Energy and economic analysis of alternatives for the valorization of hydrogen rich stream produced in the aqueous phase reforming of pyrolysis bio-oil aqueous fraction.

Aqueous phase reforming has been explored for renewable H2 production from waste biomass. Promising results have been reported for pyrolysis bio-oil aqueous fractions (AFB), but economical assessments are needed to determine process feasibility, which requires both energy consumption minimization and optimal H2 valorization. This work compares different alternatives using process simulation and economic evaluation computational tools. Experimental results and a specific thermodynamic model are used to set mass balances. An adequate heat integration allows to reduce the process energy demand, covering the 100 % of the reactor duty. Optimal H2 unit cost is achieved if part of the produced H2 is valorized for energy self-covering and the rest is commercialized. Renewable H2 net production of c.a. 3.3 kgH2/m3 of treated AFB at a preliminary 1-2 €/kg unit cost is estimated, which can be considered as competitive with green H2, even though a case of diluted AFB is considered.

Laminar N-Doped Carbon Materials from a Biopolymer for Use as a Catalytic Support for Hydrodechlorination Catalysts.

Nitrogen-doped porous carbons were prepared using a chitosan biopolymer as both a carbon and nitrogen precursor and metallic salts (CaCl2 and ZnCl2-KCl) as a templating agent with the aim of evaluating their performance as catalyst supports. Mixtures of chitosan and templating salts were prepared by simple grinding subjected to pyrolysis and finally washed with water to remove the salts. The resulting materials were characterized, showing that homogeneous nitrogen doping of carbon was achieved (7-9% wt.) thanks to the presence of a nitrogen species in the chitosan structure. A lamellar morphology was developed with carbon sheets randomly distributed and folded on themselves, creating slit-shaped pores. Substantial porosity was observed in both the micropore and mesopore range with a higher surface area and microporosity in the case of the materials prepared by ZnCl2-KCl templating and a larger size of mesopores in the case of ZnCl2. Catalysts with well-dispersed Pd nanoparticles (around 10 nm in diameter size) were synthesized using the chitosan-based carbons obtained both by salt templating and direct chitosan pyrolysis and tested in the aqueous phase hydrodechlorination of 4-chlorophenol. The fast and total removal of 4-chlorophenol was observed in the case of catalysts based on carbons obtained by templating with CaCl2 and ZnCl2-KCl in spite of the low metal content of the catalysts (0.25% Pd, wt.).

High load drug release systems based on carbon porous nanocapsule carriers. Ibuprofen case study.

This work shows the application of carbon nanocapsules as carriers for sodium ibuprofen release. Hard templating was used to prepare spherical carbon nanocapsules (mean diameter and thick shell of 690 and 70 nm, respectively), exhibiting both micro and mesoporosity. For comparison purposes, a microporous commercial activated carbon and a home-made mesoporous CMK-3 were also studied. All carbons showed similar drug uptake, although microporous commercial carbon and nanocapsules showed higher uptake at low equilibrium concentration due to higher adsorption potential in micropores. Higher and faster release of sodium ibuprofen was observed for carbon nanocapsules at pH 1.8 and 7.4 for a starting load ca. 250 mg g-1. Subsequent loading of carbon nanocapsules by successive evaporation cycles led to a remarkable load of ca. 6010 mg g-1 thanks to sodium ibuprofen filling the internal void volume. In spite of the very high load a fast release was observed at pH 7.4, reaching a release of ca. 100% of the initial sodium ibuprofen load. However, a much slower and lower release was observed at pH 1.8. Thus, the system developed has interesting features for oral drug administration thanks to low toxicity of porous carbon, low release in gastric medium and important release in intestinal medium.

Encapsulated Ionic Liquids for CO2 Capture: Using 1-Butyl-methylimidazolium Acetate for Quick and Reversible CO2 Chemical Absorption.

The potential advantages of applying encapsulated ionic liquid (ENIL) to CO2 capture by chemical absorption with 1-butyl-3-methylimidazolium acetate [bmim][acetate] are evaluated. The [bmim][acetate]-ENIL is a particle material with solid appearance and 70 % w/w in ionic liquid (IL). The performance of this material as CO2 sorbent was evaluated by gravimetric and fixed-bed sorption experiments at different temperatures and CO2 partial pressures. ENIL maintains the favourable thermodynamic properties of the neat IL regarding CO2 absorption. Remarkably, a drastic increase of CO2 sorption rates was achieved using ENIL, related to much higher contact area after discretization. In addition, experiments demonstrate reversibility of the chemical reaction and the efficient ENIL regeneration, mainly hindered by the unfavourable transport properties. The common drawback of ILs as CO2 chemical absorbents (low absorption rate and difficulties in solvent regeneration) are overcome by using ENIL systems.

Encapsulated ionic liquids (ENILs): from continuous to discrete liquid phase.

Encapsulated ionic liquid (ENIL) material was developed, consisting of ionic liquid (IL) introduced into carbon submicrocapsules. ENILs contain >85% w/w of IL but discretized in submicroscopic encapsulated drops, drastically increasing the surface contact area with respect to the neat fluid. ENIL materials were here tested for gas separation processes, obtaining a drastic increase in mass transfer rate.

Computational approach to nuclear magnetic resonance in 1-Alkyl-3-methylimidazolium ionic liquids.

A quantum-chemical computational approach to accurately predict the nuclear magnetic resonance (NMR) properties of 1-alkyl-3-methylimidazolium ionic liquids has been performed by the gauge-including atomic orbitals method at the B3LYP/6-31++G** level using different simulated ionic liquid environments. The first molecular model chosen to describe the ionic liquid system includes the gas-phase optimized structures of ion pairs and separated ions of a series of imidazolium salts containing methyl, butyl, and octyl substituents and PF6-, BF4-, and Br- anions. In addition, a continuum polarizable model of solvation has been applied to predict the effects of the medium polarity on the molecular properties of 1,3-dimethylimidazolium hexafluorophosphate (MmimPF6). Furthermore, the specific acidic and basic solute-solvent interactions have been simulated by a discrete solvation model based on molecular clusters formed by MmimPF6 species and a discrete number of water molecules. The computational prediction of the NMR spectra allows a consistent interpretation of the dispersed experimental evidence in the literature. The following are main contributions of this work: (a) Theoretical results state the presence of a chemical equilibrium between ion-pair aggregates and solvent-separated counterions of 1-alkyl-3-methylimidazolium salts which is tuned by the solvent environment; thus, strong specific (acidic and basic) and nonspecific (polarity and polarizability) solvent interactions are predicted favoring the dissociated ionic species. (b) The calculated 1H and 13C NMR properties of these ionic liquids are revealed as highly dependent on the nature of solute-solvent interactions. Thus, the chemical shift of the hydrogen atom in position two of the imidazolium ring is deviated to high values by the specific interactions with water molecules, whereas nonspecific interaction with water (as a solvent) affects, in the opposite direction, this 1H NMR parameter. (c) Last, current calculations support the presence of hydrogen bonding between counterions, suggesting the importance of this interaction in the properties of the solvent in the 1-alkyl-3-methylimidazolium ionic liquids.