High-pressure gas solubility in multicomponent solvent systems for hydroformylation. Part II: Syngas solubility

摘要

High-pressure solubility of syngas with a molar ratio of hydrogen (H2) and carbon monoxide (CO) of 1:1 was investigated in various solvents like n-decane, dimethylformamide (DMF), 1-dodecene and n-dodecanal as well as in mixtures of n-decane and DMF and in a mixture of 1-dodecene, n-dodecanal, n-decane and DMF at temperatures between 302 K and 367 K and at pressures of up to 14 MPa. Moreover, the H2 solubility in 1-dodecene and n-dodecanal was measured in the same pressure and temperature range. The solubility measurements were performed in a high-pressure volume-variable view cell using a visual synthetic method. For modeling and prediction of the gas solubility (H2, CO, and syngas (H2/CO)) in the considered solvents, the Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT) was used. The systems containing one gas (H2 or CO) and one solvent were modeled accurately by applying temperature-independent binary interaction parameters (k_(ij)'s). These k_(ij)'s were used to predict the syngas solubility in pure solvents and their mixtures without further adjustments. The k_(ij) between H2 and CO was always set to zero. The results showed that PC-SAFT is able to predict the syngas solubility in pure solvents with an average relative deviation of 3.1-12.0%. Syngas solubility in the n-decane/DMF mixture was predicted with a deviation of 7.2%.