J. Bedia

Anion effects on kinetics and thermodynamics of CO2 absorption in ionic liquids

A thermogravimetric technique based on a magnetic suspension balance operating in dynamic mode was used to study the thermodynamics (in terms of solubility and Henrys law constants) and kinetics (i.e., diffusion coefficients) of CO2 in the ionic liquids [bmim][PF6], [bmim][NTf2], and [bmim][FAP] at temperatures of 298.15, 308.15, and 323.15 K and pressures up to 20 bar. The experimental technique employed was shown to be a fast, accurate, and low-solvent-consuming method to evaluate the suitability of the ionic liquids (ILs) to be used as CO2 absorbents. Thermodynamic results confirmed that the solubility of CO2 in the ILs followed the order [bmim][FAP] > [bmim][NTf2] > [bmim][PF6], increasing with decreasing temperatures and increasing pressures. Kinetic data showed that the diffusion coefficients of CO2 in the ILs followed a different order, [bmim][NTf2] > [bmim][FAP] > [bmim][PF6], increasing with increasing temperatures and pressures. These results evidenced the different influence of the IL structure and operating conditions on the solubility and absorption rate of CO2, illustrating the importance of considering both thermodynamic and kinetic aspects to select adequate ILs for CO2 absorption. On the other hand, the empirical Wilke-Chang correlation was successfully applied to estimate the diffusion coefficients of the systems, with results indicating the suitability of this approach to foresee the kinetic performance of ILs to absorb CO2. The research methodology proposed herein might be helpful in the selection of efficient absorption solvents based on ILs for postcombustion CO2 capture.

Zr-doped TiO2 supported on delaminated clay materials for solar photocatalytic treatment of emerging pollutants.

Solar light-active Zr-doped TiO2 nanoparticles were successfully immobilized on delaminated clay materials by a one-step sol-gel route. Fixing the amount of TiO2 at 65wt.%, this work studies the influence of Zr loading (up to 2%) on the photocatalytic activity of the resulting Zr-doped TiO2/clay materials. The structural characterization demonstrates that all samples were formed by a delaminated clay with nanostructured anatase assembled on its surface. The Zr dopant was successfully incorporated into the anatase lattice, resulting in a slight deformation of the anatase crystal and the reduction of the band gap. These materials exhibit high surface area with a disordered mesoporous structure formed by TiO2 particles (15-20nm) supported on a delaminated clay. They were tested in the solar photodegradation of antipyrine, usually used as an analgesic drug and selected as an example of emerging pollutant. High degradation rates have been obtained at low antipyrine concentrations and high solar irradiation intensities with the Zr-doped TiO2/clay catalyst, more effective than the undoped one. This work demonstrates the potential application of the synthesis method for preparing novel and efficient solar-light photocatalysts based on metal-doped anatase and a delaminated clay.

Ammonia capture from the gas phase by encapsulated ionic liquids (ENILs)

Encapsulated ionic liquids (ENILs) based on carbonaceous submicrocapsules were designed, synthesized and applied to the sorption of NH3 from gas streams. The ENILs were prepared using three different task-specific ILs with adequate properties for NH3 capture: 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate (EtOHmimBF4), choline bis(trifluoromethylsulfonyl)imide (CholineNTf2) and tris(2-hydroxyethyl)methylammonium methylsulfate [(EtOH)3MeNMeSO4]. The ENILs synthesized were analyzed by different techniques to assess their morphology, chemical composition, porous structure and thermal stability. The capture of NH3 was tested in fixed-bed experiments under atmospheric pressure. The influence of the type and load of IL, temperature (30, 45 and 60 °C) and NH3 inlet concentration was analyzed. Desorption of NH3 from the exhausted ENILs was also studied at atmospheric pressure and temperatures in the range of 150 to 200 °C. The ENILs prepared with task-specific ILs were found to be suitable for NH3 capture in the fixed-bed operation. These systems can be a promising alternative to conventional absorption or adsorption due to: (i) high sorption capacity controlled by IL selection, (ii) remarkable mass transfer rate, (iii) low sensitiveness to high temperatures of the gas stream, (iv) fast and complete regeneration of the exhausted ENIL at mild conditions; and (v) recovery of NH3.

Effects of pH value and calcium hardness on the removal of 1,1,1-trichloroethane by immobilized nanoscale zero-valent iron on silica based supports

Immobilizing nanoscale zero-valent iron (NZVI) particles on silica-based supports is an effective way to overcome the NZVI aggregation. The pH value and calcium hardness can change the aggregation kinetics and alter the stability of the suspensions of NZVI-silica based materials, thus change the reactivity of these NZVI-silica based materials to remove chlorinated aliphatic hydrocarbons (CAHs). The removal of CAHs by these NZVI-silica based materials includes adsorption by silica based supports and degradation by NZVI particles. Using 1,1,1-TCA and mesoporous hydrated silica (mHS) as model chlorinated aliphatic hydrocarbon (CAH) and silica based support, the effects of pH value and Ca2+ concentration on both the adsorption and adsorption-degradation processes of CAHs by NZVI-silica based materials were studied. The structural and textural features, suspension stability, particle size distribution, and Zeta potential of the materials under various conditions were characterized by different techniques. Both decreasing initial pH value and increasing Ca2+ concentration can reduce the Zeta potential of mHS and lead to the aggregation of mHS particles, thus inhibiting the removal of 1,1,1-TCA via adsorption by mHS through decreasing the number of sites for adsorption. Low initial pH value can accelerate the corrosion of NZVI core and remove the passivation layer, thus promoting the removal of 1,1,1-TCA via adsorption-degradation by NZVI@mHS. Ca2+ can decrease the sites for adsorption and form precipitates which can block mesoporous channels, thus hinder the 1,1,1-TCA removal via adsorption-degradation by NZVI@mHS.

Chloroform conversion into ethane and propane by catalytic hydrodechlorination with Pd supported on activated carbons from lignin

Conversion of chloroform (TCM) by gas-phase catalytic hydrodechlorination (HDC) has been addressed to maximize the selectivity to ethane and propane. Several own-made Pd (1 wt%) catalysts have been tested. The catalysts were prepared by incipient wetness impregnation of five different activated carbons. These carbons were obtained by chemical activation of lignin with different activating agents, namely, H3PO4, ZnCl2, FeCl3, NaOH and KOH. The catalysts were fully characterized by N2 adsorption–desorption at −196 °C, CO2 adsorption at 0 °C, TPR, NH3-TPD, XRD, XPS and TEM. The activating agents provided important differences in the characteristics of activated carbon supports, and hence in the resulting catalysts, in terms of their porous texture, surface acidity, Pd oxidation state and Pd particle size distribution. NaOH and KOH activation led to carbons with the highest surface areas (2158 and 2991 m2 g−1, respectively) and low Pd0/Pdn+ ratios, while ZnCl2- and H3PO4-activated carbons yielded the highest surface acidity and mean Pd particle sizes. The analysis of the TOF values revealed that the HDC of TCM on these catalysts is a structure-sensitive reaction, increasing TOF values with Pd particle size. The best results, in terms of selectivity to ethane and propane, were obtained with the catalysts supported on KOH- and NaOH-activated carbons. The former allowed 80% selectivity to the target compounds at almost complete dechlorination (>99%) at 300 °C. The KOH-based catalyst showed fairly good stability at a reaction temperature of 200 °C.