Separation of Azeotropic Refrigerant Mixtures Using Ionic Liquids

Abstract

Refrigeration and air-conditioning systems are widespread throughout modern society, from the refrigerated cold chain that provides fresh foods and storage of medicines to the air conditioning of homes and buildings. Refrigeration is viewed as one of the most transformative engineering achievements of the 20th century and the demand for cooling will continue to increase as economic conditions improve and the climate continues to warm; however, refrigerants do come with an environmental cost. In 1987, the Montreal Protocol phased out chlorofluorocarbon (CFC) refrigerants because of their high ozone depletion potential (ODP). The replacements, typically mixtures of hydrofluorocarbons (HFCs), are safe for the Earth's ozone layer, but most have high global warming potentials (GWPs). HFCs account for 7.8% of total global greenhouse gas emissions, with 63% of that from “indirect” emissions (i.e., energy for running the system). As a result, 197 countries signed the Kigali agreement in 2016 to phase out high-GWP HFCs, with the goal of reducing emissions by 80% in the next 20 years. Millions of metric tons (mts) of high-GWP refrigerants will need to be reclaimed, but there are no good methods for separating and recycling the individual components, given that many are azeotropic mixtures. Currently, there is no means of separating azeotropic HFC mixtures, and the refrigerants will ultimately have to be incinerated. The commercial HFC mixture R-410A containing 50 wt.% HFC-32 (GWP = 675) and 50 wt.% HFC-125 (GWP = 3500) is a prime example. The HFC-32 can be reused when separated in new low-GWP products such as R-454B (69 wt% HFC-32 and 31 wt% HFO-1234yf) with a 75% lower GWP than R-410A. Ionic liquids are being developed that can separate azeotropic HFC mixtures based on differences in solubility and used as entrainers in extractive distillation. This presentation will provide experimental data on the solubility of HFCs in ionic liquids that have been measured using gravimetric microbalances and modeling using the Peng-Robinson equation of state. ASPEN Plus simulations will show how a pilot process has been designed that can continuously separate azeotropic refrigerant mixtures such as R-410A.