Development of a new static synthetic apparatus for phase equilibrium measurements

Abstract

Phase equilibrium data plays a significant role in the design and optimization of industrial separation schemes, such as distillation and absorption units. These separation processes are utilised for the purification of valuable chemicals, which play a pivotal role in daily human life. Separation units are operated at various conditions of temperature and pressure, however it is common for most units to operate in the moderate pressure region (100-500 kPa). On the contrary, there is a lack of phase equilibrium data available in the moderate pressure region, thus prompting an interest in this area.

In this study, a new static synthetic cell was tested, and the experimental apparatus was successfully set up and commissioned. Some key features of this design include a total working cell volume of 60 cm3 (which reduces the amount of chemicals required compared to conventional static synthetic cells) and equilibrium is achieved faster. In addition, two high-accuracy Teledyne Isco pumps were utilised for the feed loading, as it is vital that the volume of chemicals dispensed into the cell be accurately determined.

The necessary calibrations were conducted and the overall uncertainties were found to be 0.06 K, 0.36 kPa and 0.1 ml for temperature, pressure and volume respectively. The following test systems were measured to determine the reproducibility of the apparatus and to verify the experimental technique:

• water (1) + 2-butanol (2) at 323.16 K • n-hexane (1) + 2-butanol (2) at 329.21 K • n-pentane (1) + 1-propanol (2) at 317.18 K • n-pentane (1) + 2-butanol (2) at 303.17 K • n-pentane (1) + ethanol (2) at 303.11 K

The test systems measured produced a good fit with the literature data, and thus the experimental apparatus was commissioned. New systems, previously unmeasured in the open literature, were measured in this study. These systems include:

• n-hexane (1) + perfluoro-n-heptane (2) at 313.21 and 333.12 K • n-pentane (1) + 2-propanol (2) at 313.11, 323.11 and 333.12 K

The data was modelled on Aspen Plus®. Since the method of operation is of the static synthetic type, no analysis of the vapour and liquid phases took place, and instead an algorithm was developed using the combined method (γ-ϕ) together with the method of Barker (1953), to convert the overall composition (zi) to liquid mole fraction (xi). The Wilson and Non-Random Two-Liquid (NRTL) activity coefficient models together with the Ideal Gas law and Hayden O’Connell second virial coefficient were utilised to regress the data. For both the fluorinated and alkane + alcohol systems, the experimental

i

data produced an excellent fit with the activity coefficient models. For both systems, azeotropes were observed, indicating poor separation of these binary combinations at specific mole fractions. This is due to the boiling point of both components being similar under certain conditions. The calculated pressure residuals were well within the overall combined uncertainty for pressure, whilst the calculated temperature residuals were slightly above the overall combined uncertainty for temperature.