Hydrogen Production from Glycerol Over Nickel Catalysts Supported on Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Modified by Mg,Zr, Ce or La

Hydrogen production from glycerol reforming in liquid (aqueous phase reforming, APR) and vapor (steam reforming SR) phase over alumina-supported nickel catalysts modified with Ce, Mg, Zr and La was studied. Characterization of catalysts by temperature programmed reduction and XPS analyses revealed important structural effects: (i) the intercalation of Mg between nickel and alumina that inhibited the alumina incorporation to nickel phases, (ii) the close contact between Ni and Zr phases and, (iii) the close surface interaction of La and Ce ions with NiO phases. The catalytic activity of the samples studied in this work clearly indicated the different catalyst functionalities necessary to carry out aqueous-phase and vapor-phase steam reforming of glycerol. For aqueous phase reforming of glycerol, the addition of Ce, La and Zr to Ni/Al₂O₃ improves the initial glycerol conversions obtained over the Ni/Al₂O₃ supported catalyst. It is suggested that the differences in catalytic activities are related with geometric effects caused by the decoration of Ni phases by Ce and La or by the close interaction between Ni and Zr. In spite that nickel catalysts showed high APR activities at initial times on stream, all samples showed, independently of support, important deactivation rates that deactivate the catalysts after few hours under operation. Catalysts characterization after APR showed the oxidation of the active metallic Ni during reaction as the main cause of the observed deactivation. In the case of the glycerol steam reforming in vapor phase, the use of Ce, La, Mg and Zr as promoters of Ni based catalysts increases the hydrogen selectivity. Differences in activity were explained in terms of enhancement in: surface nickel concentration (Mg), capacity to activate steam (Zr) and stability of nickel phases under reaction conditions (Ce and La).     

Hydrogen Production with a Microchannel Reactor by Tri-Reforming; Reaction System Comparison and Catalyst Development

In this work, Pt based mono and bimetallic catalysts were tested under conditions of tri-reforming (TR). All the catalysts contained 25% of CeO₂ and a metal loading of 2.5 or 5.0% (wt%). The bimetallic catalysts contained 2.5% Pt and 2.5% of Me, where Me?=?Ni, Co, Mo, Pd, Fe, Re, Y, Cu or Zn. For all the experiments, a synthetic biogas which consisted of 60% CH₄ and 40% CO₂ (vol.) was mixed with water, S/C?=?1.0, and oxygen, O₂/CH₄?=?0.25, and fed to a fixed bed reactor (FBR) system or a microreactor. The 2.5Pt catalyst was used in order to compare the performance of each reaction system. The tests were performed at reaction temperatures between 700 and 800?°C, and at volume hourly space velocities (VHSV) between 100 L_N/(h g_cat) and 200 L_N/(h g_cat) for the FBR system and between 1000 L_N/(h g_cat) and 2000 L_N/(h g_cat) for the microreactor, at atmospheric pressure. Then, all catalysts were deposited into microchannel reactors and tested at a constant VHSV of 2000 L_N/(h g_cat) and reaction temperatures between 700 and 800?°C. Catalysts under investigation were characterized applying the following techniques: inductively coupled plasma optical emission spectroscopy (ICP-OES), N₂ Physisorption, Temperature Programmed Reduction (TPR), CO chemisorption, Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). The microreactor was identified as the most efficient and promising reaction system, and the 2.5(Pt–Pd) catalyst as the bimetallic formulation with the highest activity. Therefore its activity and stability was compared with the reference 5.0Pt catalyst at 700?°C and VHSV of 2000 L_N/(h g_cat) for more than 100 h. Although slightly lower activity was measured operating with the 2.5(Pt–Pd) catalyst, a significant reduction of the Pt content compared to the reference 5.0Pt catalyst was achieved through the incorporation of Pd.     

Hydrometallurgical process development for the production of a zinc sulphate liquor suitable for electrowinning

This study deals with the development of an innovative hydrometallurgical process for zinc recovery from Waelz Oxide, a concentrate of zinc and lead oxides obtained pyrometallurgically from the treatment of EAF dusts.Its main objective is the production of a zinc sulphate liquor to be used as feedstock in electrolytic processes. The process requires different stages to achieve this goal. The first stage consists of a double-sulphuric-acid-leaching, achieving a 88% lixiviation of the zinc present in the Waelz Oxide. After the leaching, to fulfil the strict requirements of an electrolysis feed, some purifying stages, such as oxidation, removing more than the 99% of the iron present in the leach liquor, and cementation to remove cadmium, lead and copper were investigated. Finally, if the concentration of some metallic impurity is above the accepted level for electrolytic processes, an additional purification stage could be considered.Through this process, sulphate zinc liquors with a zinc purity of around 99.75%, containing less than 135 ppm of metallic impurities, could be obtained.     

Biogas steam and oxidative reforming processes for synthesis gas and hydrogen production in conventional and microreactor reaction systems

In this work, a renewable source, biogas, was used for synthesis gas and hydrogen generation by steam reforming (SR) or oxidative reforming (OR) processes. Several Ni-based catalysts and a bimetallic Rh–Ni catalyst supported on magnesia or alumina modified with oxides like CeO₂ and ZrO₂ were used. For all the experiments, a synthetic biogas which consisted of 60% CH₄ and 40% CO₂ (vol.) was fed and tested in a fixed bed reactor system and in a microreactor reaction system at 1073 K and atmospheric pressure. The catalysts which achieved high activity and stability were impregnated in a microreactor to explore the viability of process intensification. For the SR process different steam to carbon ratios, S/C, varied from 1.0 to 3.0 were used. In the case of OR process the O₂/CH₄ ratio was varied from 0.125 to 0.50. Comparing conventional and microreactor reaction systems, one order of magnitude higher TOF and productivity values were obtained in the microreactors, while for all the tested catalysts a similar activity results were achieved. Physicochemical characterization of catalysts samples by ICP-AES, N₂ physisorption, H₂ chemisorption, TPR, SEM, XPS and XRD showed differences in chemical state, metal–support interactions, average crystallite sizes and redox properties of nickel and rhodium metal particles, indicating the importance of the morphological and surface properties of metal phases in driving the reforming activity.     

Natural and synthetic iron oxides for hydrogen storage and purification

In this paper, the hydrogen storage capacity of some synthetic and natural iron oxides is presented. The results of the activity tests and characterization techniques of natural and synthetic iron oxides (N₂ adsorption–desorption isotherms, temperature-programmed reduction, X-ray diffraction, and plasma atomic emission spectroscopy) suggest that the use of chromium on iron oxide systems improved their hydrogen storage capacity. This is related to the capacity of chromium to modify the iron oxide reduction profile when Cr was incorporated. A direct reduction from Fe₃O₄ to Fe was observed as the mechanism for H₂ storage. In addition, natural oxides as commercial Superfine and Densinox-L oxides are proved to be suitable materials to store and purify H₂ due to their high stability during different cycles of reduction and oxidation. The best results among the natural ones were Densinox-L and among the synthetic ones Fe–10Cr.     

Effect of redox additives over Ni/Al2O3 catalysts on syngas production via methane catalytic partial oxidation

Alumina-supported nickel catalysts modified with redox (Mo, Mn and Sn) oxides were tested in the catalytic partial oxidation (CPO) of methane and the wet catalytic partial oxidation (wet-CPO) of methane for syngas production. The influence of different reaction parameters on the performance of these systems was studied for both reactions. Certain insights on catalyst surface structure were revealed by means of X-ray photoelectron spectroscopy (XPS) and thermal programmed reduction (TPR). The joint analysis of all the results led to certain correlations between the structure of the catalysts and catalytic activity, indicating that the redox additives to some extent modify the stability of the active nickel phase by altering the nickel–alumina interface interaction.     

COMBINED EFFECT OF FLUORINE AND ZINC INCORPORATION ON THE HDS ACTIVITY OF Co-Mo CATALYSTS

Conventional HDS-catalysts consist of Co and Mo supported on Y-Al₂O₃. The addition of Zn as a second promoter or the alumina acidification with F increase the catalitye activity in HDS of commercial feeds (Fierro et al., 1984; Boorman et al., 1984). In this paper the combined effect of both Zn and F incorporation is discussed. A series of Zn-Co-Mo catalysts supported on fluorinated alumina (0.0 -2.0 wt% F) was prepared and tested for HDS activity using a commercial gas-oil. The data gathered showed a decrease in HDS activity for intermediate F contents (0.4 - 1.0 wt%). This result could be tentatively explained through alumina surface deterioration during impregnation with NH₄HF₂ solutions al low pH.     

Power-to-Gas: Storing surplus electrical energy. Study of catalyst synthesis and operating conditions

Energy storage is needed in order to sustain the energy system on renewable energies like wind and solar power. Power-to-Gas (PtG) is a technology that enables the storage of the renewable electricity in a chemical carrier such as hydrogen, via water electrolysis, or methane, via carbon dioxide methanation. In this work a series of catalysts based on nickel and alumina, the catalyst commonly employed for carbon dioxide methanation, have been synthesised employing different calcination temperatures to study the influence of this parameter in the activity of the catalysts. As a result of this study 673 K was determined as the most suitable Moreover, the catalysts have also been tested at different pressures to determine the most suitable operating pressure. Although due to Le Chatelier's Principle a higher pressure results in an increasing yield, the study carried out proved that 10 bar is the most suitable pressure as the difference in the yield when increasing the pressure it is not high enough taking into account the costs and risks associated with higher pressures.