Enhanced solubility of hydrogen and carbon monoxide in propane‐ and propylene‐expanded liquids

Abstract

Conventional propylene hydroformylation occurs in a gas‐expanded liquid phase. Reliable knowledge of the phase equilibria of such systems, including the solubilities of CO and H2 in propylene‐expanded solvents, is essential for rational process design and development. Herein, we report the vapor–liquid equilibrium (VLE) data of the following ternary systems involving CO, H2, propane, propylene, toluene and NX‐795 at temperatures from 70 to 90°C and pressures up to 1.5 MPa: propane/H2/toluene, propane/CO/toluene, propylene/H2/toluene, propylene/CO/toluene, propane/H2/NX‐795, propane/CO/NX‐795, propylene/H2/NX‐795 and propylene/CO/NX‐795. The solubilities of H2 and CO in either propane‐expanded or propylene‐expanded phases are observed to be greater than those in the neat organic solvents, by as high as 78% at 70°C and 1.5 MPa. By modeling the vapor and the liquid phases as pseudo‐binary systems, the Peng‐Robinson equation of state (PR‐EoS) with van der Waals’ mixing rules and binary interaction parameters is shown to satisfactorily predict the experimental VLE data. © 2017 American Institute of Chemical Engineers AIChE J, 64: 970–980, 2018

Enriching Propane/Propylene Mixture by Selective Propylene Hydroformylation: Economic and Environmental Impact Analyses

“…The annual butyraldehyde capacity for the plant scale simulations was set at 300000 tons/year at a 0.9 on-stream factor (i.e., 328 on-stream days). The data for simulating the CATOFIN PDH and conventional PHF process were obtained from literature and patents. , The data for simulating the PXL process were obtained from laboratory-scale experiments. , To simplify the process for better convergence, the mass and energy balances for PDH catalyst regeneration were calculated separately. The operating parameters are summarized in Table .…”

“…The UNIQUAC package available in Aspen software was used to predict the relevant thermodynamic properties, while the Peng–Robinson equation of state was employed for phase equilibrium modeling. The fluid package employed in this work was validated in a previous thermodynamic study of the propylene hydroformylation system . It was also successfully employed in the sustainability analysis of higher olefin hyroformylation in CO 2 -expanded liquids .…”

“…Recently, we demonstrated that refinery-grade propane/propylene mixtures can be used directly for propylene hydroformylation without the need for purification to obtain polymer-grade propylene. , The mixed propylene/propane feed also provides reaction benefits by volumetrically expanding the reaction mixture to yield gas-expanded liquids (GXLs) with tunable physicochemical properties. Unlike conventional reaction media, the H 2 /CO ratio in GXL media can be enhanced by simply increasing the partial pressure of propane. , For rhodium/triphenylphosphine catalyzed propylene hydroformylation performed between 70 and 100 °C and pressures up to 2.0 MPa, the n/i aldehyde ratio is increased by up to 45% in propane-expanded liquids (PXLs) .…”

“…Recently, we demonstrated that refinery-grade propane/propylene mixtures can be used directly for propylene hydroformylation without the need for purification to obtain polymer-grade propylene. , The mixed propylene/propane feed also provides reaction benefits by volumetrically expanding the reaction mixture to yield gas-expanded liquids (GXLs) with tunable physicochemical properties. Unlike conventional reaction media, the H 2 /CO ratio in GXL media can be enhanced by simply increasing the partial pressure of propane. , For rhodium/triphenylphosphine catalyzed propylene hydroformylation performed between 70 and 100 °C and pressures up to 2.0 MPa, the n/i aldehyde ratio is increased by up to 45% in propane-expanded liquids (PXLs) . Given that the refinery-grade propylene feedstock (55% propylene + 45% propane) costs up to 50% less than polymer-grade propylene, the PXL-based hydroformylation process has potential energy savings and economic/environmental benefits …”

Chemical Synthesis of Adipic Acid from Glucose and Derivatives: Challenges for Nanocatalyst Design

“…Later, Smith and co-workers reported another Rh-catalyzed protocol and furthered the selectivity to 74% for adipaldehyde, which can be oxidized to adipic acid using oxone . Liu and co-workers reported cost-effective hydroformylation processes, which show significant environmental and economic promises for industrial implementation. − Overall, the protocol of the butadiene route offers a nitric-acid free route to access adipic acid, but its yield and efficiency requires significant improvement compared to the convention cyclohexane route. Obviously, there is a strong need to develop alternative oxidants for this process.…”