Phase Equilibria in Systems of Morpholine, Acetonitrile, and n-Alkanes

Article pubs.acs.org/jced

Phase Equilibria in Systems of Morpholine, Acetonitrile, and n‑Alkanes Ole Riechert,† Tim Zeiner,‡ and Gabriele Sadowski*,† †

Laboratory of Thermodynamics and ‡Laboratory of Fluid Separations, Department of Biochemical and Chemical Engineering, TU Dortmund University, Emil-Figge-Straße 70, D-44227 Dortmund, Germany ABSTRACT: This work presents investigations on the liquid−liquid equilibria (LLE) of ternary systems composed of morpholine, acetonitrile, and an n-alkane at 298.15 K and atmospheric pressure. The investigated nalkanes were n-hexane, n-heptane, and n-octane. The experimental data were compared to predictions using the perturbed chain-statistical associating fluid theory (PC-SAFT). The predictions are based on pure-component parameters fitted to vapor pressures and liquid densities as well as on binary parameters fitted to binary systems’ phase equilibria. For that purpose, the vapor−liquid equilibrium of the morpholine/acetonitrile system was measured at 100 mbar and modeled with PC-SAFT. Binary interaction parameters for acetonitrile/n-alkane systems were obtained from a correlation as a function of the n-alkane carbon number. This correlation, together with the other pure-component and binary parameters, was used to make predictions on ternary systems with n-alkanes longer than n-octane, for which data were taken from literature. All ternary LLE predictions were in satisfactory agreement with experimental data.

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INTRODUCTION Morpholine (Figure 1) is a secondary amine that is used as an intermediate for a broad variety of pharmaceuticals, crop

for TMS solvent selection, recent research also accounts for the effects of the reactants on the LLE, e.g., for hydroformylation,8,9 where the reactant miscibility leads to increased acetonitrile concentrations in the alkane-rich phase and therewith to increased catalyst leaching. Hence, comprehensive modeling of the LLE of reactant/TMS systems is of high importance for selecting the best TMS. The homogeneous-catalyzed hydroamination of myrcene with morpholine is usually performed in a TMS composed of acetonitrile and n-heptane,4 where the catalyst enriches in the polar acetonitrile-rich phase.4 It is expected that the length of the alkane determines the width of the miscibility gap and therewith the catalyst leaching. Lee et al.10 correlated experimental data of ternary systems composed of the acetonitrile, morpholine, and n-alkanes from n-octane to ndodecane using NRTL.11 However, gE-models, such as NRTL, do not provide information on fluid density, which is of special interest for the design of liquid−liquid separations, whereas the perturbed chain-statistical associating fluid theory (PC-SAFT) is known to predict fluid densities in binary and ternary systems reasonably well.12 In this work, reactant/acetonitrile/n-alkane systems for hydroamination were modeled with PC-SAFT. The latter was already successfully applied to model the LLE of the TMS ndecane/dimethylformamide used for the hydroformylation of 1dodecene9 and the TMS composed of acetonitrile and nalkanes with the hydroamination reactant myrcene.8

Figure 1. Molecular structure of morpholine.

protection agents, dyes, and optical brighteners.1 Serving as a stereotype for secondary amines, morpholine is a popular model substrate for aminations2 or hydroaminations.3 One such example based on renewable feedstock is the hydroamination of β-myrcene (myrcene) with morpholine4 by homogeneous catalysis using a palladium catalyst with 1,4-bis(diphenylphosphino)butane as ligand.4 In homogeneous catalysis, catalyst recycling is a crucial factor for industrial feasibility of the process. Behr et. al5 introduced the concept of thermomorphic multicomponent solvent (TMS) systems, where catalyst recycling is performed based on temperature-dependent liquid−liquid equilibria (LLE). The basic idea is that the mixture of solvents, reactants, and products is homogeneous at reaction temperature. This enables a fast bulk reaction by avoiding transport resistances through interphases. Upon cooling, the mixture forms two phases, where ideally one phase carries the catalyst and the product enriches in the other phase. So far, TMS solvent selection is often based on heuristics and polarity considerations like Hansen parameters.6,7 Whereas initially only the interactions of the solvents were considered © 2015 American Chemical Society

Received: February 24, 2015 Accepted: June 1, 2015 Published: June 11, 2015 2098

DOI: 10.1021/acs.jced.5b00175 J. Chem. Eng. Data 2015, 60, 2098−2103

Journal of Chemical & Engineering Data

Article

In this work, the influence of the second hydroamination reactant, morpholine, on the LLE in the above-mentioned TMS is investigated by applying the same modeling strategy for acetonitrile/n-alkane systems as developed earlier.8 Modeling results are compared to experimental data for systems containing n-hexane, n-heptane, and n-octane measured within this work as well as to literature data for n-decane and ndodecane systems.10

Table 1. Chemicals Used for Experiments within This Study purity

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THEORY The experimental data were modeled using PC-SAFT.13 This is a modified version of the SAFT equation of state14 applying the perturbation theory of Barker and Henderson15,16 to a hardchain reference fluid. The reference system accounts for repulsive interactions between the molecules. This hard-chain reference fluid is perturbed by attractive interactions such as dispersion or association. Associative interactions, however, are not considered within this work. Moreover, polar interactions as result of permanent and induced dipoles17 are accounted for. Within PC-SAFT, each type of interaction is considered by a separate contribution to the residual Helmholtz energy (eq 1): a res = a hc + adisp + aassoc + adipole

(1)

uij =

(σi + σj) 2 ui + uj (1 − kij)

supplier

%

acetonitrile dibutyl ether n-heptane n-hexane n-octane morpholine tetrahydrofuran

Prolabo Sigma-Aldrich Merck KGaA Merck KGaA Sigma-Aldrich Alfa Aesar Merck KGaA

99.9 99.3 99 99 >99.0 99 99.9

composed of 475 mg of solution, 25 mg of dibutyl ether as internal standard, and 500 mg of tetrahydrofuran. All measurements were performed as triplets. The GC system Agilent Technology 7890A instrument was equipped with an HP 5 column (5% phenyl methyl siloxan; 30 m, 0.32 mm, 0.25 μm) and a flame ionization detector as in our previous work.8 Vapor−Liquid Equilibrium (VLE) Measurements. VLE measurements of binary systems were performed using a glass apparatus (Normag, Ilbisheim, Germany) equipped with electrical heating, an oil-filled double-jacketed equilibrium chamber, and a water-cooled condenser for the vapor phase. Temperatures were measured within the isolating oil-heated jacket and in the equilibrium chamber using a PT100 platinum resistance thermometer with a precision of ± (0.15 + 0.002·(T − 273.15)) K. The pressure inside the equilibrium chamber was adjusted by a vacuum pump (Vacuubrand PC 3004 Vario, Vacuubrand, Wertheim, Germany). The experimental procedure was the same as described earlier.8 Liquid−Liquid Equilibrium (LLE) Measurements. LLE measurements of ternary mixtures were performed as described elsewhere.8 Concentrations of the corresponding phases were determined by GC. Temperature control was achieved by an oil thermostat and a PT100 resistance thermometer with a precision of ± (0.15 + 0.002·(T − 273.15)) K. At target temperature, stirring was continued for at least 5 min. After that, the mixture was allowed to settle. The mixture was in thermodynamic equilibrium after about 1 h, which was indicated by complete clearance of the corresponding phases. This assumption was confirmed by several measurements for longer periods of time, which were carried out prior to the reported measurements. Each mixture was investigated twice from two independent preparations.

where the superscript “res” refers to residual, “hc” to the hardchain reference fluid, “disp” to dispersive interactions, “assoc” to associative interactions, and “dipole” to polarizable dipole interactions as described by Kleiner and Gross.17 Within PC-SAFT, a molecule i is considered as a chain of mi segments. These segments are described as spheres with a segment diameter σi. Attractive dispersion forces between two segments are characterized by an energy parameter ui/kB.13 Polar interactions are considered by the permanent dipole moment μD and the polarizability αi.17 Values for μD can be obtained from literature or fitted to experimental data. Polarizabilites are tabulated for a variety of substances but can also be calculated from refractive indexes using the Debye equation or the Clausius−Masotti equation in the case of molecules without permanent dipole moment.8,18,19 Model parameters for pure substances are usually fitted to pure-component vapor pressures and liquid density data. Mixtures are modeled using Berthelot−Lorenz combining rules:

σij =

chemical

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(2)

RESULTS AND DISCUSSION Parameter Estimation. Pure Components. All substances except morpholine were already modeled with PC-SAFT.8 Thus, pure-component parameters had to be estimated only for morpholine. This was done by fitting the three PC-SAFT parameters, σi, mi, and ui/kB, as well as the permanent dipole moment of morpholine to vapor pressure19,21−27 and liquid density20−24 data. The polarizability of morpholine was calculated from the refractive index25 as described elsewhere.8 All morpholine parameters are listed in Table 2. Using these parameters, liquid density20−24 and vapor pressure23,26−32 data of pure morpholine can be calculated with an average relative deviation (ARD) of 1.58 % and 0.99 %, respectively. The PC-SAFT parameters of all other components considered within this work can also be found in Table 2. Binary Systems. The applied TMS was already investigated in a previous work.8 For a quantitative modeling of the LLE in

(3)

Herein, kij is the binary interaction parameter which has to be fitted to binary phase equilibria data for the correction of the dispersion energy between unlike species.

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MATERIALS All chemicals used in this work can be found in Table 1, with information on purity and supplier. The chemicals were applied without further purification. In the case of acetonitrile, the water content was checked periodically by Karl−Fischer titration and was found to be less than 100 ppm.

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METHODS Gas Chromatography (GC) Analysis. Quantification of component concentrations in the different phases was performed by GC. A typical sample for GC analysis was 2099



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Table 2. Pure-Component Parameters Applied in This Study

a

σ

ui/kB

μD

α

substance

m

Å

K

D

Å3

ref

acetonitrile morpholine n-decane n-dodecane n-hexane n-heptane n-octane

2.3627 3.2296 4.6627 5.3060 3.0576 3.4831 3.8176

3.1855 3.3144 3.8384 3.8959 3.7983 3.8049 3.8373

225.14 270.80 243.87 249.21 236.77 238.4 242.78

3.4315 2.7200

4.400 9.408a 19.100b 22.750b 11.000b 13.610b 15.900b

17 this study 13 13 13 13 13

Polarizability was calculated from refractive index at 589 nm and 20 °C.33 bPolarizability data were taken from ref 25.

systems composed of acetonitrile and n-alkanes, kij is described as a function of temperature following eq 4:8 a kij(T ) = +b (4) T

As shown in Figure 2, PC-SAFT describes the VLE, using the parameters in Tables 2 and 4, in very good agreement with the experimental data (AAD and ARD of 1.26 K and 0.39 %, respectively).

where a and b are functions of the number of carbon atoms of the n-alkane,8 as given in eqs 5 and 6. a = −0.002·[C‐atoms] + 56.197

(5)

b = 0.005·[C‐atoms] − 0.2012

(6)

Using this correlation, the upper critical solution temperatures of the solvent systems composed of acetonitrile and nalkanes could be described in remarkably good agreement with experimental data.8 Complete homogeneity of acetonitrile/nalkane systems is guaranteed at temperatures above 348.5 K for n-hexane, above 357.1 K for n-heptane, above 364.4 K for noctane, and above 397.4 K for n-dodecane. At these temperatures, the TMSs can be used as solvent systems for homogeneous reactions. At lower temperatures, these systems form two phases, which allows for catalyst recycling. The binary PC-SAFT parameter of the acetonitrile/morpholine system was fitted to VLE experiments at 100 mbar. Experimental data for this system are summarized in Table 3.

Figure 2. VLE of morpholine with acetonitrile at 100 mbar. Symbols are the experimental data as reported in Table 3; solid line is PC-SAFT calculation using the parameters in Tables 2 and 4.

Table 4. Binary Interaction Parameters kij Used within This Study

Table 3. VLE of Morpholine/Acetonitrile at 100 mbar Measured within This Worka

a

T K 35

294.49 295.35 300.15 304.35 312.05 318.15 321.55 322.75 327.05 332.25 333.95 334.15 335.05 335.85 336.15 336.8532

xvapor morpholine

u(x)

xliquid morpholine

u(x)

0 0.0005 0.025 0.117 0.236 0.364 0.445 0.48 0.595 0.7957 0.856 0.851 0.907 0.920 0.945 1

− 9.95·10−6 0.002 0.004 0.009 0.004 0.007 0.04 0.008 0.0005 0.001 0.002 0.002 0.002 0.001 −

0 0.066 0.302 0.498 0.711 0.809 0.847 0.8664 0.9119 0.951 0.961 0.9621 0.9698 0.9699 0.973 1

− 0.005 0.003 0.005 0.002 0.004 0.006 0.001 0.001 0.002 0.002 0.001 0.0002 0.0004 0.001 −

substance i

substance j

kija

ref

acetonitrile acetonitrile n-alkanes

n-alkanes morpholine morpholine

kij(T) = a/T + b −0.02 0

8 this study this study

See eqs 5 and 6 for definitions of a and b.

The binary interaction parameter between n-alkanes and morpholine was set to zero, as these binary systems’ VLEs were predicted with high accuracy (e.g., AAD of 4.52 K and ARD of 1.20 % for n-heptane34). Prediction of Ternary Systems. Using the abovesummarized binary interaction parameters (Table 4) of the binary system composed of acetonitrile and morpholine as well as the expression for kij in the TMS composed of acetonitrile and n-alkanes8 (Table 4), ternary systems’ LLEs were predicted at 298.15 K and atmospheric pressure without any further parameter fitting. Predictions of LLE for ternary systems composed of acetonitrile, morpholine, and an n-alkane were carried out for n-hexane (Figure 3), n-heptane (Figure 4), and n-octane (Figure 5) systems to study the influence of different n-alkanes. The corresponding data are reported in Tables 5, 6, and 7. Results for the n-octane system (Figure 5) are in good agreement with recently published data of Lee et al.,10 which confirms the accuracy of our measurements. The two-phase region increases with increasing chain length of the alkane

a

Standard uncertainties u(x) of the measured mole fractions x are reported. Standard uncertainty in temperature: (0.15 + 0.002·(T − 273.15)) K. 2100



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Table 5. Concentrations of the Corresponding Phases of the LLE in the n-Hexane/Acetonitrile/Morpholine Systems at 298.15 K and Ambient Pressure Measured in This Worka top bottom top bottom top bottom

xn‑hexane

u(x)

xacetonitrile

u(x)

xmorpholine

u(x)

0.926 0.050 0.877 0.070 0.830 0.096

0.005 0.004 0.004 0.004 0.005 0.004

0.060 0.909 0.070 0.761 0.077 0.630

0.005 0.004 0.003 0.007 0.004 0.008

0.0153 0.0412 0.0531 0.169 0.093 0.274

0.0004 0.0008 0.0007 0.003 0.001 0.004

a

Standard uncertainties u(x) of the measured mole fractions x are reported. Standard uncertainty in temperature: (0.15 + 0.002·(T − 273.15)) K.

Figure 3. LLE of the system n-hexane/acetonitrile/morpholine at 298.15 K and ambient pressure: △, mixing points; ☆, experimental data of the corresponding phases (Table 5); dashed lines are experimental tie lines; the solid black line corresponds to the predictions with PC-SAFT using the parameters in Tables 2 and 4.

Table 6. Concentrations of the Corresponding Phases of the LLE in the n-Heptane/Acetonitrile/Morpholine Systems at 298.15 K and Ambient Pressure Measured in This Worka top bottom top bottom top bottom top bottom

xn‑heptane

u(x)

xacetonitrile

u(x)

xmorpholine

u(x)

0.85 0.091 0.86 0.041 0.82 0.09 0.70 0.132

0.04 0.002 0.05 0.004 0.04 0.02 0.02 0.006

0.12 0.818 0.12 0.911 0.09 0.65 0.11 0.418

0.04 0.003 0.05 0.005 0.04 0.03 0.02 0.009

0.031 0.091 0.018 0.0483 0.086 0.259 0.195 0.45

0.002 0.002 0.001 0.0009 0.003 0.004 0.006 0.01

a


Figure 4. LLE of the system n-heptane/acetonitrile/morpholine at 298.15 K and ambient pressure: △, mixing points; ☆, experimental data of the corresponding phases (Table 6); dashed lines are experimental tie lines; the solid black line corresponds to the predictions with PC-SAFT using the parameters in Tables 2 and 4.

Table 7. Concentrations of the Corresponding Phases of the LLE in the n-Octane/Acetonitrile/Morpholine Systems at 298.15 K and Ambient Pressure Measured in This Worka top bottom top bottom top bottom

xn‑octane

u(x)

xacetonitrile

u(x)

xmorpholine

u(x)

0.918 0.0261 0.70 0.084 0.784 0.0451

0.001 0.0002 0.01 0.004 0.008 0.0003

0.082 0.908 0.097 0.49 0.091 0.73

0.001 0.004 0.001 0.01 0.002 0.01

0.0 0.066 0.199 0.43 0.125 0.22

0.002 0.003 0.009 0.01 0.007 0.01

a


correctly, as shown for the solvent system acetonitrile/nheptane in Figure 6. The model also predicts the slope of the tie-lines in good agreement with experimental data for low

Figure 5. LLE of the system n-octane/acetonitrile/morpholine at 298.15 K and ambient pressure: △, mixing points; ☆, experimental data of the corresponding phases (Table 7); dashed lines are experimental tie lines; □ and solid gray lines are literature data;10 the solid black line corresponds to the predictions with PC-SAFT using the parameters in Tables 2 and 4.

(Figures 3 to 5), which is captured reasonably well by the PCSAFT prediction. Morpholine serves as solubilizer in the TMS, causing a homogeneous system at morpholine concentrations above 50 mol %. This has to be considered when designing the hydroamination process, because increasing acetonitrile concentrations in the alkane-rich product phase correspond to increasing catalyst leaching.36 Morpholine accumulates in all cases in the acetonitrile-rich phase (Figures 3 to 5). PC-SAFT predicts this behavior

Figure 6. LLE of the system n-heptane/acetonitrile/morpholine at 298.15 K and ambient pressure: △, mixing points; ☆, experimental data of the corresponding phases (dashed lines, Table 6); dashed lines are experimental tie lines; the solid black lines correspond to the prediction (tie lines and binodal) with PC-SAFT using the parameters in Tables 2 and 4. 2101



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Figure 7. PC-SAFT prediction of LLE in ternary systems composed of acetonitrile, morpholine, and n-alkanes using the parameters in Tables 2 and 4 and compared with literature data.10 The considered alkanes were n-decane at 298.15 K (a) as well as n-dodecane at 298.15 K (b) and 313.15 K (c).

five ternary systems with n-alkanes ranging from n-hexane to ndodecane and at two different temperatures. In contrast, recent literature modeling with NRTL11 used nine binary parameters per ternary system and temperature without a possible extrapolation to other temperatures or n-alkane chain lengths. Together with our previous work,8 the proposed modeling approach provides a comprehensive thermodynamic description (binary systems’ LLE and VLE as well as ternary systems’ LLE) of the hydroamination reaction system in TMS composed of acetonitrile and n-alkanes. Both reactants, myrcene and morpholine, act as solubilizers in solvent systems composed of acetonitrile and n-alkanes. Because in TMS the miscibility gap is used for catalyst recycling, solubilizing effects may dramatically influence the catalyst recycling efficiency. Concerning the choice of the n-alkane as part of the TMS, longer n-alkanes cause larger miscibility gaps; therefore, from a thermodynamic point of view, dodecane or longer alkanes would be the best choice for this issue. Although for a proper solvent selection also other aspects (reactivity, viscosity, time for phase separation, availably, etc.) need to be considered, this work allows for a model-based thermodynamic optimization of the TMS during hydroamination process development.

morpholine concentrations, whereas the slope of the tie-lines is underestimated for higher morpholine concentrations (Figure 6). (The latter did not improve by fitting a non-zero binary interaction parameter to the n-alkane/morpholine system.) Commonly applied reactant concentrations for the hydroamination, however, are less than 5 mol % of morpholine,4 and in this region the binodals as well as the slope of the tie lines are captured quite well. As the applied correlation of the binary interaction parameter of acetonitrile/n-alkane binary systems is generally applicable, it was also used to predict ternary systems with n-decane and ndodecane. The predictions were validated against literature data from Lee et al.10 at 298.15 K for both alkanes and at 313.15 K for dodecane (Figure 7). Using only one parameter set (Tables 2 and 4), the predicted binodals are again in good agreement with the experimental data covering different chain lengths of the alkane as well as different temperatures. In contrast, the NRTL correlation applied by Lee et al.10 used nine binary parameters per temperature and ternary system. Moreover, PCSAFT parameters used in this work were solely fitted to binary systems, whereas Lee et al.10 fitted the NRTL parameters to the ternary systems.

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CONCLUSION This work presented measurements of the TMS composed of acetonitrile and n-alkanes and the reactant morpholine for homogeneously catalyzed hydroamination reactions. The liquid−liquid equilibria of the ternary systems were measured for the first time for the alkanes n-hexane and n-heptane at 298.15 K and successfully modeled using PC-SAFT. The vapor−liquid equilibrium of morpholine/acetonitrile was measured at 100 mbar, and the data were used to determine the binary interaction parameter of this subsystem. For the subsystems composed of acetonitrile and an n-alkane, we used an earlier proposed8 expression of the binary interaction parameter as a function of the alkane chain length. The third binary interaction parameter between the n-alkanes and morpholine was set to zero for all considered systems. Based on the parameter fitting to pure components (purecomponent parameters) and binary systems, the LLE of the ternary systems was predicted as a function of the n-alkane chain length. The predictions were validated against the new experimental data obtained within this work as well as against literature data.10 The predictions were found in good agreement with experimental data. In total, five binary parameters (one for acetonitrile/morpholine and four for all acetonitrile/n-alkane systems) were used to predict the LLEs in

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Funding

The authors thank the research cluster SusChemSys. The project “Sustainable Chemical Synthesis (SusChemSys)” is cofinanced by the European Regional Development Fund (ERDF) and the state North Rhine-Westphalia, Germany, under the Operational Programme “Regional Competitiveness and Employment” 2007−2013. Notes

The authors declare no competing financial interest.

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ABBREVIATIONS AND VARIABLES a Helmholtz energy, J·mol−1 a parameter of the temperature-dependent kij expression AAD average absolute deviation α polarizability, Å3 ARD average relative deviation, % b parameter of the temperature-dependent kij expression GC gas chromatography superscript

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hc i j kij

hard chain component i component j binary interaction parameter between components i and j LLE liquid−liquid equilibrium m segment number μD dipole moment, D p pressure, Pa PC-SAFT perturbed chain-statistical associating fluid theory res residual σ segment diameter, Å T temperature, K TMS thermomorphic multicomponent solvent u/kB dispersion energy parameter, K u(x) standard uncertainty VLE vapor−liquid equilibrium x mole fraction

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REFERENCES

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Phase Equilibria in Systems of Morpholine, Acetonitrile, and n-Alkanes

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