmented approach than for the homosegmented approach. Therefore, the heterosegmented approach for dodecanal was also employed to model the LLE data of the system DMF/ decane/dodecanal at 283.15 and 288.15 K. The results presented in Figure 4b reveal that modeled and experimental data coincide well for all temperatures investigated. 4.3. Hydroformylation Experiments. The influence of the solvent system on the rhodium-catalyzed reaction was investigated. Hydroformylation experiments in pure DMF and pure decane as well as in the TMS system DMF/decane (50:50 (g/g)) were carried out. Concerning the hydroformylation experiments in the TMS system, it was assumed, that the phase behavior of the ternary system DMF/decane/tridecanal is similar to that of the system DMF/decane/dodecanal. Therefore the selection of adequate working points for the hydroformylation experiments was based on the LLE data of the system DMF/decane/dodecanal (Figure 4). The working points for the hydroformylation experiments were chosen at 16 wt % 1-dodecene and a DMF/decane ratio of 50:50 (g/g). The polar DMF-containing phase contained the catalyst, while the apolar decane-containing phase enabled separation of the aldehyde product. As can be seen in Table 5, aldehyde yields Y of 84% were achieved with high n/iso ratios of 98:2 in all solvent systems. As

Values calculated with eq 2. bValues calculated with eq 3.

As can be seen from Figure 3, modeled and experimentally determined LLE data coincide well for all temperatures investigated. The change from an open miscibility gap to a closed miscibility gap with rising temperature is described correctly. The ternary LLE data were modeled without introducing additional parameters. The binary interaction parameters kij which were fitted for the LLE of the binary subsystems DMF/decane and DMF/1-dodecene were also used in the calculation of the ternary system. Measured and modeled LLE data of the ternary systems coincide best for 298.15 K and 333.15 K. This corresponds to the findings for the subsystems DMF/decane and DMF/1-dodecene, whereby discrepancies between experimental and calculated LLE data increased slightly at higher temperatures. 4.2.4. DMF/Decane/Dodecanal. The pure-component parameters for decane and DMF are the same as those employed to model the LLE data of the system DMF/decane. Dodecanal was described as polar. The dipole moment of dodecanal was treated as a fitted parameter. In Table 2, two sets of pure-component parameters for dodecanal are listed: one for the homosegmented case and one for the heterosegmented case. The values of the binary interaction parameters of the system DMF/decane/dodecanal are listed in Table 4 for the homosegmented as well as for the heterosegmented approach for dodecanal. Figure 4 presents the experimental LLE data of the system DMF/decane/dodecanal at 298.15 K in comparison with modeling results for both, the homosegmented and the heterosegmented approach for dodecanal. The representation of the experimental data employing the homosegmented approach for dodecanal is insufficient. The reason for this result might be the structure of the dodecanal molecule. A characteristic feature of the dodecanal molecule is that it has a long apolar alkyl tail on the one hand and a polar headgroup containing the carbonyl group on the other hand. That is, the molecule shows two different domains one being apolar and the other being polar. By using the homosegmented approach to describe the dodecanal molecule, the two-domain characteristic is probably not accounted for adequately. For the heterosegmented approach, the molecule was thought to consist of two domains, one being the apolar alkyl tail and the other representing the polar headgroup with the carbonyl group. As parameters of the alkyl tail, the pure-

Table 5. Results of Hydroformylation Experiments by Varying the Solvent Systema DMF/decane (g/g)

X (%)

Yaldehydes (%)

Yolefins (%)

Yalkane (%)

n/iso

DMF/decane (g/g)

1:0 0:1 1:1

99 99 99

84 84 84

11 11 11

4 4 4

98:2 98:2 98:2

1:0 0:1 1:1

a

Reaction conditions: 0.045 mol 1-dodecene (7.56 g), 1-dodecene =16 wt %, 4.5 × 10−5 mol Rh(acac)(CO)2 (11.6 mg), substrate/metal = 1000:1, ligand = Biphephos, metal/ligand = 1:5, 50 mL solvent, 800 rpm, 30 bar CO/H2, CO/H2 = 1:1, 373.15 K, 5 h.

byproduct 11% isomeric olefins and 4% alkane were detected. Consequently, the hydroformylation can be carried out homogeneously in pure solvents as well as in the TMS system,

Table 4. Binary Interaction Parameters of the System DMF/Decane/Dodecanal for the Homosegmented and the Heterosegmented Approach for Dodecanal homosegmented approach

a

T (K)

kDMF/decane

283.15 288.15 298.15

0.0267 0.0251 0.0220

a

heterosegmented approach

kDMF/dodecanal

kdecane/dodecanal

kDMF/dodecanal‑taila

−0.0100 −0.0100 −0.0100

−0.0050 −0.0050 −0.0050

0.0267 0.0251 0.0220

kDMF/dodecanal‑head

kdecane/dodecanal‑tail

kdecane/dodecanal‑head

0.0000 0.0000 0.0000

0.0000 0.0000 0.0000

0.0100 0.0100 0.0100

Values calculated with eq 2. 10302



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which is one-phase at reaction temperature and biphasic at separation temperature. Moreover, the reaction progress expressed in terms of the aldehyde yield in the different solvent systems was investigated. Figure 5 shows that there is no significant difference of the

Table 7. Catalyst Recycling of the Hydroformylation of 1Dodecene in the TMS System DMF/Decane run

Yaldehydes (%)

Yolefins (%)

Yalkane (%)

n/iso

Rh (ppm)

P (ppm)

1 2 3 4 5 6b 7 8

78 72 72 74 72 77 75 78

17 19 23 15 24 19 18 17

4 5 4 4 2 4 4 4

98:2 98:2 98:2 92:8 84:16 92:8 96:4 98:2

11 6 4 3 3 3 4 6

53 22 9 20 14 35 40 36

Reaction conditions: 0.0068 mol distilled 1-dodecene, 6.8 × 10−6 mol Rh(acac)(CO)2, ligand = Biphephos, metal/ligand = 1:20, 3.7 mL distilled DMF, 4.8 mL distilled decane, 20 bar CO/H2, T = 373.15 K, 650 rpm, 2 h, run 1−4: addition of DMF. bAddition of 13.6 × 10−5 mol Biphephos. a

linear aldehyde were achieved. Finally, the leaching of the catalyst system into the product phase was analyzed. The lowest leaching of the rhodium catalyst (7 ppm) and phosphorus ligand (7 ppm) was detected at a phase composition of DMF/decane = 50:50 (g/g) (see Table 6). Therefore effective separation of the polar DMF-containing catalyst phase and the apolar decane-containing product phase was achieved. The successful application of the TMS system DMF/decane for catalyst recycling has been demonstrated for the rhodium-catalyzed hydroformylation of 1-dodecene.

Figure 5. Aldehyde yield over time in different solvent systems for the hydroformylation of 1-dodecene. Symbols are experimental data: ● DMF system; ■ decane system; ◮ TMS system. Reaction conditions: 0.045 mol 1-dodecene (7.56 g), 1-dodecene = 16 wt %, 4.5 × 10−5 mol Rh(acac)(CO)2 (11.6 mg), substrate/metal = 1000:1, ligand = Biphephos, metal/ligand = 1:5, 50 mL solvent, 800 rpm, 30 bar CO/H2, CO/H2 = 1:1, 373.15 K, 5 h.

5. CONCLUSION The concept of thermomorphic multicomponent solvent (TMS) systems was applied to the homogeneously rhodiumcatalyzed hydroformylation of 1-dodecene in the TMS system DMF/decane using Rh(acac)(CO)2/Biphephos as catalyst system. Thermodynamic studies dealing with the temperature-dependent influence of the olefin and the aldehyde on the LLE of the TMS system were performed as the basis for the selection of adequate working points for hydroformylation experiments in the TMS system. Experimental LLE data were measured for the TMS system DMF/decane, the binary subsystem DMF/1-dodecene and for the ternary systems DMF/decane/1-dodecene and DMF/decane/dodecanal. Concerning the influence of 1-dodecene (hydroformylation educt) on the LLE of the TMS system, it was shown that the olefin acts as moderate solubilizer. That is the miscibility of DMF and decane increases if the concentration of the olefin rises. The temperature dependency of this effect investigated between 298.15 and 343.15 K was found to be rather distinctive. The solubilizing effect of the aldehyde (hydroformylation product), mentioned before by Behr et al.27 for nonanal in the TMS system propylene carbonate/dodecane/p-xylene, was con-

reaction progress in DMF, decane, and the TMS system. In all reactions, the same aldehyde yield of 84% was achieved. This proves that the solvents did not have a limiting influence on the reaction progress. Next, the DMF/decane weight ratio was varied in hydroformylation experiments. Table 6 shows that the aldehyde yield increases from 79 to 87% when less DMF and more decane was used in the reaction media. Different phase compositions were applicable to the hydroformylation of 1-dodecene. The recycling of the catalyst in the TMS system DMF/ decane was accomplished in eight runs. After homogeneous reaction and separation of the apolar decane-containing product phase at room temperature, the polar DMF-containing catalyst phase was reused. Table 7 shows that aldehyde yields up to 78% were achieved. The reaction proceeded very well over all eight recycling runs. Very high n/iso ratios up to 98:2 were achieved. In recycling run four and five, the n/iso ratio decreased. After adding fresh ligand high selectivity toward the

Table 6. Results of Hydroformylation Experiments by Varying DMF/Decane Weight Ratioa DMF/decane (wt %)

Xolefins (%)

Yaldehydes (%)

Yolefins (%)

Yalkane (%)

n/iso

Rh (ppm)

P (ppm)

70:30 60:40 50:50 40:60 30:70

84 86 87 89 90

79 82 83 86 87

16 14 13 11 10

5 4 4 3 3

98:2 99:1 99:1 99:1 98:2

12 12 7 17 24

26 19 7 25 26

a

Reaction conditions: substrate = 1-dodecene, catalyst-precursor = Rh(acac)(CO)2, substrate/metal = 1000:1, ligand = Biphephos, metal/ligand = 1:5, 50 mL solvent, polar solvent = DMF, apolar solvent = decane, 800 rpm, 30 bar CO/H2, CO/H2 = 1:1, 373.15 K, 3 h. 10303



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firmed. In comparison to the influence of the olefin, the solubilizing effect of dodecanal was found to be much stronger. The temperature dependency of the solubilizing effect of the aldehyde, investigated at temperatures between 283.15 and 298.15 K, was shown to be rather weak. Despite the strong influence of the aldehyde on the LLE of the TMS system DMF/decane, the TMS concept is applicable from the thermodynamic point of view. The experimental LLE data were successfully modeled employing the PCP-SAFT equation of state. A heterosegmented approach for the long-chain aldehyde was applied to model the LLE data for the ternary system DMF/decane/ dodecanal. The new modeling concept explicitly accounts for the molecular structure of the aldehyde consisting of an apolar alkyl tail and a polar headgroup. It was shown that results provided by using the heterosegmented approach coincide much better with the corresponding experimental data than results employing the common homosegmented approach to describe the aldehyde molecule. Regarding hydroformylation experiments, the influence of the reaction medium on the reaction performance and catalyst recycling was studied. It was demonstrated that the reaction proceeds very well at different DMF/decane ratios with aldehyde yields up to 87% and n/iso ratios up to 99:1. Compared to the findings of Yang et al.32 who reported n/iso ratios of 1:1 in the solvent system polyethylenglycole 400/1,4dioxane/n-heptane (catalyst: Rh(acac)(CO)2/phosphite ligand), the reaction performance is improved considerably. The separation of the product from the catalyst phase was furthermore successfully realized. The lowest catalyst leaching of 7 ppm was found at a DMF/decane ratio of 50:50 (g/g). That is, the application of the TMS system DMF/decane provides efficient catalyst recovery and recycling performance for the rhodium-catalyzed hydroformylation of 1-dodecene.

4

i

μi 2 μj 2 mimj

j

∑∑ α

β

×

∑∑∑ α

4

J2,DD = iαjβ

∑ ∑ ∑ xixjxk

⎛

β

γ

i

j

(miziαmjzjβ)1/2

a 2n

+

(miziαmjzjβ)1/2

(miziαmjzjβ)1/2 − 1 (miziαmjzjβ)1/2

×

b1n (miziαmjzjβ)1/2 − 2 (miziαmjzjβ)1/2

b 2n

with miziαmjzjβ ≤ 2

(from ref 37)

cn , iαjβkγ = c0n + +

×

(10)

(miziαmjzjβmk zkγ )1/3 − 1 (miziαmjzjβmk zkγ )1/3

c1n

(miziαmjzjβmk zkγ )1/3 − 1 (miziαmjzjβmk zkγ )1/3 (miziαmjzjβmk zkγ )1/3 − 2 (miziαmjzjβmk zkγ )1/3

c 2n

with miziαmjzjβmk zkγ ≤ 2

(from ref 37)

(11)

The model constants a[0−2]n, b[0−2]n, and c[0−2]n are fitted by Gross and Vrabec37 to molecular simulation data by Stoll et al.49 comprising vapor pressure data, saturated liquid, and vapor density data as well as viral coefficients.

■

ASSOCIATED CONTENT

S Supporting Information *

Experimental LLE data for the binary systems DMF/decane and DMF/1-dodecene and for the ternary systems DMF/ decane/1-dodecene and DMF/decane/dodecanal (Tables S1− S5). This material is available free of charge via the Internet at http://pubs.acs.org.

■

J2,DD iαjβ σ 3iαjβziαzjβ

AUTHOR INFORMATION

Corresponding Author

μi 2 μj 2 μk 2

*E-mail: [email protected] (A.B.), gabriele. [email protected] (G.S.).

mimjmk

The authors declare no competing financial interest.

σiαjβσiαkγσjβkγziαzjβzkγ εiαjβ ⎞ n ⎟η kT ⎠

(miziαmjzjβ)1/2 − 1

bn , iαjβ = b0n +

Notes

■

J3,DD iαjβkγ

∑ ⎜⎝an,iαjβ + bn,iαjβ n=0

k

(miziαmjzjβ)1/2


×

(9)

(5)

a3 4 ρ2 = −π NkT 3 (kT )3

a1n

(miziαmjzjβ)1/2


+

(4)

∑ ∑ xixj


an , iαjβ = a0n +

■

a2 ρ = −π NkT (kT )2

(8)

n=0

APPENDIX Combining the PCP-SAFT equation of state and the heterosegmented PC-SAFT concept required adapting the dipolar expression by Gross and Vrabec.37 That is, an additional summation over all segment types has to be accounted for if a molecule is treated as being heterosegmented. The expression for the dipolar contribution by Gross and Vrabec37 including the summation over all segment types is obtained as follows a /NkT adipole = 2 NkT 1 − a3 / a 2

∑ ciαjβkγηn

J3,DD = iαjβkγ

ACKNOWLEDGMENTS This work is part of the Sonderforschungsbereich/Transregio 63 “Integrated Chemical Processes in Liquid Multiphase Systems”. The authors thank the Deutsche Forschungsgemeinschaft (DFG) for financial support and the Umicore AG & Co. KG for the donation of the rhodium catalyst Rh(acac)(CO)2.

(6)

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(13) Baricelli, P. J.; Lujano, E.; Modrono, M.; Marrero, A. C.; Garcia, Y. M.; Fuentes, A.; Sanchez-Delgado, R. A. Rhodium-catalyzed hydroformylation of C6 alkenes and alkene mixturesA comparative study in homogeneous and aqueous-biphasic media using PPh3, TPPTS and TPPMS ligands. J. Organomet. Chem. 2004, 689 (23), 3782−3792. (14) Dabbawala, A. A.; Parmar, D. U.; Bajaj, H. C.; Jasra, R. V. CoCl2(TPPTS)2 catalyzed hydroformylation of 1-octene and 1-decene in the presence of surfactant and co-solvents in a biphasic medium. J. Mol. Catal. A: Chem. 2008, 282 (1−2), 99−106. (15) Haumann, M.; Koch, H.; Schomäcker, R. Hydroformylation in microemulsions: conversion of an internal long chain alkene into a linear aldehyde using a water soluble cobalt catalyst. Catal. Today 2003, 79 (1−4), 43−49. (16) Haumann, M.; Yildiz, H.; Koch, H.; Schomäcker, R. Hydroformylation of 7-tetradecene using Rh-TPPTS in a microemulsion. Appl. Catal., A 2002, 236 (1−2), 173−178. (17) Hapiot, F.; Leclercq, L.; Azaroual, N.; Fourmentin, S.; Tilloy, S.; Monflier, E. Rhodium-Catalyzed Hydroformylation Promoted by Modified Cyclodextrins: Current Scope and Future Developments. Curr. Org. Synth. 2008, 5, 162−172. (18) Desset, S. L.; Cole-Hamilton, D. J.; Foster, D. F. Aqueousbiphasic hydroformylation of higher alkenes promoted by alkylimidazolium salts. Chem. Commun. 2007, 19, 1933−1935. (19) Riisager, A.; Eriksen, K. M.; Wasserscheid, P.; Fehrmann, R. Propene and 1-octene hydroformylation with silica-supported, ionic liquid-phase (SILP) Rh-phosphine catalysts in continuous fixed-bed mode. Catal. Lett. 2003, 90 (3−4), 149−153. (20) Fujita, S. I.; Akihara, S.; Fujisawa, S.; Arai, M. Hydroformylation of 1-hexene using polymer-supported rhodium catalysts in supercritical carbon dioxide. J. Mol. Catal. A: Chem. 2007, 268 (1−2), 244−250. (21) Koeken, A. C. J.; de Bakker, S. J. M.; Costerus, H. M.; van den Broeke, L. J. P.; Deelman, B. J.; Keurentjes, J. T. F. Evaluation of pressure and correlation to reaction rates during homogeneously catalyzed hydroformylation in supercritical carbon dioxide. J. Supercrit. Fluids 2008, 46 (1), 47−56. (22) Patcas, F.; Maniut, C.; Ionescu, C.; Pitter, S.; Dinjus, E. Supercritical carbon dioxide as an alternative reaction medium for hydroformylation with integrated catalyst recycling. Appl. Catal., B 2007, 70 (1−4), 630−636. (23) Behr, A.; Henze, G.; Johnen, L.; Awungacha, C. Advances in thermomorphic liquid/liquid recycling of homogeneous transition metal catalysts. J. Mol. Catal. A: Chem. 2008, 285 (1−2), 20−28. (24) Behr, A.; Fängewisch, C. Rhodium-catalysed synthesis of branched fatty compounds in temperature-dependent solvent systems. J. Mol. Catal. A: Chem. 2003, 197 (1−2), 115−126. (25) Behr, A.; Roll, R. Temperaturgesteuerte MehrkomponentenLö sungsmittelsysteme für homogene übergangsmetallkatalysierte Reaktionen. Chem. Ing. Tech. 2005, 77 (6), 748−752. (26) Behr, A.; Henze, G.; Obst, D.; Turkowski, B. Selection process of new solvents in temperature-dependent multi-component solvent systems and its application in isomerising hydroformylation. Green Chem. 2005, 7 (9), 645−649. (27) Behr, A.; Obst, D.; Turkowski, B. Isomerizing hydroformylation of trans-4-octene to n-nonanal in multiphase systems: acceleration effect of propylene carbonate. J. Mol. Catal. A: Chem. 2005, 226 (2), 215−219. (28) Shaharun, M. S.; Dutta, B. K.; Mukhtar, H.; Maitra, S. Hydroformylation of 1-octene using rhodium-phosphite catalyst in a thermomorphic solvent system. Chem. Eng. Sci. 2010, 65 (1), 273− 281. (29) Tijani, J.; El Ali, B. Selective thermomorphic biphasic hydroformylation of higher olefins catalyzed by HRhCO(PPh3)3/ P(OPh)3. Appl. Catal., A 2006, 303 (2), 158−165. (30) Behr, A.; Roll, R. Hydroaminomethylation in thermomorphic solvent systems. J. Mol. Catal. A: Chem. 2005, 239, 180−184. (31) Behr, A.; Miao, Q. A new temperature-dependent solvent system based on polyethylene glycol 1000 and its use in rhodium

NOMENCLATURE a = Helmholtz free energy k = Boltzmann constant m = segment number N = total number of molecules T = temperature t = time w = mass fraction x = mole fraction Y = yield z = segment fraction a[0−2]n = model constants b[0−2]n = model constants c[0−2]n = model constants

Greek Letters

ε/k = dispersion-energy parameter ρ = number density μ = dipole moment σ = segment diameter

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REFERENCES

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Hydroformylation of 1-Dodecene in the Thermomorphic Solvent

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