Phase Equilibria for the Hydroaminomethylation of 1-Decene

Abstract

This work focuses on the measuring and modeling of phase equilibria of interest for the hydroaminomethylation of 1-decene with syngas (CO/H2) and diethylamine to N,N-diethylundecan-1-amine and water in a solvent system of methanol and n-dodecane. H2 solubilities were measured in undecanal and N,N-dimethyldodecan-1-amine at 343 and 363 K between 2 and 4 MPa via the isochoric saturation method. Vapor–Liquid equilibrium data were measured for the binary systems methanol/N,N-diethylundecan-1-amine, 1-decene/diethylamine, and 1-decene/N,N-diethylundecan-1-amine at temperatures between 299 and 372 K and at pressures of 0.005, 0.018, 0.025, or 0.030 MPa. Liquid–Liquid equilibria were measured in the ternary systems methanol/n-dodecane/diethylamine, methanol/n-dodecane/undecanal, and methanol/n-dodecane/N,N-diethylundecan-1-amine at 0.1 MPa and at temperatures ranging from 278.15 to 308.15 K. Measured and available phase-equilibrium data from literature were modeled using perturbed-chain polar statistical associating fluid theory. This then allowed for modeling the Henry’s law constant for H2 and CO in the liquid components (methanol, n-dodecane, 1-decene, diethylamine, undecanal, N,N-diethylundecan-1-amine, and water) at 373.15 and 393.15 K.

Predicting Solvent Effects on Homogeneity and Kinetics of the Hydroaminomethylation: A Thermodynamic Approach Using PC-SAFT

“…Using pure methanol as the solvent, the reaction medium was predicted to be homogeneous up to water contents of w water = 0.34 at 373.15 K ( w water = 0.39 at 398.15 K). If pure DDC is used instead, phase separation occurs at water weight fractions higher than 0.001 at 373.15 K and higher than 0.002 at 398.15 K. Hence, the water tolerance of the RA is greater than that of the HYFO (Figure ), which can be attributed to the increased amount of DEA in the system and its strong solubilizing effect compared to alkenes and aldehydes. , …”

“…If pure DDC is used instead, phase separation occurs at water weight fractions higher than 0.001 at 373.15 K and higher than 0.002 at 398.15 K. Hence, the water tolerance of the RA is greater than that of the HYFO (Figure 3), which can be attributed to the increased amount of DEA in the system and its strong solubilizing effect compared to alkenes and aldehydes. 19,35 As a result of the water formed during the reaction (see Figure 1), it is not possible to perform the RA in pure DDC without the occurrence of phase separation (Figure 4). At 373.15 K, a homogeneous liquid at the end of the reaction can only be obtained at contents in the solvent mixture of up to 50 wt % DDC.…”

“…All reactions were investigated in a TMS of methanol and n-dodecane (DDC), which in recently published works 14−18 was found to be a promising solvent system. The pure-component PC-SAFT parameters and the binary interactions between all components involved in the HAM as well as between these and the solvents were investigated in detail in earlier works, 19,20 providing an almost complete set of PC-SAFT parameters. In this work, the LLE of the multicomponent reaction system is predicted using PC-SAFT.…”