Diapositiva 1

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Simulation of Supported Ionic Liquid Phase (SILP)
by COSMO-RS to select appropiate adsorbents
J. Palomar, J. Lemus, M.A. Gilarranz, J.J.
Rodríguez Sección de Ingeniería Química.
Universidad Autónoma de Madrid, 28049 Madrid,
Spain
e-mail pepe.palomar_at_uam.es
INTRODUCTION
Supported ionic liquid phase (SILP) is a recent
concept where a fine film of ionic liquid is
immobilized in a solid phase, combining the
advantages of ionic liquids (ILs) (non
volatility, high solvent capacity) with those of
heterogeneous support materials. In separation
applications, the use of SILP has been studied to
facilitate selective transport of substrates
across membranes. In reactions, as hydrogenation
and hydroformylation, SILP has been proved to be
more active and selective than common systems.(1)
The application of predictive theoretical
models to estimate thermodynamic parameters of
ILs is of great interest, principally for the
proper selection of the component ions. In this
study, COSMO-RS method will be applied to predict
equilibrium data of the complex SILP triphasic
systems, which involved transfer phenomena of
solutes from the aqueous or gaseous phase to IL
phase to support phase. Concerning to simulation
of SILP, current studies were centered on
screening among type and amount of IL phase on
activated carbon (as solid support phase) to
obtain a combination with the required properties
(higher affinity toward the solute).
COMPUTATIONAL DETAILS
Thermodynamic Parameters by COSMO-RS
SILP Scheme
Molecular Model
Computational methods
Gas / Liquid Phase
Solutes
Quantum-chemical calculations Molecular
geometries were optimized at B3LYP/6-31G
level in the ideal gas-phase. ILs were simulated
using ion-paired structures. SILP systems were
simulated with a load of 40 (w/w) of IL on
activated carbon support. COSMO-RS
calculations Themodynamic parameters were
obtained by COSMOtherm software, using BP_TZVP_
C21_0105 parameterization. Experimental Data
Experimental data Log K and Log P were reported
from ref. 2, Log Kow were reported from ref. 3
and Kd were reported from ref. 4.
Water
Solvent IL Phase
SO2
H2
Solutes
Propene
H2S
Ion Pair Model
Ionic Liquid Phase
IL AC Phase
Activated Carbon
Solid Support Phase
RESULTS
BIPHASIC SYSTEMS COSMO-RS VALIDATION
TRIPHASIC SYSTEMS SILP SIMULATION for Henry
Constant
Affinity
(w/w) IL in AC
ANALYSIS AND CONCLUSIONS

• COSMO-RS predictions of equilibrium data have
  been validated for the cases of biphasic systems
  (LG, LL and LS) of interest in SILP simulations
• Henry constant (H) and Log P quantify the
  affinity of IL for solute from gas and aqueous
  phases, respectively.
• Log Kow indicates the stability of SILP in
  aqueous phase.
• Kd reports the affinity of support AC for IL
  from aqueous phase.
• COSMO-RS simulation of triphasic systems can be
  effectively used to design SILP materials
  according to affinity of IL on the support for
  the solute from gas or liquid phases.

BIBLIOGRAPHY (1) Riisager A, Fehrmann R,
Haumann M and Wasserscheid P. Supported ionic
liquid phase (SILP) catalysis. An innovative
concept for homogeneous catalysis in continuous
fixed-bed reactors. European Journal of Inorganic
Chemistry. 2006, 4, 695-706 (2) Michael H.
Abraham and William E. Acree, Jr. Comparative
analysis of solvation and selectivity in room
temperature ionic liquids using the Abraham
linear free energy relationship. Green Chemistry,
2006, 8, 906-915 (3) http//ilthermo.boulder.nist
.gov (4) Palomar J, Lemus J, Gilarranz MA and
Rodríguez JJ. Adsorption of ionic liquids from
aqueous effluents by activated carbon. Carbon,
2009. DOI10.1016/j.carbon.2009.03.028
Acknowledgements to CCCFC of UAM for
computational facilities.