Fundamental Catalysis and Engineering Challenges in Energy Harvesting

This commentary aims to stimulate further thoughts on pyrolysis technology by highlighting some aspects that are not yet fully resolved. Biocrude pyrolysis oil looks like petroleum oil in appearance, but the composition, energy content, and production process are quite different from those in petroleum oil. Therefore, the question arises on what can be done to make the pyrolysis oil technology-process and product-more attractive for commercial use. In the author's view, the perception created has been that it is a ready-to-use technology, only waiting for a political or business decision to progress in the implementation. There are however many research-related questions not yet answered. From this perspective, three areas involving catalysis and engineering aspects are discussed. First, the energy balance in the reactor is a poorly understood area. In other words, where does the energy required to maintain an endothermal reaction come from, especially in locations where utilities are scarce? Then, options to create additional value to make the technology more competitive and commercially viable are discussed. Finally, one of the least investigated topics, the performance of biocrude pyrolysis oil mixtures and its acid-catalyzed upgraded counterparts, is addressed

Crotonaldehyde hydrogenation on Rh/TiO2 catalysts. In situ DRIFTS studies

The surface and catalytic properties in the vapor-phase hydrogenation of crotonaldehyde on Rh/TiO2 has been studied. It was found that a partial reduction of the support produces a surface decoration of the metal component. Thus, interfacial sites are created, which are responsible of an increase in the selectivity to crotyl alcohol, via enhancement of the polarization of the C=O bond. Photoelectron spectra revelead that rhodium is in different oxidation states, with a contribution of ca. 20 % Rhd + and 80 % Rhº species for LTR catalyst and only a slight increase of Rhd + for HTR catalyst. TEM studies revelead that Rh has metal particle size close 3 nm with small increases in the catalyst reduced at high temperature. DRIFTS essayed carried out under reaction conditions allowed to identify crotonaldehyde species strongly adsorbed through the C=C bond and weakly coordinated through both the C=C and C=O bonds. After reduction at 723 K an increase in the peak at 1660 cm-1 ascribed to an interaction between the carbonyl group and the surface, was observed. This peak seems to be stabilized at interfacial Rh/TiOx sites The deactivation in crotyl alcohol formation can be ascribed to the generation of strongly chemisorbed asymmetric carboxylate species detected by band at 1740 cm-1. This band grows at expense of crotonaldehyde O s - bonded intermediate chemisorbed on coordinatively unsaturated sites (Lewis acid sites) responsible of the crotyl alcohol obtaintion (detected by a band at 1653 cm-1). Additionally, a small band at 2068 cm-1 assigned to CO adsorbed on transition metals, which increases with time on-stream may explain the deactivation of the catalysts in flow systems

Molecular-level understanding of interfacial carbonates in stabilizing CuO-ZnO(Al2O3) catalysts

A descriptor of active CuO-ZnO(Al2O3) methanol-synthesis and water–gas-shift catalysts is the presence of high-temperature carbonates (HT-CO3) in the oxidic catalyst precursor. Previous reports have shown that such HT-CO3 lead to an appropriate interaction between the oxides; as a result, a high Cu surface area (or Cu-Zn or Cu/ZnO interphase areas) can be achieved. Yet, their nature is not well understood. In this study, the nature of these carbonates was investigated by experimental and theoretical methods in the oxidic precatalyst. A calcined Cu-Zn-Al hydrotalcite model compound revealed to have well-dispersed ZnO and CuO phases, together with highly stable HT-CO3. It was hypothesized that these HT-CO3 groups may be placed at critical locations at nano-scale as a glue, thus avoiding the growth of the oxide crystallites during calcination. This is an excellent pre-condition to achieve a high Cu surface area (or Cu-Zn or Cu/ZnO interphase areas) upon reduction, and therefore a high activity. To prove that, first-principles calculations were carried out based on the density functional theory (DFT); alumina was not considered in the model as the experimental data showed it to be amorphous but it may still have an effect. Comprehensive calculations provided evidence that such carbonate groups favourably bind the CuO and ZnO together at the interface, rather than being isolated on the individual oxide surfaces. The results strongly suggest that the HT-CO3 groups are part of the structure, in the calcined precatalyst, where they would prevent thermal sintering through a bonding mechanism between CuO and ZnO particles, which is a novel interpretation of this important catalyst descriptor

Tooling up Heterogeneous Catalysis through Fenton's Chemistry. Detemplation and functionalization of micro- and mesoporous materials.

This paper discusses the use of Fenton's chemistry for catalyst preparation. This technology, based on the generation of OH(center dot) radicals from H(2)O(2) in presence of Fe-cations, has been applied for the treatment of wastewater to remove organic pollutants. In this study, it is shown that the Fenton's reaction is very effective for detemplation and functionalization of micro- and mesoporous materials. Three examples will be discussed.</p

Thermal detemplation of SBA-15 mesophases. Effect of the activation protocol on the framework contraction

<p>The potential use of the solvothermal extraction (SE) as a preliminary step to calcination for detemplating SBA-15 mesophases is investigated; aiming to reduce the amount of organics to be burnt and thereby the corresponding structural shrinkage. A systematic study was carried out by soxhlet extraction on mesophases hydrothermally aged between 90 and 130 degrees C. The mesophases containing variable amounts of template were then treated by calcination or pyrolysis/calcination. TGA was applied to quantify the template amount after the various treatments. The as obtained materials were characterized by SAXS and Ar ad/desorption for structural and textural information while H-1 NMR gave information about the integrity of the as-recycled template.</p><p>The study shows that solvothermal conditions remove considerably the template, typically from 50 to 10-20 wt.%, mainly extracted from the primary mesopores. Possible reuse of the extracted template is questionable as it is poor in polyethyleneoxide compared to the synthesis block-copolymer, Pluronic P123. For all thermal protocols applied (direct calcination, calcination after solvent-extraction or pyrolysis/calcination after solvent extraction), the thermal shrinkage decreases with the aging temperature; that is consistent with the condensation degree of the silica. For each mesophase, it was found that the thermal shrinkage becomes less pronounced when the material is fully templated; thus the template can serve as structural support or can control the mass transfer of O-2 and thereby the oxidation rate of the template burning. (c) 2013 Elsevier Inc. All rights reserved.</p>

Silica promoted self-assembled mesoporous aluminas. Impact of the silica precursor on the structural, textural and acidic properties

This paper investigates the effect of silica addition on the structural, textural and acidic properties of an evaporation induced self-assembled (EISA) mesoporous alumina. Two silica addition protocols were applied while maintaining the EISA synthesis route. The first route is based on the addition of a Na-free colloidal silica suspension (Ludox (R)), and the second method consists of the co-hydrolysis of tetraethyl orthosilicate (TEOS) with aluminium tri-sec-butoxide, to favour a more intimate mixing of the Al- and Si-hydrolysed species. The properties of the so derived materials were compared to the SiO2-free counterpart. The SiO2 addition was always beneficial from a structural and textural standpoint. TEOS appears to have a truly promoting effect; the ordering, surface area and pore volume are all improved. For Ludox (R), the enhancement comes from the formation of smaller pores by a densification of the structure. The crystallization of gamma-alumina depends on the interaction between the Al- and Si-species in the mesophase. Ludoe-based materials achieved crystallization at 750 degrees C but the intimate mixing in the TEOS-based mesophases shows a suppression of the phase transformation by 50-100 degrees C, with respect to the SiO2-free counterpart. This reduces the textural features substantially. For all SiO2-modified materials, the enhancement in the surface area is not accompanied by a concomitant improvement of total acidity, and the formation of weak Lewis acid sites was promoted. These effects were ascribed to SiO2 migration to the surface that blocks part of the acidity. (C) 2014 Elsevier B.V. All rights reserved