The present work expands previous modeling knowledge on facilitated transport membranes for olefin/paraffin separation. A new robust and practical mathematical model for the description of light olefin flux in composite polymer/ionic liquid/Ag + membranes is reported. The model takes into account three different transport mechanisms, i.e., solution-diffusion, fixed-site carrier and mobile carrier transport mechanisms. Fixed-site carrier contribution that appears thanks to the bounding of silver cations with the polymer chains is described through a "hopping parameter". Furthermore, given that the addition of an ionic liquid to the membrane composition promotes carrier mobility, the inclusion of a dedicated expression is necessary for a realistic description of mobile-carrier transport phenomena. The contribution of each mechanism in weighted based on the membrane composition. In order to check the model suitability, simulated values have been matched to experimental data obtained by continuous flow propane/propylene permeation experiments through PVDF-HFP/BMImBF 4 /AgBF 4 composite membranes, working with 50:50 gas mixtures at different temperature and pressure. The resultant model offers good predictions for olefin flux and provides a very useful tool for process optimization and scaling-up. To our knowledge, this is the first time that mobile and fixed site carrier mechanisms performance are simultaneously modeled considering the influence of temperature, pressure and carrier loading.

The growing production of polyolefins, mainly polyethylene and polypropylene, currently demands increasing outputs of polymer-grade light olefins. The most commonly adopted process for the separation of olefin/paraffin mixtures is performed by energy intensive high pressure or cryogenic distillation, which is considered the most expensive operation in the petrochemical industry. The use of membrane technology offers a compact and modular solution for capital and energy savings, thanks to process intensification. In this work, we move one step forward in the design of hybrid propane/propylene separation systems, using computer aided modeling tools to identify economically optimal combinations of distillation and state-of-the-art membranes. A model is proposed to optimize a hybrid configuration, whereby the membrane performs the bulk separation and the distillation column is intended for the final product polishing, accounting for membrane investment cost and process operating expenses.The decision variables are the membrane area and the column reflux ratio, and the

A practical approach to fixed-site-carrier facilitated transport modeling for the separation of propylene/propane mixtures through silver-containing polymeric membranes, Separation and Purification Technology (2017),

Separation of light gaseous olefins from paraffin's of the refinery process off-gasses has been traditionally performed by cryogenic distillation, which is a highly capital and energy intensive operation. This handicap creates an incentive for the investigation of alternative olefin/paraffin separation technologies. In this regard, membrane technology supposes a potential solution for process intensification. Previous works of our research group reported the use of facilitated transport composite membranes integrating the use of PVDF-HFP polymer, BMImBF 4 ionic liquid and AgBF 4 silver salt. In this type of membranes, the silver cations react selectively and reversibly with the olefin, allowing the separation via mobile and fixed carrier mechanisms. Ionic liquids were selected as membrane additives because in addition to their negligible vapor pressure that avoids solvent losses by evaporation, they provide stability to the metallic cation dissolved inside, and modify the structure improving the facilitated transport. This technology offers a commercial attractive separation alternative thanks to their modular form of operation, high values of selectivity and permeability and low operational costs. In the present work, propane/propylene permeation experiments involving the use ionic liquids and different membrane compositions were performed. Moreover, basing on the transport and equilibrium parameters previously obtained, a mathematical model description of the system will be proposed fitting the remaining parameters and allowing the design and optimization of the propane/propylene separation process at industrial levels.

In this work, we explore the capabilities of an NLP optimization model to determine the viability of facilitated transport membrane processes intended to replace traditional distillation currently employed for propane/propylene separation. An NLP optimization model for multistage membrane processes has been formulated, introducing the mathematical description of the facilitated transport mechanisms in the PVDF-HFP/BMImBF 4 /AgBF 4 membranes previously developed by our research group. For the first time, a simultaneous optimization of the process and the membrane material (i.e., carrier concentration) has been performed, thanks to the implementation of the governing equations for the fixed site and mobile carrier mechanisms. Once the model is solved in GAMS it returns the optimal membrane area, carrier loading and permeate pressure of each stage based on Net Present Value Cost (NPVC) minimization. Different process flow sheets were evaluated and the results show prominent reductions on NPVC for facilitated transport multistage processes when compared to distillation.

In this work, a comprehensive analysis of PVDF-HFP/BMImBF 4 /AgBF 4 facilitated transport membranes for olefin/paraffin separation is presented. Previous works of our research group have reported high flux and propylene selectivity under dry conditions and using synthetic gas mixtures, highlighting the promising potential of these experimental evidence for the previously theorized facilitated transport mechanisms and reveal a major influence of feed gas humidity on membrane performance. On the other hand, the industrial gas mixture produces no deviation from synthetic feed conditions due to trace contaminants. Finally, the carrier deactivation in long-term permeation has been quantified through a mathematical expression.