VLE MEASUREMENTS FOR ASYMMETRIC MIXTURES OF FISCHER-TROPSCH HYDROCARBONS

Thies, Mark C.

Clemson University (United States)

关键词: Propane;    01 Coal, Lignite, And Peat;    37 Inorganic, Organic, Physical And Analytical Chemistry;    Phase Studies;    Hexadecane;   

DOI  :  10.2172/828222
RP-ID  :  NONE
RP-ID  :  FG26-01NT41293
RP-ID  :  828222

美国|英语

来源: UNT Digital Library

【 摘 要 】

The ability to model the thermodynamic phase behavior of long-chain and short-chain alkane mixtures is of considerable industrial and theoretical interest. However, attempts to accurately describe the phase behavior of what we call asymmetric mixtures of hydrocarbons (AMoHs) have met with only limited success. Vapor-liquid equilibrium (VLE) data are surprisingly scarce, and the limited data that are available suggest that cubic equations of state may not be capable of fitting (much less predicting) the phase behavior of AMoHs. The following tasks, which address the problems described above, were accomplished during the one-year period of this Phase I UCR grant: (1) A continuous-flow apparatus was modified for the measurement of AMoHs and used to measure VLE for propane + hexadecane mixtures at temperatures from 473 to 626 K and pressures up to the mixture critical pressures of about 100 bar. (2) The extent to which cubic vs. modern, statistical mechanics-based equations of state (EoS) are applicable to AMoHs was evaluated. Peng-Robinson (PR) was found to be a surprisingly accurate equation for fitting AMoHs, but only if its pure component parameters were regressed to liquid densities and vapor pressures. However, even this form of PR was still not a predictive equation, as there was a significant variation of kij with temperature. In spite of its deficiencies in terms of vapor-phase predictions and modeling of the critical region, PC-SAFT was found to be the most appropriate EoS for truly predicting the phase behavior of highly asymmetric mixtures of alkanes. (3) Finally, a dense-gas extraction (DGE) apparatus was designed and constructed for the fractionation of F-T waxes into cuts of pure oligomers. Such oligomers are needed in g-sized quantities to perform VLE measurements with long-chain alkanes with carbon numbers greater than 40. The dense gas and the solute mixture to be extracted are contacted in a packed column that has a separation power significantly greater than what can be achieved in one equilibrium stage. Thus, wax oligomer purities are expected to be much better than what can be obtained by conventional supercritical extraction processes.