Recent Improvement on H2 Production by Liquid Phase Reforming of Glycerol: Catalytic Properties and Performance,and Deactivation Studies

Recently new Pt/Ni-based γ-Al₂O₃ catalysts have been developed in our laboratory with a good performance for H₂ production by aqueous phase reforming of glycerol. This paper reviews these developments based on the study of the catalytic properties and performance, as well as their deactivation mechanisms. These works have led to set new perspectives related to the enhancement of catalysts hydrothermal stability and to the reduction of the deactivation processes.     

Effect of ZrO2 addition on Ni/Al2O3 catalyst to produce H2 from glycerol

In this work, ZrO₂ was employed as support and as Al₂O₃ modifier of Ni based catalysts due to its special interesting characteristics. The catalytic activity of these systems was studied in steam reforming of glycerol to produce H₂. As the activity results at 773 K and 873 K showed, the NiZ catalyst allowed low glycerol conversion and H₂ production when compared to the NiγA catalyst. Moreover, the NiZ catalyst was not able to reform intermediate liquid products into gaseous products.     

Micro reactor hydrogen production from ethylene glycol reforming using Rh catalysts supported on CeO2 and La2O3 promoted α-Al2O3

In this work the validation of ethylene glycol (EG) as raw material for hydrogen production by steam reforming (SR) and oxidative steam reforming (OSR) reactions was studied using microchannel testing reactors. The experiments were carried out at a steam to carbon ratio (S/C) of 4.0, several temperatures and atmospheric pressure. Rh based catalysts were designed using α-Al₂O₃ modified with different contents of CeO₂ or La₂O₃ oxides as their supports. Different temperatures were tested for SR experiments (725, 675 and 625 °C) at a volume hourly space velocity (VHSV) of 200 NL/h g_cat as well as different VHSV (300 and 100 NL/h g_cat) at a constant temperature of 675 °C. In the case of OSR experiments, only the effect of the VHSV was studied at 675 °C. A long term experiment was carried out with the 2.5Rh–20Ce catalyst which lasted over 115 h in stable conditions. The catalysts physicochemical properties were studied by their characterization using the following techniques: ICP-AES, N₂ physisorption, TPR, TEM, XRD and XPS.     

PdCu membrane integration and lifetime in the production of hydrogen from methane

PdCu membranes prepared by sequential electroless plating were integrated into a hydrogen production and purification process. Hydrogen was produced from methane through catalytic partial oxidation and wet catalytic partial oxidation with Ni-based catalysts. Membrane permeance was measured with thermal cycles in an inert and hydrogen atmosphere at 673 and 773 K. Permeability was 1.98·10⁻³ mol/(smPa^0.5) at 673 K and 2.62·10⁻³ mol/(smPa^0.5) at 773 K. The optimum sweep gas flow required in the membrane module when operating with hydrogen-containing mixtures was selected. Peak hydrogen recovery was obtained using 15–20% of the feed to the module as sweep gas flow. Membranes were then placed downstream of the hydrogen production reactor. The CO and H₂O percentages fed to the membrane module did not have a major impact on membrane behavior. Around 60–67% of the hydrogen fed to the membrane module was separated, regardless of its composition.     

Glycerol steam reforming over Ni catalysts supported on ceria and ceria-promoted alumina

In this paper glycerol steam reforming over Ni catalysts supported on bare CeO₂ and Al₂O₃, and CeO₂-promoted Al₂O₃ to produce H₂ was studied. The catalytic activity results for the NiAl5Ce and NiAl10Ce catalysts showed that the incorporation of low ceria loadings enhances the activity of the NiAl catalyst prepared using a similar composition to the commercial Ni/Al₂O₃ catalysts. The catalyst surface characterization revealed that the good behaviour of the NiAl5Ce and the NiAl10Ce catalysts depends on the stabilization of Ni° particles which is promoted by the formation of nickel–ceria interactions. The increase of ceria content reduced the capacity of the NiAl20Ce catalyst to convert intermediate oxygenated hydrocarbons into H₂.     

Hydrogen production from methane and natural gas steam reforming in conventional and microreactor reaction systems

Ni-based (over MgO and Al₂O₃) and noble metal-based (Pd and Pt over Al₂O₃) catalysts were prepared by wet impregnation method and thereafter impregnated in microreactors. The catalytic activity was measured at several temperatures, atmospheric pressure and different steam to carbon, S/C, ratios. These conditions were the same for conventional, fixed bed reactor system, and microreactors. Weight hourly space velocity, WHSV, was maintained equal in order to compare the activity results from both reaction systems. For microreactor systems, similar activities of Ni-based catalyst were measured in the steam methane reforming (SMR) activity tests, but not in the case of natural gas steam reforming tests. When noble metal-based catalysts were used in the conventional reaction system no significant activity was measured but all catalysts showed some activity when they were tested in the microreactor systems. The analysis by SEM and TEM revealed a carbon-free surface for Ni-based catalyst as well as carbon filaments growth in case of noble metal-based catalysts.     

Preface to International Symposium of Catalysis for Clean Energy and Sustainable Chemistry (CCESC2018)

Topics in Catalysis -     

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

Abstract

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.     

Hydrodesulfurization and hydrogenation of model compounds on silica-alumina supported bimetallic systems

Silica-alumina supported Pd catalysts with a second metal such as Cu, Ru or Pt have been prepared (nominal content: 1 wt%) and tested in the naphthalene hydrogenation (HYD) and dibenzothiophene hydrodesulfurization (HDS) model reactions. These catalysts were characterized by means of temperature-programmed reduction, NH₃ temperature-programmed desorption and photoelectron spectroscopy techniques. The combined use of all these techniques revealed that only in the case of PtPd system a rather uniform distribution of the metals across the pore network is achieved. Another important observation was that the PtPd system exhibited strong Brönsted acid sites. The highest HYD and HDS activities of the PtPd bimetallic catalyst can be related not only to a high dispersion of the metals and their uniform distribution but also to its strong Brönsted acidity. The PtPd system presented the highest DBT conversion (83.1%) and the highest C-S hydrogenolysis activity as illustrated by the lowest S-containing products (21.9 wt%) as compared with the much higher S-containing products (54.8 wt%) obtained with the monometallic Pd/ASA catalyst under the same experimental conditions.     

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).