INNOVATIVE PROCESS DESIGN USING MEMBRANE CONTACTORS FOR THE SEPARATION OF OLEFIN/PARAFFIN MIXTURES M. Fallanza, A. Ortiz, D. Gorri, I.

Ortiz* Advanced Separation Processes Group Dep. Chemical Engineering & Inorganic Chemistry; University of Cantabria, Av Castros s/n 39005 Santander Spain; Phone: 34 942 201585, Fax: 34 942 201591; * contact e-mail: ortizi@unican.es Scientific Topic: Membrane separation
Light olefins such as ethylene and propylene are essential petrochemical feedstocks that play an essential role in many chemical syntheses and industrial processes. Thus, the separation of olefins from paraffins is a task of primary importance in the petrochemical industry. Among a number of different alternatives, reactive absorption with ionic liquid-silver complexes presents a great potential to intensify the conventional separation process based on cryogenic distillation. The separation process is based on the capacity of olefins to react with silver ions via -bound complex formation mechanism. This reaction can be easily reverted by temperature or pressure swings. Room temperature ionic liquids (RTILs) were selected as reaction media because in addition to their well-known and remarkable properties, they offer high olefin-capacity, more affinity for the olefinic compounds compared to saturated hydrocarbons, resistance to chemical and process conditions and they also offer stability to the solubilised metal cation. In order to implement this separation process, membrane contactors have been selected to make the contact between Ag+-RTIL reaction medium and propylene-propane gas mixtures, thus allowing high propylene fluxes in a modular, small, robust, safe and a cheaper way. In previous works, the solvent potential of the ionic liquid for the olefin/paraffin separation were assessed, and the viability on the use of gas-liquid membrane contactors to carry out the separation was proved by our research group [1-5]. In this work we develop a methodology to intensify the separation process based on the use of a transverse flow membrane contactor implemented in an innovative system design using an automated control apparatus. This system allows to operate with absorption-desorption cycling tests, integrating the use of membrane contactors and the major strengths of the pressure swing adsorption technique. By this way one module replaced the two devices required in conventional absorption processes and at the same time it is possible to operate in short time cycles with high absorption and desorption rates. Moreover, the mass transfer phenomena in the system were analysed and it was observed that the improved fluid-dynamics of the transverse flow membrane contactor leads to an overall mass transfer coefficient 17.6 times higher than that reported previously using a parallel-flow contactor. Thus, the reactive absorption of propylene using ionic liquids-silver complexes in the transverse flow membrane contactor has provided promising results, showing a process intensification by a factor of 17.4 in terms of mass transfer per specific area compared to a conventional stirred tank reactor system.
[1] A. Ortiz, A. Ruiz, D. Gorri, and I. Ortiz. Room temperature ionic liquid with silver salt as efficient reaction media for propylene/propane separation: Absorption equilibrium. Separation and Purification Technology, 63 (2008) 311. [2] A. Ortiz, L.M. Galn Sanchez, D. Gorri, A.B. De Haan, and I. Ortiz. Reactive ionic liquid media for the separation of propylene/propane gaseous mixtures. Industrial and Engineering Chemistry Research, 49 (2010) 7227. [3] A. Ortiz, L.M. Galn, D. Gorri, A.B. De Haan, and I. Ortiz. Kinetics of reactive absorption of propylene in RTIL-Ag+ media. Separation and Purification Technology, 73 (2010) 106. [4] A. Ortiz, D. Gorri, A. Irabien, and I. Ortiz. Separation of propylene/propane mixtures using Ag +-RTIL solutions. Evaluation and comparison of the performance of gas-liquid contactors. Journal of Membrane Science, 360 (2010) 130. [5] M. Fallanza., A. Ortiz, D. Gorri, I. Ortiz. Effect of liquid flow on the separation of propylene/propane mixtures with a gas/liquid membrane contactor using Ag+-RTIL solutions. Desalination and Water Treatment, 27 (2011) 123.

Acknowledgements: This research has been funded by the Spanish Ministry of Science and Innovation (Projects CTQ2008-00690/PPQ and CTM2006-00317).